OA17684A

OA17684A - Heterocycle-substituted bicyclic azole pesticides.

Info

Publication number: OA17684A
Application number: OA1201600091
Authority: OA
Inventors: David Alan Clark; Breena Gloriana FRAGA; Wenming Zhang
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2013-09-13
Filing date: 2014-09-09
Publication date: 2017-07-14

Abstract

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, Noxides, and salts thereof, and A, R1 , m, X1 , X2 , X3 , X 4 , Y1 , Y2 and Y3 are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the invention.

Description

TiTLE

HETEROCYCLE-SUBSTITUTED BICYCLIC AZOLE PESTICIDES

FIELD OFTHE INVENTION

This invention relates to certain substituted bicyclic azoles, their /V-oxides, salts and compositions suitable for agronomie and nonagronomic uses, and methods of their use for controlling invertebrate pests such as arthropode in both agronomie and nonagronomic environments.

BACKGROUND OFTHE INVENTION

The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomie crops can cause significant réduction in productivity and thereby resuit in increased costs to the consumer. The control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or hâve different sites of action.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including ail géométrie and stereoisomers), /V-oxides, and salts thereof, and compositions containing them and their use for controlling invertebrate pests:

i wherein

Q is

Q-2

Q-3

A is CH, CR¹ or N;

each R¹ is independently halogen, cyano, nitro, C^-C₄ alkyl, C-|-C₄ haloalkyl, C-|-C₄alkoxy, C-|-C₄ haloalkoxy, C-i-C₄ alkylthio or C₁-C₄ haloalkylthio;

m is 0, 1, 2 or 3;

X¹, X², X³ and X⁴ are each independently CR², CR³ or N, provided that (i) one of X¹, X², X³and X⁴ is CR², and (ii) no more than one of X¹, X², X³ and X⁴ is N;

R² is C(=Z)NR⁶R⁷, N(R⁸)C(=Z)R⁹, C(=NR¹⁰)R¹¹ or Q^a; each Z is independently O or S;

each R³ is independently H, halogen, cyano, nitro, C-|-C₄ alkyl, C-t-C₄ haloalkyl, C-|-C₄alkoxy or C₁-C₄ haloalkoxy;

Y¹ is O, S or NR⁴;

Y² is N or CR^5a;

Y³ is N or CR^5b;

R⁴ is H or C-|-C₄ alkyl;

R^5a is H, halogen, cyano, nitro, C-|-C₄ alkyl, C₃-C₆ cycloalkyl, C-|-C₄ haloalkyl, C₁-C₄alkoxy or C-!-C₄ haloalkoxy;

R^5b is H, halogen, cyano, nitro, Ci-C₄ alkyl, C₃-C₆ cycloalkyl, C-i-C₄ haloalkyl, Ct-C₄alkoxy or C-i-C₄ haloalkoxy;

R⁶ is H, NR¹⁵R¹⁶, OR¹⁷, C(=NR^1o)R¹¹, C(O)OR²¹, C(O)NR¹⁵R¹⁶, C(O)R²², S(O)nR²³ or Q^b; or C·]—C6 alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted or substituted with at least one R^x;

R⁷ is H or Q^b; or C-|-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted or substituted with at least one R^x; or .

R⁶ and R⁷ are taken together with the nitrogen atom to which they are attached to form a 3- to 10-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, said ring being unsubstituted or substituted with up to 4 R^x; or

R⁶ and R⁷ are taken together as =S(O)_PR¹⁸R¹⁹ or =S(=NR²⁰)R¹⁸R¹⁹; .

each R^x is independently halogen, cyano, nitro, hydroxy, Q-Cg alkyl, C^Cg haloalkyl, C3C6 cycloalkyl, C-i-Cg alkoxy, C-|-C6 haloalkoxy, C3-C6 cycloalkoxy, C(=NR^)R’'\ C(O)OR²¹, C(O)NR¹⁵R¹⁶, OC(O)R²², NR²⁵R²⁶, NR²⁴C(O)R²², C(O)R²², S(O)nR²³, Si(R²⁸)3, OSi(R²⁸)3 or Q^b;

R⁸ is H, C(O)OR²¹, C(O)NR¹⁵R¹⁶, C(O)R²², S(O)nR²³ or Q^b; or C^-Cg alkyl, C3-C₆cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted or substituted with at least one R^x;

R⁹ is H, C(=NR¹⁰)R¹¹, OR²¹ or NR¹⁵R¹⁶; or C^-Cg alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl or C2-C6 alkynyl, each unsubstituted or substituted with at least one R^x; or phenyl, phenoxy or a 5- or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C₆ cycloalkyl, C^-04 haloalkyl, C·,—C₄ alkoxy and C-|-C₄ haloalkoxy; or a 3- to 6-membered heterocyclic nonaromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 1 carbon atom ring member is independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, each ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-I-C4 alkyl, C₃-C₆ cycloalkyl, C-|-C₄ haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy;

each R¹⁰ is independently OR¹², S(O)_nR¹³ or NHR¹⁴;

each R¹¹ is independently H; or Ο,-Ο6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl or C2-C6 alkynyl, each unsubstituted or substituted with at least one R^x; or Ci-C6 alkoxy, C-iC₆ haloalkoxy, C₃-C₆ cycloalkoxy, C(O)OR²¹, C(O)NR¹⁵R¹⁶, NR²⁵R²⁶, NR²⁴C(O)R²², C(O)R²² or Q^b;

each R¹² is independently C1-C4 alkyl, C₃-C₆ cycloalkyl, C1-C4 haloalkyl, 0(0^22, S(O)_nR¹³ or Q^b;

each R¹³ is independently C1-C4 alkyl or C-1-C4 haloalkyl;

R¹⁴ is 0,—C4 alkyl, C3-C6 cycloalkyl, C-|-C4 haloalkyl, C(O)R²² or C(O)OR²¹; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, 0^4 alkyl, C3-C₆ cycloalkyl, C1-C4 haloalkyl, Ο·,-Ο₄ alkoxy and Ο·,-Ο₄ haloalkoxy;

each R¹⁵ is independently H, Ο,-Ο6 alkyl, 0,-04 haloalkyl, C(O)R²⁷ or S(O)2R²⁷; or phenyl or a 5- or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C₆ cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy and 0·,-0₄ haloalkoxy;

each R¹⁶ is independently H, C-|-C₆ alkyl or 0-,-0₄ haloalkyl; or

R¹⁵ and R¹⁶ are taken together with the nitrogen atom to which they are attached to form a

3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=0) and C(=S) and the sulfur atom ring member is selected from S, S(0) or S(0)2, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-,-04 alkyl, C₃-C₆ cycloalkyl, Οϊ-Ο₄ haloalkyl, C-1-C4 alkoxy and 0,-0₄haloalkoxy;

R¹⁷ is C-,—C₄ alkyl, C₃-C₆ cycloalkyl or C-,-C₄ haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C₃-C₆ cycloalkyl, 0,-0₄ haloalkyl, C1-C4 alkoxy and C-,-04 haloalkoxy;

each R¹⁸ is independently U-C4 alkyl or C1-C4 haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-|-C₄ alkyl, C₃-C₆ cycloalkyl, C-|-C₄ haloalkyl, Ci-C₄ alkoxy and C-|-C₄ haloalkoxy;

each R¹⁹ is independently C-|-C₄ alkyl or Ci-C₄ haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C^-CU alkyl, C₃-C₆ cycloalkyl, Ci-C₄ haloalkyl, Cî-C₄ alkoxy and C!-C₄ haloalkoxy; or

R¹⁸ and R¹⁹ are taken together with the sulfur atom to which they are attached to form a ring;

R²⁰ is H, cyano, Cî-CU alkyl, C-|-C4 haloalkyl or C(O)R²²; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-i-CU alkyl, C3-C₆ cycloalkyl, C-|-C₄ haloalkyl, C-j—C₄ alkoxy and C-|-C₄ haloalkoxy;

each R²¹ is independently C^-CL alkyl, Ci-C₄ haloalkyl, C₃-C₆ cycloalkyl or C₃-C₆halocycloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, Ci-C₄alkyl, C₃-C₆ cycloalkyl, C-|-C₄ haloalkyl, C^Czi alkoxy and C-|-C₄ haloalkoxy;

each R²² is independently Οϊ-Ο₄ alkyl, C-|-C₄ haloalkyl, C₃-C₆ cycloalkyl or C₃-C₆halocycloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, Cî-C₄alkyl, C₃-C₆ cycloalkyl, C-|-C₄ haloalkyl, Ci-C₄ alkoxy and Cî-C₄ haloalkoxy;

each R²³ is independently C^-CU alkyl, C-|-C₄ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₃-C₆ cycloalkylalkyl or C₃-C₆ halocycloalkylalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C!-C₄ alkyl, C₃-C₆ cycloalkyl, C-|—C₄ haloalkyl, Cî-C₄ alkoxy and Ci-C₄ haloalkoxy;

each R²⁴ is independently Cî-C₄ alkyl;

each R²⁵ is independently H, C-i-C₄ alkyl or C^-CU haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-|-C₄ alkyl, C₃-C₆ cycloalkyl, Cp-C^ haloalkyl, Ci-C₄ alkoxy and Cî-C₄ haloalkoxy;

each R²⁶ is independently C1-C4 alkyl or C-|-C₄ haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-|-C₄ alkyl, C₃-C₆ cycloalkyl, C-|-C₄ haloalkyl, C-|-C₄ alkoxy and Cq-C₄ haloalkoxy; or

R²⁵ and R²⁶ are independently taken together with the nitrogen atom to which they are attached to form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, Ci-C₄ alkyl, C₃-C₆ cycloalkyl, Ci-C₄ haloalkyl, Ci-C₄ alkoxy and C-|-C₄ haloalkoxy;

each R²⁷ is independently C^Cg alkyl, C^-Cg haloalkyl, Ci-C6 alkoxy, Ο·|-Ο6 haloalkoxy or Nr²⁹r30;

or phenyl or a 5- or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, U-CL alkyl, C₃-C₆ cycloalkyl, C-|-C₄ haloalkyl, C^-CL alkoxy and Ci-C₄ haloalkoxy;

each R²⁸ is independently U-Cg alkyl, C₃-C₆ cycloalkyl or phenyl;

each R²⁹ is independently H or Q^b; or C-|-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂C₆ alkynyl, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, Οί-Ο₄alkyl, C₃-C₆ cycloalkyl, Cq-C₄ haloalkyl, C--C4 alkoxy and C!-C₄ haloalkoxy;

each R³⁰ is independently H or Q^b; or C^-Cg alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂C₆ alkynyl, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-|-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, Cî-C₄ alkoxy and Ci-C₄ haloalkoxy; or

R²⁹ and R³⁰ are taken together with the nitrogen atom to which they are attached to form a 3- to 10-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, said ring being unsubstituted or substituted with up to 4 substituents independently selected from the group consisting of halogen, cyano, nitro, C-|-C₄ alkyl, C₃-C₆ cycloalkyl, C!-C₄ haloalkyl, C-|-C₄ alkoxy and 0^04 haloalkoxy;

Q^a is a 5- to 10-membered aromatic ring or ring System, each ring or ring System containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 3 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, each ring or ring System being unsubstituted or substituted with at least one R^x; or a 3- to 6-membered partially saturated ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, each ring unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, alkyl, C₃-C₆ cycloalkyl, C-1-C4 haloalkyl, C-1-C4 alkoxy and C-1-C4 haloalkoxy;

each Q^b is independently phenyl, a 5- or 6-membered heterocyclic aromatic ring or a 3- to

6-membered heterocyclic non-aromatic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, each ring unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, θ!-θ₄ alkyl, C₃-C₆ cycloalkyl, C1-C4 haloalkyl, C-i-04 alkoxy and C-i-04 haloalkoxy;

each n is independently 0, 1 or 2; and p is 1 or 2.

This invention also provides a composition comprising a compound of Formula 1, an /V-oxide or a sait thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. In one embodiment, this invention also provides a composition for controlling an invertebrate pest comprising a compound of Formula 1, an /V-oxide or a sait thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising at least one additional biologically active compound or agent.

This invention further provides a spray composition for controlling an invertebrate pest comprising a compound of Formula 1, an /V-oxide or a sait thereof, or the compositions described above, and a propellant. This invention also provides a bait composition for controlling an invertebrate pest comprising a compound of Formula 1, an A/-oxide or a sait thereof, or the compositions described in the embodiments above, one or more food materials, optionally an attractant, and optionally a humectant.

This invention further provides a trap device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.

This invention provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1, an /V-oxide or a sait thereof, (e.g., as a composition described herein). This invention also relates to such method wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1, an /V-oxide or a sait thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent.

This invention also provides a method for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of Formula 1, an /V-oxide or a sait thereof, (e.g., as a composition described herein). This invention also relates to the treated seed. This invention further provides a method for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of Formula 1, an /V-oxide or a sait thereof, (e.g., as a composition described herein). This invention also provides for the use of a compound of Formula 1, an /V-oxide or a sait thereof, (e.g., as a composition described herein) in protecting an animal from an invertebrate pest.

This invention also provides a method for increasing vigor of a crop plant comprising contacting the crop plant, the seed from which the crop plant is grown or the locus (e.g., growth medium) of the crop plant with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein).

DETAILS OFTHE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains”, “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of éléments is not necessarily limited to only those éléments but may include other éléments not expressiy listed or inhérent to such composition, mixture, process or method.

The transitional phrase “consisting of’ excludes any element, step, or ingrédient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of’ appears in a clause of the body of a claim, ratherthan immediately following the preamble, it limits only the element set forth in that clause; other éléments are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of’ is used to define a composition or method that includes materials, steps, features, components, or éléments, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or éléments do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of’ occupies a middle ground between “comprising” and “consisting of’.

Where applicants hâve defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of’ or “consisting of.”

Further, unless expressiy stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or présent) and B is false (or not présent), A is false (or not présent) and B is true (or présent), and both A and B are true (or présent).

Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

As referred to in this disclosure, the term “invertebrate pest” includes arthropods, gastropods, nematodes and helminths of économie importance as pests. The term “arthropod” includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term “gastropod” includes snails, slugs and other Stylommatophora. The term “nematode” includes members of the phylum Nematoda, such as phytophagous nematodes and helminth nematodes parasitizing animais. The term “helminth” includes ail of the parasitic worms, such as roundworms (phylum Nematoda), heartworms (phylum Nematoda, class Secernentea), flukes (phylum Platyhelminthes, class Tematoda), acanthocephalans (phylum Acanthocephala), and tapeworms (phylum Platyhelminthes, class Cestoda).

In the context of this disclosure “invertebrate pest control” means inhibition of invertebrate pest development (including mortality, feeding réduction, and/or mating disruption), and related expressions are defined analogously.

The term “agronomie” refers to the production of field crops such as forfood and fiber and includes the growth of maize or corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (e.g., berries and cherries) and other specialty crops (e.g., canola, sunflower and olives).

The term “nonagronomic” refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and végétation management, public health (i.e. human) and animal health (e.g., domesticated animais such as pets, livestock and poultry, undomesticated animais such as wildlife) applications.

The term “crop vigor” refers to rate of growth or biomass accumulation of a crop plant. An “increase in vigor” refers to an increase in growth or biomass accumulation in a crop plant relative to an untreated control crop plant. The term “crop yield” refers to the return on crop material, in terms of both quantity and quality, obtained after harvesting a crop plant. An “increase in crop yield” refers to an increase in crop yield relative to an untreated control crop plant.

The term “biologically effective amount” refers to the amount of a biologically active compound (e.g., a compound of Formula 1) sufficient to produce the desired biological effect when applied to (i.e. contacted with) an invertebrate pest to be controlled or its environment, or to a plant, the seed from which the plant is grown, or the locus of the plant (e.g., growth medium) to protect the plant from injury by the invertebrate pest or for other desired effect (e.g., increasing plant vigor).

The position of the variable R^ in the structure of Formula 1 is described by the numbering System shown below.

A wavy line in a structure fragment dénotés the attachment point of the fragment to the remainder of the molécule. For example, when the variable Q in Formula 1 is defined as Q-1, the wavy line bisecting the bond in Q-1 means that Q-1 is attached to the remainder of the structure of Formula 1 at said position, as shown below.

In structures Q-1, Q-2, Q-3 and Q-4, the variables X¹, X², X³ and X⁴ are defined as each being independently CR², CR³ or N, provided that (i) one of X¹, X², X³ and X⁴ is CR², and (ii) no more than one of X¹, X², X³ and X⁴ is N. This définition of X¹, X², X³ and X⁴ describes sixteen possible combinations of X¹, X², X³ and X⁴, shown in the table below.

Combination	£	Xï	x!	£
1	CR²	CR³	CR³	CR³
2	CR²	N	CR³	CR³
3	CR²	CR³	N	CR³
4	CR²	CR³	CR³	N

5	CR³	CR²	CR³	CR³
6	N	CR²	CR³	CR³
7	CR³	CR²	N	CR³
8	CR³	CR²	CR³	N
9	CR³	CR³	CR²	CR³
10	N	CR³	CR²	CR³
11	CR³	N	CR²	CR³
12	CR³	CR³	CR²	N
13	CR³	CR³	CR³	CR²
14	N	CR³	CR³	CR²
15	CR³	N	CR³	CR²
16	CR³	CR³	N	CR²

In the above recitations, the term “alkyl”, used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl” includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as

1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. “Alkylthio” includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term “halogen”, either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include F3C-, CICH2-, CF3CH2- and CF3CCI2-. The terms “halocycloalkyl”, “haloalkoxy”, “haloalkylthio”, “haloalkenyl”, “haloalkynyl”, and the like, are defined analogously to the term “haloalkyl”. Examples of “haloalkoxy” include CF3O-, CCI3CH2O-, HCF2CH2CH2O- and CF3CH2O-. Examples of “haloalkylthio” include CCI3S-, CF3S-, CCI₃CH₂S- and CICH₂CH2CH₂S-.

The chemical abbreviations S(O) and S(=O) as used herein represent a sulfinyl moiety. The chemical abbreviations SO2, S(O)2 and S(=O)2 as used herein represent a sulfonyl moiety. The chemical abbreviations C(O) and C(=O) as used herein represent a carbonyl moiety. The chemical abbreviations CO2, C(O)O and C(=O)O as used herein represent an oxycarbonyl moiety. “CHO” means formyl.

The total number of carbon atoms in a substituent group is indicated by the “Cj-Cj” prefix where i and j are numbers from 1 to 6. For example, C1-C4 alkylsulfonyl désignâtes methylsulfonyl through butylsulfonyl; C2 alkoxyalkyl désignâtes CH3OCH2-; C3 alkoxyalkyl désignâtes, for example, CH3CH(OCH3)-, CH3OCH2CH2- or CH3CH2OCH2-; and C4 alkoxyalkyl désignâtes the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2- and CH3CH2OCH2CH2-.

When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents, e.g., (Rl)_m, m is 0, 1, 2 or 3. Further, when the subscript indicates a range, e.g. (R)j_j, then the number of substituents may be selected from the integers between i and j inclusive. When a group contains a substituent which can be hydrogen, for example R^ or R⁴, then when this substituent is taken as hydrogen, it is recognized that this is équivalent to said group being unsubstituted. When a variable group is shown to be optionally attached to a position, for example (R^m wherein m may be 0, then hydrogen may be at the position even if not recited in the variable group définition. When one or more positions on a group are said to be “not substituted” or “unsubstituted”, then hydrogen atoms are attached to take up any free valency.

Unless otherwise indicated, a “ring” or “ring System” as a component of Formula 1 (e.g., substituent Q^a) is carbocyclic or heterocyclic. The term “ring System” dénotés two or more fused rings. The terms “bicyclic ring system” and “fused bicyclic ring System” dénoté a ring System consisting of two fused rings, which can be “ortho-fused”, “bridged bicyclic” or “spirobicyclic”. An “ortho-fused bicyclic ring system” dénotés a ring system wherein the two constituent rings hâve two adjacent atoms in common. A “bridged bicyclic ring System” is formed by bonding a segment of one or more atoms to nonadjacent ring members of a ring. A “spirobicyclic ring System” is formed by bonding a segment of two or more atoms to the same ring member of a ring. The term “fused heterobicyclic ring System” dénotés a fused bicyclic ring System in which at least one ring atom is not carbon. The term “ring member” refers to an atom or other moiety (e.g., C(=O), C(=S), S(O) or S(O)2) forming the backbone of a ring or ring System.

The terms “carbocyclic ring”, “carbocycle” or “carbocyclic ring system” dénoté a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon. The terms “heterocyclic ring”, “heterocycle” or “heterocyclic ring system” dénoté a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless otherwise indicated, a carbocyclic ring or heterocyclic ring can be a saturated or unsaturated ring. “Saturated” refers to a ring having a backbone consisting of atoms linked to one another by single bonds; unless otherwise specified, the remaining atom valences are occupied by hydrogen atoms. Unless otherwise stated, an “unsaturated ring” may be partially unsaturated or fully unsaturated. The expression “fully unsaturated ring” means a ring of atoms in which the bonds between atoms in the ring are single or double bonds according to valence bond theory and furthermore the bonds between atoms in the ring include as many double bonds as possible without double bonds being cumulative (i.e. no C=C=C or C=C=N). The term “partially unsaturated ring” dénotés a ring comprising at least one ring member bonded to an adjacent ring member through a double bond and which conceptually potentially accommodâtes a number of non-cumulated double bonds between adjacent ring members (i.e. in its fully unsaturated counterpart form) greater than the number of double bonds présent (i.e. in its partially unsaturated form).

Unless otherwise indicated, heterocyclic rings and ring Systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

“Aromatic” indicates that each ofthe ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and in which (4n + 2) π électrons, where n is a positive integer, are associated with the ring to comply with Hückel’s rule. The term “aromatic ring system” dénotés a carbocyclic or heterocyclic ring system in which at least one ring of the ring

System is aromatic. When a fully unsaturated carbocyclic ring satisfies Hückel’s rule, then said ring is also called an “aromatic ring” or “aromatic carbocyclic ring”.

The term “aromatic carbocyclic ring System” dénotés a carbocyclic ring System in which at least one ring of the ring System is aromatic. When a fully unsaturated heterocyclic ring satisfies Hückel’s rule, then said ring is also called a “heteroaromatic ring”, “aromatic heterocyclic ring” or “heterocyclic aromatic ring”. The term “aromatic heterocyclic ring System” dénotés a heterocyclic ring System in which at least one ring of the ring System is aromatic. The term “nonaromatic ring System” dénotés a carbocyclic or heterocyclic ring System that may be fully saturated, as well as partially or fully unsaturated, provided that none of the rings in the ring System are aromatic. The term “nonaromatic carbocyclic ring System” dénotés a carbocyclic ring in which no ring in the ring System is aromatic. The term “nonaromatic heterocyclic ring System” dénotés a heterocyclic ring System in which no ring in the ring System is aromatic.

The term “optionally substituted” in connection with the heterocyclic rings refers to groups which are unsubstituted or hâve at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following définitions shall apply unless otherwise indicated. The term optionally substituted is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.” Unless otherwise indicated, an optionally substituted group may hâve a substituent at each substitutable position of the group, and each substitution is independent of the other.

When a substituent is a 5- or 6-membered nitrogen-containing heterocyclic ring, it may be attached to the remainder of Formula 1 though any available carbon or nitrogen ring atom, unless otherwise described. As noted above, Q^a can be (among others) phenyl optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of Invention. An example of phenyl optionally substituted with one to five substituents is the ring illustrated as U-1 in Exhibit 1, wherein R^v is R^x as defined in the Summary of the Invention for Q^a and r is an integer from 0 to 5.

As noted above, Q^b can be (among others) a 5- or 6-membered heterocyclic aromatic ring, optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of Invention. Examples of a 5- or 6-membered unsaturated aromatic heterocyclic ring optionally substituted with from one or more substituents include the rings U-2 through U-61 illustrated in Exhibit 1 wherein R^v is any substituent as defined in the Summary of the Invention for Q^b and r is an integer from 0 to 4, limited by the number of available positions on each U group. As U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42 and U-43 hâve only one available position, for these U groups r is limited to the integers 0 or 1, and r being 0 means that the U group is unsubstituted and a hydrogen is présent at the position indicated by (R^v)rExhibit 1

(R^v)_r

(R^V)r .N7 ^JrKf·	(R^V)_r .N/ ^JT	4 (R^v)_r S—⁷ 2	(R^v)i \=/
U-12	U-13	U-14	U-15

(R^v)_r

U-11

U-20

N—O

U-19

U-21

U-22 U-23

U-24 U-25 δ 3 4 m^vi_T

U-26 U-27 U-28

U-29

U-30

N—N

U-32

N—N

U-34

U-35

U-39

U-40

U-41

U-42

U-43 U-44 U-45 (R^v)r

N—N

U-46

N—N

U-47

N=N

U-48 (R^V)r

(R^v)_r ^-PV

U-50

U-51

U-56

N

U-58

and

U-60 ⁴ (R^V)r

U-61

As noted above, Q^a can be (among others) an 8-, 9- or 10-membered ortho-fused bicyclic ring System optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of Invention. Examples of 8-, 9- or 10-membered orthofused bicyclic ring System optionally substituted with from one or more substituents include the 5 rings U-81 through U-123 illustrated in Exhibit 3 wherein R^v is any substituent as defined in the Summary of the Invention for Q^a, and r is typically an integer from 0 to 4.

U-97 U-98 U-99 U-100

U-101 U-102 U-103 U-104

U-105 U-106 U-107 U-108

U-109 U-110 U-111 U-112

U-113 U-114 U-115 U-116

U-117 U-118 U-119 U-120

U-121 U-122 U-123

Although R^v groups are shown in the structures U-1 through U-123, it is noted that they do not need to be présent since they are optional substituents. Note that when R^v is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or R^v. Note that when the 5 attachment point between (R^v)r and the U group is illustrated as floating, (R^v)r can be attached to any available carbon atom or nitrogen atom of the U group. Note that when the attachment point on the U group is illustrated as floating, the U group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the U group by replacement of a hydrogen atom. Note that some U groups can only be substituted with less than 4 R^v groups (e.g., U-2 through U-5, U-7 through U-48, and U-52 through U-61).

A wide variety of synthetic methods are known in the art to enable préparation of aromatic and nonaromatic heterocyclic rings and ring Systems; for extensive reviews see the eight volume set of Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees editorsin-chief, Pergamon Press, Oxford, 1984 and the twelve volume set of Comprehensive Heterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds of this invention can exist as one or more stereoisomers. Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as géométrie isomers) and atropisomers. Atropisomers resuit from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit bénéficiai effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively préparé said stereoisomers. For a comprehensive discussion of ail aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

This invention comprises ail stereoisomers, conformational isomers and mixtures thereof in ail proportions as well as isotopic forms such as deuterated compounds.

One skilled in the art will appreciate that not ail nitrogen-containing heterocycles can form /V-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form /V-oxides. One skilled in the art will also recognize that tertiary amines can form /V-oxides. Synthetic methods for the préparation of /V-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and 3-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as f-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the préparation of /V-oxides hâve been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academie Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academie Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academie Press.

One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of the compounds of Formula 1 are useful for control of invertebrate pests. The salts of the compounds of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. When a compound of Formula 1 contains an acidic moiety such as a carboxylic acid or phénol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnésium or barium. Accordingly, the présent invention comprises compounds selected from Formula 1, /V-oxides and suitable salts thereof.

Compounds selected from Formula 1, stereoisomers, tautomers, /V-oxides, and salts thereof, typically exist in more than one form, and Formula 1 thus includes ail crystalline and non-crystalline forms of the compounds that Formula 1 represents. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molécules in the crystal lattice. Although polymorphs can hâve the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molécules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound represented by Formula 1 can exhibit bénéficiai effects (e.g., suitability for préparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1. Préparation and isolation of a particular polymorph of a compound represented by Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and températures. Compounds of this invention may exist as one or more crystalline polymorphs. This invention comprises both individual polymorphs and mixtures of polymorphs, including mixtures enriched in one polymorph relative to others. For a comprehensive discussion of polymorphism see R. Hilfiker, Ed., Polymorphism In the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

Embodiments of the présent invention as described in the Summary of the Invention include those described below. In the following Embodiments, référencé to “a compound of Formula 1” includes the définitions of substituents specified in the Summary of the Invention unless further defined in the Embodiments.

Embodiment 1. A compound of Formula 1 wherein Q is Q-1, Q-2 or Q-3.

Embodiment 2. A compound of Formula 1 wherein Q is Q-1, Q-2 or Q-3, and Υθ is CR^b.

Embodiment 3. A compound of Formula 1 wherein Q is Q-1 or Q-2.

Embodiment 4. A compound of Formula 1 wherein Q is Q-1.

Embodiment 5. A compound of Formula 1 wherein Q is Q-1, and γ! is O or S.

Embodiment 6. A compound of Formula 1 wherein Q is Q-1, and Y¹ is S.

Embodiment 7. A compound of Formula 1 wherein Q is Q-1, and γ1 is O.

Embodiment 8. A compound of Formula 1 wherein Q is Q-2.

Embodiment 9. A compound of Formula 1 wherein Q is Q-2, and Y² is CR^5a.

Embodiment 10. A compound of Formula 1 or any of Embodiments 1-9 wherein A is CH, CR1 or N, and R¹ is halogen.

Embodiment 11. A compound of Embodiment 10 wherein A is CH, CF or N.

Embodiment 11a. A compound of Embodiment 10 wherein A is CF or N.

Embodiment 12. A compound of Embodiment 10 wherein A is CH or CF. Embodiment 13. A compound of Embodiment 10 wherein A is CH.

Embodiment 14. A compound of Embodiment 10 wherein A is N.

Embodiment 15. A compound of Formula 1 or any of Embodiments 1-9 wherein m is 1, and Fd is C-|—C₄ alkyl, Οί-Ο₄ haloalkyl, C₁-C₄ alkoxy or halogen.

Embodiment 16. A compound of Embodiment 15 wherein R^ is CF3, OMe, Me, or F.

Embodiment 17. A compound of Embodiment 16 wherein R^ is CF3, OMe, Me, or F, and is in the 4-position.

Embodiment 18. A compound of Embodiment 17 wherein R^ is CF3, and is in the 4position.

Embodiment 19. A compound of Formula 1 or any of Embodiments 1-9 wherein m is 0.

Embodiment 20. A compound of Formula 1 or any of Embodiments 1-19 wherein is CR², and X², X³ and X^ are each independently CR³; orX² is CR², and X\ X³and χ4 are each independently CR³.

Embodiment 21. A compound of Embodiment 20 wherein X¹ is CR², and X², X³ and X^ are each independently CR³.

Embodiment 22. A compound of Embodiment 20 wherein X² is CR², and x\ X³ and X^ are each independently CR³.

Embodiment 23. A compound of Formula 1 or any of Embodiments 1-22 wherein each R³is independently H or halogen.

Embodiment 24. A compound of Embodiment 23 wherein each R³ is independently H or F.

Embodiment 25. A compound of Embodiment 24 wherein each R³ is H.

Embodiment 26. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=Z)NR^eR⁷, C(=NR¹⁰)R¹¹ or Q^a.

Embodiment 27. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=NR¹⁰)R¹¹.

Embodiment 28. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=NR¹⁰)R¹¹; R¹⁰ is C1-C4 alkoxy; and R¹¹ is Cr-C4 alkyl substituted with S(O)_nR²³.

Embodiment 29. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=Z)NR⁶R⁷ or Q^a.

Embodiment 30. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=Z)NR⁶R⁷.

Embodiment 31. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=O)NR⁶R⁷.

Embodiment 32. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=S)NR⁶R⁷.

Embodiment 33. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=O)NR⁶R⁷; and R⁶ is H, C(O)OR²¹, C(O)R²² or C^Ce alkyl.

Embodiment 35. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=O)NR⁶R⁷; and R⁶ is H, C(O)OMe, C(O)Me or methyl.

Embodiment 36. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=O)NR⁶R⁷; and R⁶ is H.

Embodiment 36a. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=O)NR⁶R⁷; and R⁶ is C(O)OMe.

Embodiment 36b. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=O)NR⁶R⁷; and R⁶ is C(O)Me.

Embodiment 36c. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is C(=O)NR⁶R⁷; and R® is methyl.

Embodiment 37. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is Q^a.

Embodiment 38. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is Q^a; and Q^a is a 5- or 6-membered aromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 3 nitrogen atoms, each ring being unsubstituted or substituted with at least one R^x.

Embodiment 39. A compound of Formula 1 or any of Embodiments 1-25 wherein R² is Q^a; and Q^a is a 5- or 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 3 nitrogen atoms, each ring being unsubstituted or substituted with at least one R^x.

Embodiment 40. A compound of Embodiment 39 wherein the heteroaromatic ring is a 5membered heteroaromatic ring.

Embodiment 41. A compound of Embodiment 40 wherein the heteroaromatic ring is a 5membered heteroaromatic ring having a nitrogen atom at the 2-position.

Embodiment 42. A compound of Embodiment 39 wherein the heteroaromatic ring is a 6membered heteroaromatic ring.

Embodiment 43. A compound of Embodiment 42 wherein the heteroaromatic ring is a 6membered heteroaromatic ring having a nitrogen atom at the 2-position.

Embodiment 44. A compound of Embodiment 43 wherein the heteroaromatic ring is a 6membered heteroaromatic ring having a nitrogen atom at the 2-position and substituted with (T-C4 haloalkyl.

Embodiment 45. A compound of Embodiment 44 wherein the heteroaromatic ring is a 6membered heteroaromatic ring having a nitrogen atom at the 2-position and substituted with CF3.

Embodiments of this invention, including Embodiments 1-45 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. In addition, embodiments of this invention, including Embodiments 1-45 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the présent invention.

Combinations of Embodiments 1-45 are illustrated by:

Embodiment A. A compound of Formula 1 wherein χ! is CR^, and X^, χ3 and X⁴ are each independently CR3; or χ2 is CR2, and , Χθ and X⁴ are each independently CR3.

Embodiment B. A compound of Embodiment A wherein

Q is Q-1 or Q-2.

Embodiment C. A compound of Embodiment B wherein

Q is Q-1; and

Y¹ is O or S.

Embodiment D. A compound of Embodiment C wherein

Q is Q-2; and

Y² is CR^5a.

Embodiment E. A compound of any of Embodiments A-D wherein

A is CH or CF; and m is 0.

Embodiment F. A compound of Formula 1 wherein

A is CH or CF;

m is 0;

Q is Q-2;

Y² is CR^5a;

X¹ is CR² and X², X² and X²*· are each CH; or X² is CR² and X\ X² and X^ are CH; R² is C(=Z)NR⁶R⁷ or Q^a.

Embodiment G. A compound of Formula 1 wherein

A is CH or CF;

m is 0;

Q is Q-2;

Y² is CR^5a;

X¹ is CR² and X², X² and X^ are each CH;

R² is C(=Z)NR⁶R⁷ or Q^a.

Embodiment H. A compound of Formula 1 wherein

A is CH or CF;

m is 0;

Q is Q-2;

Y² is CR^5a;

X² is CR² and X¹, X² and X^ are CH;

R² is C(=Z)NR⁶R⁷ or Q^a.

Embodiment I. A compound of Formula 1 wherein

A is CH;

m is 0;

Q is Q-2;

Y² is CR^5a;

R^5a is H;

X¹ is CR² and X², X² and X^ are each CH; or X² is CR² and X^, X² and X^ are CH; R² is C(O)NR⁶R⁷; and

R⁶ is H.

Embodiment J. A compound of Formula 1 wherein

A is CH;

m is 0;

Q is Q-2;

Y² is CR^5a;

R^5a is H;

X¹ is CR² and X², X³ and X⁴ are each CH;

R² is C(O)NR⁶R⁷; and

R⁶ is H.

Embodiment K. A compound of Formula 1 wherein

A is CH;

m is 0;

Q is Q-2;

Y² is CR^5a;

R^5a is H;

X² is CR² and X¹, X³ and X⁴ are CH;

R² is C(O)NR⁶R⁷; and

R⁶ is H.

Spécifie embodiments include compounds of Formula 1 selected from the group consisting of (compound numbers refer to Index Tables A-N):

A/-(1 -methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide (compound 8);

A/-cyclopropyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide (compound 14);

A/-cyclohexyl-2-(3-pyridinyl)-2/7-indazole-4-carboxamide (compound 16);

2-(3-pyridinyl)-A/-(2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide (compound 19); 2-(3-pyridinyl)-/\/-[(tetrahydro-2-furanyl)methyl]-2/-/-indazole-5-carboxamide (compound 41 ); methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate (compound 42); /V-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide (compound 51);

A/-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide (compound 54); 2-(3-pyridinyl)-A/-(2-pyrimidinylmethyl)-2H-indazole-5-carboxamide (compound 55); and A/-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2/7-indazole-5-carboxamide (compound 76).

Of note is that compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomie and nonagronomic invertebrate pests.

Of particular note, for reasons of invertebrate pest control spectrum and économie importance, protection of agronomie crops from damage or injury caused by invertebrate pests by controlling invertebrate pests are embodiments of the invention. Compounds of this invention because of their favorable translocation properties or systemicity in plants also protect foliar or other plant parts which are not directly contacted with a compound of Formula 1 or a composition comprising the compound.

Also noteworthy as embodiments of the présent invention are compositions comprising a compound of any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said compositions optionally further comprising at least one additional biologically active compound or agent.

Further noteworthy as embodiments of the présent invention are compositions for controlling an invertebrate pest comprising a compound of any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said compositions optionally further comprising at least one additional biologically active compound or agent. Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of any of the preceding Embodiments (e.g., as a composition described herein).

Embodiments of the invention also include a composition comprising a compound of any of the preceding Embodiments, in the form of a soil drench liquid formulation. Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the soil with a liquid composition as a soil drench comprising a biologically effective amount of a compound of any of the preceding Embodiments.

Embodiments of the invention also include a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding Embodiments and a propellant. Embodiments of the invention further include a bait composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding Embodiments, one or more food materials, optionally an attractant, and optionally a humectant. Embodiments of the invention also include a device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.

Embodiments of the invention also include methods for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of any of the preceding Embodiments.

Embodiments of the invention also include methods for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of any of the preceding Embodiments.

Embodiments of the invention also include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1, an /V-oxide or a sait thereof, (e.g., as a composition described herein), provided that the methods are not methods of medical treatment of a human or animal body by therapy.

This invention also relates to such methods wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1, an /V-oxide or a sait thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent, provided that the methods are not methods of medical treatment of a human or animal body by therapy.

One or more of the following methods and variations as described in Schemes 1-13 can be used to préparé the compounds of Formula 1. The définitions of substituents in the compounds of Formulae 1-23 below are as defined above in the Summary of the Invention unless otherwise noted. Compounds of Formulae 1a-1g are various subsets of the compounds of Formula 1, and ail substituents for Formulae 1a-1g are as defined above for Formula 1. The following abbreviations are used: THF is tetrahydrofuran, DMF is /V,/V-dimethylformamide, NMP is /V-methylpyrrolidinone, Ac is acetate, MS is mesylate, Tf is triflate, and Nf is nonaflate.

Compounds of Formula 1a (Formula 1 wherein Q is Q-1, Q-3 or Q-4) can be prepared as shown in Scheme 1 by the coupling of a heterocyclic compound of Formula 2 (wherein LG is a suitable leaving group such as Cl, Br, I, Tf or Nf) with a heterocyclic compound of Formula 3 (wherein M is a suitable métal or metalloid such as a Mg, Zn or B species) in the presence of a catalyst and appropriate ligand. Catalysts can be generated from transition metals such as Pd (for example Pd(OAc)₂ or Pd₂(dba)₃ and mono- or bi-dentate ligands such as PPh₃, PCy₃, PtBu₃, x-phos, xantphos, s-phos, and dppf. Typical bases used include carbonates such as sodium carbonate or césium carbonate, phosphates such as potassium triphosphate, amines such as ethyldiisopropylamine, or alkoxides such as sodium tert-butoxide. Typical solvents include THF, dioxane, toluene, éthanol, DMF, water or mixtures thereof. Typical reaction températures range from ambient température to the boiling point of the solvent.

Scheme 1

wherein Q is Q-l, Q-3 or Q-4 la

Compounds of Formula 1a (Formula 1 wherein Q is Q-1, G-3 or Q-4) can also be prepared as shown in Scheme 2 by the coupling of a compound of Formula 4 with a compound of Formula 5 (wherein LG is a suitable leaving group such as Cl, Br, I, Tf or Nf) in the presence of a catalyst and an appropriate ligand. A variety of catalysts can be used in the method of Scheme 2, and these can be generated from a transition métal species such as copper or Pd (for example complexes such as Pd(OAc)₂ or Pd₂(dba)₃) and a ligand. Typical ligands may be mono- or bi-dentate, and include PPh₃, PCy₃, Pt-Bu₃, x-phos, xantphos, s-phos, and dppf. Typical bases used include carbonates such as sodium carbonate or césium carbonate, phosphates such as potassium triphosphate, amines such as ethyldiisopropylamine or alkoxides such as sodium tert-butoxide. Additives such as molecular sieves, Bu₄N⁺Br' or copper or silver salts (e.g., AgOAc) can be bénéficiai. Typical reaction solvents include THF, dioxane, toluene, éthanol, DMF, water, or mixtures thereof. Typical reaction températures range from ambient température to the boiling point of the solvent. For examples, see Chemical Communications 2011, 47(17), pages 5043-5045; Journal ofthe American Chemical Society 2010, 132(11), pages 3674-3675; Heterocycles 2011, 83(6), pages 1371-1376; U.S. Patent Application Publication 20090076266; Bulletin ofthe Chemical Society of Japan 1998, 71(2), pages 467-473; Tetrahedron Letters 2008, 49(10), pages 1598-1600; and Tetrahedron Letters 2010, 57(42), pages 5624-5627.

Scheme 2

la wherein Q is Q-l, Q-3 or Q-4

Compounds of Formula 2 wherein LG is halogen can be prepared from the corresponding amines by treatment with a source of ON⁺ such as isoamyl nitrite or t-butyl nitrite or nitrous acid in the presence of a halogen source such as CuBr₂ or BnNEt₃ ⁺Br‘. Preferred reaction conditions include aqueous or organic solvents such as THF or acetonitrile, and reaction températures ranging from 0 °C to the boiling point ofthe solvent.

Compounds of Formula 2 wherein LG is Cl or Br can also be prepared from the corresponding hydroxy compounds by treatment with a halogenating agent such as POCI₃, PCI₅, PBr₃ or SOCI₂. Compounds of Formula 2 wherein LG is OMS or OTf can also be prepared from the corresponding hydroxy compounds by treatment with MsCI or Tf₂O.

Compounds of Formula 4 can be prepared from the corresponding amine compounds by treatment with a source of ON⁺ such as isoamyl nitrite or t-butyl nitrite. Preferred reaction conditions include ethereal solvents such as THF at températures ranging from ambient température to the boiling point ofthe solvent.

Compounds of Formula 6 can be prepared by electrophilic halogénation of the corresponding compounds of Formula 7 by treatment with a halogenating agent such as Nbromosuccinimide in a suitable solvent such as DMF, NMP or acetic acid at températures ranging from ambienttempérature up to the boiling point ofthe solvent (Scheme 3).

Scheme 3

2-Aminobenzothiazoles of Formula 8 can be prepared from ortho-unsubstituted anilines of Formula 9 and a thiocyanate anion (wherein M is K⁺, Na⁺ or Bu₄N⁺) as shown in Scheme 4. The reaction can be conducted in a single step in acetic acid for example, or through the intermediacy of a thio-urea followed by oxidation. Suitable oxidants include bromine.

Scheme 4

MSCN, bromine, acetic acid or MSCN, sulfuric acid, then bromine

M is K⁺, Na⁺or Bu₄N⁺

Compounds of Formula 1b can be prepared from compounds of Formula 10 by the method shown in Scheme 5, in which a compound of Formula 10 is treated with an azide 10 reagent (for example, sodium azide or tetrabutylammonium azide). Typical reaction conditions include DMF or NMP as solvent, and reaction températures ranging from 80 °C to the boiling point of the solvent.

Scheme 5

LG is a leaving group such Jb as F or NO2

Compounds of Formula 1b can also be prepared from compounds of Formula 10a by the method shown in Scheme 5a, in which a compound of Formula 10a is treated with triethyl phosphite.

Scheme 5a

10a

LG is NO₂ lb

Compounds of Formulae 10 and 10a are Schiff bases and can be prepared by methods known in the art (see, for example, March, J., Advanced Organic Chemistry, Wiley, 1992, pages 896-898.

Compounds of Formula 1c can be prepared from compounds of Formula 11 by the method shown in Scheme 6 via oxidation of a compound of Formula 11 with molecular oxygen or a peroxide such as t-butyl hydroperoxide in the presence of a copper (II) catalyst such as Cu(OAc)₂ or CuBr₂. Typical reaction conditions included alcoholic solvents such as t-amyl alcohol, DMF, NMP or aqueous ammonia, and reaction températures from 60 °C to the boiling point of the solvent.

Scheme 6

i

(Rbm

Cu(II), oxidant

----->-

le

2-Aminoazo compounds of Formula 11 can be prepared by reaction of an aniline of Formula 9 with a diazonium sait of Formula 12 by methods known in the art (see, for example, March, J., Advanced Organic Chemistry, Wiley, 1992, pages 525-526). Compounds of Formula 11 can also be prepared by reaction of an aryl nitroso compound of Formula 13 with a diamine of Formula 14 in a solvent such as acetic acid. These two methods are shown in Scheme 7.

Scheme Ί

Compounds of Formula 1d can be prepared by condensation of a compound of Formula 14 (wherein Lg is a suitable leaving group such as Cl or Br) with an aminopyridine or aminodiazine of Formula 16 as shown in Scheme 8. Typical reaction conditions include an alcoholic solvent such as éthanol or toluene, and a reaction température range from ambient température to the boiling point of the solvent. The pyridine nitrogen can optionally be protected as a BH₃ adduct, an N-oxide, or a 2- or 6-halopyridine dérivative.

Scheme 8

NH₂ +

Compounds of Formula 1e can be prepared as shown in Scheme 9 by the cycloaddition of 2-aminopyridines of Formula 15 with arylnitriles of Formula 16 (see, for example, Journal ofthe American Chemical Society 2009, 131(42), pages 15080-15081, and WO 2013041472.

Scheme 9

Compounds of Formula 1e can also be prepared by rearrangement of compounds of Formula 17 by treatment with base as shown in Scheme 10 (see, for example, J. Het Chem 1970, 7 page 1019). Compounds of Formula 17 can be prepared by methods described in WO 2008006540 and J. Org. Chem., 1966, page 251.

Scheme 10

Intermediates of Formula 18 can be prepared by the method shown in Scheme 11 by treatment of a 2-aminopyridine of Formula 15 with an isocyanate followed by hydroxylamine and 5 a suitable base such as triethylamine.

Scheme 11

1. EtOC(O)NCS ----->-

2. NH₂OH-HC1, base

Compounds of Formula wherein Q is Q-4 can also be prepared by the method described in Synthesis Example 6.

Compounds of Formula 1f can be prepared as shown in Scheme 12 by oxidative cyclization of an aryl aldéhyde of Formula 20 with an aniline of Formula 19 bearing an orthohalogen, preferably iodine, in the presence of sulfur which acts as both a source of sulfur and as an oxidizing agent. The reaction is carried out in the presence of a base such as K₂CO₃ in a 15 suitable solvent such as water or DMF, and is catalyzed by the addition of copper salts (for example, Cul or CuCI₂) and preferably a suitable ligand such as 1,10-phenanthroline. Typical reaction températures range from 70 °C to the boiling point of the solvent.

Scheme 12

Compounds of Formula 1f can also be prepared by cyclization of 2-halothioamides of

Formula 21 as shown in the second reaction of Scheme 12 with a base such as KOtBu, NaH,

DBU or Cs₂CO₃ in a suitable solvent such as toluene or DMF, optionally with the addition of copper salts such as Cul, and preferably a suitable ligand such as 1,10-phenanthroline. This reaction can also be catalyzed by Pd species such as that prepared from Pd₂(dba)₃ and (tBu)₂P-o-biphenyl, a base such as Cs₂CO₃ in a suitable solvent, such as 1,2-dimethoxyethane or dioxane. Typical reaction températures range from 80 °C to the boiling point of the solvent. For 10 copper- and Pd-catalyzed reactions, the halogen substituent on the compound of Formula 21 is preferably Br or I. For example, see Journal of Organic Chemistry 2006, 71(5), pages 18021808; Tetrahedron Letters 2003, 44(32), pages 6073-6077; Synthetic Communications 1991, 21(5), pages 625-33; and Eur. Pat. Appl. No. 450420.

Compounds of Formula 1f can also be prepared by the oxidative cyclization of thioamides 15 of Formula 22 as shown in the third reaction of Scheme 12. Oxidants typically used in this method include bromine or iodine, DDQ and K₃Fe(CN)₆. For example, see Tetrahedron 2007, 63(41), pages 10276-10281; Synthesis 2007, (6), 819-823; and U.S. Pat. Appl. Publ., 20120215154.

The three methods described in Scheme 12 can be used to préparé compounds wherein X¹-X⁴ are carbon atoms, or wherein one of X¹-X⁴ is a nitrogen (for example, see J. Heterocyclic Chem. 2009, 46, page 1125 and référencés cited therein).

Compounds of Formula 1, and intermediates used in the préparation of compounds of Formula 1, wherein Z is S can be prepared by thionation of the corresponding compounds wherein Z is O with, for example, Lawesson’s reagent (CAS No. 19172-47-5), Belleau’s reagent (CAS No. 88816-02-8) or P₂S₅. The thionation reactions are typically conducted in solvents such as toluene, xylenes or dioxane, and at elevated température from 80 °C to the boiling point of the solvent.

Compounds of Formula 1 wherein R² is C(O)NR⁶R⁷ can be prepared by carbonylation of the corresponding compounds wherein R² is halogen (preferably Br or I), or wherein R² is a sulfonate (for example, triflate or nonaflate). The reaction is performed in the presence of a source of carbon monoxide such as carbon monoxide gas or Mo(CO)₆ at pressures between atmospheric pressure and 25 bar, optionally with microwave heating, and generally at elevated températures in the range of 80 to 160 °C. Typical réaction solvents include DMF, NMP, toluene or ethereal solvents such as THF or dioxane.

Compounds of Formula 1 wherein R² is Q^a can be prepared as shown in Scheme 13. The method of Scheme 13 is similar to the method described in Scheme 1; M is a suitable métal or metalloid such as a Mg, Zn or B species, and R² corresponds to LG in Scheme 1 and is a suitable leaving group such as Cl, Br, I, Tf or Nf.

Scheme 13

Compounds of Formula 1 wherein R² is Q^a and Q^a is bonded to Q via a nitrogen atom in Q^a can be prepared by a method similar to that of Scheme 13. In this method, M in the compound of Formula 23 is hydrogen. Coupling reagents include copper(l) salts such as Cul, and a suitable ligand such as trans-bis(/\/,/V-dimethyl-1,2-cyclohexanediamine. Typical reaction conditions include a solvent such as toluene or dioxane, and an elevated réaction température ranging from 80 °C to the boiling point of the solvent.

Examples of intermediates useful in the préparation of compounds of this invention are shown in Tables 1-1 through 1-16. The following abbreviations are used in the Tables which follow: Me means methyl, Et means ethyl, Ph means phenyl, C(O) means carbonyl and CHO 5 means formyl.

TABLE 1-1

Ais CH

R	R
-COOH	-C(O)OMe
-C(O)OEt	cyano
-C(O)CI	-C(O)OPh
-C(O)O(4-nitrophenyl)	-C(O)Me
-CHO	Cl
Br	1
-OS(O)₂CF₃	nh₂
nitro

Aïs CF

Aïs N

R	R
-COOH	-C(O)OMe
-C(O)OEt	cyano
-C(O)CI	-C(O)OPh
-C(0)0(4-nitrophenyl)	-C(O)Me
-CHO	Cl
Br	1
-OS(O)₂CF₃	nh₂
nitro

TABLE 1-2

H

Aïs CH

Aïs CF

R	R
-COOH	-C(O)OMe
-C(O)OEt	cyano
-C(O)CI	-C(O)OPh

-C(O)O(4-nitrophenyl)	-C(O)Me
-CHO	Cl
Br	1
-OS(O)₂CF₃	nh₂
nitro

A is N

TABLE 1-3

Ais CH

R	R
-COOH	-C(O)OMe
-C(O)OEt	cyano
-C(O)CI	-C(O)OPh
-C(O)O(4-nitrophenyl)	-C(O)Me
-CHO	Cl
Br	1
-OS(O)₂CF₃	nh₂

nitro

Ais CF

Aïs N

TABLE 1-4

F

Ais CH

R

-COOH	-C(O)OMe
-C(O)OEt	cyano
-C(O)CI	-C(O)OPh
-C(O)O(4-nitrophenyl)	-C(O)Me
-CHO	Cl
Br	I
-OS(O)₂CF₃	nh₂
nitro

Ais CF

R	R
-COOH	-C(O)OMe
-C(O)OEt	cyano
-C(O)CI	-C(O)OPh
-C(O)O(4-nitrophenyl)	-C(O)Me
-CHO	Cl
Br	I
-OS(O)₂CF₃	nh₂
nitro

A is N

Table I-5 is identical to Table 1-1, except that the structure shown under the heading Table 1-1 is replaced by the structure shown above.

TABLE 1-6

Table I-6 is identical to Table 1-1, except that the structure shown under the heading Table 1-1 is replaced by the structure shown above.

Table 1-7 is identical to Table 1-1, except that the structure shown under the heading Table 1-1 is replaced by the structure shown above.

Table I-8 is identical to Table 1-1, except that the structure shown under the heading Table 1-1 is replaced by the structure shown above.

TABLE 1-9

Table 1-9 is identical to Table 1-1, except that the structure shown under the heading Table 1-1 is replaced by the structure shown above.

TABLE 1-10

Table 1-10 is identical to Table 1-1, except that the structure shown under the heading Table 1-1 is replaced by the structure shown above.

TABLE 1-11

Table I-4 is identical to Table 1-1, except that the structure shown under the heading Table 1-1 is replaced by the structure shown above.

TABLE 1-12

TABLE 1-13

Table 1-13 is identical to Table 1-1, except that the structure shown under the heading

Table 1-1 is replaced by the structure shown above.

TABLE 1-14

Table 1-14 is identical to Table 1-1, except that the structure shown under the heading

Table 1-1 is replaced by the structure shown above.

TABLE 1-15

Table 1-15 is identical to Table 1-1, except that the structure shown under the heading

Table 1-1 is replaced by the structure shown above.

TABLE 1-16

Table 1-16 is identical to Table 1-1, except that the structure shown under the heading Table 1-1 is replaced by the structure shown above.

It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities présent in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after introduction of the reagents depicted in the individual schemes, additional routine synthetic steps not described in detail may be needed to complété the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to préparé the compounds of Formula 1.

One skilled in the art will also recognize that compounds of Formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and réduction reactions to add substituents or modify existing substituents.

Without further élaboration, it is believed that one skilled in the art using the preceding description can utilize the présent invention to its fullest extent. The following Synthesis Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Synthesis Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not hâve necessarily been prepared by a particular préparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographie solvent mixtures or where otherwise indicated. Parts and percentages for chromatographie solvent mixtures are by volume unless otherwise indicated. 1HNMR spectra are reported in ppm downfield from tetramethylsilane; “s” means singlet, “d” means doublet, “t” means triplet, “q” means quartet, “m” means multiplet, “dd” means doublet of doublets, “dt” means doublet of triplets, “br s” means broad singlet. DMF means A/,A/-dimethylformamide. Compound numbers refer to Index Tables A-N.

SYNTHESIS EXAMPLE 1

Préparation of /V-[2-(methylthio)ethyl]-2-(3-pyridinyl)-7-benzothiazolecarboxamide (compound 84)

Step A: Préparation of 3-[(aminothioxomethyl)amino]benzoic acid ethyl ester

Ethyl 3-aminobenzoate (35.25 g, 213.6 mmol) was dissolved in chlorobenzene (250 mL) and cooled to -10 °C. Concentrated sulfuric acid (5.93 mL) was added followed by KSCN (21.76 g) and 18-crown-6 (600 mg), and the reaction mixture was heated at 100 °C for 14 hours. Hexanes was added to the cooled mixture, and the precipitated solid was isolated by filtration. The solid was slurried in a mixture of water and hexanes, and the slurry was stirred for 1 hour. The solid was isolated by filtration and dried in vacuo ovemight to give the title compound as a gray solid (40.7 g). ¹H NMR (DMSO-dg) □: 10.10 + 9.87 (two s, 1H), 8.08 + 8.05 (two s, 1H), 7.66-7.80 (m, 2H), 7.43-7.51 (m, 1H), 8.0-7.0 (br s, 2H), 4.28-4.35 (m, 2H), 1.29-1.35 (m, 3H).

Step B: Préparation of 2-amino-7-benzothiazolecarboxylic acid ethyl ester

The product of Step A was taken up in chloroform (300 mL) and acetic acid (200 mL) and bromine (21 mL) in chloroform (100 mL) was added dropwise over 1.5 hours. The reaction mixture was then heated at 70 °C for 4 hours, cooled, fïltered, and the isolated solid was washed with 50 mL of 1:1 acetone/chloroform. The solid was added to a solution of Na2CO3 (25 g) in water (400 mL) and stirred for 20 minutes. The suspension was fïltered, and the isolated solid was washed with water, and dried in vacuo ovemight to give the title compound (6.73 g) as a white solid. The organic filtrate was concentrated and re-slurried in 100 mL of 1:1 chloroform/acetone, and processed as described above to give an additional 8.1 g of white solid (90% purity, the remaining 10% being the regioisomeric benzothiazole). ¹H NMR (DMSO-dg) □: 7.66 (dd, J=7.7, 0.9 Hz, 1H), 7.60 (s, 1H), 7.57 (dd, 1H), 7.35 (t, J=7.8 Hz, 1H), 4.37 (q, J=7.1 Hz, 2H), 1.36 (t, J=7.1 Hz, 3H).

Step C: Préparation of 2-chloro-7-benzothiazolecarboxylic acid ethyl ester

The product of Step B (7.97 g, 9:1 mixture of regioisomers, 35.9 mmol) was added portionwise over 45 minutes to a mixture of ferf-butylnitrite (7.1 mL) and CuCl2 (5.31 g) in acetonitrile (360 mL) at 65 °C. After stirring for an additional 15 minutes, the cooled mixture was extracted 6 times with hexanes. The combined extracts were concentrated to give the title compound (5.85 g) as a yellow solid. The acetonitrile layer was diluted with water (200 mL), extracted with hexanes, and the hexane fraction was filtered through a pad of silica gel eluting with butyl chloride to yield an additional 0.55 g of product upon concentration. ¹H NMR (CDCI3) □ : 8.14 (d, 2H), 7.58 (t, 1H), 4.49 (q, J=7.1 Hz, 2H), 1.47 (t, J=7.2 Hz, 3H).

Step D: Préparation of 2-(3-pyridinyl)-7-benzothiazolecarboxylic acid

The product of Step C (6.2 g, 9:1 mixture of regioisomers) was combined with 3pyridinylboronic acid (3.79 g), PPh₃ (1.35 g) and Na2CC>3 (5.44 g) in toluene (100 mL), water (25 mL) and éthanol (15 mL), and the reaction mixture was sparged with nitrogen for 5 minutes. Pd2dba3 (588 mg) was added, and the reaction mixture was heated at reflux for 4 hours. The cooled reaction mixture was diluted with water, extracted twice with dichloromethane, and the combined organic extracts were dried over MgSO4 and concentrated. The residue was purified by column chromatography (silica gel eluted with 10% to 50% ethyl acetate in hexanes) to give an orange solid (6.7 g) Recrystallization from éthanol (25 mL) yielded the ethyl ester of the title compound (5.65 g) as the single desired regioisomer. ¹H NMR (CDCI3) □: 9.38 (br s, 1H), 8.75 (br s, 1H), 8.44 (dt, J=8.0, 1.9 Hz, 1H), 8.30 (dd, J=8.2, 1.1 Hz, 1H), 8.19 (dd, J=7.6, 1.1 Hz, 1H), 7.62 (t, 1H), 7.47 (dd, J=8.4, 4.4 Hz, 1H), 4.53 (q, J=7.2 Hz, 2H), 1.50 (t, J=7.2 Hz, 3H).

The product obtained above was dissolved in éthanol (100 mL) and treated with a 1N solution of NaOH (24.8 mL). The reaction mixture was heated at reflux for 1.5 hours before being cooled, neutralized with concentrated HCl (2.0 mL), and concentrated. The residue was dried in vacuo to give a mixture of the title compound and NaCl, which was used without further purification in the next step.

Step E: Préparation of A/-[2-(methylthio)ethyl]-2-(3-pyridinyl)-7-benzothiazolecarboxamide

Thionyl chloride (40 mL) was added to the product of Step D (0.55 g), and the reaction mixture was heated at reflux for 3 hour. The reaction mixture was then cooled and concentrated. The resulting residue was suspended in toluene and concentrated to yield the crude acid chloride, which was used without further purification.

The crude acid chloride (containing 120 mol% NaCI, 114 mg, 0.3 mmol) was treated with dichloromethane (5 mL), MeSCH2CH2NH2 (33 DL) and triethylamine (125 DL), and the reaction mixture was then stirred at ambient température for 14 hours. The reaction mixture was diluted with a saturated aqueous solution of NaHCC>3, extracted twice with dichloromethane, and dried over MgSOzp The combined organic layers were concentrated, and the residue was purified by column chromatography (silica gel eluted with 30% ethyl acetate in hexanes to 100% ethyl acetate) to give 65 mg of the title compound, a compound of this invention. ¹H NMR (CDCI₃) □: 9.39 (d, J=1.7 Hz, 1H), 8.74 (d, J=3.3 Hz, 1H), 8.40-8.47 (dt, 1H), 8.26 (dd, J=8.0, 0.9 Hz, 1H), 7.71 (dd, J=7.6, 0.9 Hz, 1H), 7.58-7.64 (t, 1H), 7.47 (dd, J=7.2, 5.0 Hz, 1H), 6.94 (brt, 1H), 3.75-3.82 (q, 2H), 2.80-2.88 (t, 2H), 2.18 (s, 3H).

SYNTHESIS EXAMPLE 2

Préparation of 2-(5-fluoro-3-pyridinyl)-A/-(2,2,2-trifluoroethyl)-6-benzothiazolecarboxamide (compound 127)

Step A: Préparation of 2-(5-fluoro-3-pyridinyl)-6-benzothiazolecarboxylic acid

Methyl 4-amino-3-iodobenzoate (1.93 g, 6.96 mmol) was combined with K2CO3 (1.92 g), Sg (668 mg), CUCI2-2H2O (119 mg), 1,10-phenanthroline (125 mg) and 5-fluoro-3pyridinecarboxaldehyde (957 mg) in H₂O (30 mL), and the reaction mixture was heated at reflux 16 hours. The cooled reaction mixture was fîltered, and the filtrate was treated with NH4CI (1.49 g). The reaction mixture was stirred at ambient température for 10 minutes, fîltered, and the solid was dried in vacuo to yield a gray solid. The solid was suspended in dioxane, the suspension was heated to reflux, cooled, and fîltered to isolate a solid. The solid was rinsed with ethyl ether to give the title compound (0.66 g). ¹H NMR (DMSO-dg) □: 9.15 (s, 1H), 8.80 (d, J=2.7 Hz, 1H), 8.65 (s, 1H), 8.39 (dt, J=9.5, 2.2 Hz, 1H), 8.10 (d, 1H), 8.05 (d, 1H), 8.0-6.5 (brs).

Step B: Préparation of 2-(5-fluoro-3-pyridinyl)-A/-(2,2,2-trifluoroethyl)-6benzothiazolecarboxamide

Thionyl chloride (5 mL) was added to the product of Step A (0.66 g), and the mixture was heated at reflux for 16 hours. The reaction mixture was then cooled and concentrated. The resulting residue was suspended in toluene and concentrated to provide the crude acid chloride, which was used without further purification.

The crude acid chloride (103 mg, 0.31 mmol) was treated with dichloromethane (5 mL), triethylamine (131 QL) and CF3CH2NH2 (29 OL), and the reaction mixture was stirred at ambient température for 3 days. The reaction mixture was diluted with a saturated aqueous solution of NaHCO₃, extracted twice with dichloromethane, and dried over MgSOzp The combined organic layers were concentrated, and the residue was purified by column chromatography (silica gel eluted with 20% to 40% ethyl acetate in hexanes) to give the title compound, a compound of this invention, as a white solid (52 mg). ¹H NMR (CDCI3) □: 9.32 (br s, 1H), 8.77 (d, J=4.3 Hz, 1H), 8.48 (d, J=1.4 Hz, 1H), 8.40 (dt, J=7.9, 2.0 Hz, 1H), 8.16 (d, J=8.5 Hz, 1H), 7.90 (dd, J=8.5, 1.7 Hz, 1H), 7.48 (dd, J=7.8, 4.7 Hz, 1H), 6.48 (brt, 1H), 4.20 (qd, J=9.0 Hz, 1H).

SYNTHESIS EXAMPLE 3

Préparation of /V-(1-methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide (compound 8)

Step A: Préparation of /V-[(2-bromo-6-fluorophenyl)methylene]-3-pyridinamine

A solution of 2-bromo-6-fluorobenzaldehyde (5 g, 24.6 mmol) and 3-aminopyridine (2.7 g, 29.5 mmol) in EtOH (4 mL) was heated to reflux overnight. The reaction mixture was concentrated and the resulting solid was purified by column chromatography (silica gel eluted with 0-40% ethyl acetate in hexanes) to afford the title compound (4.5 g) as an orange solid. ¹H NMR (CDCI3) □: 8.66-8.70 (s, 1H), 8.48-8.53 (m, 2H), 7.52-7.58 (m, 1H), 7.41-7.48 (m, 1H), 7.31-7.37 (m, 1H), 6.95-7.06 (m, 2H).

Step B: Préparation of 4-bromo-2-(3-pyridinyl)-2F/-indazole

A solution of the product of Step A (4.5 g, 16.1. mmol) and NaN3 (1.2 g, 19.3 mmol) in DMF (20 mL) was heated to 90 °C for 24 hours. The cooled mixture was diluted with water and extracted 3 times with dichloromethane. The combined organic layers were dried (MgSC>4), filtered, concentrated, and the residue was purified by column chromatography (silica gel eluted with 0-30% ethyl acetate in hexanes) to give the title compound (4.0 g) as a yellow solid. ¹H NMR (CDCI3) □: 9.21 (d, J=2.4 Hz, 1H), 8.69 (dd, J=4.8, 1.3 Hz, 1H), 8.46-8.49 (d, 1H), 8.28 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 7.73 (d, J=8.7 Hz, 1H), 7.50 (ddd, J=8.2, 4.8, 0.7 Hz, 1H), 7.31 (d, 1H), 7.21 (dd, J=8.7, 7.3 Hz, 1H).

Step C: Préparation of /V-(1-methylethyl)-2-(3-pyridinyl)-2F/-indazole-4-carboxamide

The product of Step B (200 mg, 0.727 mmol), isopropylamine (183 pL, 2.18 mmol), transbis(acetato)bis[o-(di-o-tolylphosphino)benzyl]dipalladium(ll) (17 mg, 0.018 mmol), tri-ieributylphosphonium tetrafluoroborate (10.5 mg, 0.036 mmol), molybdenum hexacarbonyl (192 mg, 0.727 mmol, 1,8-diazabicycloundec-7-ene (473 pL, 2.18 mmol) and DMF (5 mL) were placed in a microwave vial and irradiated at 160 °C for 40 minutes. The reaction mixture was then cooled to room température and filtered through a pad of Celite®. The filtrate was diluted with a saturated solution of NaHCC>3 and extracted with dichloromethane. The organic layer was dried (MgSOzj), filtered, concnentrated, and the residue was purified by column chromatography (silica gel eluted with 0-10% acetone in chloroform). Trituration of the resulting solid with ethyl ether provided the title compound, a compound of this invention, as a white solid (45 mg). ¹H NMR (CDCI3) □: 9.26 (d, J=2.2 Hz, 1H), 9.09 (d, J=0.9 Hz, 1H), 8.67 (dd, J=4.7, 1.4 Hz, 1H), 8.29 (ddd, J=8.3, 2.6, 1.4 Hz, 1H), 7.92 (dt, J=8.5, 0.9 Hz, 1H), 7.48 (m, 1H), 7.31-7.41 (m, 2H), 6.15 (s, 1H), 4.31-4.41 (m, 1H), 1.33 (d, J=6.6 Hz, 6H).

SYNTHESIS EXAMPLE 4

Préparation of 2-(3-pyridinyl)-A/-[1 -(2,2,2-trifluoroethyl)]imidazo[1,2-a]pyridine-6-carboxamide (compound 457)

Step A: Préparation of 2-(3-pyridinyl)imidazo[1,2-a]pyridine-6-carboxylic acid methyl ester

Following the procedure described in US Patent Application Publication No. 20110189794, to a mixture of methyl 6-aminonicotinate (5.0 g, 33 mmol) in éthanol (140 mL) at 60 °C was added solid sodium bicarbonate (5.52 g, 65.7 mmol), followed by 3(bromoacetyl)pyridine hydrogen bromide sait (10.16 g, 36.2 mmol). The resulting mixture was heated to reflux for 9 hours. The reaction mixture was then cooled, concentrated, and saturated aqueous sodium bicarbonate solution (50 mL) and dichloromethane (50 mL) were added to the resulting residue. The aqueous phase was extracted with dichloromethane (5 X 30 mL). The combined organic phases were concentrated and purified by column chromatography (silica gel eluted with ethyl acetate) to give the title compound.

Step B: Préparation of 2-(3-pyridinyl)-/V-[1-(2,2,2-trifluoroethyl)]imidazo[1,2-a]pyridine-6carboxamide

A mixture of the ester prepared in Step A (0.4 g, 2.4 mmol) and aqueous NaOH (1 N, 7.1 mL, 7.1 mmol) was stirred in methanol (10 mL) for 2 hours. The reaction mixture was then concentrated under reduced pressure to remove methanol, and the resulting aqueous solution was neutralized with 1N HCl to pH 5 to precipitate the carboxylic acid. The solid carboxylic acid was isolated by filtration, dried, and used directly in the next step without further purification.

A mixture of the carboxylic acid prepared above (0.31 g, 1.30 mmol), EDC-HCI (0.27 g, 1.43 mmol), HOBt-H2O (0.22 g, 1.43 mmol), and triethylamine (0.72 mL, 5.2 mmol) in DMF (10 mL) was stirred at 40 °C for 30 minutes. A quarter of the reaction mixture volume was then removed, treated with CF3CH2NH2 (0.13 g, 1.3 mmol), and stirred at 40 °C ovemight. The reaction mixture was then concentrated under vacuum to remove DMF, and the residue was purified by column chromatography (silica gel eluted with ethyl acetate:methanol:triethylamine, 8:1:1) to obtain 43.8 mg of the title compound, a compound of this invention.

SYNTHESIS EXAMPLE 5

Préparation of methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate (compound 42)

Step A: Préparation of 4-nitro-[(3-pyridinylimino)methyl]benzoic acid methyl ester

A solution of methyl 3-formyl-4-nitrobenzoate (5 g, 25 mmol) and 3-aminopyridine (2.7 g, 30 mmol) in éthanol (4 mL) was heated to reflux ovemight. The reaction mixture was then cooled, concentrated under reduced pressure, and the resulting crude solid was purified by silica gel chromatography (eluting with 0-40% ethyl acetate/hexanes) to afford 4.5 g of the title product as an orange solid.

Step B: Préparation of 2-(3-pyridinyl)-2/-/-indazole-4-carboxylic acid methyl ester

A solution of the product of Step A (4.5 g, 16 mmol) and sodium azide (1.2 g, 19 mmol) in DMF (20 mL) was heated to 90 °C for 16 hours. The reaction mixture was then cooled to room température and diluted with water. The resulting two layers were separated, and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over magnésium sulfate, filtered, and concentrated under reduced pressure. The resulting crude solid was purified by silica gel chromatography (0-30% ethyl acetate/hexantes ) to afford 4.0 g of the title product as a yellow solid.

Step C: Préparation of 2-(3-pyridinyl)-2H-indazole-4-carbonyl chloride

The methyl ester prepared in Step B (4.1 g, 16 mmol) was dissolved in methanol (150 mL), 50% sodium hydroxide in water (7.1 mL) was added, and the reaction mixture was heated to reflux for 4 hours. The reaction mixture was then cooled to room température, and the solvent was removed under reduced pressure. The crude product was acidified with aqueous 1N HCl, and the resulting precipitate was isolated by filtration, washed with diethyl ether, and dried under reduced pressure at 60 °C overnight. The crude carboxylic acid was then redissolved in thionyl chloride (60 mL), and the reaction mixture was heated to 75 °C. The reaction mixture was then cooled to room température and the solvent was removed under reduced pressure. The crude carbonyl chloride was used in the next step without further purification.

Step D: Préparation of methyl 2-[[2-(3-pyridinyl)-2H-indazol-5yl]carbonyl]hydrazinecarboxylate

The acyl chloride prepared in Step C (200 mg, 0.836 mmol) was combined with hydrazinocarboxylate (82 mg, 0.91 mmol) in dichloromethane (5 mL). The reaction mixture was cooled to 0 °C, and triethylamine (360 pi, 2.51 mmol) was added dropwise. The reaction was warmed to room température and allowed stirred overnight. The reaction mixture was then cooled and quenched with saturated aqueous sodium bicarbonate solution. The two layers were separated, and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over magnésium sulfate, filtered, and concentrated under reduced pressure. The resulting crude solid was purified by silica gel chromatography (20-80% ethyl acetate/hexanes) to yield the title compound, a compound of this invention, as a white solid.

SYNTHESIS EXAMPLE 6

Préparation of 2-(3-pyridinyl)-A/-[(tetrahydro-2-furanyl)methyl]pyrazolo[1,5-a]pyridine-5carboxamide (compound 467)

Step A: Préparation of 3-(dimethoxymethyl)-5-(3-pyridinyl)-1 H-pyrazole

Lithium hexamethyldisilane (55 mL of a 1.0M solution in tetrahydrofuran, 55 mmoles) was added to a solution of 3-acetylpyridine (5.5 mL, 50 mmoles), methyl dimethoxy acetate (6.7 mL, 55 mmoles) and anhydrous tetrahydrofuran (100 mL) with cooling at-45 °C. The resulting reaction mixture was allowed to warm to 25 °C over 1 hour, and stirred at this température for 3 hours. The reaction mixture was then concentrated under reduced pressure, and the residue was suspended in methanol (50 mL) and concentrated under reduced pressure. The resulting residue was suspended in methanol (150 mL) and treated with hydrazine monohydrate (2.62 mL, 55 mmoles) and glacial acetic acid (6.29 mL, 110 mmoles), and the reaction mixture was heated at reflux for 14 hours. The resulting reaction mixture was cooled to 25 °C and concentrated under reduced pressure. The residue was partitioned between ethyl acetate (200 mL) and 1N aqueous sodium hydroxide solution (100 mL). The layers were separated, and the organic layer was washed successively with 1N aqueous sodium hydroxide solution (50 mL) and brine (50 mL), dried over anhydrous magnésium sulfate, and concentrated under reduced pressure to yield 8.83 g ofthe title compound as a beige solid.

¹H NMR (CDCI₃): δ 10.5 (br s, 1H) 9.03 (d, 1H), 8.57 (dd, 1H), 8.09 (dt, 1H), 7.34 (dd, 1H), 6.65 (s, 1H), 5.63 (s, 1H), 3.39 (s, 6H).

Step B: Préparation of 5-(3-pyridinyl)-1 /7-pyrazole-3-carboxaldehyde

To a solution of the product from Step A (715 mg, 3.3 mmoles) and chloroform (5 mL) was added a solution of trifluoroacetic acid (2.5 mL) and water (2.5 mL); the reaction mixture température was maintained below 5 °C with an ice-water bath. The reaction mixture was then stirred at 0-5 °C for 2 hours, treated with triethylamine (5 mL) at 0 °C, stirred for 15 minutes, treated with water (10 mL), and filtered to isolate a brown solid. This solid was washed with chloroform (20 mL) and water (20 mL), and air dried to yield 605 mg of the title compound as a light beige solid that was used in the next step without further purification.

Step C: Préparation of 2-(3-pyridinyl)pyrazolo[1,5-a]pyridine-5-carboxylic acid ethyl ester

A mixture ofthe productfrom Step B (596 mg, 3.4 mmoles), ethyl-4-bromocrotonate (75%, 0.95 mL, 5.2 mmoles), anhydrous potassium carbonate (1.42 g, 10.3 mmoles) and anhydrous A/,A/-dimethylformamide (17 mL) was stirred at 25 °C for 14 hours. The reaction mixture was then partitioned between ethyl acetate and saturated aqueous ammonium chloride solution, and the organic layer was separated, washed with water (3X), brine, dried over anhydrous magnésium sulfate, and concentrated under reduced pressure to give a crude product. This resulting product was purified by MPLC on a 24 g silica column eluting with 0 to 100% ethyl acetate in hexanes to give the title compound as a light beige solid (105 mg).

¹H NMR (CDCI₃): δ 9.20 (d, 1H), 8.63 (dd, 1H), 8.50 (d, 1H), 8.33 (d, 1H), 8.27 (dt, 1H), 7.43-7.35 (m, 2H), 7.05 (s, 1H), 4.43 (q, 2H), 1.44 (t, 3H).

Step D: Préparation of 2-(3-pyridinyl)-A/-[(tetrahydro-2-furanyl)methyl]pyrazolo[1,5a]pyridine-5-carboxamide

To a solution of the product from Step C (31 mg, 0.11 mmoles), tetrahydrofurfurylamine (0.12 mL, 1.2 mmoles), and anhydrous toluene (2.3 mL) was added trimethylaluminum (0.6 mL of a 2.0M solution in toluene, 1.2 mmoles). The resulting solution was stirred for 2 hours at 25 °C, for 2 hours at 80 °C, and then cooled to 0 °C and treated carefully with water (3 mL). The resulting reaction mixture was stirred at 25 °C for 15 minutes, treated with a saturated aqueous solution of sodium-potassium tartrate (2 mL), stirred for 30 minutes, and then partitioned between dichloromethane and water. The organic layer was separated, dried over anhydrous magnésium sulfate, and concentrated under reduced pressure to isolate a brown residue that was triturated with diethyl etherto yield the title compound, a compound of this invention, as a beige solid (15 mg).

¹H NMR (CDCI3): δ 9.19 (d, 1H), 8.63 (dd, 1H), 8.51 (d, 1H), 8.26 (dt, 1H), 8.03 (s, 1H), 7.39 (dd, 1H), 7.16 (dd, 1H), 7.00 (s, 1H), 6.60 (brs, 1H), 4.10 (qd, 1H), 3.93 (dt, 1H), 3.89-3.76 (m, 2H), 3.38-3.29 (m, 1H), 2.11-2.02 (m, 1H), 2.00-1.83 (m, 3H).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 24d can be prepared. The following abbreviations are used in the Tables which follow: t means tertiary, smeans secondary, /means iso, cmeans cyclo, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, CN means cyano, Ph means phenyl, Py means pyridinyl, -NO2 means nitro, S(O)Me means methylsulfinyl, and S(O)2Me means methylsulfonyl.

A at the beginning of a fragment définition dénotés the attachment point of said fragment to the remainder of the molécule; for example, -CH2CH2OMe dénotés the fragment 2-methoxyethyl. Cyclic fragments are represented by the use of two within parenthèses; for example, the fragment 1-pyrrolidinyl is represented by N(-CH2CH2CH2CH2-), wherein a nitrogen atom is bonded to both terminal carbon atoms of the four-carbon chain, as illustrated below.

z : λ remainder of molécule \_______________Z

TABLE 1a

H

Ais CH

R	R	R
Me	Et	Pr
i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-ch₂ch=ch₂
-CH₂C2CH	-C(Me)₂C^CH	-ch₂ch₂f
-CH2CHF2	-CH₂CF₃	-CH(Me)CF₃
-ch₂ch₂cf₃	-ch₂cf₂cf₃	-CH2CF2CH3
-CH2CH2CF2CF3	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-CH₂CH₂OEt
-CH₂CH₂CH2OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH₂S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH2CH₂SO₂Me	-CH₂CH₂SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH2CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me

-CH(Me)CH₂S(O)Me	-CH₂CH2S(O)CH₂CF3	-CH2CH2SCH2CF3
-CH2CH2SO2CH2CF3	-CH2CH2SO2CH2CH2CF3	-CH2CH2SCH2CH2CF3
-CH₂CH2S(O)CH₂CH₂CF3	-ch₂cn	-CH2CH2CN
-C(Me)₂CN	-CH₂CH2N(i-Pr)₂	-CH2CH2N(Me)2
-CH2CH(OMe)₂	c-Pr	c-Bu
1-methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-d if I uo rocyclo b uty I
3-oxetanyl	-CH2(oxiranyl)	3-thietanyl-1,1 -dioxide
3-thietanyl-1 -oxide	-CH2(CH(-OC(Me)₂OCH₂- ))	-CH2(tetrahydro-2-furanyl)
-CH2(2-furanyl)	tetrahydro-2-furanyl	-CH2(2-thienyl)
-CH₂(CH(-OCH₂CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂
-OCH2CH=CH₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-NHCO₂CH₂CF3	-C(O)CO₂Me
-C(O)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF3	-NHC(O)CH2CH₂CF3	-NHC(O)Et
-NHC(O)CH₂CF₃	-NHSO₂CF₃	-NHSO₂CH₂CF3
-NHSO2CH2CH2CF3	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF₃-2-pyridinyl)	-NH(4-CF3-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF3-2-pyrimidinyl)	-NH(5-CF₃-2-pyridinyl)

-NH(4-CF3-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-NH(4-methyl-2-pyridinyl)
-NH(3-methyl-2-pyridinyl)	-NH(5-methyl-2-pyrimidinyl)	-N H(5-methyl-2-pyridinyl )
-NH(4-methyl-2-pyrimidinyl)	-NH(6-methoxy-2-pyridinyl)	-NH(4-methoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2- pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH2(6-CF3-2-pyridinyl)	-CH2(4-CF3-2-pyridinyl)
-CH2(3-CF3-2-pyridinyl)	-CH2(5-CF3-2-pyrimidinyl)	-CH2(5-CF3-2-pyridinyl)
-CH2(4-CF3-2-pyrimidinyl)	-CH2(6-methyl-2-pyridinyl)	-CH2(4-methyl-2-pyridinyl)
-CH2(3-methyl-2-pyridinyl)	-CH2(5-methyl-2- pyrimidinyl)	-CH2(5-methyl-2-pyridinyl)
-CH2(4-methyl-2-pyrimidinyl)	-CH2(6-methoxy-2- pyridinyl)	-CH2(4-methoxy-2- pyridinyl)
-CH2(3-methoxy-2-pyridinyl)	-CH2(5-methoxy-2- pyrimidinyl)	-CH2(5-methoxy-2- pyridinyl)
-CH2(4-methoxy-2- pyrimidinyl)	-CH2(5-pyrimidinyl)	-CH2(6-bromo-2-pyridinyl)
-CH2(2-pyrimidinyl)	-CH₂(3-(OCF₃)phenyl)	-CH2(2-thiazolyl)
-CH2(5-methyl-2-pyrazinyl)	-CH2(4-pyridinyl)	-CH2(2-pyridinyl)
Ph	3-pyridinyl	-CH2(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH2CH2(2-pyridinyl)
4-pyridinyl	4-CF3-2-pyridinyl	-CH2CH2CH2(2-pyridinyl)
3-CF3-2-pyridinyl	4-CF3-2-pyrimidinyl	6-CF3-2-pyridinyl
5-CF3-2-pyridinyl	5-CF3-2-pyrazinyl	5-CF3-2-pyrimidinyl
-CH₂CH₂N(- C(O)CH₂CH₂C(O)-)	-CH2CH2CH2(1-imidazolyl)	-CH(-C(O)OCH₂CH₂-)
-CH2(4-pyrimidinyl)	pyridazinyl	6-CF3-3-pyrazinyl

Ais CF

R	R	R
Me	Et	Pr

i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-CH₂CH=CH₂
-ch₂c=ch	-C(Me)₂CsCH	-ch₂ch₂f
-ch₂chf₂	-CH₂CF₃	-CH(Me)CF₃
-ch₂ch₂cf₃	-ch₂cf₂cf₃	-CH₂CF₂CH₃
-ch₂ch₂cf₂cf₃	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-CH₂CH₂OEt
-CH₂CH₂CH₂OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH₂S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH₂CH₂SO₂Me	-CH₂CH₂SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH₂CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH₂CH₂S(O)CH₂CF₃	-CH₂CH₂SCH₂CF₃
-CH₂CH₂SO₂CH₂CF₃	-CH₂CH₂SO₂CH₂CH₂CF₃	-ch₂ch₂sch₂ch₂cf₃
-CH₂CH₂S(O)CH₂CH₂CF₃	-ch₂cn	-ch₂ch₂cn
-C(Me)₂CN	-CH₂CH₂N(i-Pr)₂	-CH₂CH₂N(Me)₂
-CH2CH(OMe)₂	c-Pr	c-Bu
1 -methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl
3-oxetanyl	-CH₂(oxiranyl)	3-thietanyl-1,1-dioxide
3-thietanyl-1 -oxide	-CH₂(CH(-OC(Me)₂OCH₂- ))	-CH₂(tetrahydro-2-furanyl)
-CH₂(2-furanyl)	tetrahydro-2-furanyl	-CH₂(2-thienyl)
-CH₂(CH(-OCH₂CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂

-och₂ch=ch₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-NHCO₂CH₂CF₃	-C(O)CO₂Me
-C(O)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF₃	-NHC(O)Et
-NHC(O)CH₂CF₃	-nhso₂cf₃	-NHSO₂CH₂CF₃
-nhso₂ch₂ch₂cf₃	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF₃-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF₃-2-pyrimidinyl)	-NH(5-CF₃-2-pyridinyl)
-NH(4-CF₃-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-N H (4-m ethyl-2-pyri d i nyl )
-N H(3-methyl-2-pyrid inyl )	-NH(5-methyl-2-pyrimidinyl)	-NH(5-methyl-2-pyridinyl)
-NH(4-methyl-2-pyrimidinyl)	-NH(6-methoxy-2-pyridinyl)	-NH(4-methoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH₂(6-CF₃-2-pyridinyl)	-CH₂(4-CF₃-2-pyridinyl)
-CH₂(3-CF₃-2-pyridinyl)	-CH₂(5-CF₃-2-pyrimidinyl)	-CH₂(5-CF₃-2-pyridinyl)
-CH₂(4-CF₃-2-pyrimidinyl)	-CH₂(6-methyl-2-pyridinyl)	-CH₂(4-methyl-2-pyridinyl)
-CH₂(3-methyl-2-pyridinyl)	-CH₂(5-methyl-2- pyrimidinyl)	-CH₂(5-methyl-2-pyridinyl)
-CH₂(4-methyl-2-pyrimidinyl)	-CH₂(6-methoxy-2- pyridinyl)	-CH₂(4-methoxy-2- pyridinyl)
-CH₂(3-methoxy-2-pyridinyl)	-CH₂(5-methoxy-2- pyrimidinyl)	-CH₂(5-methoxy-2- pyridinyl)
-CH₂(4-methoxy-2- pyrimidinyl)	-CH₂(5-pyrimidinyl)	-CH₂(6-bromo-2-pyridinyl)

-CH2(2-pyrimidinyl)	-CH₂(3-(OCF₃)phenyl)	-CH2(2-thiazolyl)
-CH2(5-methyl-2-pyrazinyl)	-CH2(4-pyridinyl)	-CH2(2-pyridinyl)
Ph	3-pyridinyl	-CH2(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH2CH2(2-pyridinyl)
4-pyridinyl	4-CF3-2-pyridinyl	-CH2CH2CH2(2-pyridinyl)
3-CF3-2-pyridinyl	4-CF3-2-pyrimidinyl	6-CF3-2-pyridinyl
5-CF3-2-pyridinyl	5-CF3-2-pyrazinyl	5-CF3-2-pyrimidinyl
-CH₂CH₂N(- C(O)CH₂CH₂C(O)-)	-CH2CH2CH2(1 -imidazolyl)	-CH(-C(O)OCH₂CH₂-)
-CH2(4-pyrimidinyl)	pyridazinyl	6-CF3-3-pyrazinyl

A is N

R	R	R
Me	Et	Pr
i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-ch₂ch=ch₂
-CH₂C=CH	-C(Me)₂CsCH	-ch₂ch₂f
-ch₂chf₂	-CH₂CF₃	-CH(Me)CF₃
-ch₂ch₂cf₃	-CH2CF2CF3	-CH₂CF₂CH3
-CH2CH2CF2CF3	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-CH₂CH₂OEt
-CH2CH2CH2OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH2S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH₂CH₂SO2Me	-CH₂CH₂SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH₂CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH2CH2S(O)CH₂CF3	-CH2CH2SCH2CF3
-CH2CH2SO2CH2CF3	-CH2CH2SO2CH2CH2CF3	-CH2CH2SCH2CH2CF3

-CH₂CH₂S(O)CH₂CH₂CF₃	-CH₂CN	-CH₂CH₂CN
-C(Me)₂CN	-CH₂CH₂N(i-Pr)₂	-CH₂CH₂N(Me)₂
-CH2CH(OMe)₂	c-Pr	c-Bu
1 -methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl
3-oxetanyl	-CH₂(oxiranyl)	3-thietanyl-1,1-dioxide
3-thietanyl-1 -oxide	-CH₂(CH(-OC(Me)₂OCH₂- ))	-CH₂(tetrahydro-2-furanyl)
-CH₂(2-furanyl)	tetrahydro-2-furanyl	-CH₂(2-thienyl)
-CH₂(CH(-OCH₂CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂
-OCH₂CH=CH₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-NHCO₂CH₂CF₃	-C(O)CO₂Me
-C(O)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF₃	-NHC(O)Et
-NHC(O)CH₂CF₃	-nhso₂cf₃	-NHSO₂CH₂CF₃
-nhso₂ch₂ch₂cf₃	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF₃-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF₃-2-pyrimidinyl)	-NH(5-CF₃-2-pyridinyl)
-NH(4-CF₃-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-N H (4-m ethy l-2-pyrid i nyl )
-NH(3-methyl-2-pyridinyl)	-NH(5-methyl-2-pyrimidinyl)	-NH(5-methyl-2-pyridinyl)

-NH(4-methyl-2-pyrimidinyl)	-NH(6-methoxy-2-pyridinyl)	-N H (4-m ethoxy-2-py rid i nyl )
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-N H (4-meth oxy-2-py ri m id i nyi )	-CH2(6-CF3-2-pyridinyl)	-CH2(4-CF3-2-pyridinyl)
-CH₂(3-CF₃-2-pyridinyl)	-CH2(5-CF3-2-pyrimidinyl)	-CH2(5-CF3-2-pyridinyl)
-CH2(4-CF3-2-pyrimidinyl)	-CH2(6-methyl-2-pyridinyl)	-CH2(4-methyl-2-pyridinyl)
-CH2(3-methyl-2-pyridinyl)	-CH2(5-methyl-2- pyrimidinyl)	-CH2(5-methyl-2-pyridinyl)
-CH2(4-methyl-2-pyrimidinyl)	-CH2(6-methoxy-2- pyridinyl)	-CH2(4-methoxy-2- pyridinyl)
-CH2(3-methoxy-2-pyridinyl)	-CH2(5-methoxy-2- pyrimidinyl)	-CH2(5-methoxy-2- pyridinyl)
-CH2(4-methoxy-2- pyrimidinyl)	-CH2(5-pyrimidinyl)	-CH2(6-bromo-2-pyridinyl)
-CH2(2-pyrimidinyl)	-CH₂(3-(OCF₃)phenyl)	-CH2(2-thiazolyl)
-CH2(5-methyl-2-pyrazinyl)	-CH2(4-pyridinyl)	-CH2(2-pyridinyl)
Ph	3-pyridinyl	-CH2(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH2CH2(2-pyridinyl)
4-pyridinyl	4-CF3-2-pyridinyl	-CH2CH2CH2(2-pyridinyl)
3-CF3-2-pyridinyl	4-CF3~2-pyrimidinyl	6-CF3-2-pyridinyl
5-CF3-2-pyridinyl	5-CF3-2-pyrazinyl	5-CF3-2-pyrimidinyl
-CH₂CH₂N(- C(O)CH₂CH₂C(O)-)	-CH2CH2CH2(1 -imidazolyl)	-CH(-C(O)OCH₂CH₂-)
-CH2(4-pyrimidinyl)	pyridazinyl	6-CF3-3-pyrazinyl

Aïs CH

R	R	R
Me	Et	Pr
i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-CH₂CH=CH₂
-ch₂chch	-C(Me)₂CECH	-ch₂ch₂f
-ch₂chf₂	-CH₂CF₃	-CH(Me)CF₃
-ch₂ch₂cf₃	-ch₂cf₂cf₃	-CH₂CF₂CH₃
-ch₂ch₂cf₂cf₃	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-CH₂CH₂OEt
-CH₂CH₂CH₂OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH₂S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH₂CH₂SO₂Me	-CH₂CH₂SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH₂CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH₂CH₂S(O)CH₂CF₃	-CH₂CH₂SCH₂CF₃
-CH₂CH₂SO₂CH₂CF₃	-ch₂ch₂so₂ch₂ch₂cf₃	-ch₂ch₂sch₂ch₂cf₃
-CH₂CH₂S(O)CH₂CH₂CF₃	-ch₂cn	-ch₂ch₂cn
-C(Me)₂CN	-CH₂CH₂N(i-Pr)₂	-CH₂CH₂N(Me)₂
-CH2CH(OMe)₂	c-Pr	c-Bu
1-methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)

-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl
3-oxetanyl	-CH₂(oxiranyl)	3-thietanyl-1,1 -dioxide
3-thietanyl-1-oxide	-CH₂(CH(-OC(Me)₂OCH₂- ))	-CH₂(tetrahydro-2-furanyl)
-CH2(2-furanyl)	tetra hyd ro-2-f u ra nyl	-CH₂(2-thienyl)
-CH₂(CH(-OCH2CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂
-OCH₂CH=CH₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-NHCO₂CH₂CF₃	-C(O)CO₂Me
-C(O)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF₃	-NHC(O)Et
-NHC(O)CH₂CF₃	-nhso₂cf₃	-NHSO₂CH₂CF₃
-nhso₂ch₂ch₂cf₃	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF₃-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF₃-2-pyrimidinyl)	-NH(5-CF₃-2-pyridinyl)
-NH(4-CF₃-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-NH(4-methyl-2-pyridinyl)
-NH(3-methyl-2-pyridinyl)	-NH(5-methyl-2-pyrimidinyl)	-NH(5-methyl-2-pyridinyl)
-NH(4-methyl-2-pyrimidinyl)	-NH(6-methoxy-2-pyridinyl)	-NH(4-methoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2- pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH₂(6-CF₃-2-pyridinyl)	-CH₂(4-CF₃-2-pyridinyl)

-CH2(3-CF3-2-pyridinyl)	-CH2(5-CF3-2-pyrimidinyl)	-CH2(5-CF3-2-pyridinyl)
-CH2(4-CF3-2-pyrimidinyl)	-CH2(6-methyl-2-pyridinyl)	-CH2(4-methyl-2-pyridinyl)
-CH2(3-methyl-2-pyridinyl)	-CH2(5-methyl-2- pyrimidinyl)	-CH2(5-methyl-2-pyridinyl)
-CH2(4-methyl-2-pyrimidinyl)	-CH2(6-methoxy-2- pyridinyl)	-CH2(4-methoxy-2- pyridinyl)
-CH2(3-methoxy-2-pyridinyl)	-CH2(5-methoxy-2- pyrimidinyl)	-CH2(5-methoxy-2- pyridinyl)
-CH2(4-methoxy-2- pyrimidinyl)	-CH2(5-pyrimidinyl)	-CH2(6-bromo-2-pyridinyl)
-CH2(2-pyrimidinyl)	-CH₂(3-(OCF₃)phenyl)	-CH2(2-thiazolyl)
-CH2(5-methyl-2-pyrazinyl)	-CH2(4-pyridinyl)	-CH2(2-pyridinyl)
Ph	3-pyridinyl	-CH2(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH2CH2(2-pyridinyl)
4-pyridinyl	4-CF3-2-pyridinyl	-CH2CH2CH2(2-pyridinyl)
3-CF3-2-pyridinyl	4-CF3-2-pyrimidinyl	6-CF3-2-pyridinyl
5-CF3-2-pyridinyl	5-CF3-2-pyrazinyl	5-CF3-2-pyrimidinyl
-CH₂CH₂N(- C(O)CH₂CH₂C(O)-)	-CH2CH2CH2(1 -imidazolyl)	-CH(-C(O)OCH₂CH₂-)
-CH2(4-pyrimidinyl)	pyridazinyl	6-CF3-3-pyrazinyl

Aïs CF

R	R	R
Me	Et	Pr
i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-CH2CH=CH₂
-ch₂csch	-C(Me)₂CHCH	-ch₂ch₂f
-ch₂chf₂	-ch₂cf₃	-CH(Me)CF₃

-ch₂ch₂cf₃	-ch₂cf₂cf₃	-CH₂CF₂CH₃
-ch₂ch₂cf₂cf₃	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-CH₂CH₂OEt
-CH₂CH₂CH₂OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH₂S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH₂CH₂SO₂Me	-CH₂CH₂SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH₂CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH₂CH₂S(O)CH₂CF₃	-CH₂CH₂SCH₂CF₃
-CH₂CH₂SO₂CH₂CF₃	-ch₂ch₂so₂ch₂ch₂cf₃	-ch₂ch₂sch₂ch₂cf₃
-CH₂CH₂S(O)CH₂CH₂CF₃	-ch₂cn	-ch₂ch₂cn
-C(Me)₂CN	-CH₂CH₂N(i-Pr)₂	-CH₂CH₂N(Me)₂
-CH2CH(OMe)₂	c-Pr	c-Bu
1 -methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl
3-oxetanyl	-CH₂(oxiranyl)	3-thietanyl-1,1-dioxide
3-thietanyl-1-oxide	-CH₂(CH(-OC(Me)₂OCH₂- ))	-CH₂(tetrahydro-2-furanyl)
-CH₂(2-furanyl)	tetrahydro-2-furanyl	-CH₂(2-thienyl)
-CH₂(CH(-OCH₂CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂
-OCH₂CH=CH₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)

-C(O)C(O)Me	-NHCO₂CH₂CF₃	-C(O)CO₂Me
-C(O)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF₃	-NHC(O)Et
-NHC(O)CH₂CF₃	-nhso₂cf₃	-NHSO₂CH₂CF₃
-nhso₂ch₂ch₂cf₃	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF₃-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF₃-2-pyrimidinyl)	-NH(5-CF₃-2-pyridinyl)
-NH(4-CF₃-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-NH(4-methyl-2-pyridinyl)
-N H(3-methyl-2-pyrid inyl )	-NH(5-methyl-2-pyrimidinyl)	-N H (5-methyl-2-pyridi nyl )
-NH(4-methyl-2-pyrimidinyl)	-NH(6-methoxy-2-pyridinyl)	-NH(4-methoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH₂(6-CF₃-2-pyridinyl)	-CH₂(4-CF₃-2-pyridinyl)
-CH₂(3-CF₃-2-pyridinyl)	-CH₂(5-CF₃-2-pyrimidinyl)	-CH₂(5-CF₃-2-pyridinyl)
-CH₂(4-CF₃-2-pyrimidinyl)	-CH₂(6-methyl-2~pyridinyl)	-CH₂(4-methyl-2-pyridinyl)
-CH₂(3-methyl-2-pyridinyl)	-CH₂(5-methyl-2- pyrimidinyl)	-CH₂(5-methyl-2-pyridinyl)
-CH₂(4-methyl-2-pyrimidinyl)	-CH₂(6-methoxy-2- pyridinyl)	-CH₂(4-methoxy-2- pyridinyl)
-CH₂(3-methoxy-2-pyridinyl)	-CH₂(5-methoxy-2- pyrimidinyl)	-CH₂(5-methoxy-2- pyridinyl)
-CH₂(4-methoxy-2- pyrimidinyl)	-CH₂(5-pyrimidinyl)	-CH₂(6-bromo-2-pyridinyl)
-CH₂(2-pyrimidinyl)	-CH₂(3-(OCF₃)phenyl)	-CH₂(2-thiazolyl)
-CH₂(5-methyl-2-pyrazinyl)	-CH₂(4-pyridinyl)	-CH₂(2-pyridinyl)
Ph	3-pyridinyl	-CH₂(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH₂CH₂(2-pyridinyl)
4-pyridinyl	4-CF₃-2-pyridinyl	-CH₂CH₂CH₂(2-pyridinyl)

3-CF3-2-pyridinyl	4-CF3-2-pyri m id inyl	6-CF3-2-pyridinyl
5-CF3-2-pyridinyl	5-CF3-2-pyrazinyl	5-CF3-2-pyrimidinyl
-CH₂CH₂N(- C(O)CH₂CH₂C(O)-)	-CH₂CH₂CH₂(1-imidazolyl)	-CH(-C(O)OCH₂CH₂-)
-CH₂(4-pyrimidinyl)	pyridazinyl	6-CF3-3-pyrazinyl

A is N

R	R	R
Me	Et	Pr
i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-CH₂CH=CH₂
-ch₂cech	-C(Me)₂CECH	-ch₂ch₂f
-ch₂chf₂	-CH₂CF₃	-CH(Me)CF₃
-CH₂CH₂CF3	-ch₂cf₂cf₃	-CH₂CF₂CH₃
-ch₂ch₂cf₂cf₃	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-CH₂CH₂OEt
-CH₂CH₂CH₂OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH₂S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH₂CH₂SO₂Me	-CH₂CH₂SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH₂CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH₂CH₂S(O)CH₂CF₃	-CH₂CH₂SCH₂CF₃
-CH₂CH₂SO₂CH₂CF₃	-ch₂ch₂so₂ch₂ch₂cf₃	-ch₂ch₂sch₂ch₂cf₃
-CH₂CH₂S(O)CH₂CH₂CF₃	-ch₂cn	-ch₂ch₂cn
-C(Me)₂CN	-CH₂CH₂N(i-Pr)₂	-CH₂CH₂N(Me)₂
-CH2CH(OMe)₂	c-Pr	c-Bu
1 -methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl

3-oxetanyl	-CH2(oxiranyl)	3-thietanyl-1,1 -dioxide
3-thietanyl-1 -oxide	-CH₂(CH(-OC(Me)₂OCH2- ))	-CH2(tetrahydro-2-furanyl)
-CH2(2-furanyl)	tetrahydro-2-furanyl	-CH2(2-thienyl)
-CH2(CH(-OCH2CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂
-och₂ch=ch₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-nhco₂ch₂cf₃	-C(O)CO₂Me
-C(O)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF₃	-NHC(O)Et
-NHC(O)CH₂CF₃	-nhso₂cf₃	-nhso₂ch₂cf₃
-NHSO₂CH₂CH2CF₃	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF₃-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF₃-2-pyrimidinyl)	-NH(5-CF₃-2-pyridinyl)
-NH(4-CF₃-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-NH(4-methyl-2-pyridinyl)
-NH(3-methyl-2-pyridinyl)	-NH(5-methyl-2-pyrimidinyl)	-NH(5-methyl-2-pyridinyl)
-NH(4-methyl-2-pyrimidinyl)	-N H (6-m ethoxy-2-pyrid i nyl )	-NH(4-methoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH2(6-CF₃-2-pyridinyl)	-CH2(4-CF₃-2-pyridinyl)
-CH2(3-CF₃-2-pyridinyl)	-CH2(5-CF₃-2-pyrimidinyl)	-CH2(5-CF₃-2-pyridinyl)

-CH2(4-CF3-2-pyrimidinyl)	-CH2(6-methyl-2-pyridinyl)	-CH2(4-methyl-2-pyridinyl)
-CH2(3-methyl-2-pyridinyl)	-CH2(5-methyl-2- pyrimidinyl)	-CH2(5-methyl-2-pyridinyl)
-CH2(4-methyl-2-pyrimidinyl)	-CH2(6-methoxy-2- pyridinyl)	-CH2(4-methoxy-2- pyridinyl)
-CH2(3-methoxy-2-pyridinyl)	-CH2(5-methoxy-2- pyrimidinyl)	-CH2(5-methoxy-2- pyridinyl)
-CH2(4-methoxy-2- pyrimidinyl)	-CH2(5-pyrimidinyl)	-CH2(6-bromo-2-pyridinyl)
-CH2(2-pyrimidinyl)	-CH₂(3-(OCF₃)phenyl)	-CH2(2-thiazolyl)
-CH2(5-methyl-2-pyrazinyl)	-CH2(4-pyridinyl)	-CH2(2-pyridinyl)
Ph	3-pyridinyl	-CH2(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH2CH2(2-pyridinyl)
4-pyridinyl	4-CF3-2-pyridinyl	-CH2CH2CH2(2-pyridinyl)
3-CF3-2-pyridinyl	4-CF3-2-pyrimidinyl	6-CF3-2-pyridinyl
5-CF3-2-pyridinyl	5-CF3-2-pyrazinyl	5-CF3-2-pyrimidinyl
-ΟΗ₂ΟΗ₂Ν(- C(O)CH₂CH₂C(O)-)	-CH2CH2CH2(Timidazolyl)	-CH(-C(O)OCH₂CH₂-)
-CH2(4-pyrimidinyl)	pyridazinyl	6-CF3-3-pyrazinyl

TABLE 1c

A is CH

R	R
N(-CH₂CH2CH₂-)	N(-CH₂CH(OMe)CH₂-)

N(-CH2CH2CF₂CH2CH2-)	N(-CH₂CH₂CH2CF2CH2-)
N(-CH2CH₂CH2CH2-)	N(-CH2CH2SCH₂CH2-)
N(-CH₂CH₂CH2CH₂CH2-)	N(-CH₂CH2OCH2CH2-)
N(-CH₂CH₂N(C(O)(c-Pr))CH2CH2-)	N(-CH₂CH2N(Me)CH₂CH2-)
N(-CH₂C(Me)₂N=CH-)	N(-CH₂CH2CH₂CH(CF3)CH₂-)
N(CH2CeCH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)
N(-CHC(O)SCH₂CH₂-)

Ais CF

R	R
N(-CH₂CH₂CH2-)	N(-CH₂CH(OMe)CH₂-)
N(-CH2CH2CF2CH₂CH2-)	N(-CH₂CH2CH2CF2CH₂-)
N(-CH2CH₂CH2CH₂-)	N(-CH₂CH2SCH₂CH2-)
N(-CH2CH2CH₂CH2CH2-)	N(-CH₂CH2OCH₂CH₂-)
N(-CH₂CH2N(C(O)(c-Pr))CH₂CH2-)	N(-CH₂CH2N(Me)CH₂CH2-)
N(-CH₂C(Me)2N=CH-)	N(-CH₂CH2CH₂CH(CF3)CH2-)
N(CH₂C=CH)2	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)
N(-CHC(O)SCH₂CH2-)

A is N

R	R
N(-CH₂CH₂CH₂-)	N(-CH₂CH(OMe)CH₂-)
N(-CH2CH₂CF2CH2CH₂-)	N(-CH2CH2CH2CF₂CH2-)
N(-CH₂CH2CH₂CH2-)	N(-CH2CH2SCH2CH₂-)
N(-CH2CH2CH2CH₂CH2-)	N(-CH₂CH2OCH₂CH₂-)
N(-CH2CH₂N(C(O)(c-Pr))CH₂CH2-)	N(-CH2CH₂N(Me)CH2CH2-)
N(-CH₂C(Me)₂N=CH-)	N(-CH2CH₂CH2CH(CF3)CH2-)

N(CH₂C=CH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)
N(-CHC(O)SCH₂CH2-)

Ais CH

R	R
N(-CH₂CH₂CH₂-)	N(-CH₂CH(OMe)CH₂-)
N(-CH2CH2CF2CH2CH2-)	N(-CH₂CH2CH2CF₂CH2-)
N(-CH₂CH2CH₂CH₂-)	N(-CH₂CH2SCH₂CH2-)
N(-CH₂CH₂CH2CH2CH₂-)	N(-CH₂CH₂OCH2CH2-)
N(-CH2CH₂N(C(O)(c-Pr))CH₂CH₂-)	N(-CH₂CH₂N(Me)CH2CH2-)
N(-CH₂C(Me)₂N=CH-)	N(-CH2CH2CH₂CH(CF3)CH₂-)
N(CH₂C=CH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)
N(-CHC(O)SCH₂CH₂-)

Ais CF

R	R
N(-CH₂CH₂CH₂-)	N(-CH₂CH(OMe)CH₂-)
N(-CH₂CH₂CF2CH2CH2-)	N(-CH₂CH₂CH2CF₂CH2-)
N(-CH₂CH₂CH2CH2-)	N(-CH₂CH₂SCH2CH₂-)
N(-CH2CH2CH₂CH₂CH2-)	N(-CH2CH₂OCH₂CH2-)

N(-CH₂CH2N(C(O)(c-Pr))CH₂CH2-)	N(-CH₂CH₂N(Me)CH2CH2-)
N(-CH₂C(Me)₂N=CH-)	N(-CH₂CH₂CH2CH(CF3)CH2-)
N(CH₂CeCH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)
N(-CHC(O)SCH₂CH₂-)

A is N

R	R
N(-CH₂CH₂CH₂-)	N(-CH₂CH(OMe)CH₂-)
N(-CH₂CH2CF2CH₂CH2-)	N(-CH₂CH2CH2CF₂CH2-)
N(-CH₂CH₂CH2CH2-)	N(-CH₂CH2SCH₂CH2-)
N(-CH2CH₂CH2CH₂CH2-)	N(-CH2CH₂OCH₂CH2-)
N(-CH₂CH₂N(C(O)(c-Pr))CH2CH2-)	N(-CH₂CH₂N(Me)CH2CH2-)
N(-CH₂C(Me)₂N=CH-)	N(-CH₂CH2CH₂CH(CF3)CH2-)
N(CH₂C=CH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)
N(-CHC(O)SCH₂CH₂-)

TABLE 1e

A is CH

R	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trif I u o rom ethyl )-2-py rid i nyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyridinyl	4-methoxy-2-pyridinyl

4-(trifluoromethyl)-2-pyridinyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-(trifluoromethyl)-2-pyridinyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-m eth oxy-3-pyrid i nyl
2-(trifluoromethyl)-3-pyridinyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trifluoromethyl)-3-pyridinyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl
5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trifluoromethyl)-3-pyridinyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-(trif 1 uoromethyl)-4-pyrid i nyl	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl
3 - (t rif 1 u o rom ethyl )-4-p y r i d i nyl	3-(CH(=NOMe))-4-pyridinyl
3-methyl-2-pyrazinyl	3-methoxy-2-pyrazinyl
3-(trifluoromethyl)-2-pyrazinyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-methoxy-2-pyrazinyl
5-(trifluoromethyl)-2-pyrazinyl	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl
6-(trif 1 uo ro methyl )-2-py razi nyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrimidinyl	4-methoxy-2-pyrimidinyl
4-(tr if 1 u orom ethy 1 )-2-p y r i m id i nyl	4-(CH(=NOMe))-2-pyrimidinyl
5-methyl-2-pyrimidinyl	5-methoxy-2-pyrimidinyl
5 - (tr if 1 uo rom ethy 1 )-2-py r i m id i nyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-(tr if 1 uo rom ethyl )-4- py r i m id i nyl	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyrimidinyl	5-methoxy-4-pyrimidinyl
5-(trifluoromethyl)-4-pyrimidinyl	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrimidinyl	6-methoxy-4-pyrimidinyl

6 - (trif I u oro m ethyl )-4-py r i m id i ny I	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1 -pyrazolyl	3-(CH(=N0Me))-1 -pyrazolyl
4-methyl-1 -pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=N0Me))-1-pyrazolyl
5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1 -pyrazolyl	5-(CH(=N0Me))-1 -pyrazolyl
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(trifluoromethyl)-1,2,3-triazin-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl
2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetrahydro-2-furanyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	phenyl
2-(trifluoromethyl)phenyl	3-(trifluoromethyl)phenyl
4-(trifluoromethyl)phenyl	6-(trifluoromethyl)-3-pyrazinyl

Ais CF

R	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trifluoromethyl)-2-pyridinyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyridinyl	4-methoxy-2-pyridinyI
4- ( trif I u o romethy I )-2-py rid i nyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-(trifluoromethyl)-2-pyridinyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-methoxy-3-pyridinyl
2-(trifluoromethyl)-3-pyridinyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trifluoromethyl)-3-pyridinyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl

5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trifluoromethyl)-3-pyridinyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-(trifluoromethyl)-4-pyridinyl	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl
3-(trifluoromethyl)-4-pyridinyl	3-(CH(=NOMe))-4-pyridinyl
3-methyl-2-pyrazinyl	3-methoxy-2-pyrazinyl
3-(trifluoromethyl)-2-pyrazinyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-methoxy-2-pyrazinyl
5 - (tr if I uo rom ethyl )-2-pyrazi ny I	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl
6-( trif I uo rom ethyl )-2-py razi nyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrimidinyl	4-m ethoxy-2-pyri m id i ny I
4-(trifluoromethyl)-2-pyrimidinyl	4-(CH(=NOMe))-2-pyrimidinyl
5-methyl-2-pyrimidinyl	5-methoxy-2-pyrimidinyl
5-(trifluoromethyl)-2-pyrimidinyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-( t rif l uo rom ethyl )-4-py r i m id i nyl	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyrimidinyl	5-methoxy-4-pyrimidinyl
5-(trifluoromethyl)-4-pyrimidinyl	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrimidinyl	6-methoxy-4-pyrimidinyl
6-(trif I uo romethyl )-4-py r i m id i nyl	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1-pyrazolyl	3-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1-pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=NOMe))-1-pyrazolyl
5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1 -pyrazolyl	5-(CH(=N0Me))-1 -pyrazolyl
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(trifluoromethyl)-1,2,3-triazin-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl

2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahyd ro-3-f u ra nyl
tetrahydro-2-furanyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	phenyl
2-(trifluoromethyl)phenyl	3-(trifluoromethyl)phenyl
4-(trifluoromethyl)phenyl	6-(trifluoromethyl)-3-pyrazinyl

A is N

R	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trifluoromethyl)-2-pyridinyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyrid i nyl	4-methoxy-2-pyridinyl
4-(trifluoromethyl)-2-pyridinyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-(trifluoromethyl)-2-pyridinyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-methoxy-3-pyridinyl
2-(trifluoromethyl)-3-pyridinyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trifluoromethyl)-3-pyridinyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl
5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trifluoromethyl)-3-pyridinyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-(trifluoromethyl)-4-pyridinyl	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl
3-(trifluoromethyl)-4-pyridinyl	3-(CH(=NOMe))-4-pyridinyl
3-methyl-2-pyrazinyl	3-methoxy-2-pyrazinyl
3-(trifluoromethyl)-2-pyrazinyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-methoxy-2-pyrazinyl

5-(trifluoromethyl)-2-pyrazinyl	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl
6-(t rif I uo rom ethyl )-2-py razi nyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrimidinyl	4-methoxy-2-pyrimidinyl
4-(trifluoromethyl)-2-pyrimidinyl	4-(CH(=NOMe))-2-pyrimidinyl
5-m ethy l-2-pyri m id i ny I	5-methoxy-2-pyrimidinyl
5-( tr if I uoro methyl )-2-py ri m id i nyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-(trifluoromethyl)-4-pyrimidinyl	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyri m id inyl	5-methoxy-4-pyrimidinyl
5-(trifluoromethyl)-4-pyrimidinyl	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrimidinyl	6-methoxy-4-pyrimidinyl
6-(trif I uo ro m ethyl )-4-py ri m id i nyl	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1 -pyrazolyl	3-(CH(=N0Me))-1 -pyrazolyl
4-methyl-1 -pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=NOMe))-1-pyrazolyl
5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1 -pyrazolyl	5-(CH(=N0Me))-1-pyrazolyl
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(trifluoromethyl)-1,2,3-triazin-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl
2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetrahydro-2-furanyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	phenyl
2-(trifluoromethyl)phenyl	3-(trifluoromethyl)phenyl
4-(trifluoromethyl)phenyl	6-(trifluoromethyl)-3-pyrazinyl

TABLE 1f

Aïs CH

R	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trifluoromethyl)-2-pyridinyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyridinyl	4-methoxy-2-pyridinyl
4-(trifluoromethyl)-2-pyridinyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-( tr if I u o rom ethy I )-2-py r i d i nyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyrid i nyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-methoxy-3-pyridinyl
2-(trifluoromethyl)-3-pyridinyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trifluoromethyl)-3-pyridinyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl
5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trifluoromethyl)-3-pyridinyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-m eth oxy-4-py rid i nyl
2-(trifluoromethyl)-4-pyridinyl	2-(CH(=NOMe))-4-pyridinyl
3-m ethyl-4-pyrid i nyl	3-methoxy-4-pyridinyl
3-(trifluoromethyl)-4-pyridinyl	3-(CH(=NOMe))-4-pyridinyl
3-methyl-2-pyrazinyl	3-methoxy-2-pyrazinyl
3-(trifluoromethyl)-2-pyrazinyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-meth oxy-2-py razi nyl
5-(trif I u o romethyl )-2-py razi nyl	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl

6-(trifluoromethyl)-2-pyrazinyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrimidinyl	4-methoxy-2-pyrimidinyl
4-( t r if 1 u o ro m ethyl )-2-pyri m id i nyl	4-(CH(=NOMe))-2-pyrimidinyl
5-methyl-2-pyrimidinyl	5-methoxy-2-pyrimidinyl
5-( tr if 1 uorom ethyl )-2-py ri m id inyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-(trifluoromethyl)-4-pyrimidinyl	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyrimidinyl	5-methoxy-4-pyrimidinyl
5-(trifluoromethyl)-4-pyrimidinyl	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrimidinyl	6-methoxy-4-pyrimidinyl
6-(trifluoromethyl)-4-pyrimidinyl	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1-pyrazolyl	3-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1 -pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=N0Me))-1 -pyrazolyl
5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1-pyrazolyl	5-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(t r if I uo rom ethy I )-1,2,3-triazi n-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl
2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetrahyd ro-2-f u ra nyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	phenyl
2-(trifluoromethyl)phenyl	3-(trifluoromethyl)phenyl
4-(trifluoromethyl)phenyl	6-(trifluoromethyl)-3-pyrazinyl

Ais CF

R	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trifluoromethyl)-2-pyridinyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyridinyl	4-methoxy-2-pyridinyl

4-(trifluoromethyl)-2-pyridinyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-(trifluoromethyl)-2-pyridinyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-methoxy-3-pyridinyl
2-( trif I u o rom ethyl )-3 - py r i d i nyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trif I uoromethyl)-3-pyrid inyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl
5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-( tr if I uo rom ethyl )-3 - py r i d i nyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-(trifluoromethyl)-4-pyridinyl	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl
3-(trif I uoromethyl )-4-pyrid inyl	3-(CH(=NOMe))-4-pyridinyl
3-methyl-2-pyrazinyl	3-methoxy-2-pyrazinyl
3-(trifluoromethyl)-2-pyrazinyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-methoxy-2-pyrazinyl
5-(trifluoromethyl)-2-pyrazinyl	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl
6-( tr if I uo rom ethyl )-2-pyrazi nyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrimidinyl	4-methoxy-2-pyrimidinyl
4-(tr if I uo romethyl )-2-py r i m id i nyl	4-(CH(=NOMe))-2-pyrimidinyl
5-methyl-2-pyrimidinyl	5-methoxy-2-pyrimidinyl
5-(trifluoromethyl)-2-pyrimidinyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-( trif I uo rom ethyl )-4-py ri m id i nyl	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyrimidinyl	5-methoxy-4-pyrimidinyl
5-(trif l uo rom ethyl )-4-py ri m id i nyl	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrimidinyl	6-methoxy-4-pyrimidinyl

6-(trifluoromethyl)-4-pyrimidinyl	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1-pyrazolyl	3-(CH(=N0Me))-1 -pyrazolyl
4-methyl-1 -pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=N0Me))-1 -pyrazolyl
5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1 -pyrazolyl	5-(CH(=N0Me))-1 -pyrazolyl
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(trif)uoromethyl)-1,2,3-triazin-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl
2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetrahyd ro-2-f u ra nyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	phenyl
2-(trifluoromethyl)phenyl	3-(trifluoromethyl)phenyl
4-(trifluoromethyl)phenyl	6-(trifluoromethyl)-3-pyrazinyl

A is N

R	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trif I uo rom ethyl )-2-py rid i nyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyridinyl	4-methoxy-2-pyridinyl
4-(t r if I uo romethyl )-2-py rid i nyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-(trifluoromethyl)-2-pyridinyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-methoxy-3-pyridinyl
2-(trifluoromethyl)-3-pyridinyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trifluoromethyl)-3-pyridinyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl

5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trifluoromethyl)-3-pyridinyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-(trifluoromethyl)-4-pyridinyl	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl
3-(trifluoromethyl)-4-pyridinyl	3-(CH(=NOMe))-4-pyridinyl
3-methyl-2-pyrazinyl	3-methoxy-2-pyrazinyl
3-(trifluoromethyl)-2-pyrazinyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-m ethoxy-2-pyrazi nyl
5-(trif I uo rom ethyl )-2-py razi ny I	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl
6-( t rif I uo rom ethyl )-2-pyrazi nyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrim id i nyl	4-methoxy-2-pyrimidinyl
4-( t rif I u orom ethyl )-2-py ri m id i nyl	4-(CH(=NOMe))-2-pyrimidinyl
5-methyl-2-pyrimidinyl	5-methoxy-2-pyrimidinyl
5-(t rif I uoro m ethyl )-2-py r i m id i nyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-(trifluoromethyl)-4-pyrimidinyl	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyrimidinyl	5-methoxy-4-pyrimidinyl
5-(trifluoromethyl)-4-pyrimidinyl	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrimidinyl	6-methoxy-4-pyrimidinyl
6-(trif I u o rom ethyl )-4- py r i m id iny I	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1 -pyrazolyl	3-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1-pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=NOMe))-1 -pyrazolyl
5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1 -pyrazolyl	5-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1,2,3-triazi n-2-yl	4-methoxy-1,2,3-triazi n-2-yl
4-(trif I uo rom ethyl )-1,2,3-triazi n-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl

2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetrahydro-2-furanyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	phenyl
2-(trifluoromethyl)phenyl	3-(trifluoromethyl)phenyl
4-(trifluoromethyl)phenyl	6-(trifluoromethyl)-3-pyrazinyl

TABLE 2a

R	R	R
Me	Et	Pr
i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-CH₂CH=CH₂
-CH₂CeCH	-C(Me)₂CECH	-ch₂ch₂f
-ch₂chf₂	-CH₂CF₃	-CH(Me)CF₃
-ch₂ch₂cf₃	-ch₂cf₂cf₃	-CH₂CF₂CH₃
-CH2CH2CF2CF3	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-CH₂CH₂OEt
-CH₂CH₂CH₂OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH₂S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH₂CH₂SO₂Me	-CH₂CH₂SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH₂CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH₂CH₂S(O)CH₂CF₃	-CH₂CH₂SCH₂CF₃

-CH2CH2SO2CH2CF3	-CH2CH2SO2CH2CH2CF3	-CH2CH2SCH2CH2CF3
-CH2CH2S(O)CH2CH₂CF3	-ch₂cn	-ch₂ch₂cn
-C(Me)₂CN	-CH₂CH₂N(i-Pr)₂	-CH₂CH₂N(Me)2
-CH2CH(OMe)₂	c-Pr	c-Bu
1 -methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl
3-oxetanyl	-CH2(oxiranyl)	3-thietanyl-1,1-dioxide
3-thietanyl-1-oxide	-CH₂(CH(-OC(Me)₂OCH₂- ))	-CH2(tetrahydro-2-furanyl)
-CH2(2-furanyl)	tetrahyd ro-2-f u ra nyl	-CH2(2-thienyl)
-CH2(CH(-OCH₂CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂
-och₂ch=ch₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-NHCO₂CH₂CF3	-C(O)CO₂Me
-C(O)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF3	-NHC(O)Et
-NHC(O)CH₂CF₃	-NHSO₂CF₃	-NHSO₂CH₂CF3
-NHSO2CH2CH2CF3	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF3-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF3-2-pyrimidinyl)	-NH(5-CF₃-2-pyridinyl)
-NH(4-CF3-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-NH(4-methyl-2-pyridinyl)

-N H(3-m ethy î-2-py rid i nyi )	-NH(5-methyi-2-pyrimidinyl)	-NH(5-rnethyl-2-pyridinyi)
-NH(4-methyl-2-pyrimidinyl)	-NH(6-methoxy-2-pyridinyl)	-NH(4-méthoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH₂(6-CF₃-2-pyrïdinyi)	-CH₂(4-CF₃-2-pyridinyl)
-CH2(3-CF3-2-pyridinyl)	-CH₂(5-CF₃-2-pyrimidinyl)	-CH₂(5-CF₃-2-pyridinyl)
-CH₂(4-CF3-2-pyrimidinyl)	-CH₂(6-methyl-2-pyridinyl)	-CH₂(4-methyl-2-pyridinyl)
-CH₂(3-methyl-2-pyridinyl)	-CH₂(5-methyl-2- pyrimidinyl)	-CH₂(5-methyl-2-pyridinyl)
-CH₂(4-methyl-2-pyrimidinyl)	-CH₂(6-methoxy-2- pyridinyl)	-CH₂(4-methoxy-2- pyridinyl)
-CH₂(3-methoxy-2-pyridinyl)	-CH₂(5-methoxy-2- pyrimidinyl)	-CH₂(5-methoxy-2- pyridinyl)
-CH₂(4-methoxy-2- pyrimidinyl)	-CH₂(5-pyrimidinyl)	-CH₂(6-bromo-2-pyridinyl)
-CH₂(2-pyrimidinyl)	-CH₂(3-(OCF₃)phenyl)	-CH₂(2-thiazolyl)
-CH₂(5-methyl-2-pyrazinyl)	-CH₂(4-pyridinyl)	-CH₂(2-pyridinyl)
Ph	3-pyridinyl	-CH₂(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH₂CH₂(2-pyridinyl)
4-pyridinyl	4-CF₃-2-pyridinyl	-CH₂CH₂CH2(2-pyridinyl)
3-CF₃-2-pyridinyl	4-CF₃-2-pyrimidinyl	6-CF₃-2-pyridinyl
5-CF₃-2-pyridinyl	5-CF₃-2-pyrazinyl	5-CF₃-2-pyrimidinyl
-CH₂CH₂N(- C(O)CH₂CH₂C(O)-)	-CH₂CH₂CH2(1 -imidazolyl)	-CH(-C(O)OCH₂CH₂-)
-CH2(4-pyrimidinyl)	pyridazinyl	6-CF₃-3-pyrazinyl

Ais CF

R	R	R
Me	Et	Pr

i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr) ;
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-ch₂ch=ch₂
-CH₂CeCH	-C(Me)₂CECH	-ch₂ch₂f
-ch₂chf₂	-CH₂CF₃	-CH(Me)CF₃
-ch₂ch₂cf₃	-ch₂cf₂cf₃	-CH₂CF₂CH₃
-ch₂ch₂cf₂cf₃	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-CH₂CH₂OEt
-CH₂CH₂CH₂OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH₂S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH₂CH₂SO₂Me	-CH₂CH₂SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH₂CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH₂CH₂S(O)CH₂CF₃	-CH₂CH₂SCH₂CF₃
-CH₂CH₂SO₂CH₂CF₃	-ch₂ch₂so₂ch₂ch₂cf₃	-ch₂ch₂sch₂ch₂cf₃
-CH₂CH₂S(O)CH₂CH₂CF₃	-ch₂cn	-ch₂ch₂cn
-C(Me)₂CN	-CH₂CH₂N(i-Pr)₂	-CH₂CH₂N(Me)₂
-CH2CH(OMe)₂	c-Pr	c-Bu
1 -methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl
3-oxetanyl	-CH₂(oxiranyl)	3-thietanyl-1,1 -dioxide
3-thietanyl-1-oxide	-CH₂(CH(-OC(Me)₂OCH₂- ))	-CH₂(tetrahydro-2-furanyl)
-CH₂(2-furanyl)	tetrahydro-2-furanyl	-CH₂(2-thienyl)
-CH₂(CH(-OCH₂CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂

-och₂çh=ch₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(0)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHG(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(0)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-NHCO₂CH₂CF₃	-C(O)CO₂Me
-C(0)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF₃	-NHC(O)Et
-NHC(O)CH₂CF₃	-nhso₂cf₃	-NHSO₂CH₂CF₃
-nhso₂ch₂ch₂cf₃	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF₃-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF₃-2-pyrinnidinyl)	-NH(5-CF₃-2-pyridinyl)
-NH(4-CF₃-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-NH(4-methyl-2-pyridinyl)
-NH(3-methyl-2-pyridinyl)	-NH(5-methyl-2-pyrimidinyl)	-NH(5-methyl-2-pyridinyl)
-NH(4-methyl-2-pyrimidinyl)	-NH(6-methoxy-2-pyridinyl)	-NH(4-methoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2- pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH₂(6-CF₃-2-pyridinyl)	-CH₂(4-CF₃-2-pyridinyl)
-CH₂(3-CF₃-2-pyridinyl)	-CH₂(5-CF₃-2-pyrimidinyl)	-CH₂(5-CF₃-2-pyridinyl)
-CH₂(4-CF₃-2-pyrimidinyl)	-CH₂(6-methyl-2-pyridinyl)	-CH₂(4-methyl-2-pyridinyl)
-CH₂(3-methyl-2-pyridinyl)	-CH₂(5-methyl-2- pyrimidinyl)	-CH₂(5-methyl-2-pyridinyl)
-CH₂(4-methyl-2-pyrimidinyl)	-CH₂(6-methoxy-2- pyridinyl)	-CH₂(4-methoxy-2- pyridinyl)
-CH₂(3-methoxy-2-pyridinyl)	-CH₂(5-methoxy-2- pyrimidinyl)	-CH₂(5-methoxy-2- pyridinyl)
-CH₂(4-methoxy-2- pyrimidinyl)	-CH₂(5-pyrimidinyl)	-CH₂(6-bromo-2-pyridinyl)

Ais N

R	R	R
Me	Et	Pr
i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-ch₂ch=ch₂
-ch₂cech	-C(Me)₂CECH	-ch₂ch₂f
-ch₂chf₂	-CH₂CF₃	-CH(Me)CF₃
-CH₂CH₂CF3	-CH2CF2CF3	-CH2CF2CH3
-CH₂CH2CF₂CF₃	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-CH₂CH₂OEt
-CH₂CH₂CH₂OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH₂S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH₂CH₂SO₂Me	-CH₂CH₂SO2Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH2CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH₂CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH2CH2S(O)CH₂CF3	-CH2CH2SCH2CF3
-CH₂CH₂SO₂CH2CF3	-CH2CH2SO2CH2CH2CF3	-CH2CH2SCH2CH2CF3

-CH₂CH2S(O)CH2CH₂CF3	-ch₂cn	-ch₂ch₂cn
-C(Me)₂CN	-CK₂CH₂N(i-Pr)2	-CH₂CH2N(Me)₂
-CH2CH(OMe)₂	c-Pr	c-Bu
1 -methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl
3-oxetanyl	-CH₂(oxiranyl)	3-thietanyl-1,1 -dioxide
3-thietanyl-1-oxide	-CH₂(CH(-OC(Me)2OCH2- ))	-CH₂(tetrahydro-2-furanyl)
-CH₂(2-furanyl)	tetrahydro-2-furanyl	-CH₂(2-thienyl)
-CH₂(CH(-OCH₂CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂
-och₂ch=ch₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF3)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-NHCO₂CH₂CF3	-C(O)CO₂Me
-C(O)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF3	-NHC(O)Et
-NHC(O)CH₂CF₃	-NHSO₂CF₃	-NHSO₂CH₂CF3
-NHSO2CH2CH2CF3	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF3-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF3-2-pyrimidinyl)	-NH(5-CF3-2-pyridinyl)
-NH(4-CF3-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-NH(4-methyl-2-pyridinyl)
-NH(3-methyl-2-pyridinyl)	-NH(5-methyl-2-pyrimidinyl)	-NH(5-methyl-2-pyridinyl)

-N H (4-m ethyl-2-py ri m id i nyl )	-NH(6-methoxy-2-pyridinyl)	-NH(4-methoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2- pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH2(6-CF3-2-pyridinyl)	-CH2(4-CF3-2-pyridinyl)
-CH2(3-CF3-2-pyridinyl)	-CH2(5-CF3-2-pyrimidinyl)	-CH2(5-CF3-2-pyridinyl)
-CH2(4-CF3-2-pyrimidinyl)	-CH2(6-methyl-2-pyridinyl)	-CH2(4-methyl-2-pyridinyl)
-CH2(3-methyl-2-pyridinyl)	-CH2(5-methyl-2- pyrimidinyl)	-CH2(5-methyl-2-pyridinyl)
-CH2(4-methyl-2-pyrimidinyl)	-CH2(6-methoxy-2- pyridinyl)	-CH2(4-methoxy-2- pyridinyl)
-CH2(3-methoxy-2-pyridinyl)	-CH2(5-methoxy-2- pyrimidinyl)	-CH2(5-methoxy-2- pyridinyl)
-CH2(4-methoxy-2- pyrimidinyl)	-CH2(5-pyrimidinyl)	-CH2(6-bromo-2-pyridinyl)
-CH2(2-pyrimidinyl)	-CH₂(3-(OCF₃)phenyl)	-CH2(2-thiazolyl)
-CH2(5-methyl-2-pyrazinyl)	-CH2(4-pyridinyl)	-CH2(2-pyridinyl)
Ph	3-pyridinyl	-CH2(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH2CH2(2-pyridinyl)
4-pyridinyl	4-CF3-2-pyridinyl	-CH2CH2CH2(2-pyridinyl)
3-CF3-2-pyridinyl	4-CF3-2-pyrimidinyl	6-CF3-2-pyridinyl
5-CF3-2-pyridinyl	5-CF3-2-pyrazinyl	5-CF3-2-pyrimidinyl
-CH₂CH₂N(- C(O)CH₂CH₂C(O)-)	-CH2CH2CH2(1-imidazolyl)	-CH(-C(O)OCH₂CH₂-)
-CH2(4-pyrimidinyl)	pyridazinyl	6-CF3-3-pyrazinyl

TABLE 2b

A is CH

R	R	R
Me	Et	Pr
i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-CH₂CH=CH₂
-ch₂c^ch	-C(Me)₂CHCH	-ch₂ch₂f
-ch₂chf₂	-CH₂CF₃	-CH(Me)CF₃
-ch₂ch₂cf₃	-ch₂cf₂cf₃	-CH₂CF₂CH₃
-ch₂ch₂cf₂cf₃	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-CH₂CH₂OEt
-CH₂CH₂CH₂OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH₂S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH₂CH₂SO₂Me	-CH₂CH₂SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH₂CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH₂CH₂S(O)CH₂CF₃	-CH₂CH₂SCH₂CF₃
-CH₂CH₂SO₂CH₂CF₃	-CH₂CH₂SO₂CH₂CH₂CF₃	-ch₂ch₂sch₂ch₂cf₃
-CH₂CH₂S(O)CH₂CH₂CF₃	-ch₂cn	-ch₂ch₂cn
-C(Me)₂CN	-CH₂CH₂N(i-Pr)₂	-CH₂CH₂N(Me)₂
-CH2CH(OMe)₂	c-Pr	c-Bu
1 -methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl

3-oxetanyl	-CH2(oxiranyl)	3-thietanyl-1,1-dioxide
3-thietany 1-1 -oxide	-CH₂(CH(-OC(Me)2OCH₂- ))	-CH2(tetrahydro-2-furanyl)
-CH2(2-furanyl)	tetra hyd ro-2-f u ra ny I	-CH2(2-thienyl)
-CH2(CH(-OCH2CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂
-och₂ch=ch₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-nhco₂ch₂cf₃	-C(O)CO₂Me
-C(O)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF₃	-NHC(O)Et
-NHC(O)CH₂CF₃	-nhso₂cf₃	-NHSO2CH₂CF₃
-NHSO₂CH2CH₂CF₃	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF₃-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF₃-2-pyrimidinyl)	-NH(5-CF₃-2-pyridinyl)
-NH(4-CF₃-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-NH(4-methyl-2-pyridinyl)
-NH(3-methyl-2-pyridinyl)	-NH(5-methyl-2-pyrimidinyl)	-NH(5-methyl-2-pyridinyl)
-NH(4-methyl-2-pyrimidinyl)	-NH(6-methoxy-2-pyridinyl)	-NH(4-methoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH2(6-CF₃-2-pyridinyi)	-CH2(4-CF₃-2-pyridinyl)
-CH2(3-CF₃-2-pyridinyl)	-CH2(5-CF₃-2-pyrimidinyl)	-CH2(5-CF₃-2-pyridinyl)

-CH2(4-CF3-2-pyrimidinyl)	-CH2(6-methyl-2-pyridinyl)	-CH2(4-methyl-2-pyridinyl)
-CH2(3-methyl-2-pyridinyl)	-CH2(5-methyl-2- pyrimidinyl)	-CH2(5-methyl-2-pyridinyl)
-CH2(4-methyl-2-pyrimidinyl)	-CH2(6-methoxy-2- pyridinyl)	-CH2(4-methoxy-2- pyridinyl)
-CH2(3-methoxy-2-pyridinyl)	-CH2(5-methoxy-2- pyrimidinyl)	-CH2(5-methoxy-2- pyridinyl)
-CH2(4-methoxy-2- pyrimidinyl)	-CH2(5-pyrimidinyl)	-CH2(6-bromo-2-pyridinyl)
-CH2(2-pyrimidinyl)	-CH2(3-(OCF3)phenyl)	-CH2(2-thiazolyl)
-CH2(5-methyl-2-pyrazinyl)	-CH2(4-pyridinyl)	-CH2(2-pyridinyl)
Ph	3-pyridinyl	-CH2(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH2CH2(2-pyridinyl)
4-pyridinyl	4-CF3-2-pyridinyl	-CH2CH2CH₂(2-pyridinyl)
3-CF3-2-pyridinyl	4-CF3-2-pyrimidinyl	6-CF3-2-pyridinyl
5-CF3-2-pyridinyl	5-CF3-2-pyrazinyl	5-CF3-2-pyrimidinyl
-CH₂CH₂N(- C(O)CH₂CH₂C(O)-)	-CH2CH2CH2( 1 -imidazolyl)	-CH(-C(O)OCH₂CH2-)
-CH2(4-pyrimidinyl)	pyridazinyl	6-CF3-3-pyrazinyl

Ais CF

R	R	R
Me	Et	Pr
i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-ch₂ch=ch₂
-ch₂csch	-C(Me)₂C=CH	-ch₂ch₂f
-ch₂chf₂	-CH₂CF₃	-CH(Me)CF₃
-CH2CH2CF3	-CH₂CF₂CF3	-CH₂CF₂CH3

-CH2CH2CF2CF3	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pr)	-ΟΗ₂ΟΗ₂ΟΕί
-CH₂CH₂CH₂OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH₂S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH₂CH₂SO₂Me	-CH₂CH2SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH2CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH2CH₂S(O)CH2CF3	-CH2CH2SCH2CF3
-CH2CH2SO2CH2CF3	-CH2CH2SO2CH2CH2CF3	-CH2CH2SCH2CH2CF3
-CH2CH2S(O)CH2CH₂CF3	-ch₂cn	-ch₂ch₂cn
-C(Me)₂CN	-CH₂CH₂N(i-Pr)₂	-CH2CH₂N(Me)₂
-CH2CH(OMe)₂	c-Pr	c-Bu
1 -methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl
3-oxetanyl	-CH2(oxiranyl)	3-thietanyl-1,1-dioxide
3-thietanyl-1-oxide	-CH2(CH(-OC(Me)₂OCH₂- ))	-CH2(tetrahydro-2-furanyl)
-CH₂(2-furanyl)	tetrahyd ro-2-fu ranyl	-CH2(2-thienyl)
-CH2(CH(-OCH₂CH2O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂
-och₂ch=ch₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-NHCO2CH2CF3	-C(O)CO₂Me

-C(0)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF₃	-NHC(O)Et
-NHC(O)CH₂CF₃	-nhso₂cf₃	-NHSO₂CH₂CF₃
-nhso₂ch₂ch₂cf₃	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF₃-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF₃-2-pyrimidinyl)	-NH(5-CF₃-2-pyridinyl)
-NH(4-CF₃-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-NH(4-methyl-2-pyridinyl)
-NH(3-methyl-2-pyridinyl)	-NH(5-methyl-2-pyrimidinyl)	-NH(5-methyl-2-pyridinyl)
-NH(4-methyl-2-pyrimidinyl)	-NH(6-methoxy-2-pyridinyl)	-NH(4-methoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2- pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH₂(6-CF₃-2-pyridinyl)	-CH₂(4-CF₃-2-pyridinyl)
-CH₂(3-CF₃-2-pyridinyl)	-CH₂(5-CF₃-2-pyrimidinyl)	-CH₂(5-CF₃-2-pyridinyl)
-CH₂(4-CF₃-2-pyrimidinyl)	-CH₂(6-methyl-2-pyridinyl)	-CH₂(4-methyl-2-pyridinyl)
-CH₂(3-methyl-2-pyridinyl)	-CH₂(5-methyl-2- pyrimidinyl)	-CH₂(5-methyl-2-pyridinyl)
-CH₂(4-methyl-2-pyrimidinyl)	-CH₂(6-methoxy-2- pyridinyl)	-CH₂(4-methoxy-2- pyridinyl)
-CH₂(3-methoxy-2-pyridinyl)	-CH₂(5-methoxy-2- pyrimidinyl)	-CH₂(5-methoxy-2- pyridinyl)
-CH₂(4-methoxy~2- pyrimidinyl)	-CH₂(5-pyrimidinyl)	-CH₂(6-bromo-2-pyridinyl)
-CH₂(2-pyrimidinyl)	-CH₂(3-(OCF₃)phenyl)	-CH₂(2-thiazolyl)
-CH₂(5-methyl-2-pyrazinyl)	-CH₂(4-pyridinyl)	-CH₂(2-pyridinyl)
Ph	3-pyridinyl	-CH₂(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH₂CH₂(2-pyridinyl)
4-pyridinyl	4-CF₃-2-pyridinyl	-CH₂CH₂CH₂(2-pyridinyl)
3-CF₃-2-pyridinyl	4-CF₃-2-pyrimidinyl	6-CF₃-2-pyridinyl

5-CF3-2-pyridinyl	5-CF3-2-pyrazinyl	5-CF3-2-pyrimidinyl
-CH₂CH2N(- C(O)CH₂CH₂C(O)-)	-CH₂CH₂CH₂(1 -imidazolyl)	-CH(-C(O)OCH₂CH₂-)
-CH₂(4-pyrimidinyl)	pyridazinyl	6-CF3-3-pyrazinyl

Ais N

R	R	R
Me	Et	Pr
i-Pr	-CH₂(c-Pr)	-CH(Me)(c-Pr)
Bu	s-Bu	i-Bu
t-Bu	-CH₂Ph	-ch₂ch=ch₂
-ch₂c^ch	-C(Me)₂CsCH	-ch₂ch₂f
-ch₂chf₂	-ch₂cf₃	-CH(Me)CF₃
-CH₂CH₂CF₃	-ch₂cf₂cf₃	-ch₂cf₂ch₃
-CH₂CH₂CF₂CF3	-CH(i-Pr)CF₃	-CH₂CH₂OMe
-CH₂OEt	-CH₂CH₂O(i-Pij	-CH₂CH₂OEt
-CH2CH₂CH2OMe	-CH₂CH(Me)OMe	-CH(Et)CH₂OMe
-CH(Me)CH₂OMe	-CH₂CH2S(O)Me	-CH₂CH₂SMe
-CH₂CH₂SEt	-CH2CH₂SO2Me	-CH₂CH₂SO₂Et
-CH₂CH₂S(O)Et	-CH₂CH₂S(O)(t-Bu)	-CH₂CH₂S(t-Bu)
-CH(Me)CH₂SMe	-CH₂CH₂SO₂(t-Bu)	-CH(Me)CH₂SO₂Me
-CH(Me)CH₂S(O)Me	-CH₂CH₂S(O)CH₂CF3	-CH2CH2SCH2CF3
-CH2CH2SO2CH2CF3	-CH2CH2SO2CH2CH2CF3	-CH2CH2SCH2CH2CF3
-CH₂CH₂S(O)CH2CH2CF3	-ch₂cn	-ch₂ch₂cn
-C(Me)₂CN	-CH₂CH2N(i-Pr)2	-CH₂CH₂N(Me)2
-CH2CH(OMe)₂	c-Pr	c-Bu
1 -methylcyclopropyl	3-methoxycyclobutyl	-CH(Ph)(c-Pr)
-CH(Me)(c-Pr)	3-thietanyl	3,3-difluorocyclobutyl
3-oxetanyl	-CH₂(oxiranyl)	3-thietanyl-1,1 -dioxide

3-th ieta nyl-1 -oxide	-CH₂(CH(-OC(Me)₂OCH₂- ))	-CH₂(tetrahydro-2-furanyI)
-CH2(2-furanyl)	tetrahydro-2-furanyl	-CH₂(2-thienyl)
-CH₂(CH(-OCH2CH₂O-)	-CH₂CO₂Me	-CH₂(2,2- difluorocyclopropyl)
-C(-CH₂CH₂-)CO₂Me	-CH(Me)CO₂Et	-CH(i-Pr)CO₂Me
-CH₂C(O)NHMe	-CH₂C(O)NMe₂	-CH(Me)C(O)NHMe
-CH(Me)C(O)NH(t-Bu)	-OCH₂(c-Pr)	-CH(Me)C(O)NMe₂
-OCH₂CH=CH₂	-NHC(O)(i-Pr)	-NHC(O)Me
-NHCO₂Me	-NHC(O)(3-pyridinyl)	-NHC(O)(t-Bu)
-NHC(O)Ph	-NH(c-hexyl)	-NHC(O)NH(i-Pr)
-NH(c-Pr)	-NHC(O)(2-thienyl)	-NH(CH₂CF₃)
-NHC(O)CF₃	-NHCO₂Et	-NHC(O)(2-furanyl)
-C(O)C(O)Me	-NHCO₂CH₂CF₃	-C(O)CO₂Me
-C(O)(2-pyridinyl)	-NHC(O)NMe₂	-NHC(O)NHMe
-NHC(O)NHCH₂CF₃	-NHC(O)CH₂CH₂CF₃	-NHC(O)Et
-NHC(O)CH₂CF₃	-nhso₂cf₃	-NHSO₂CH₂CF₃
-nhso₂ch₂ch₂cf₃	-NH(2-pyridinyl)	-NH(3-pyridinyl)
-NH(4-pyridinyl)	-NH(2-pyrimidinyl)	-NH(4-pyrimidinyl)
-NH(5-pyrimidinyl)	-NH(6-CF₃-2-pyridinyl)	-NH(4-CF₃-2-pyridinyl)
-NH(3-CF₃-2-pyridinyl)	-NH(5-CF₃-2-pyrimidinyl)	-NH(5-CF₃-2-pyridinyl)
-NH(4-CF₃-2-pyrimidinyl)	-NH(6-methyl-2-pyridinyl)	-NH(4-methyl-2-pyridinyl)
-NH(3-methyl-2-pyridinyl)	-NH(5-methyl-2-pyrimidinyl)	-NH(5-methyl-2-pyridinyl)
-NH(4-methyl-2-pyrimidinyl)	-NH(6-methoxy-2-pyridinyl)	-NH(4-methoxy-2-pyridinyl)
-NH(3-methoxy-2-pyridinyl)	-NH(5-methoxy-2pyrimidinyl)	-NH(5-methoxy-2-pyridinyl)
-NH(4-methoxy-2-pyrimidinyl)	-CH₂(6-CF₃-2-pyridinyl)	-CH₂(4-CF₃-2-pyridinyl)
-CH₂(3-CF₃-2-pyridinyl)	-CH₂(5-CF₃-2-pyrimidinyl)	-CH₂(5-CF₃-2-pyridinyl)
-CH₂(4-CF₃-2-pyrimidinyl)	-CH ₂(6-m ethyl-2-pyrid i nyl )	-CH₂(4-methyl-2-pyridinyl)

100

-CH2(3-methyl-2-pyridinyl)	-CH₂(5-methyl-2- pyrimidinyl)	-CH₂(5-methyl-2-pyridinyl)
-CH2(4-methyl-2-pyrimidinyl)	-CH₂(6-methoxy-2- pyridinyl)	-CH₂(4-methoxy-2- pyridinyl)
-CH₂(3-methoxy-2-pyridinyl)	-CH₂(5-methoxy-2- pyrimidinyl)	-CH₂(5-methoxy-2- pyridinyl)
-CH₂(4-methoxy-2- pyrimidinyl)	-CH₂(5-pyrimidinyl)	-CH₂(6-bromo-2-pyridinyl)
-CH₂(2-pyrimidinyl)	-CH₂(3-(OCF₃)phenyl)	-CH₂(2-thiazolyl)
-CH₂(5-methyl-2-pyrazinyl)	-CH₂(4-pyridinyl)	-CH₂(2-pyridinyl)
Ph	3-pyridinyl	-CH₂(3-pyridinyl)
2-pyridinyl	2-pyrazinyl	-CH₂CH₂(2-pyridinyl)
4-pyridinyl	4-CF₃-2-pyridinyl	-CH₂CH2CH₂(2-pyridinyl)
3-CF3-2-pyridinyl	4-CF₃-2-pyrimidinyl	6-CF₃-2-pyridinyl
5-CF3-2-pyridinyl	5-CF₃-2-pyrazinyl	5-CF₃-2-pyrimidinyl
-CH₂CH₂N(- C(O)CH₂CH₂C(O)-)	-CH₂CH₂CH2(1-imidazolyl)	-CH(-C(O)OCH₂CH₂-)
-CH₂(4-pyrimidinyl)	pyridazinyl	6-CF₃-3-pyrazinyl

TABLE 2c

Aïs CH

R	R
N(-CH₂CH₂CH₂-)	N(-CH₂CH(OMe)CH₂-)
N(-CH₂CH2CF2CH₂CH2-)	N(-CH₂CH2CH2CF₂CH2-)
N(-CH₂CH₂CH2CH2-)	N(-CH2CH₂SCH₂CH2-)

101

N(-CH2CH2CH2CH2CH₂-)	N(-CH₂CH2OCH2CH2-)
N(-CH₂CH2N(C(O)(c-Pr))CH₂CH2-)	N(-CH2CH2N(Me)CH₂CH2-)
N(-CH₂C(Me)2N=CH-)	N(-CH2CH2CH₂CH(CF3)CH2-)
N(CH₂C=CH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)
N(-CHC(O)SCH₂CH₂-)

A is CF

R	R
N(-CH₂CH2CH₂-)	N(-CH₂CH(OMe)CH₂-)
N(-CH₂CH2CF₂CH2CH₂-)	N(-CH2CH₂CH2CF2CH2-)
N(-CH2CH₂CH₂CH2-)	N(-CH2CH2SCH₂CH2-)
N(-CH2CH2CH2CH₂CH2-)	N(-CH₂CH2OCH₂CH2-)
N(-CH₂CH2N(C(O)(c-Pr))CH₂CH2-)	N(-CH2CH₂N(Me)CH₂CH2-)
N(-CH₂C(Me)₂N=CH-)	N(-CH2CH2CH₂CH(CF3)CH2-)
N(CH₂CeCH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)
N(-CHC(O)SCH₂CH₂-)

A is N

R	R
N(-CH₂CH₂CH2-)	N(-CH₂CH(OMe)CH₂-)
N(-CH₂CH₂CF2CH2CH2-)	N(-CH2CH2CH2CF₂CH2-)
N(-CH2CH₂CH₂CH2-)	N(-CH₂CH2SCH₂CH2-)
N(-CH2CH₂CH2CH2CH2-)	N(-CH₂CH₂OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH₂CH2-)	N(-CH₂CH₂N(Me)CH₂CH2-)
N(-CH₂C(Me)₂N=CH-)	N(-CH₂CH2CH₂CH(CF3)CH2-)
N(CH₂C=CH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)

102

N(-CHC(O)SCH₂CH₂-)

TABLE 2d

Ais CH

R	R
N(-CH₂CH₂CH₂-)	N(-CH₂CH(OMe)CH₂-)
N(-CH₂CH₂CF₂CH₂CH₂-)	N(-CH₂CH₂CH₂CF₂CH₂-)
N(-CH₂CH₂CH₂CH₂-)	N(-CH₂CH₂SCH₂CH₂-)
N(-CH₂CH₂CH₂CH₂CH₂-)	N(-CH₂CH₂OCH₂CH₂-)
N(-CH₂CH₂N(C(O)(c-Pr))CH₂CH₂-)	N(-CH₂CH₂N(Me)CH₂CH₂-)
N(-CH₂C(Me)₂N=CH-)	N(-CH₂CH₂CH₂CH(CF₃)CH₂-)
N(CH₂C=CH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)
N(-CHC(O)SCH₂CH₂-)

Aïs CF

R	R
N(-CH₂CH₂CH₂-)	N(-CH₂CH(OMe)CH₂-)
N(-CH₂CH₂CF₂CH₂CH₂-)	N(-CH₂CH₂CH₂CF₂CH₂-)
N(-CH₂CH₂CH₂CH₂-)	N(-CH₂CH₂SCH₂CH₂-)
N(-CH₂CH₂CH₂CH₂CH₂-)	N(-CH₂CH₂OCH₂CH₂-)
N(-CH₂CH₂N(C(O)(c-Pr))CH₂CH₂-)	N(-CH₂CH₂N(Me)CH₂CH₂-)
N(-CH₂C(Me)₂N=CH-)	N(-CH₂CH₂CH₂CH(CF₃)CH₂-)
N(CH₂CsCH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)

103

N(-CHC(O)SCH₂CH₂-)

AisN

R	R
N(-CH₂CH₂CH₂-)	N(-CH₂CH(OMe)CH₂-)
N(-CH₂CH₂CF₂CH₂CH₂-)	N(-CH₂CH₂CH₂CF₂CH₂-)
N(-CH₂CH₂CH₂CH₂-)	N(-CH₂CH₂SCH₂CH₂-)
N(-CH₂CH₂CH₂CH₂CH₂-)	N(-CH₂CH₂OCH₂CH₂-)
N(-CH₂CH₂N(C(O)(c-Pr))CH₂CH₂-)	N(-CH₂CH₂N(Me)CH₂CH₂-)
N(-CH₂C(Me)₂N=CH-)	N(-CH₂CH₂CH₂CH(CF₃)CH₂-)
N(CH₂CeCH)₂	N(Et)₂
N(Pr)CH₂(c-Pr)	N(Et)(c-hexyl)
N(-CHC(O)SCH₂CH₂-)

TABLE 2e

H

A is CH

R	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trifluoromethyl)-2-pyridinyl	3-(CH(=NOMe))-2-pyridinyl
4-m ethyl-2-pyrid i ny 1	4-methoxy-2-pyridinyl
4-(trifluoromethyl)-2-pyridinyl	4-(CH(=NOMe))-2-pyridinyl
5-m ethyl-2-pyrid i ny 1	5-methoxy-2-pyridinyl
5-(trifluoromethyl)-2-pyridinyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl

104

2-methyl-3-pyridiny!	2-methoxy-3-pyridinyl
2-(trifluoromethyl)-3-pyridinyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trifluoromethyl)-3-pyridinyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl
5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trifluoromethyl)-3-pyridinyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-( tr if 1 u o romethyl )-4- py r i d i ny 1	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl
3-(trifluoromethyl)-4-pyridinyl	3-(CH(=NOMe))-4-pyridinyl
3-methyl-2-pyrazinyl	3-methoxy-2-pyrazinyl
3-(trifluoromethyl)-2-pyrazinyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-methoxy-2-pyrazinyl
5-(trifluoromethyl)-2-pyrazinyl	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl
6-(trifluoromethyl)-2-pyrazinyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrimidinyl	4-methoxy-2-pyrimidinyl
4-(t rif 1 u o rom ethyl )-2-py r i m id i nyl	4-(CH(=NOMe))-2-pyrimidinyl
5-m ethy l-2-pyri m id i ny 1	5-methoxy-2-pyrimidinyl
5-(trifluoromethyl)-2-pyrimidinyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-(tr if 1 uo rom ethyl )-4- py r i m id i nyl	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyrimidinyl	5-methoxy-4-pyrimidinyl
5-(trifluoromethyl)-4-pyrimidinyl	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrimidinyl	6-methoxy-4-pyrimidinyl
6-(trifluoromethyl)-4-pyrimidinyl	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1 -pyrazolyl	3-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1 -pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=NOMe))-1 -pyrazolyl

105

5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1 -pyrazolyl	5-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(trifluoromethyl)-1,2,3-triazin-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl
2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetrahydro-2-furanyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	6-(trif I uo ro m ethyl )-3-pyrazi ny I

Ais CF

R	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(tr if I uo rom ethyl )-2-pyri d i nyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyrid i nyl	4-methoxy-2-pyridinyl
4-( t r if I u o romethyl )-2-py r i d i nyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-(trifluoromethyl)-2-pyridinyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-methoxy-3-pyridinyl
2-(t r i f I uorom ethyl )-3-py r i d i nyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trifluoromethyl)-3-pyridinyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl
5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trif I uo rom ethyl )-3-py rid i ny I	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-(trif I uo rom ethyl )-4-py rid i nyl	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl
3-(trifluoromethyl)-4-pyridinyl	3-(CH(=NOMe))-4-pyridinyl

106

3-methyl-2-pyrazinyl	3-methoxy-2-pyrazinyl
3-(trifluoromethyl)-2-pyrazinyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-m eth oxy-2-pyrazi nyl
5-(trifluoromethyl)-2-pyrazinyl	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-m ethoxy-2-pyrazi nyl
6-(trifluoromethyl)-2-pyrazinyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrimidinyl	4-methoxy-2-pyrimidinyl
4-(trifluoromethyl)-2-pyrimidinyl	4-(CH(=NOMe))-2-pyrimidinyl
5-methyl-2-pyrimidinyl	5-methoxy-2-pyrimidinyl
5 - (tr if 1 u o ro m ethyl )-2-py ri m id i nyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-(t r if 1 uo rom ethyl )-4-py ri m i d i nyl	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyrimidinyl	5-methoxy-4-pyrimidinyl
5-( t r if I uo rom ethyl )-4-pyri m id i ny 1	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrim id i nyl	6-methoxy-4-pyrimidinyl
6-(trifluoromethyl)-4-pyrimidinyl	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1 -pyrazolyl	3-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1 -pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=NOMe))-1 -pyrazolyl
5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1 -pyrazolyl	5-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(trifluoromethyl)-1,2,3-triazin-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl
2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetra hyd ro-2-fu ra nyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	6-(trifluoromethyl)-3-pyrazinyl

A is N

R

107

3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trifluoromethyl)-2-pyridinyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyridinyl	4-methoxy-2-pyridinyl
4-(trifluoromethyl)-2-pyridinyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-(trif 1 uo romethy 1 )-2-py ri d i nyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-methoxy-3-pyridinyl
2-(trif 1 uo rom ethyl )-3 - py r i d i ny 1	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trif 1 uoromethyl)-3-pyrid i nyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl
5-(t rif 1 uoromethyl)-3-pyrid inyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trifluoromethyl)-3-pyridinyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-(trif 1 uo rom ethyl )-4- py r i d i nyl	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl
3-(trifluoromethyl)-4-pyridinyl	3-(CH(=NOMe))-4-pyridinyl
3-methyl-2-pyrazinyl	3-m eth oxy-2-pyrazi nyl
3 - (trif 1 uo rom ethyl )-2-pyrazi nyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-methoxy-2-pyrazinyl
5-(trifluoromethyl)-2-pyrazinyl	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl
6-(t r if 1 uo romethyl )-2-py razi nyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrimidinyl	4-methoxy-2-pyrimidinyl
4-( t r if 1 u o romethyl )-2-py r i m id i ny 1	4-(CH(=NOMe))-2-pyrimidinyl
5-methyl-2-pyrimidinyl	5-methoxy-2-pyrimidinyl
5-(trifluoromethyl)-2-pyrimidinyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-(tr if 1 uorom ethyl )-4-p y r i m id i nyl	2-(CH(=NOMe))-4-pyrimidinyl

108

5-methyl-4-pyrimidinyl	5-methoxy-4-pyrimidinyl
5-(trifluoromethyl)-4-pyrimidinyl	5-(CH(=NOMe))-4-pyrimidinyl
6-m ethy l-4-pyri m id i ny 1	6-methoxy-4-pyrimidinyl
6-(trifluoromethyl)-4-pyrimidinyl	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1-pyrazolyl	3-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1 -pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=NOMe))-1 -pyrazolyl
5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1 -pyrazolyl	5-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(trifluoromethyl)-1,2,3-triazin-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl
2-(2-thiazolyl)-4-thiazolyl	2-(2-pyri m i d i n y I )ethy n y I
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetra hyd ro-2-fu ra nyl	4,5-d ihyd ro-3-isoxazolyl
3-isoxazolyl	6-(trifluoromethyl)-3-pyrazinyl

TABLE 2f

Ais CH

R	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trif I uo rom ethyl )-2-py rid i nyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyridinyl	4-methoxy-2-pyridinyl
4-(tr if I uo rom ethyl )-2-py rid i nyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-( tr if I u o romethyl )-2-pyrid i nyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl

109

6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-methoxy-3-pyridinyl
2-(trifluoromethyl)-3-pyridinyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trifluoromethyl)-3-pyridinyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl
5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trifluoromethyl)-3-pyridinyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-(trifluoromethyl)-4-pyridinyl	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl
3-(trifluoromethyl)-4-pyridinyl	3-(CH(=NOMe))-4-pyridinyl
3-methyl-2-pyrazinyl	3-methoxy-2-pyrazinyl
3-(trifluoromethyl)-2-pyrazinyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-methoxy-2-pyrazinyl
5-(trifluoromethyl)-2-pyrazinyl	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl
6-(trifluoromethyl)-2-pyrazinyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrimidinyl	4-methoxy-2-pyrimidinyl
4-(trifluoromethyl)-2-pyrimidinyl	4-(CH(=NOMe))-2-pyrimidinyl
5-methyl-2-pyrimidinyl	5-m ethoxy-2-py ri m id i ny I
5-(trifluoromethyl)-2-pyrimidinyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-(tr if 1 u orom ethyl )-4- p y r i m id i ny 1	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyrimidinyl	5-methoxy-4-pyrimidinyl
5-(trifluoromethyl)-4-pyrimidinyl	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrimidinyl	6-methoxy-4-pyrimidinyl
6-(trifluoromethyl)-4-pyrimidinyl	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1 -pyrazolyl	3-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1 -pyrazolyl	4-methoxy-1 -pyrazolyl

110

4-(trifluorome>hyl)-1~pyrazolyi	4-(CH(--NOMe))-1-pyrazolyi
5-methy!-1 -pyrazolyi	5-methoxy-1-pyrazolyi
5-(trifluoromethyl)-1 -pyrazolyi	5-(CH(=NOMe))-1 -pyrazolyi
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(trifluoromethyl)-1,2,3-triazin-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl
2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetra hyd ro-2-f u ra nyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	6-(trifluoromethyl)-3-pyrazinyl

Aïs CF

R	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trifluoromethyl)-2-pyridinyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyridinyl	4-methoxy-2-pyridinyl
4-(trifluoromethyl)-2-pyridinyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-(trifluoromethyl)-2-pyridinyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-methoxy-3-pyridinyl
2-(trifluoromethyl)-3-pyridinyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trifluoromethyl)-3-pyridinyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl
5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trifluoromethyl)-3-pyridinyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-(trifluoromethyl)-4-pyridinyl	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl

ΪΠ

3-(trif 1 uo rorn ethyl )-=4-py ri d i nyl	3-(CH(=NOMe))-44pyridinyi ’
3-methyi-2-pyrazinyi	3-methoxy-2-pyrazinyl
3-(trif 1 uo rom ethyl )-2-py razi nyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-m ethoxy-2-pyrazi nyl
5-(trifluoromethyl)-2-pyrazinyl	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl
6-(trifluoromethyl)-2-pyrazinyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyri m id inyl	4-methoxy-2-pyrimidinyl
4-(trifluoromethyl)-2-pyrimidinyl	4-(CH(=NOMe))-2-pyrimidinyl
5-methyl-2-pyrimidinyl	5-methoxy-2-pyrimidinyl
5-( t r if 1 uo rom ethyl )-2-py r i m id i nyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-methoxy-4-pyrimidinyl
2-(trif 1 uoromethyl)-4-pyri m id inyl	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyri m id inyl	5-methoxy-4-pyrimidinyl
5-(trifluoromethyl)-4-pyrimidinyl	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrimidinyl	6-methoxy-4-pyrimidinyl
6-( trif 1 uo rom ethyl )-4- py r i m id inyl	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1 -pyrazolyl	3-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1 -pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=NOMe))-1 -pyrazolyl
5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1 -pyrazolyl	5-(CH(=N0Me))-1-pyrazolyl
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(trifluoromethyl)-1,2,3-triazin-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl
2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetrahydro-2-furanyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	6-(trifluoromethyl)-3-pyrazinyl

A is N

112 Π1

• / R ;	R
3-methyl-2-pyridinyl	3-methoxy-2-pyridinyl
3-(trifluoromethyl)-2-pyridinyl	3-(CH(=NOMe))-2-pyridinyl
4-methyl-2-pyridinyl	4-methoxy-2-pyridinyl
4-(trifluoromethyl)-2-pyridinyl	4-(CH(=NOMe))-2-pyridinyl
5-methyl-2-pyridinyl	5-methoxy-2-pyridinyl
5-(trifluoromethyl)-2-pyridinyl	5-(CH(=NOMe))-2-pyridinyl
6-methyl-2-pyridinyl	6-methoxy-2-pyridinyl
6-(trifluoromethyl)-2-pyridinyl	6-(CH(=NOMe))-2-pyridinyl
2-methyl-3-pyridinyl	2-methoxy-3-pyridinyl
2-(trifluoromethyl)-3-pyridinyl	2-(CH(=NOMe))-3-pyridinyl
4-methyl-3-pyridinyl	4-methoxy-3-pyridinyl
4-(trifluoromethyl)-3-pyridinyl	4-(CH(=NOMe))-3-pyridinyl
5-methyl-3-pyridinyl	5-methoxy-3-pyridinyl
5-(trifluoromethyl)-3-pyridinyl	5-(CH(=NOMe))-3-pyridinyl
6-methyl-3-pyridinyl	6-methoxy-3-pyridinyl
6-(trifluoromethyl)-3-pyridinyl	6-(CH(=NOMe))-3-pyridinyl
2-methyl-4-pyridinyl	2-methoxy-4-pyridinyl
2-(trifluoromethyl)-4-pyridinyl	2-(CH(=NOMe))-4-pyridinyl
3-methyl-4-pyridinyl	3-methoxy-4-pyridinyl
3-(trifluoromethyl)-4-pyridinyl	3-(CH(=NOMe))-4-pyridinyl
3-methyl-2-pyrazinyl	3-methoxy-2-pyrazinyl
3-(trifluoromethyl)-2-pyrazinyl	3-(CH(=NOMe))-2-pyrazinyl
5-methyl-2-pyrazinyl	5-methoxy-2-pyrazinyl
5-(trifluoromethyl)-2-pyrazinyl	5-(CH(=NOMe))-2-pyrazinyl
6-methyl-2-pyrazinyl	6-methoxy-2-pyrazinyl
6-(trifluoromethyl)-2-pyrazinyl	6-(CH(=NOMe))-2-pyrazinyl
4-methyl-2-pyrimidinyl	4-m ethoxy-2-py ri m id i nyl
4-(tr if 1 uo ro methyl )-2-py ri m id i nyl	4-(CH(=NOMe))-2-pyrimidinyl
5-methyl-2-pyri m id inyl	5-methoxy-2-pyrimidinyl
5-( tr if 1 uo romethyl )-2-py ri m i d i nyl	5-(CH(=NOMe))-2-pyrimidinyl
2-methyl-4-pyrimidinyl	2-m ethoxy-4-py ri m id i nyl

113

2-(t rif I u orom ethyl )-4-py ri m id i ny I	2-(CH(=NOMe))-4-pyrimidinyl
5-methyl-4-pyrimidinyl	5-methoxy-4-pyrimidinyl
5-( tr if I uo rom ethyl )-4- py r i m id i nyl	5-(CH(=NOMe))-4-pyrimidinyl
6-methyl-4-pyrimidinyl	6-m eth oxy-4-py ri m id i nyl
6-(trifluoromethyl)-4-pyrimidinyl	6-(CH(=NOMe))-4-pyrimidinyl
3-methyl-1 -pyrazolyl	3-methoxy-1 -pyrazolyl
3-(trifluoromethyl)-1 -pyrazolyl	3-(CH(=NOMe))-1 -pyrazolyl
4-methyl-1 -pyrazolyl	4-methoxy-1 -pyrazolyl
4-(trifluoromethyl)-1 -pyrazolyl	4-(CH(=NOMe))-1 -pyrazolyl
5-methyl-1 -pyrazolyl	5-methoxy-1 -pyrazolyl
5-(trifluoromethyl)-1 -pyrazolyl	5-(CH(=N0Me))-1 -pyrazolyl
4-methyl-1,2,3-triazin-2-yl	4-methoxy-1,2,3-triazin-2-yl
4-(trifluoromethyl)-1,2,3-triazin-2-yl	4-(CH(=NOMe))-1,2,3-triazin-2-yl
6-(2-pyrimidinyl)-2-pyridinyl	2-(2-pyridinyl)-4-thiazolyl
2-(2-thiazolyl)-4-thiazolyl	2-(2-pyrimidinyl)ethynyl
1,3,4-oxadiazol-2-yl	tetrahydro-3-furanyl
tetrahydro-2-furanyl	4,5-dihydro-3-isoxazolyl
3-isoxazolyl	6-(trifluoromethyl)-3-pyrazinyl

TABLE 3a

Table 3a is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

114

TABLE 3c

H

O

Table 3c is identical to Table 1c, except that the structure shown under the heading

Table 1c is replaced by the structure shown above.

TABLE 3e

H

Table 3e is identical to Table 1e, except that the structure shown under the heading

Table 1e is replaced by the structure shown above.

TABLE 4a

H

Table 4a is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 4c

H

115

Table 4c is identical to Table 1c, except that the structure shown under the heading Table 1c is replaced by the structure shown above.

TABLE 4e

H

R

Table 4e is identical to Table 1e, except that the structure shown under the heading

Table 1e is replaced by the structure shown above.

TABLE 5a

Table 5a is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 5b

Table 5b is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

116

Table 5c is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 5d

Table 5d is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 5e

Table 5e is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

117

TABLE 5f

Table 5f is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 6a

Table 6a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 6c

Table 6c is identical to Table 1c, except that the structure shown under the heading Table 1c is replaced by the structure shown above.

TABLE 6e

118

Table 6e is identical to Table 1e, except that the structure shown under the heading Table 1e is replaced by the structure shown above.

Table 7a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 7c

Table 7c is identical to Table 1c, except that the structure shown under the heading

Table 1c is replaced by the structure shown above.

TABLE 7e

Table 7e is identical to Table 1e, except that the structure shown under the heading

Table 1e is replaced by the structure shown above.

119

TABLE 8a

Table 8a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 8c

Table 8c is identical to Table 1c, except that the structure shown under the heading Table 1c is replaced by the structure shown above.

TABLE 8e

Table 8e is identical to Table 1e, except that the structure shown under the heading Table 1e is replaced by the structure shown above.

TABLE 9a

Table 9a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

120

TABLE 9c

F

Table 9c is identical to Table 1c, except that the structure shown under the heading

Table 1c is replaced by the structure shown above.

TABLE 9e

H

F

Table 9e is identical to Table 1e, except that the structure shown under the heading Table 1e is replaced by the structure shown above.

TABLE 10a

Table 10a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

Table 10b is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

Table 10c is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 10d

Table 10d is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 11a fl H ?

122

Table 11a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 11b

Table 11b is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 11c

Table 11c is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 11d

O _H och₃

Table 11d is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 12a

123

Table 12a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 12c

Table 12c is identical to Table 1c, except that the structure shown under the heading

Table 1c is replaced by the structure shown above.

TABLE 12e

Table 12e is identical to Table 1e, except that the structure shown under the heading

Table 1e is replaced by the structure shown above.

TABLE 13a

Table 13a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 13c

R'

124

Table 13c is identical to Table 1 c, except that the structure shown under the heading

Table 1c is replaced by the structure shown above.

TABLE 13e

N V—_N

Table 13e is identical to Table 1e, except that the structure shown under the heading

Table 1e is replaced by the structure shown above.

TABLE 14a

Table 14a is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 14c

Table 14c is identical to Table 1c, except that the structure shown under the heading

Table 1c is replaced by the structure shown above.

TABLE 14e

125

Table 14e is identical to Table 1e, except that the structure shown under the heading

Table 1e is replaced by the structure shown above.

TABLE 15a

Table 15a is identical to Table 1 a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 15c

Table 15c is identical to Table 1c, except that the structure shown under the heading

Table 1c is replaced by the structure shown above.

TABLE 15e

Table 15e is identical to Table 1e, except that the structure shown under the heading Table 1e is replaced by the structure shown above.

TABLE 16a

126

Table 16a is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 16c

Table 16c is identical to Table 1c, except that the structure shown under the heading

Table 1c is replaced by the structure shown above.

TABLE 16e

Table 16e is identical to Table 1e, except that the structure shown under the heading

Table 1e is replaced by the structure shown above.

TABLE 17a

Table 17a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 17c

R'

127

Table 17c is identical to Table 1c, except that the structure shown under the heading Table 1c is replaced by the structure shown above.

TABLE 17e

Table 17e is identical to Table 1e, except that the structure shown under the heading

Table 1e is replaced by the structure shown above.

TABLE 18a

Table 18a is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

Table 18c is identical to Table 1c, except that the structure shown under the heading Table 1c is replaced by the structure shown above.

TABLE 18e

128

Table 18e is identical to Table 1e, except that the structure shown under the heading Table 1e is replaced by the structure shown above.

Table 19a is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 19c

Table 19c is identical to Table 1c, except that the structure shown under the heading

Table 1c is replaced by the structure shown above.

TABLE 19e

Table 19e is identical to Table 1e, except that the structure shown under the heading Table 1e is replaced by the structure shown above.

TABLE 20a

H

129

Table 20a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 20b

O

Table 20b is identical to Table 1e, except that the structure shown under the heading

Table 1e is replaced by the structure shown above.

TABLE 21a

Table 21a is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 21 b

Table 21 b is identical to Table 1e, except that the structure shown under the heading Table 1e is replaced by the structure shown above.

TABLE 22a

NOMe

130

Table 22a is identical to Table 1a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 22b

R^NOMe

Table 22b is identical to Table 1e, except that the structure shown under the heading

Table 1e is replaced by the structure shown above.

TABLE 23a

NOMe

Table 23a is identical to Table 1 a, except that the structure shown under the heading

Table 1a is replaced by the structure shown above.

TABLE 23b

NOMe

Table 23b is identical to Table 1e, except that the structure shown under the heading Table 1e is replaced by the structure shown above.

TABLE 24a

H

131

Table 24a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 24b

Table 24b is identical to Table 1c, except that the structure shown under the heading Table 1c is replaced by the structure shown above.

TABLE 25a

R

Table 25a is identical to Table 1a, except that the structure shown under the heading Table 1a is replaced by the structure shown above.

TABLE 25b

Table 25b is identical to Table 1 c, except that the structure shown under the heading Table 1c is replaced by the structure shown above.

A compound of this invention will generally be used as an invertebrate pest control active ingrédient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier. The formulation or composition ingrédients are selected to be consistent with the

132 physical properties of the active ingrédient, mode of application and environmental factors such as soil type, moisture and température.

Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrâtes), suspensions, émulsions (including microemulsions, oil in water émulsions, flowable concentrâtes and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated émulsion, microemulsion, oil in water émulsion, flowable concentrate and suspoemulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingrédient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingrédient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingrédient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation Systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other désirable végétation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic uptake.

The formulations will typically contain effective amounts of active ingrédient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

133

Weight Percent

Active
	Ingrédient	Diluent	Surfactant
Water-Dispersible and Watersoluble Granules, Tablets and Powders	0.001-90	0-99.999	0-15
Oil Dispersions, Suspensions, Emulsions, Solutions (including Emulsifiable Concentrâtes)	1-50	40-99	0-50
Dusts	1-25	70-99	0-5
Granules and Pellets	0.001-99	5-99.999	0-15
High Strength Compositions	90-99	0-10	0-2

Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins étal., 5 Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.

Liquid diluents include, for example, water, Λ/,/V-dimethylalkanamides (e.g., /V./V-dimethylformamide), limonene, dimethyl sulfoxide, /V-alkylpyrrolidones (e.g., /V-methylpyrrolidinone), alkyl phosphates (e.g., triethylphosphate), ethylene glycol, triethylene 10 glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylène carbonate, paraffins (e.g., white minerai oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycérine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acétates such 15 as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters alkyl and aryl benzoates, γ-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as méthanol, éthanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl

134 alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycérol esters of saturated and unsaturated fatty acids (typically

Cg-C22)> such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycérol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

The solid and liquid compositions of the présent invention often include one or more surfactants. When added to a liquid, surfactants (also known as “surface-active agents”) generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilie groups in a surfactant molécule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the présent compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylène oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycérides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phénol ethoxylates and dodecyl phénol ethoxylates (prepared from the phénols and ethylene oxide, propylene oxide, butylène oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylène oxide or mixtures thereof); fatty acid esters, glycérol esters, lanolin-based dérivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycérol fatty acid esters; other sorbitan dérivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols

135 (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.

Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate dérivatives; lignin and 5 lignin dérivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phénol ethoxylates; protein-based surfactants; sarcosine dérivatives; styryl phénol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of 10 ethoxylated alcohols; sulfonates of amines and amides such as Λ/,/V-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their dérivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides;

amines such as /V-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylène oxide or mixtures thereof); amine salts such as amine acétates and diamine salts; quatemary ammonium salts such as quatemary salts, 20 ethoxylated quatemary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the présent compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including 25 McCutcheon’s Emulsifiers and Détergents, annual American and International Editions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Détergents, Seventh Edition, John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such

136 polyorganosiloxanes), sédimentation of active ingrédients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobiais), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), évaporation (évaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acétates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon’s Volume 2: Functional Materials, annual International and North American éditions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.

The compound of Formula 1 and any other active ingrédients are typically incorporated into the présent compositions by dissolving the active ingrédient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrâtes, can be prepared by simply mixing the ingrédients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the activecontaining solvent upon dilution with water. Active ingrédient slurries, with particle diameters of up to 2,000 pm can be wet milled using media mills to obtain particles with average diameters below 3 pm. Aqueous slurries can be made into finished suspension concentrâtes (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 pm range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomération techniques. See Browning, “Agglomération”, Chemical Engineering, December 4, 1967, pp 147-48, Perry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

For further information regarding the art of formulation, see T. S. Woods, “The Formulator’s Toolbox - Product Forms for Modem Agriculture” in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of

137

Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;

U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed 5 Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance étal.,

Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

In the following Examples, ail formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-N. Without further élaboration, it is believed 10 that one skilled in the art using the preceding description can utilize the présent invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated.

Example A

High Strenqth Concentrate

Compound 8 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

Example B

Wettable Powder

Compound 14 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%

Example C

Granule

Compound 16 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0%

U.S.S. No. 25-50 sieves)

Example D

Extruded Pellet

138

Compound 19 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%

Example E

Emulsifiable Concentrate

Compound 41 10.0% polyoxyethylene sorbitol hexoleate 20.0%

Cg-C-j g fatty acid methyl ester 70.0%

Example F

Microemulsion

Compound 42 5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%

Example G

Seed Treatment

Compound 51 20.00% polyvinylpyrrolidone-vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water 65.75%

Example H

Fertilizer Stick

Compound 54 2.5% pyrrolidone-styrene copolymer 4.8% tristyrylphenyl 16-ethoxylate 2.3%

139

talc	0.8%
corn starch	5.0%
slow-release fertilizer	36.0%
kaolin	38.0%
water	10.6%
Example I
Suspension Concentrate
compound 55	35%
butyl polyoxyethylene/polypropylene block copolymer	4.0%
stearic acid/polyethylene glycol copolymer	1.0%
styrene acrylic polymer	1.0%
xanthan gum	0.1%
propylene glycol	5.0%
silicone based defoamer	0.1%
1,2-benzisothiazolin-3-one	0.1%
water	53.7%
Example J
Emulsion in Water
compound 76	10.0%
butyl polyoxyethylene/polypropylene block copolymer	4.0%
stearic acid/polyethylene glycol copolymer	1.0%
styrene acrylic polymer	1.0%
xanthan gum	0.1%
propylene glycol	5.0%
silicone based defoamer	0.1%
1,2-benzisothiazolin-3-one	0.1%
aromatic petroleum based hydrocarbon	20.0
water	58.7%

Example K

Oil Dispersion

25%

15% compound 19 polyoxyethylene sorbitol hexaoleate

140

organically modified bentonite clay	2.5%
fatty acid methyl ester	57.5%
Exemple L
Suspoemulsion
compound 42	10.0%
imidacloprid	5.0%
butyl polyoxyethylene/polypropylene block copolymer	4.0%
stearic acid/polyethylene glycol copolymer	1.0%
styrene acrylic polymer	1.0%
xanthan gum	0.1%
propylene glycol	5.0%
silicone based defoamer	0.1%
1,2-benzisothiazolin-3-one	0.1%
aromatic petroleum based hydrocarbon	20.0%
water	53.7%

Compounds of this invention exhibit activity against a wide spectrum of invertebrate pests.

These pests include invertebrates inhabiting a variety of environments such as, for example, 5 plant foliage, roots, soil, harvested crops or other foodstuffs, building structures or animal integuments. These pests include, for example, invertebrates feeding on foliage (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or animal blood or tissues, and thereby causing injury or damage to, for example, growing or stored agronomie crops, forests, greenhouse crops, ornamentals, nursery crops, stored foodstuffs or fiber products, or houses or 10 other structures or their contents, or being harmful to animal health or public health. Those skilled in the art will appreciate that not ail compounds are equally effective against ail growth stages of ail pests.

These présent compounds and compositions are thus useful agronomically for protecting field crops from phytophagous invertebrate pests, and also nonagronomically for protecting 15 other horticultural crops and plants from phytophagous invertebrate pests. This utility includes protecting crops and other plants (i.e. both agronomie and nonagronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide advantageous traits. Examples of such traits include tolérance to herbicides, résistance to phytophagous pests (e.g., insects, mites, aphids, spiders, nematodes, snails, plant

141 pathogenic fungi, bacteria and viruses), improved plant growth, increased tolérance of adverse growing conditions such as high or low températures, low or high soil moisture, and high salinity, increased flowering or fruiting, greater harvest yields, more rapid maturation, higher quality and/or nutritional value of the harvested product, or improved storage or process properties of the harvested products. Transgenic plants can be modified to express multiple traits. Examples of plants containing traits provided by genetic engineering or mutagenesis include varieties of corn, cotton, soybean and potato expressing an insecticidal Bacillus thuringiensis toxin such as YIELD GARD®, KNOCKOUT³, STARLINK®, BOLLGARD®, NuCOTN® and NEWLEAF®, INVICTA RR2 PRO^M, _and herbicide-tolerant varieties of corn, cotton, soybean and rapeseed such as ROUNDUP READY®, LIBERTY LINK®, IMI®, STS® and CLEARFIELD®, as well as crops expressing A/-acetyltransferase (GAT) to provide résistance to glyphosate herbicide, or crops containing the HRA gene providing résistance to herbicides inhibiting acetolactate synthase (ALS). The présent compounds and compositions may interact synergistically with traits introduced by genetic engineering or modified by mutagenesis, thus enhancing phenotypic expression or effectiveness of the traits or increasing the invertebrate pest control effectiveness of the présent compounds and compositions. In particular, the présent compounds and compositions may interact synergistically with the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide greaterthan-additive control of these pests.

Compositions of this invention can also optionally comprise plant nutrients, e.g., a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnésium, iron, copper, boron, manganèse, zinc, and molybdenum. Of note are compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnésium. Compositions of the présent invention which further comprise at least one plant nutrient can be in the form of liquids or solids. Of note are solid formulations in the form of granules, small sticks or tablets. Solid formulations comprising a fertilizer composition can be prepared by mixing the compound or composition of the présent invention with the fertilizer composition together with formulating ingrédients and then preparing the formulation by methods such as granulation or extrusion. Alternatively solid formulations can be prepared by spraying a solution or suspension of a compound or composition of the présent invention in a volatile solvent onto a previous prepared fertilizer composition in the form of dimensionally stable mixtures, e.g., granules, small sticks or tablets, and then evaporating the solvent.

142

Nonagronomic uses refer to invertebrate pest control in the areas other than fields of crop plants. Nonagronomic uses of the présent compounds and compositions include control of invertebrate pests in stored grains, beans and other foodstuffs, and in textiles such as clothing and carpets. Nonagronomic uses of the présent compounds and compositions also include invertebrate pest control in ornamental plants, forests, in yards, along roadsides and railroad rights of way, and on turf such as lawns, golf courses and pastures. Nonagronomic uses of the présent compounds and compositions also include invertebrate pest control in houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo or other animais. Nonagronomic uses of the présent compounds and compositions also include the control of pests such as termites that can damage wood or other structural materials used in buildings.

Nonagronomic uses of the présent compounds and compositions also include protecting human and animal health by controlling invertebrate pests that are parasitic or transmit infectious diseases. The controlling of animal parasites includes controlling external parasites that are parasitic to the surface of the body of the host animal (e.g., shoulders, armpits, abdomen, inner part of the thighs) and internai parasites that are parasitic to the inside of the body of the host animal (e.g., stomach, intestine, lung, veins, under the skin, lymphatic tissue). External parasitic or disease transmitting pests include, for example, chiggers, ticks, lice, mosquitoes, flies, mites and fleas. Internai parasites include heartworms, hookworms and helminths. Compounds and compositions of the présent invention are suitable for systemic and/or non-systemic control of infestation or infection by parasites on animais. Compounds and compositions of the présent invention are particularly suitable for combating external parasitic or disease transmitting pests. Compounds and compositions of the présent invention are suitable for combating parasites that infest agricultural working animais, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, hens, turkeys, ducks, geese and bees; pet animais and domestic animais such as dogs, cats, pet birds and aquarium fish; as well as socalled experimental animais, such as hamsters, guinea pigs, rats and mice. By combating these parasites, fatalities and performance réduction (in terms of méat, milk, wool, skins, eggs, honey, etc.) are reduced, so that applying a composition comprising a compound of the présent invention allows more économie and simple husbandry of animais.

Examples of agronomie or nonagronomic invertebrate pests include eggs, larvae and adults of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia

143 nonagrioides Lefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm (Spodoptera frugiperda J. E. Smith), beet armyworm (Spodoptera exigua Hübner), cotton leafworm (Spodoptera littoralis Boisduval), yellowstriped armyworm (Spodoptera ornithogalli Guenée), black cutworm (Agrotis ipsilon Hufnagel), velvetbean caterpillar (Anticarsia gemmatalis Hübner), green fruitworm (Lithophane antennata Walker), cabbage armyworm (Barathra brassicae Linnaeus), soybean looper (Pseudoplusia includens Walker), cabbage looper (Trichoplusia ni Hübner), tobacco budworm (Heliothis virescens Fabricius)); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hübner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae: Crambinae) such as sod worm (Herpetogramma licarsisalis Walker), sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer (Neoleucinodes elegantalis Guenée), green leafroller (Cnaphalocrocis medinalis), grape leaffolder (Desmia funeralis Hübner), melon worm (Diaphania nitidalis Stoll), cabbage center grub (Helluala hydralis Guenée), yellow stem borer (Scirpophaga incertulas Walker), early shoot borer (Scirpophaga infuscatellus Snellen), white stem borer (Scirpophaga innotata Walker), top shoot borer (Scirpophaga nivella Fabricius), dark-headed rice borer (Chilo polychrysus Meyrick), striped riceborer (Chilo suppressalis Walker), cabbage cluster caterpillar (Crocidolomia binotalis English)); leafrollers, budworms, seed worms, and fruit worms in the family Tortricidae (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck), citrus false codling moth (Cryptophlebia leucotreta Meyrick), citrus borer (Ecdytolopha aurantiana Lima), redbanded leafroller (Argyrotaenia velutinana Walker), obliquebanded leafroller (Choristoneura rosaceana Harris), light brown apple moth (Epiphyas postvittana Walker), European grape berry moth (Eupoecilia ambiguella Hübner), apple bud moth (Pandemis pyrusana Kearfott), omnivorous leafroller (Platynota stultana Walsingham), barred fruit-tree tortrix (Pandemis cerasana Hübner), apple brown tortrix (Pandemis heparana Denis & Schiffermüller)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus), peach fruit borer (Carposina niponensis Walsingham), peach twig borer (Anarsia lineatella Zeller), potato tuberworm (Phthorimaea operculella Zeller), spotted teniform leafminer (Lithocolletis blancardella Fabricius), Asiatic apple leafminer (Lithocolletis ringoniella Matsumura), rice leaffolder (Lerodea eufala Edwards), apple leafminer (Leucoptera scitella Zeller)); eggs, nymphs

144 and adults of the order Blattodea including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella germanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)), smoky brown cockroach (Periplaneta fuliginosa Service), Australian Cockroach (Periplaneta australasiae Fabr.), lobster cockroach (Nauphoeta cinerea Olivier) and smooth cockroach (Symploce pallens Stephens)); eggs, foliar feeding, fruit feeding, root feeding, seed feeding and vesicular tissue feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)), annual bluegrass weevil (Listronotus maculicollis Dietz), bluegrass billbug (Sphenophorus parvulus Gyllenhal), hunting billbug (Sphenophorus venatus vestitus), Denver billbug (Sphenophorus cicatristriatus Fahraeus)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers in the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera virgifera LeConte)); chafers and other beetles from the family Scarabaeidae (e.g., Japanese beetle (Popillia Japonica Newman), oriental beetle (Anomala orientalis Waterhouse, Exomala orientalis (Waterhouse) Baraud), northern masked chafer (Cyclocephala borealis Arrow), southern masked chafer (Cyclocephala immaculata Olivier or C. lurida Bland), dung beetle and white grub (Aphodius spp.), black turfgrass ataenius (Ataenius spretulus Haldeman), green June beetle (Cotinis nitida Linnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/June beetles (Phyllophaga spp.) and European chafer (Rhizotrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae.

In addition, agronomie and nonagronomic pests include: eggs, adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, bed bugs (e.g., Cimex lectularius Linnaeus) from the family Cimicidae, planthoppers from the families Fulgoroidae and Delphacidae, treehoppers from the family

145

Membracidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxéra from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, chinch bugs (e.g., hairy chinch bug (B/issus leucopterus hirtus Montandon) and southern chinch bug (B/issus insularis Barber)) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae.

Agronomie and nonagronomic pests also include : eggs, larvae, nymphs and adults ofthe order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychus medanieli McGregor)); fiat mites in the family Tenuipalpidae (e.g., citrus fiat mite (Brevipalpus lewisi McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodicidae, grain mites in the family Glycyphagidae; ticks in the family Ixodidae, commonly known as hard ticks (e.g., deer tick (Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma americanum Linnaeus)) and ticks in the family Argasidae, commonly known as soft ticks (e.g., relapsing fever tick (Ornithodoros turicata), common fowl tick (Argas radiatus)); scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; eggs, adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), bush locust (Zonocerus spp.), house cricket (Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket (Scapteriscus vicinus Scudder) and southern mole cricket (Scapteriscus borellii Giglio-Tos)); eggs, adults and immatures of the order Diptera including leafminers (e.g., Liriomyza spp. such as serpentine vegetable leafminer (Liriomyza sativae Blanchard)), midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bot flies (e.g., Gastrophiius spp., Oestrus spp.), cattle grubs

146 (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids, and other Nematocera; eggs, adults and immatures of the order Thysanoptera including onion thrips {Thrips tabaci Lindeman), flower thrips {Frankliniella spp.), and other foliar feeding thrips; insect pests of the order Hymenoptera including ants of the Family Formicidae including the Florida carpenter ant {Camponotus floridanus Buckley), red carpenter ant {Camponotus ferrugineus Fabricius), black carpenter ant {Camponotus pennsylvanicus De Geer), white-footed ant {Technomyrmex albipes fr. Smith), big headed ants {Pheidole sp.), ghost ant {Tapinoma melanocephalum Fabricius); Pharaoh ant {Monomorium pharaonis Linnaeus), little fire ant {Wasmannia auropunctata Roger), fire ant {Solenopsis geminata Fabricius), red imported fire ant {Solenopsis invicta Buren), Argentine ant {Iridomyrmex humilis Mayr), crazy ant {Paratrechina longicornis Latreille), pavement ant {Tetramorium caespitum Linnaeus), cornfield ant {Lasius alienus Forster) and odorous house ant {Tapinoma sessile Say). Other Hymenoptera including bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies {Neodiprion spp.; Cephus spp.); insect pests of the order Isoptera including termites in the Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g., Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen) families, the eastern subterranean termite {Reticulitermes flavipes Kollar), western subterranean termite {Reticulitermes hesperus Banks), Formosan subterranean termite {Coptotermes formosanus Shiraki), West Indian drywood termite {Incisitermes immigrans Snyder), powder post termite {Cryptotermes brevis Walker), drywood termite {Incisitermes snyderi Light), southeastern subterranean termite {Reticulitermes virginicus Banks), western drywood termite {Incisitermes minor Hagen), arboreal termites such as Nasutitermes sp. and other termites of économie importance; insect pests of the order Thysanura such as silverfish {Lepisma saccharina Linnaeus) and firebrat {Thermobia domestica Packard); insect pests of the order Mallophaga and including the head louse {Pediculus humanus capitis De Geer), body louse {Pediculus humanus Linnaeus), chicken body louse {Menacanthus stramineus Nitszch), dog biting louse {Trichodectes canis De Geer), fluff louse {Goniocotes gallinae De Geer), sheep body louse {Bovicola ovis Schrank), short-nosed cattle louse {Haematopinus eurysternus Nitzsch), long-nosed cattle louse {Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animais; insect pests of the order Siphonoptera including the oriental rat flea {Xenopsylla cheopis Rothschild),

147 cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus) and other fleas afflicting mammals and birds. Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus).

Examples of invertebrate pests of stored grain include larger grain borer (Prostephanus truncatus), lesser grain borer (Rhyzopertha dominica), rice weevil (Stiophilus oryzae), maize weevil (Stiophilus zeamais), cowpea weevil (Callosobruchus maculatus), red flour beetle (Tribolium castaneum), granary weevil (Stiophilus granarius), Indian meal moth (Plodia interpunctella'), Mediterranean flour beetle (Ephestia kuhniella) and fiat or rusty grain beetle (Cryptolestis ferrugineus).

Compounds of the présent invention may hâve activity on members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lésion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e. ail economically important flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).

Compounds of the invention may hâve activity against pests in the order Lepidoptera (e.g., Alabama argillacea Hübner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenée (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hübner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis & Schiffermüller (grape berry moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white butterfly),

148

Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hübner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hübner (cabbage looper) and Tuta absoluta Meyrick (tomato leafminer)).

Compounds of the invention hâve significant activity on members from the order Homoptera including: Acyrthosiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis erysimi Kaltenbach (turnip aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosiphum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid), and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp. (adelgids); Phylloxéra devastatrix Pergande (pecan phylloxéra); Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris (potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestes quadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler (green leafhopper), Nephotettix nigropictus Stâl (rice leafhopper), Nilaparvata lugens Stâl (brown planthopper), Peregrinus maidis Ashmead (corn planthopper), Sogatella furcifera Horvath (white-backed planthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAtee white apple leafhopper, Erythroneoura spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San José scale); Planococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla).

149

Compounds of this invention also hâve activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), B/issus leucopterus leucopterus Say (chinch bug), Cimex lectularius Linnaeus (bed bug) Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schâffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp. (complex of seed bugs), Halymorpha halys Stâl (brown marmorated stink bug), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper). Other insect orders controlled by compounds of the invention include Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the généra Agriotes, Athous or Limonius).

Note that some contemporary classification Systems place Homoptera as a suborder within the order Hemiptera.

Of note is use of compounds of this invention for controlling western flower thrips (Frankliniella occidentalis). Of note is use of compounds of this invention for controlling potato leafhopper (Empoasca fabae). Of note is use of compounds of this invention for controlling cotton melon aphid (Aphis gossypii). Of note is use of compounds of this invention for controlling green peach aphid (Myzus persicae). Of note is use of compounds of this invention for controlling sweetpotato whitefly (Bemisia tabaci).

Compounds of the présent invention may also be useful for increasing vigor of a crop plant. This method comprises contacting the crop plant (e.g., foliage, flowers, fruit or roots) or the seed from which the crop plant is grown with a compound of Formula 1 in amount sufficient to achieve the desired plant vigor effect (i.e. biologically effective amount). Typically the compound of Formula 1 is applied in a formulated composition. Although the compound of Formula 1 is often applied directly to the crop plant or its seed, it can also be applied to the locus of the crop plant, i.e. the environment of the crop plant, particularly the portion of the environment in close enough proximity to allow the compound of Formula 1 to migrate to the crop plant. The locus relevant to this method most commonly comprises the growth medium

150 (i.e. medium providing nutrients to the plant), typically soil in which the plant is grown. Treatment of a crop plant to increase vigor of the crop plant thus comprises contacting the crop plant, the seed from which the crop plant is grown or the locus of the crop plant with a biologically effective amount of a compound of Formula 1.

Increased crop vigor can resuit in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by excellent seed germination, crop emergence and crop stand; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., measured by leaf area index), plant height, number of tillers (e.g., for rice), root mass and overall dry weight of végétative mass of the crop; (c) improved crop yields, as demonstrated by time to flowering, duration of flowering, number of flowers, total biomass accumulation (i.e. yield quantity) and/or fruit or grain grade marketability of produce (i.e. yield quality); (d) enhanced ability of the crop to withstand or prevent plant disease infections and arthropod, nematode or mollusk pest infestations; and (e) increased ability of the crop to withstand environmental stresses such as exposure to thermal extremes, suboptimal moisture or phytotoxic chemicals.

The compounds of the présent invention may increase the vigor of treated plants compared to untreated plants by killing or otherwise preventing feeding of phytophagous invertebrate pests in the environment of the plants. In the absence of such control of phytophagous invertebrate pests, the pests reduce plant vigor by consuming plant tissues or sap, or transmiting plant pathogens such as viruses. Even in the absence of phytophagous invertebrate pests, the compounds of the invention may increase plant vigor by modifying metabolism of plants. Generally, the vigor of a crop plant will be most significantly increased by treating the plant with a compound of the invention if the plant is grown in a nonideal environment, i.e. an environment comprising one or more aspects adverse to the plant achieving the full genetic potential it would exhibit in an idéal environment.

Of note is a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising phytophagous invertebrate pests. Also of note is a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment not comprising phytophagous invertebrate pests. Also of note is a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising an amount of moisture less than idéal for supporting growth of the crop plant. Of note is a method for increasing vigor of a crop plant wherein the crop is rice. Also of note is a method for increasing vigor of a crop plant wherein the crop is maize (corn). Also of note is a method for increasing vigor of a crop plant wherein the crop is soybean.

151

Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including insecticides, fungicides, nematocides, bactéricides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agronomie and nonagronomic utility. Thus the présent invention also pertains to a composition comprising a biologically effective amount of a compound of Formula 1, at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and at least one additional biologically active compound or agent. For mixtures of the présent invention, the other biologically active compounds or agents can be formulated together with the présent compounds, including the compounds of Formula 1, to form a premix, or the other biologically active compounds or agents can be formulated separately from the présent compounds, including the compounds of Formula 1, and the two formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.

Examples of such biologically active compounds or agents with which compounds of this invention can be formulated are insecticides such as abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen ([(3S,4/?,4a/?,6S,6aS,12R,12aS,12bS)-3[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12btri methyl-11 -oxo-9-(3-pyridinyl)-2F/, 11 H-naphtho[2,1 -b]pyrano[3,4-e]pyran-4-yl]methyl cyclopropanecarboxylate), amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, , buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole (3bromo-1-(3-chloro-2-pyridinyl)-A/-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1A7pyrazole-5-carboxamide), cyclaniliprole (3-bromo-A/-[2-bromo-4-chloro-6-[[(1 cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1/7-pyrazole-5-carboxamide), cycloprothrin, cycloxaprid ((5S,8F?)-1-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9nitro-5,8-Epoxy-1H-imidazo[1,2-a]azepine) cyflumetofen, cyfluthrin, beta-eyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb,

152 fenpropathrin, fenvalerate, fipronil, flometoquin (2-ethyl-3,7-dimethyl-6-[4(trifluoromethoxy)phenoxy]-4-quinolinyl methyl carbonate), flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin (methyl (aE)-2-[[2-chloro-4(trifluoromethyl)phenoxy]methyl]-a-(methoxymethylene)benzeneacetate), flufensulfone (5chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole), fluhexafon, fluopyram, flupiprole (1-[2,6dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]1 A/-pyrazole-3-carbonitrile), flupyradifurone (4-[[(6-chloro-3-pyridinyl)methyl](2,2difluoroethyl)amino]-2(5/7)-furanone), fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, heptafluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl

2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate), hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl (1/?,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate), metaflumizone, metaldehyde, methamidophos, methidathion, methiodicarb, methomyl, methoprene, methoxychlor, metofluthrin, methoxyfenozide, metofluthrin, monocrotophos, monofluorothrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 3-(2-cyano-1-propen-1-yl)-2,2dimethylcyclopropanecarboxylate), nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide (1,3,5-trimethyl-/\/-(2methyl-1-oxopropyl)-/V-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1(trifluoromethyl)ethyl]phenyl]-1 H-pyrazole-4-carboxamide), pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin (methyl (a£z)-2-[[[2-[(2,4dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-a(methoxymethylene)benzeneacetate), pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor (Λ/[methyloxido[1-[6-(trifluoromethyl)-3-pyridinyl]ethyl]-À⁴-sulfanylidene]cyanamide), tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethylfluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2,3,3tetramethylcyclopropanecarboxylate), tetraniliprole, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen (3-phenyl-5-(2-thienyl)-1,2,4-oxadiazole), tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumezopyrim (2,4-dioxo-1-(5-pyrimidinylmethyl)-3-[3(trifluoromethyl)phenyl]-2H-pyrido[1,2-a]pyrimidinium inner sait), triflumuron, Bacillus

153 thuringiensis delta-endotoxins, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.

Of note are insecticides such as abamectin, acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambdacyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin, flufensulfone, flupiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide, metofluthrin, monofluorothrin, nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultapsodium, tralomethrin, triazamate, triflumezopyrim, triflumuron, Bacillus thuringiensis deltaendotoxins, ail strains of Bacillus thuringiensis and ail strains of nucleo polyhedrosis viruses.

One embodiment of biological agents for mixing with compounds of this invention include entomopathogenic bacteria such as Bacillus thuringiensis, and the encapsulated deltaendotoxins of Bacillus thuringiensis such as MVP® and MVPII® bioinsecticides prepared by the CelICap® process (CelICap®, MVP® and MVPII® are trademarks of Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi such as green muscardine fungus; and entomopathogenic (both naturally occurring and genetically modified) viruses including baculovirus, nucleopolyhedro virus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus (GV) such as Cydia pomonella granulosis virus (CpGV).

Of particular note is such a combination where the other invertebrate pest control active ingrédient belongs to a different chemical class or has a different site of action than the compound of Formula 1. In certain instances, a combination with at least one other invertebrate pest control active ingrédient having a similar spectrum of control but a different site of action will be particularly advantageous for résistance management. Thus, a composition of the présent invention can further comprise a biologically effective amount of at least one additional

154 invertebrate pest control active ingrédient having a similar spectrum of control but belonging to a different chemical class or having a different site of action. These additional biologically active compounds or agents include, but are not limited to, acetylcholinesterase (AChE) inhibitors such as the carbamates methomyl, oxamyl, thiodicarb, triazamate, and the organophosphates chlorpyrifos; GABA-gated chloride channel antagonists such as the cyclodienes dieldrin and endosulfan, and the phenylpyrazoles ethiprole and fipronil; sodium channel modulators such as the pyrethroids bifenthrin, cyfluthrin, befa-cyfluthrin, cyhalothrin, /ambc/a-cyhalothrin, cypermethrin, deltamethrin, dimefluthrin, esfenvalerate, metofluthrin and profluthrin; nicotinic acetylcholinereceptor (nAChR) agonists such as the neonicotinoids acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, and thiamethoxam, and sulfoxaflor; nicotinic acétylcholine receptor (nAChR) allosteric activators such as the spinosyns spinetoram and spinosad; chloride channel activators such as the avermectins abamectin and emamectin; juvénile hormone mimics such as diofenolan, methoprene, fenoxycarb and pyriproxyfen; sélective homopteran feeding blockers such as pymetrozine and flonicamid; mite growth inhibitors such as etoxazole; inhibitors of mitochondrial ATP synthase such as propargite; ucouplers of oxidative phosphorylation via disruption of the proton gradient such as chlorfenapyr; nicotinic acétylcholine receptor (nAChR) channel blockers such as the nereistoxin analogs cartap; inhibitors of chitin biosynthesis such as the benzoylureas flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron and triflumuron, and buprofezin; dipteran moulting disrupters such as cyromazine; ecdysone receptor agonists such as the diacylhydrazines methoxyfenozide and tebufenozide; octopamine receptor agonists such as amitraz; mitochondrial complex III électron transport inhibitors such as hydramethylnon; mitochondrial complex I électron transport inhibitors such as pyridaben; voltage-dependent sodium channel blockers such as indoxacarb; inhibitors of acetyl CoA carboxylase such as the tetronic and tetramic acids spirodiclofen, spiromesifen and spirotetramat; mitochondrial complex Il électron transport inhibitors such as the β-ketonitriles cyenopyrafen and cyflumetofen; ryanidine receptor modulators such as the anthranilic diamides chlorantraniliprole, cyantraniliprole and cyantraniliprole, diamides such as flubendiamide, and ryanodine receptor ligands such as ryanodine; compounds wherein the target site responsible for biological activity is unknown or uncharacterized such as azadirachtin, bifenazate, pyridalyl, pyrifluquinazon and triflumezopyrim; microbial disrupters of insect midgut membranes such as Bacillus thuringensis and the delta-endotoxins they produce and Bacillus sphaericus; and biological agents including

155 nucleo polyhedro viruses (NPV) and other naturally occurring or genetically modified insecticidal viruses.

Further examples of biologically active compounds or agents with which compounds of this invention can be formulated are: fungicides such as acibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl (including benalaxylM), benodanil, benomyl, benthiavalicarb (including benthiavalicarb-isopropyl), benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, copper hydroxide, copper oxychloride, copper sulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole (including diniconazole-M), dinocap, dithianon, dithiolanes, dodemorph, dodine, econazole, etaconazole, edifenphos, enoxastrobin (also known as enestroburin), epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenaminstrobin, fenarimol, fenbuconazole, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone, flometoquin, fluazinam, fludioxonil, flufenoxystrobin, flumorph, fluopicolide, fluopyram, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fthalide (also known as phthalide), fuberidazole, furalaxyl, furametpyr, hexaconazole, hymexazole, guazatine, imazalil, imibenconazole, iminoctadine albesilate, iminoctadine triacetate, iodicarb, ipconazole, isofetamid, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, mandestrobin, maneb, mapanipyrin, mepronil, meptyldinocap, metalaxyl (including metalaxylM/mefenoxam), metconazole, methasulfocarb, metiram, metominostrobin, metrafenone, myclobutanil, naftitine, neo-asozin (ferrie methanearsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron, penflufen, penthiopyrad, perfurazoate, phosphorous acid (including salts thereof, e.g., fosetyl-aluminm), picoxystrobin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributacarb, pyrifenox, pyriofenone, perisoxazole, pyrimethanil, pyrifenox, pyrrolnitrin, pyroquilon, quinconazole, quinmethionate, quinoxyfen, quintozene, silthiofam, sedaxane, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquin,

156 teclofthalam, tecloftalam, tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolprocarb, tolyfluanid, triadimefon, triadimenol, triarimol, triazoxide, tribasic copper sulfate, triclopyricarb, tridemorph, trifloxystrobin, triflumizole, trimoprhamide tricyclazole, trifloxystrobin, triforine, triticonazole, uniconazole, validamycin, valifenalate (also known as valifenal), vinclozolin, zineb, ziram, zoxamide and 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1 -piperidinyl]2-[5-methyl-3-(trifluoromethyl)-1F/-pyrazol-1-yl]ethanone; nematocides such as fluopyram, spirotetramat, thiodicarb, fosthiazate, abamectin, iprodione, fluensulfone, dimethyl disulfide, tioxazafen, 1,3-dichloropropene (1,3-D), metam (sodium and potassium), dazomet, chloropicrin, fenamiphos, ethoprophos, cadusaphos, terbufos, imicyafos, oxamyl, carbofuran, tioxazafen, Bacillus firmus and Pasteuria nishizawae; bactéricides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad.

In certain instances, combinations of a compound of this invention with other biologically active (particularly invertebrate pest control) compounds or agents (i.e. active ingrédients) can resuit in a greater-than-additive (i.e. synergistic) effect. Reducing the quantity of active ingrédients released in the environment while ensuring effective pest control is always désirable. When synergism of invertebrate pest control active ingrédients occurs at application rates giving agronomically satisfactory levels of invertebrate pest control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load.

Compounds of this invention and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis deltaendotoxins). Such an application may provide a broader spectrum of plant protection and be advantageous for résistance management. The effect of the exogenously applied invertebrate pest control compounds of this invention may be synergistic with the expressed toxin proteins.

General references for these agricultural protectants (i.e. insecticides, fungicides, nematocides, acaricides, herbicides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2^nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.

For embodiments where one or more of these various mixing partners are used, the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically

157 between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1). One skilled in the art can easily détermine through simple expérimentation the biologically effective amounts of active ingrédients necessary for the desired spectrum of biological activity. It will be évident that including these additional components can expand the spectrum of invertebrate pests controlled beyond the spectrum controlled by the compound of Formula 1 alone.

Table A lists spécifie combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the présent invention. The first column of Table A lists the spécifie invertebrate pest control agents (e.g., “Abamectin” in the first line). The second column of Table A lists the mode of action (if known) or chemical class of the invertebrate pest control agents. The third column of Table A lists embodiment(s) of ranges of weight ratios for rates at which the invertebrate pest control agent can be applied relative to a compound of Formula 1 (e.g., “50:1 to 1:50” of abamectin relative to a compound of Formula 1 by weight). Thus, for example, the first line of Table A specifically discloses the combination of a compound of Formula 1 with abamectin can be applied in a weight ratio between 50:1 to 1:50. The remaining Unes of Table A are to be construed similarly. Of further note Table A lists spécifie combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the présent invention and includes additional embodiments of weight ratio ranges for application rates.

Table A

Invertebrate Pest Control Agent	Mode of Action or Chemical Class	Typical Weight Ratio
Abamectin	chloride channel activator	50:1 to 1:50
Acetamiprid	nicotinic acetylcholinereceptor (nAChR) agonist	150:1 to 1:200
Amitraz	octopamine receptor agonists	200:1 to 1:100
Avermectin	macrocyclic lactones	50:1 to 1:50
Azadirachtin	unknown site of action	100:1 to 1:120
Beta-cyfluthrin	sodium channel modulators	150:1 to 1:200
Bifenthrin	sodium channel modulators	100:1 to 1:10
Buprofezin	chitin biosynthesis inhibitors	500:1 to 1:50
Cartap	nicotinic acétylcholine receptor (nAChR)	100:1 to 1:200

158

Invertebrate Pest Control Agent	Mode of Action or Chemical Class	Typical Weight Ratio
	channel blocker
Chlorantraniliprole	ryanodine receptor modulator	100:1 to 1:120
Chlorfenapyr	uncouplers of oxidative phosphorylation	300:1 to 1:200
Chlorpyrifos	acetylcholinesterase inhibitor	500:1 to 1:200
Clothianidin	nicotinic acétylcholine receptor (nAChR) agonist	100:1 to 1:400
Cyantraniliprole	Ryanodine receptor modulator	100:1 to 1:120
Cyfluthrin	sodium channel modulator	150:1 to 1:200
Cyhalothrin	sodium channel modulator	150:1 to 1:200
Cypermethrin	sodium channel modulator	150:1 to 1:200
Cyromazine	dipteran moulting disrupter	400:1 to 1:50
Deltamethrin	sodium channel modulators	50:1 to 1:400
Dieldrin	GABA-gated chloride channel antagonist	200:1 to 1:100
Dinotefuran	nicotinic acétylcholine receptor (nAChR) agonist	150:1 to 1:200
Diofenolan	juvénile hormone mimic	150:1 to 1:200
Emamectin	chloride channel activator	50:1 to 1:10
Endosulfan	GABA-gated chloride channel antagonist	200:1 to 1:100
Esfenvalerate	sodium channel modulator	100:1 to 1:400
Ethiprole	GABA-regulated chloride channel antagonist	200:1 to 1:100
Fenothiocarb		150:1 to 1:200
Fenoxycarb	juvénile hormone mimic	500:1 to 1:100
Fenvalerate	sodium channel modulator	150:1 to 1:200
Fipronil	GABA-regulated chloride channel antagonist	150:1 to 1:100
Flonicamid	sélective homopteran feeding blocker	200:1 to 1:100
Flubendiamide	ryanodine receptor modulator	100:1 to 1:120
Flufenoxuron	chitin biosynthesis inhibitor	200:1 to 1:100
Hexaflumuron	chitin biosynthesis inhibitor	300:1 to 1:50

159

Invertebrate Pest Control Agent	Mode of Action or Chemical Class	Typical Weight Ratio
Hydramethylnon	mitochondrial Complex III électron transport inhibitors	150:1 to 1:250
Imidacloprid	nicotinic acétylcholine receptor (nAChR) agonist	1000:1 to 1:1000
Indoxacarb	voltage-dependent sodium channel blocker	200:1 to 1:50
Lambda-cyhalothrin	sodium channel modulator	50:1 to 1:250
Lufenuron	chitin biosynthesis inhibitor	500:1 to 1:250
Metaflumizone	voltage-dependent sodium channel blocker	200:1 to 1:200
Methomyl	acetylcholinesterase inhibitor	500:1 to 1:100
Methoprene	juvénile hormone mimic	500:1 to 1:100
Methoxyfenozide	ecdysone receptor agonist	50:1 to 1:50
Nitenpyram	nicotinic acétylcholine receptor (nAChR) agonist	150:1 to 1:200
Nithiazine	nicotinic acétylcholine receptor (nAChR) agonist	150:1 to 1:200
Novaluron	chitin biosynthesis inhibitor	500:1 to 1:150
Oxamyl	acetylcholinesterase inhibitors	200:1 to 1:200
Pymetrozine	sélective homopteran feeding blocker	200:1 to 1:100
Pyrethrin	sodium channel modulator	100:1 to 1:10
Pyridaben	mitochondrial Complex 1 électron transport inhibitor	200:1 to 1:100
Pyridalyl	unknown site of action	200:1 to 1:100
Pyriproxyfen	juvénile hormone mimic	500:1 to 1:100
Ryanodine	ryanodine receptor ligand	100:1 to 1:120
Spinetoram	nicotinic acétylcholine receptor (nAChR) allosteric activator	150:1 to 1:100
Spinosad	nicotinic acétylcholine receptor (nAChR) allosteric activators	500:1 to 1:10
Spirodiclofen	acetyl CoA carboxylase inhibitor	200:1 to 1:200
Spiromesifen	acetyl CoA carboxylase inhibitor	200:1 to 1:200

160

Invertebrate Pest Control Agent	Mode of Action or Chemical Class	Typical Weight Ratio
Tebufenozide	eedysone receptor agonist	500:1 to 1:250
Thiacloprid	nicotinic acétylcholine receptor (nAChR) agonist	100:1 to 1:200
Thiamethoxam	nicotinic acétylcholine receptor (nAChR) agonist	1250:1 to 1:1000
Thiodicarb	acetylcholinesterase inhibitors	500:1 to 1:400
Thiosultap-sodium	Nicotinic acétylcholine receptor (nAChR) channel blocker	150:1 to 1:100
Tralomethrin	sodium channel modulator	150:1 to 1:200
Triazamate	acetyl cholinestérase inhibitors	250:1 to 1:100
Triflumezopyrim
Triflumuron	chitin synthesis inhibitor	200:1 to 1:100
Bacillus thuringiensis	biological agents	50:1 to 1:10
Bacillus thuringiensis delta-endotoxin	biological agents	50:1 to 1:10
NPV (e.g., Gemstar)	biological agents	50:1 to 1:10

Of note is the composition of the présent invention wherein the at least one additional biologically active compound or agent is selected from the Invertebrate Pest Control Agents listed in Table A above.

The weight ratios of a compound, including a compound of Formula 1, an /V-oxide or a sait thereof, to the additional invertebrate pest control agent typically are between 1000:1 and 1:1000, with one embodiment being between 500:1 and 1:500, another embodiment being between 250:1 and 1:200 and another embodiment being between 100:1 and 1:50.

Listed below in Tables B1 to B10 are embodiments of spécifie compositions comprising a compound of Formula 1 (compound numbers refer to compounds in Index Tables A-N) and an 10 additional invertebrate pest control agent.

Table B1

Mixture No.

Cmpd. and invertebrate Pest No. Control Agent

Mixture No.

Cmpd. and Invertebrate Pest No. Control Agent

	161
Mixture No.	Cmpd. No.	and	Invertebrate Pest Control Agent
B1-1	8	and	Abamectin
B1-2	8	and	Acetamiprid
B1-3	8	and	Amitraz
B1-4	8	and	Avermectin
B1-5	8	and	Azadirachtin
B1-6	8	and	Bensultap
B1-7	8	and	Beta-cyfluthrin
B1-8	8	and	Bifenthrin
B1-9	8	and	Buprofezin
B1-10	8	and	Cartap
B1-11	8	and	Chlorantraniliprole
B1-12	8	and	Chlorfenapyr
B1-13	8	and	Chlorpyrifos
B1-14	8	and	Clothianidin
B1-15	8	and	Cyantraniliprole
B1-16	8	and	Cyfluthrin
B1-17	8	and	Cyhalothrin
B1-18	8	and	Cypermethrin
B1-19	8	and	Cyromazine
B1-20	8	and	Deltamethrin
B1-21	8	and	Dieldrin
B1-22	8	and	Dinotefuran
B1-23	8	and	Diofenolan
B1-24	8	and	Emamectin
B1-25	8	and	Endosulfan
B1-26	8	and	Esfenvalerate
B1-27	8	and	Ethiprole
B1-28	8	and	Fenothiocarb

Mixture No.	Cmpd. No.	and	Invertebrate Pest Control Agent
B1-38	8	and	Indoxacarb
B1-39	8	and	Lambda-cyhalothrin
B1-40	8	and	Lufenuron
B1-41	8	and	Metaflumizone
B1-42	8	and	Methomyl
B1-43	8	and	Methoprene
B1-44	8	and	Methoxyfenozide
B1-45	8	and	Nitenpyram
B1-46	8	and	Nithiazine
B1-47	8	and	Novaluron
B1-48	8	and	Oxamyl
B1-49	8	and	Phosmet
B1-50	8	and	Pymetrozine
B1-51	8	and	Pyrethrin
B1-52	8	and	Pyridaben
B1-53	8	and	Pyridalyl
B1-54	8	and	Pyriproxyfen
B1-55	8	and	Ryanodine
B1-56	8	and	Spinetoram
B1-57	8	and	Spinosad
B1-58	8	and	Spirodiclofen
B1-59	8	and	Spiromesifen
B1-60	8	and	Spirotetramat
B1-61	8	and	Sulfoxaflor
B1-62	8	and	Tebufenozide
B1-63	8	and	Tefluthrin
B1-64	8	and	Thiacloprid
B1-65	8	and	Thiamethoxam

162

Mixture No.	Cmpd. No.	and	Invertebrate Pest Control Agent
B1-29	8	and	Fenoxycarb
B1-30	8	and	Fenvalerate
B1-31	8	and	Fipronil
B1-32	8	and	Flonicamid
B1-33	8	and	Flubendiamide
B1-34	8	and	Flufenoxuron
B1-35	8	and	Hexaflumuron
B1-36	8	and	Hydramethylnon
B1-37	8	and	Imidacloprid

Mixture No.	Cmpd. No.	and	Invertebrate Pest Control Agent
B1-66	8	and	Thiodicarb
B1-67	8	and	Thiosultap-sodium
B1-68	8	and	Tolfenpyrad
B1-69	8	and	Tralomethrin
B1-70	8	and	T riazamate
B1-71	8	and	Triflumezopyrim
B1-72	8	and	Triflumuron
B1-73	8	and	Bacillus thuringiensis
			Bacillus
B1-74	8	and	thuringiensis delta-
			endotoxin
B1-75	8	and	NPV (e.g., Gemstar)

Table B2

Table B2 is identical to Table B1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 14. For example, the first mixture 5 in Table B2 is designated B2-1 and is a mixture of compound 14 and the additional invertebrate pest control agent abamectin.

Table B3

Table B3 is identical to Table B1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 16. For example, the first mixture 10 in Table B3 is designated B3-1 and is a mixture of compound 16 and the additional invertebrate pest control agent abamectin.

Table B4

Table B4 is identical to Table B1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 19. For example, the first mixture 15 in Table B4 is designated B4-1 and is a mixture of compound 19 and the additional invertebrate pest control agent abamectin.

163

Table B5

Table B5 is identical to Table B1, exceptthat each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 41. For example, the first mixture in Table B5 is designated B5-1 and is a mixture of compound 41 and the additional invertebrate pest control agent abamectin.

Table B6

Table B6 is identical to Table B1, exceptthat each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 42. For example, the first mixture in Table B6 is designated B6-1 and is a mixture of compound 42 and the additional invertebrate pest control agent abamectin.

Table B7

Table B7 is identical to Table B1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 51. For example, the first mixture in Table B7 is designated B7-1 and is a mixture of compound 51 and the additional invertebrate pest control agent abamectin.

Table B8

Table B8 is identical to Table B1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 54. For example, the first mixture in Table B8 is designated B8-1 and is a mixture of compound 54 and the additional invertebrate pest control agent abamectin.

Table B9

Table B9 is identical to Table B1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 55. For example, the first mixture in Table B9 is designated B9-1 and is a mixture of compound 55 and the additional invertebrate pest control agent abamectin.

Table B10

Table B10 is identical to Table B1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 76. For example, the first mixture in Table B10 is designated B10-1 and is a mixture of compound 76 and the additional invertebrate pest control agent abamectin.

164

The spécifie mixtures listed in Tables B1 to B10 typically combine a compound of Formula 1 with the other invertebrate pest agent in the ratios specified in Table A.

Listed below in Tables C1 to C10 are spécifie mixtures comprising a compound of

Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Tables A-N) and an additional invertebrate pest control agent. Tables C1 to C10 further list spécifie weight ratios typical of the mixtures of Tables C1 to C10. For example, the first weight ratio entry of the first line of Table C1 specifically discloses the mixture of Compound 8 of Index Table A with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C1

Mixtur e No.	Cmpd an Invertebrate Pest d Control Agent No.	Typical Mixture Ratios (by weight)
C1-1	an 8 Abamectin d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-2	an 8 Acetamiprid	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-3	an 8 Amitraz d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-4	an 8 Avermectin d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-5	an 8 Azadirachtin d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-6	an 8 Bensultap d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-7	an 8 Beta-cyfluthrin	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-8	an 8 Bifenthrin d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-9	an 8 Buprofezin d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0

165

C1-10	8	an	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
d	Cartap
C1-11	8	an	Chlorantraniliprol	100:	10:	5:	2:	1:	1:	1:	1:1	1:10
		d	e	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-12	8	d	Chlorfenapyr	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-13	8	d	Chlorpyrifos	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-14	8	d	Clothianidin	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-15	8	d	Cyantraniliprole	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-16	8	d	Cyfluthrin	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
01-17	8	d	Cyhalothrin	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-18	8	d	Cypermethrin	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-19	8	d	Cyromazine	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-20	8	d	Deltamethrin	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-21	8	d	Dieldrin	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-22	8	d	Dinotefuran	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-23	8	d	Diofenolan	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-24	8	d	Emamectin	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	T.	1:	1:	1:1	1:10
C1-25	8	d	Endosulfan	1	1	1	1	1	2	5	0	0

166

C1-26	an 8 Esfenvalerate d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-27	an 8 Ethiprole	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-28	an 8 Fenothiocarb d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-29	an 8 Fenoxycarb	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-30	an 8 Fenvalerate d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-31	an 8 Fipronil d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-32	an 8 Flonicamid d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-33	an 8 Flubendiamide d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-34	an 8 Flufenoxuron d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-35	an 8 Hexaflumuron d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-36	an 8 Hydramethylnon	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-37	an 8 Imidacloprid	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-38	an 8 Indoxacarb d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-39	an Lambda- 8 d cyhalothrin	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-40	an 8 Lufenuron d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
C1-41	an 8 Metaflumizone d	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0

167

C1-42	8	an	100: 1	10: 1	5: 1	2: 1	1: 1	1: 2	1: 5	1:1 0	1:10 0
d	Methomyl
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-43	8	d	Methoprene	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-44	8	d	Methoxyfenozide	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-45	8	d	Nitenpyram	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-46	8	d	Nithiazine	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-47	8	d	Novaluron	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-48	8	d	Oxamyl	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-49	8	d	Phosmet	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-50	8	d	Pymetrozine	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-51	8	d	Pyrethrin	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-52	8	d	Pyridaben	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-53	8	d	Pyridalyl	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-54	8	d	Pyriproxyfen	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-55	8	d	Ryanodine	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-56	8	d	Spinetoram	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-57	8	d	Spinosad	1	1	1	1	1	2	5	0	0

168

		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-58	8	d	Spirodiclofen	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-59	8	d	Spiromesifen	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-60	8	d	Spirotetramat	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-61	8	d	Sulfoxaflor	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-62	8	d	Tebufenozide	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-63	8	d	Tefluthrin	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-64	8	d	Thiacloprid	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-65	8	d	Thiamethoxam	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-66	8	d	Thiodicarb	1	1	1	1	1	2	5	0	0
C1-67		an	Thiosultap-	100:	10:	5:	2:	1:	1:	1:	1:1	1:10
8
		d	sodium	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-68	8	d	Tolfenpyrad	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-69	8	d	Tralomethrin	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-70	8	d	Triazamate	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-71	8	d	Triflumezopyrim	1	1	1	1	1	2	5	0	0
		an		100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-72	8	d	Triflumuron	1	1	1	1	1	2	5	0	0
		an	Bacillus	100:	10:	5:	2:	1:	1:	1:	1:1	1:10
C1-73	8	d	thuringiensis	1	1	1	1	1	2	5	0	0

169

C1-74

8

an d

Bacillus thuringiensis delta-endotoxin

100: 1

10: 1

5: 1

2: 1

1: 1

1: 2

1: 5

1:1 0

1:10 0

C1-75

8

an d

NPV (e.g., Gemstar)

100: 1

10: 1

5: 1

2: 1

1: 1

1: 2

1: 5

1:1 0

1:10 0

Table C2

Table C2 is identical to Table C1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 14. For example, the first weight ratio entry of the first line of Table C2 specifically discloses the mixture of Compound 14 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C3

Table C3 is identical to Table C1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 16. For example, the first weight ratio entry of the first line of Table C3 specifically discloses the mixture of Compound 16 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C4

Table C4 is identical to Table C1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 19. For example, the first weight ratio entry of the first line of Table C4 specifically discloses the mixture of Compound 19 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C5

Table C5 is identical to Table C1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 41. For example, the first weight ratio entry of the first line of Table C5 specifically discloses the mixture of Compound 41 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C6

Table C6 is identical to Table C1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 42. For example, the first weight ratio entry of the first line of Table C6 specifically discloses the mixture of Compound 42 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

170

Table C7

Table C7 is identical to Table C1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 51. For example, the first weight ratio entry of the first line of Table C7 specifically discloses the mixture of Compound 51 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C8

Table C8 is identical to Table C1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 54. For example, the first weight ratio entry of the first line of Table C8 specifically discloses the mixture of Compound 54 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C9

Table C9 is identical to Table C1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 55. For example, the first weight ratio entry of the first line of Table C9 specifically discloses the mixture of Compound 55 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C10

Table C10 is identical to Table C1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 76. For example, the first weight ratio entry of the first line of Table C10 specifically discloses the mixture of Compound 76 with abamectin applied in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Listed below in Tables D1 to D10 are embodiments of spécifie compositions comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Tables A-N) and an additional fungicide.

Table D1

Mixture No.	Cmpd. No.	and	Fungicide	Mixture No.	Cmpd. No.	and	Fungicide
D1-1	8	and	Probenazole	D1-17	8	and	Difenoconazole
D1-2	8	and	Tiadinil	D1-18	8	and	Cyproconazole
D1-3	8	and	Isotianil	D1-19	8	and	Propiconazole
D1-4	8	and	Pyroquilon	D1-20	8	and	Fenoxanil
D1-5	8	and	Metominostrobin	D1-21	8	and	Ferimzone

171

Mixture No.	Cmpd. No.	and	Fungicide	Mixture No.	Cmpd. No.	and	Fungicide
D1-6	8	and	Flutolanil	D1-22	8	and	Fthalide
D1-7	8	and	Validamycin	D1	23	8	and	Kasugamycin
D1-8	8	and	Furametpyr	D1	24	8	and	Picoxystrobin
D1-9	8	and	Pencycuron	D1	25	8	and	Penthiopyrad
D1-10	8	and	Simeconazole	D1	26	8	and	Famoxadone
D1-11	8	and	Orysastrobin	D1	27	8	and	Cymoxanil
D1-12	8	and	Trifloxystrobin	D1	28	8	and	Proquinazid
D1-13	8	and	Isoprothiolane	D1	29	8	and	Flusilazole
D1-14	8	and	Azoxystrobin	D1	30	8	and	Mancozeb
D1-15	8	and	Tricyclazole	D1	31	8	and	Copper hydroxide
D1-16	8	and	Hexaconazole	D1	32	8	and	(a)

(a) 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-

3-(trifluoromethyl)-1F/-pyrazol-1-yl]ethanone

Table D2

Table D2 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 14. For example, the first mixture in Table D2 is designated D2-1 and is a mixture of compound 14 and the additional fungicide probenazole.

Table D3

Table D3 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 16. For example, the first mixture in Table D3 is designated D3-1 and is a mixture of compound 16 and the additional fungicide probenazole.

Table D4

Table D4 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 19. For example, the first mixture in Table D4 is designated D4-1 and is a mixture of compound 19 and the additional fungicide probenazole.

172

Table D5

Table D5 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 41. For example, the first mixture in Table D5 is designated D5-1 and is a mixture of compound 41 and the additional fungicide probenazole.

Table D6

Table D6 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 42. For example, the first mixture in Table D6 is designated D6-1 and is a mixture of compound 42 and the additional fungicide probenazole.

Table D7

Table D7 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 51. For example, the first mixture in Table D7 is designated D7-1 and is a mixture of compound 51 and the additional fungicide probenazole.

Table D8

Table D8 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 54. For example, the first mixture in Table D8 is designated D8-1 and is a mixture of compound 54 and the additional fungicide probenazole.

Table D9

Table D9 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 55. For example, the first mixture in Table D9 is designated D9-1 and is a mixture of compound 55 and the additional fungicide probenazole.

Table D10

Table D10 is identical to Table D1, except that each reference to compound 8 in the column headed “Cmpd. No.” is replaced by a reference to compound 76. For example, the first mixture in Table D10 is designated D10-1 and is a mixture of compound 76 and the additional fungicide probenazole.

173

Invertebrate pests are controlled in agronomie and nonagronomic applications by applying one or more compounds of this invention, typically in the form of a composition, in a biologically effective amount, to the environment of the pests, including the agronomie and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.

Thus the présent invention comprises a method for controlling an invertebrate pest in agronomie and/or nonagronomic applications, comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the compounds of the invention, or with a composition comprising at least one such compound or a composition comprising at least one such compound and a biologically effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a compound of the invention and a biologically effective amount of at least one additional biologically active compound or agent include granular compositions wherein the additional active compound is présent on the same granule as the compound of the invention or on granules separate from those of the compound of the invention.

To achieve contact with a compound or composition of the invention to protect a field crop from invertebrate pests, the compound or composition is typically applied to the seed of the crop before planting, to the foliage (e.g., leaves, stems, flowers, fruits) of crop plants, or to the soil or other growth medium before or after the crop is planted.

One embodiment of a method of contact is by spraying. Alternatively, a granular composition comprising a compound of the invention can be applied to the plant foliage or the soil. Compounds of this invention can also be effectively delivered through plant uptake by contacting the plant with a composition comprising a compound of this invention applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants. Of note is a composition of the présent invention in the form of a soil drench liquid formulation. Also of note is a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of the présent invention or with a composition comprising a biologically effective amount of a compound of the présent invention. Of further note is this method wherein the environment is soil and the composition is applied to the soil as a soil drench formulation. Of further note is that compounds of this invention are also effective by localized application to the locus of infestation. Other methods of contact include application of a compound or a composition of the invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear tags, boluses, foggers, fumigants, aérosols,

174 dusts and many others. One embodiment of a method of contact is a dimensionally stable fertilizer granule, stick or tablet comprising a compound or composition of the invention. The compounds of this invention can also be impregnated into materials for fabricating invertebrate control devices (e.g., insect netting).

Compounds of the invention are useful in treating ail plants, plant parts and seeds. Plant and seed varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which a heterologous gene (transgene) has been stably integrated into the plant's or seed's genome. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.

Genetically modified plant and seed cultivars which can be treated according to the invention include those that are résistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold température, soil salinity, etc.), or that contain other désirable characteristics. Plants and seeds can be genetically modified to exhibit traits of, for example, herbicide tolérance, insect-resistance, modified oil profiles or drought tolérance. Useful genetically modified plants and seeds containing single gene transformation events or combinations of transformation events are listed in Table Z. Additional information for the genetic modifications listed in Table Z can be obtained from the following databases:

http://www2.oecd.org/biotech/byidentifier.aspx http://www.aphis.usda.gohttp://gmoinfo.jrc.ec.europa.eu

The following abbreviations are used in Table Z which follows: toi. is tolérance, res. is résistance, SU is sulfonylurea, ALS is acetolactate synthase, HPPD is 4-Hydroxyphenylpyruvate Dioxygenase, NA is Not Available?

Table Z

Crop	Event Name	Event Code	T rait(s)	Gene(s)
Alfalfa	J101	MON-00101-	Glyphosate toi.	cp4 epsps
		8		(aroA:CP4)
Alfalfa	J163	MON-	Glyphosate toi.	cp4 epsps
		00163-7		(aroA:CP4)
Canola*	23-18-17 (Event	CGN-89465-	High lauric acid oil	te

175

Canola*	18) 23-198 (Event 23)	2 CGN-89465- 2	High lauric acid oil	te
Canola*	61061	DP-061061- 7	Glyphosate toi.	gat4621
Canola*	73496	l DP-073496- Λ	Glyphosate toi.	gat4621
Canola*	GT200 (RT200)	H- MON-89249- 2	Glyphosate toi.	cp4 epsps (aroA:CP4); goxv247
Canola*	GT73 (RT73)	MON- 00073-7	Glyphosate toi.	cp4 epsps (aroA:CP4); goxv247
Canola*	HCN10 (Topas 19/2)	NA	Glufosinate toi.	bar
Canola*	HCN28 (T45)	ACS- BN008-2	Glufosinate toi.	pat(syn)
Canola*	HCN92 (Topas 19/2)	ACS- BN007-1	Glufosinate toi.	bar
Canola*	MON88302	MON- 88302-9	Glyphosate toi.	cp4 epsps (aroA:CP4)
Canola*	MPS961	NA	Phytate breakdown	phyA
Canola*	MPS962	NA	Phytate breakdown	phyA
Canola*	MPS963	NA	Phytate breakdown	phyA
Canola*	MPS964	NA	Phytate breakdown	phyA
Canola*	MPS965	NA	Phytate breakdown	phyA
Canola*	MS1 (B91-4)	ACS- BN004-7	Glufosinate toi.	bar
Canola*	MS8	ACS- BN005-8	Glufosinate toi.	bar
Canola*	OXY-235	ACS- BN011-5	Oxynil toi.	bxn
Canola*	PHY14	NA	Glufosinate toi.	bar

176

Canola*	PHY23	NA	Glufosinate toi.	bar
Canola*	PHY35	NA	Glufosinate toi.	bar
Canola*	PHY36	NA	Glufosinate toi.	bar
Canola*	RF1 (B93-101)	ACS- BN001-4	Glufosinate toi.	bar
Canola*	RF2 (B94-2)	ACS- BN002-5	Glufosinate toi.	bar
Canola*	RF3	ACS- BN003-6	Glufosinate toi.	bar
Bean	EMBRAPA5.1	EMB-PV051- 1	Disease res.	ac1 (sense and antisense)
Brinjal (Eggplant)	EE-1		Insect res.	crylAc
Carnation	11 (7442)	FLO-07442- 4	SU toi..; modified flower color	surB; dfr; hfl (f3'5'h)
Carnation	11363 (1363A)	FLO-11363- 1	SU toi.; modified flower color	surB; dfr; bp40 (f3'5'h)
Carnation	1226A (11226)	FLO-11226- 8	SU toi.; modified flower color	surB; dfr; bp40 (f3'5'h)
Carnation	123.2.2 (40619)	FLO-40619- 7	SU toi.; modified flower color	surB; dfr; hfl (f3'5’h)
Carnation	123.2.38 (40644)	FLO-40644- 4	SU toi.; modified flower color	surB; dfr; hfl (f3'5’h)
Carnation	123.8.12	FLO-40689- 6	SU toi.; modified flower color	surB; dfr; bp40 (f3'5'h)
Carnation	123.8.8 (40685)	FLO-40685- 1	SU toi.; modified flower color	surB; dfr; bp40 (f3'5'h)
Carnation	1351A (11351)	FLO-11351- 7	SU toi.; modified flower color	surB; dfr; bp40 (f3'5'h)
Carnation	1400A (11400)	FLO-11400- 2	SU toi.; modified flower color	surB; dfr; bp40 (f3'5'h)
Carnation	15	FLO- 00015-2	SU toi.; modified flower color	surB; dfr; hfl (f3'5'h)

177

Carnation	16	FLO- 00016-3	SU toi.; modified flower color	surB; dfr; hfl (f3'5'h)
Carnation	4	FLO- 00004-9	SU toi.; modified flower color	surB; dfr; hfl (f3'5'h)
Carnation	66	FLO- 00066-8	SU toi.; delayed senescence	surB; acc
Carnation	959A(11959)	FLO-11959- 3	SU toi.; modified flower color	surB; dfr; bp40 (f3'5'h)
Carnation	988A (11988)	FLO-11988- 7	SU toi.; modified flower color	surB; dfr; bp40 (f3'5'h)
Carnation	26407	IFD-26497-2	SU toi.; modified flower color	surB; dfr; bp40 (f3'5'h)
Carnation	25958	IFD-25958-3	SU toi.; modified flower color	surB; dfr; bp40 (f3'5'h)
Chicory	RM3-3	NA	Glufosinate toi.	bar
Chicory	RM3-4	NA	Glufosinate toi.	bar
Chicory	RM3-6	NA	Glufosinate toi.	bar
Cotton	19-51 a	DD-01951A- 7	ALS herbicide toi.	S4-HrA
Cotton	281-24-236	l DAS-24236- 5	Glufosinate toi.; insect res.	pat (syn); cry1 F
Cotton	3006-210-23	DAS-21023- 5	Glufosinate toi.; insect res.	pat (syn); crylAc
Cotton	31707	NA	Oxynil toi.; insect res.	bxn; crylAc
Cotton	31803	NA	Oxynil toi.; insect res.	bxn; crylAc
Cotton	31807	NA	Oxynil toi.; insect res.	bxn; crylAc
Cotton	31808	NA	Oxynil toi.; insect res.	bxn; crylAc
Cotton	42317	NA	Oxynil toi.; insect res.	bxn; crylAc
Cotton	BNLA-601	NA	Insect res.	crylAc
Cotton	BXN10211	BXN 10211-9	Oxynil toi.	bxn; crylAc
Cotton	BXN10215	BXN10215-4	Oxynil toi.	bxn; crylAc
Cotton	BXN10222	BXN 10222-2	Oxynil toi.	bxn; crylAc
Cotton	BXN10224	BXN10224-4	Oxynil toi.	bxn; crylAc

178

Cotton	COT102	SYN-IR102- 7 SYN-IR67B- 1	Insect res.	vip3A(a)
Cotton	COT67B	Insect res.	crylAb
Cotton	COT202	Insect res.	vip3A
Cotton	Event 1	NA	Insect res.	crylAc
Cotton	GMFCrylA	GTL-	Insect res.	cry1Ab-Ac
		GMF311-7
Cotton	GHB119	BCS-GH005- 8 BCS-GH002- ς	Insect res.	cry2Ae
Cotton	GHB614	Glyphosate toi.	2mepsps
Cotton	GK12	□ NA	Insect res.	cry1Ab-Ac
Cotton	LLCotton25	ACS-GH001- Q	Glufosinate toi.	bar
Cotton	MLS9124	O NA	Insect res.	cry1C
Cotton	MON1076	MON-89924- O	Insect res.	crylAc
Cotton	MON1445	Z MON-01445-	Glyphosate toi.	cp4 epsps
		2		(aroA:CP4)
Cotton	MON15985	MON-15985- 7	Insect res.	crylAc; cry2Ab2
Cotton	MON1698	l MON-89383-	Glyphosate toi.	cp4 epsps
		1		(aroA:CP4)
Cotton	MON531	MON-00531- O	Insect res.	crylAc
Cotton	MON757	Ό MON-00757- 7	Insect res.	crylAc
Cotton	MON88913	l MON-88913-	Glyphosate toi.	cp4 epsps
		8		(aroA:CP4)
Cotton	Nqwe Chi 6 Bt	NA	Insect res.	NA?
Cotton	SKG321	NA	Insect res.	cry1A; CpTI
Cotton	T303-3	BCS-GH003-	Insect res.; glufosinate	crylAb; bar

179

		6	toi.
Cotton	T304-40	BCS-GH004-	Insect res.; glufosinate	crylAb; bar
		7	toi.
Cotton	CE43-67B		Insect res.	crylAb
Cotton	CE46-02A		Insect res.	crylAb
Cotton	CE44-69D		Insect res.	crylAb
Cotton	1143-14A		Insect res.	crylAb
Cotton	1143-51B		Insect res.	crylAb
Cotton	T342-142		Insect res.	crylAb
Cotton	PV-GHGT07		Glyphosate toi.	cp4 epsps
	(1445)			(aroA:CP4)
Cotton	EE-GH3		Glyphosate toi.	mepsps
Cotton	EE-GH5		Insect res.	crylAb
Cotton	MON88701	MON-88701-	Dicamba & glufosinate	Modified dmo; bar
		3	toi.
Cotton	OsCrl 1		Anti-allergy	Modified Cryj
Creeping	ASR368	SMG-	Glyphosate toi.	cp4 epsps
Bentgrass		36800-2		(aroA:CP4)
Eucalyptus	20-C		Sait toi.	codA
Eucalyptus	12-5C		Sait toi.	codA
Eucalyptus	12-5B		Sait toi.	codA
Eucalyptus	107-1		Sait toi.	codA
Eucalyptus	1/9/2001		Sait toi.	codA
Eucalyptus	2/1/2001		Sait toi.	codA
Eucalyptus			Cold toi.	des9
Flax	FP967	CDC-FL001- o	ALS herbicide toi.	als
Lentil	RH44	Z	Imidazolinone toi.	als
Maize	3272	SYN-E3272-	Modified alpha-amylase	amy797E
Maize	5307	□ SYN-05307- 1 DAS-59122-	Insect res.	ecry3.1Ab
Maize	59122	Insect res.; glufosinate	cry34Ab1;

180

		7
Maize	676	PH-000676- 7
Maize	678	PH-000678- 9
Maize	680	PH-000680- 2
Maize	98140	DP-098140- 6
Maize	Bt10	NA
Maize	Bt176 (176)	SYN-EV176- 9
Maize	BVLA430101	NA
Maize	CBH-351	ACS-ZM004- 3
Maize	DAS40278-9	DAS40278-9
Maize	DBT418	DKB-89614- 9
Maize	DLL25(B16)	DKB-89790- 5
Maize	GA21	MON-00021- 9
Maize	GG25
Maize	GJ11
Maize	FI117
Maize	GAT-ZM1
Maize	LY038	REN-00038- 3
Maize	MIR162	SYN-IR162- 4
Maize	MIR604	SYN-IR604- 5

toi.	cry35Ab1; pat
Glufosinate toi.;	pat; dam
pollination control
Glufosinate toi.;	pat; dam
pollination control
Glufosinate toi.;	pat; dam
pollination control
Glyphosate toll; ALS	gat4621; zm-hra
herbicide toi.
Insect res.; glufosinate	crylAb; pat
toi.
Insect res.; glufosinate	crylAb; bar
toi.
Phytate breakdown	phyA2
Insect res.; glufosinate	cry9C; bar
toi.
2,4-D toi.	aad-1
Insect res.; glufosinate	crylAc; pinll; bar
toi.
Glufosinate toi.	bar
Glyphosate toi.	mepsps
Glyphosate toi.	mepsps
Glyphosate toi.	mepsps
Glyphosate toi.	mepsps
Glufosinate toi.	pat
Increased lysine	cordapA
Insect res.	vip3Aa20
Insect res.	mcry3A

181

Maize	MON801 (MON80100)	MON801	Insect res.; glyphosate toi.
Maize	MON802	MON-80200-	Insect res.; glyphosate
		7	toi.
Maize	MON809	PH-MON-	Insect res.; glyphosate
		809-2	toi.
Maize	MON810	MON-00810-	Insect res.; glyphosate
		6	toi.
Maize	MON832	NA	Glyphosate toi.
Maize	MON863	MON-00863-	Insect res.
		5
Maize	MON87427	MON-87427-	Glyphosate toi.
		7
Maize	MON87460	MON-87460-	Drought toi.
		4
Maize	MON88017	MON-88017-	Insect res.; glyphosate
		3	toi.
Maize	MON89034	MON-89034-	Insect res.
		3
Maize	MS3	ACS-ZM001-	Glufosinate toi.;
		9	pollination control
Maize	MS6	ACS-ZM005-	Glufosinate toi.;
		4	pollination control
Maize	NK603	MON-00603-	Glyphosate toi.
		6
Maize	T14	ACS-ZM002- 1	Glufosinate toi.

crylAb; cp4 epsps (aroA:CP4);

goxv247 crylAb; cp4 epsps (aroA:CP4);

goxv247 cp4 epsps (aroA:CP4);

goxv247 cry3Bb1 cp4 epsps (aroA:CP4) cspB cry3Bb1 ; cp4 epsps (aroA:CP4) cry2Ab2; cry1A.1O5 bar; barnase bar; barnase cp4 epsps (aroA:CP4) pat(syn)

182

Maize	T25	ACS-ZM003-	Glufosinate toi.	pat(syn)
Maize	TC1507	Z DAS-01507- 1	Insect res.; glufosinate toi.	cry1 Fa2; pat
Maize	TC6275	DAS-06275- 8	Insect res.; glufosinate toi.	mocrylF; bar
Maize	VIP1034		Insect res.; glufosinate toi.	vip3A; pat
Maize	43A47	DP-043A47- 3	Insect res.; glufosinate toi.	cry1F; cry34Ab1; cry35Ab1; pat
Maize	40416	DP-040416- 8	Insect res.; glufosinate toi.	cry1F; cry34Ab1; cry35Ab1; pat
Maize	32316	DP-032316- 8	Insect res.; glufosinate toi.	cry1F; cry34Ab1; cry35Ab1 ; pat
Maize	4114	DP-004114- 3	Insect res.; glufosinate toi.	cry1F; cry34Ab1; cry35Ab1; pat
Melon	Melon A	NA	Delayed ripening/senescence	sam-k
Melon	Melon B	NA	Delayed ripening/senescence	sam-k
Papaya	55-1	CUH-CP551- 8 CUH-CP631- 7 NA	Disease res.	prsv cp
Papaya	63-1	Disease res.	prsv cp
Papaya	Huanong No. 1	Disease res.	prsv rep
Papaya	X17-2	UFL-X17CP- c	Disease res.	prsv cp
Pétunia	Petunia-CHS	Ό NA	Modified product quality	CHS suppres.sion
Plum	C-5	ARS- PLMC5-6	Disease res.	ppv cp
Canola**	ZSR500	NA	Glyphosate toi.	cp4 epsps (aroA:CP4); goxv247

183

Canola**	ZSR502	NA
Canola**	ZSR503	NA
Poplar	Bt poplar	NA
Poplar	Hybrid poplar clone 741	NA
Poplar	trg300-1
Poplar	trg300-2
Potato	1210 amk	NA
Potato	2904/1 kgs	NA
Canola**	ZSR500	NA
Canola**	ZSR502	NA
Potato	ATBT04-27	NMK-89367- 8
Potato	ATBT04-30	NMK-89613- 2
Potato	ATBT04-31	NMK-89170- 9
Potato	ATBT04-36	NMK-89279- 1
Potato	ATBT04-6	NMK-89761- 6
Potato	BT06	NMK-89812- 3
Potato	BT10	NMK-89175- 5

Glyphosate toi. Glyphosate toi. Insect res. Insect res.	cp4 epsps (aroA:CP4); goxv247 cp4 epsps (aroA:CP4); goxv247 crylAc; API crylAc; API
High cellulose	AaXEG2
High cellulose	AaXEG2
Insect res.	cry3A
Insect res.	cry3A
Glyphosate toi.	cp4 epsps (aroA:CP4); goxv247
Glyphosate toi.	cp4 epsps (aroA:CP4); goxv247
Insect res.	cry3A
Insect res.	cry3A
Insect res.	cry3A
Insect res.	cry3A
Insect res.	cry3A
Insect res.	cry3A
Insect res.	cry3A

184

Potato	BT12	NMK-89601- 8 NMK-89167- β	Insect res.	cry3A
Potato	BT16	Insect res.	cry3A
Potato	BT17	□ NMK-89593-	Insect res.	cry3A
Potato	BT18	y NMK-89906- 7	Insect res.	cry3A
Potato	BT23	l NMK-89675- 1 BPS-25271- 9	Insect res.	cry3A
Potato	EH92-527-1	Modified starch/carbohydrate	gbss (antisense)
Potato	HLMT15-15	NA	Insect & disease res.	cry3A; pvy cp
Potato	HLMT15-3	NA	Insect & disease res.	cry3A; pvy cp
Potato	HLMT15-46	NA	Insect & disease res.	cry3A; pvy cp
Potato	RBMT15-101	NMK-89653- β	Insect & disease res.	cry3A; pvy cp
Potato	RBMT21-129	Ό NMK-89684- 1	Insect & disease res.	cry3A; plrv orf1 ; plrv orf2
Potato	RBMT21-152	NA	Insect & disease res.	cry3A; plrv orf1 ; plrv orf2
Potato	RBMT21-350	NMK-89185- 6	Insect & disease res.	cry3A; plrv orf1 ; plrv orf2
Potato	RBMT22-082	NMK-89896- 6	Insect & disease res.; Glyphosate toi.	cry3A; plrv orf1 ; plrv orf2; cp4 epsps (aroA:CP4)
Potato	RBMT22-186	NA	Insect & disease res.; Glyphosate toi.	cry3A; plrv orf1 ; plrv orf2; cp4 epsps (aroA:CP4)
Potato	RBMT22-238	NA	Insect & disease res.; Glyphosate toi.	cry3A; plrv orf1 ; plrv orf2; cp4 epsps (aroA:CP4)
Potato	RBMT22-262	NA	Insect & disease res.;	cry3A; plrv orf1 ;

185

Potato	SEMT15-02	NMK-89935-	Glyphosate toi. Insect & disease res.	plrv orf2; cp4 epsps (aroA:CP4) cry3A; pvy cp
Potato	SEMT15-07	y NA	Insect & disease res.	cry3A; pvy cp
Potato	SEMT15-15	NMK-89930- A	Insect & disease res.	cry3A; pvy cp
Potato	SPBT02-5	q. NMK-89576- 1 NMK-89724- C	Insect res.	cry3A
Potato	SPBT02-7	Insect res.	cry3A
Rice	7Crp#242-95-7	□	Anti-allergy	7crp
Rice	7Crp#10	NA	Anti-allergy	7crp
Rice	GM Shanyou 63	NA	Insect res.	crylAb; crylAc
Rice	Huahui-1/TT51-1	NA	Insect res.	crylAb; crylAc
Rice	LLRICE06	ACS-OS001- A	Glufosinate toi.	bar
Rice	LLRICE601	BCS-OS003- 7 ACS-OS002- C	Glufosinate toi.	bar
Rice	LLRICE62	Glufosinate toi.	bar
Rice	Tarom molaii + crylAb	0 NA	Insect res.	crylAb (truncated)
Rice	GAT-OS2		Glufosinate toi.	bar
Rice	GAT-0S3		Glufosinate toi.	bar
Rice	PE-7		Insect res.	CrylAc
Rice	7Crp#10	NA	Anti-allergy	7crp
Rice	KPD627-8		High tryptophan	0ASA1D
Rice	KPD722-4		High tryptophan	0ASA1D
Rice	KA317		High tryptophan	0ASA1D
Rice	HW5		High tryptophan	0ASA1D
Rice	HW1		High tryptophan	0ASA1D
Rice	B-4-1-18		Erect leaves semidwarf	Δ OsBRH

186

Ri ce	G-3-3-22		Semidwarf	OSGA2ox1
Ri ce	AD77		Disease res.	DEF
Ri ce	AD51		Disease res.	DEF
Ri ce	AD48		Disease res.	DEF
Ri ce	AD41		Disease res.	DEF
Rice	13pNasNaatAprt1		Low iron toi.	HvNASI; HvNAAT- A; APRT
Ri ce	13pAprt1		Low iron toi.	APRT
Rice	gHvNASIgHvNAAT-1		Low iron toi.	HvNASI; HvNAAT- A; HvNAAT-B
Rice	gHvlDS3-1		Low iron toi.	HvlDS3
Rice	gHvNAATI		Low iron toi.	HvNAAT-A; HvNAAT-B
Rice	gHvNAS1-1		Low iron toi.	HvNASI
Rice	NIA-OS006-4		Disease res.	WRKY45
Rice	NIA-OS005-3		Disease res.	WRKY45
Rice	NIA-OS004-2		Disease res.	WRKY45
Rice	NIA-OS003-1		Disease res.	WRKY45
Rice	NIA-OS002-9		Disease res.	WRKY45
Rice	NIA-OS001-8		Disease res.	WRKY45
Rice	OsCrl 1		Anti-allergy	Modified Cryj
Rice	17053		Glyphosate toi.	cp4 epsps (aroA:CP4)
Rice	17314		Glyphosate toi.	cp4 epsps (aroA:CP4)
Rose	WKS82/130-4-1	IFD-52401-4	Modified flower color	5AT; bp40 (f3'5'h)
Rose	WKS92 /130-9-1	IFD-52901-9	Modified flower color	5AT; bp40 (f3'5'h)
Soybean	260-05 (G94-1, G94-19, G168)	NA	Modified oil/fatty acid	gm-fad2-1 (silencing locus)
Soybean	A2704-12	ACS- GM005-3	Glufosinate toi.	pat
Soybean	A2704-21	ACS- GM004-2	Glufosinate toi.	pat

187

Soybean	A5547-127	ACS- GM006-4	Glufosinate toi.	pat
Soybean	A5547-35	ACS- GM008-6	Glufosinate toi.	pat
Soybean	CV127	BPS-CV127-	Imidazolinone toi.	csr1-2
Soybean	DAS68416-4	y DAS68416-4	Glufosinate toi.	pat
Soybean	DP305423	DP-305423- 1	Modified oil/fatty acid; ALS herbicide toi.	gm-fad2-1 (silencing locus); gm-hra
Soybean	DP356043	DP-356043- 5	Modified oil/fatty acid; glyphosate toi.	gm-fad2-1 (silencing locus); gat4601
Soybean	FG72	MST-FG072- 3	Glyphosate & HPPD toi.	2mepsps; hppdPF W336
Soybean	GTS 40-3-2 (40- 3-2)	MON-04032- 6	Glyphosate toi.	cp4 epsps (aroA:CP4)
Soybean	GU262	ACS- GM003-1	Glufosinate toi.	pat
Soybean	MON87701	MON-87701-	Insect res.	crylAc
Soybean	MON87705	Z MON-87705- 6	Modified oil/fatty acid; glyphosate toi.	fatb1-A (sense & antisense); fad2-1A (sense & antisense); cp4 epsps (aroA:CP4)
Soybean	MON87708	MON-87708- 9	Dicamba & glyphosate toi.	dmo; cp4 epsps (aroA:CP4)
Soybean	MON87769	MON-87769- 7	Modified oil/fatty acid; glyphosate toi.	Pj.D6D; Nc.Fad3; cp4 epsps (aroA:CP4)
Soybean	MON89788	MON-89788- 1	Glyphosate toi.	cp4 epsps (aroA:CP4)

188

Soybean	W62	ACS- GM002-9	Glufosinate toi.	bar
Soybean	W98	ACS- GM001-8	Glufosinate toi.	bar
Soybean	MON87754	MON-87754- 1 DAS-21606	High oil	dgat2A
Soybean	DAS21606	Aryloxyalkanoate & glufosinate toi.	Modified aad-12; pat
Soybean	DAS44406	DAS-44406- 6	Aryloxyalkanoate, glyphosate & glufosinate toi.	Modified aad-12; 2mepsps; pat
Soybean	SYHT04R	SYN-0004R- 8	Mesotrione toi.	Modified avhppd
Soybean	9582.814.19.1	Insect res. & glufosinate toi.	crylAc, cry1F, PAT
Squash	CZW3	SEM- 0CZW3-2	Disease res.	cmv cp, zymv cp, wmv cp
Squash	ZW20	SEM- 0ZW20-7	Disease res.	zymv cp, wmv cp
Sugar	GTSB77	SY-GTSB77-	Glyphosate toi.	cp4 epsps
Beet	(T9100152)	8		(aroA:CP4); goxv247
Sugar Beet	H7-1	KM-000H71- 4	Glyphosate toi.	cp4 epsps (aroA:CP4)
Sugar Beet	T120-7	ACS-BV001- 3	Glufosinate toi.	pat
Sugar Beet	T227-1		Glyphosate toi.	cp4 epsps (aroA:CP4)
Sugarcane	NXI-1T		Drought toi.	EcbetA
Sunflower	X81359		Imidazolinone toi.	als
Sweet Pepper	PK-SP01	NA	Disease res.	cmv cp

189

Tobacco	C/F/93/08-02	NA	Oxynil toi.	bxn
Tobacco	Vector 21-41	NA	Reduced nicotine	NtQPTI (antisense)
Tomato	1345-4	NA	Delayed ripening/senescense	acc (truncated)
Tomato	35-1-N	NA	Delayed ripening/senescense	sam-k
Tomato	5345	NA	Insect res.	crylAc
Tomato	8338	CGN-89322- 3	Delayed ripening/senescense	accd
Tomato	B	SYN-0000B- 6	Delayed ripening/senescense	pg (sense or antisense)
Tomato	Da	SYN- 0000DA-9	Delayed ripening/senescense	pg (sense or antisense)
Sunflower	X81359		Imidazolinone toi.	als
Tomato	Da Dong No 9	NA	Modified product	NA
Tomato	F (1401F, h38F,	SYN-0000F-	Delayed	pg (sense or
	11013F,7913F)	1	ripening/senescense	antisense)
Tomato	FLAVR SAVR™	CGN-89564- 2	Delayed ripening/senescense	pg (sense or antisense)
Tomato	Huafan No 1	NA	Delayed ripening/senescense	anti-efe
Tomato	PK-TM8805R (8805R)	NA	Disease res.	cmv cp
Wheat	MON71800	MON- 71800-3	Glyphosate toi.	cp4 epsps (aroA:CP4)

* Argentine, ** Polish, # Eggplant

Treatment of genetically modified plants and seeds with compounds of the invention may resuit in super-additive or synergistic effects. For example, réduction in application rates, broadening of the activity spectrum, increased tolérance to biotic/abiotic stresses or enhanced

190 storage stability may be greater than expected from just simple additive effects of the application of compounds of the invention on genetically modified plants and seeds.

Compounds of this invention are also useful in seed treatments for protecting seeds from invertebrate pests. In the context of the présent disclosure and claims, treating a seed means contacting the seed with a biologically effective amount of a compound of this invention, which is typically formulated as a composition of the invention. This seed treatment protects the seed from invertebrate soil pests and generally can also protect roots and other plant parts in contact with the soil of the seedling developing from the germinating seed. The seed treatment may also provide protection of foliage by translocation of the compound of this invention or a second active ingrédient within the developing plant. Seed treatments can be applied to ail types of seeds, including those from which plants genetically transformed to express specialized traits will germinate. Représentative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin or those expressing herbicide résistance such as glyphosate acetyltransferase, which provides résistance to glyphosate. Seed treatments with compounds of this invention can also increase vigor of plants growing from the seed.

One method of seed treatment is by spraying or dusting the seed with a compound of the invention (i.e. as a formulated composition) before sowing the seeds. Compositions formulated for seed treatment generally comprise a film former or adhesive agent. Therefore typically a seed coating composition of the présent invention comprises a biologically effective amount of a compound of Formula 1, an A/-oxide or sait thereof, and a film former or adhesive agent. Seed can be coated by spraying a flowable suspension concentrate directly into a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wetted powders, solutions, suspoemulsions, emulsifiable concentrâtes and émulsions in water can be sprayed on the seed. This process is particularly useful for applying film coatings on seeds. Various coating machines and processes are available to one skilled in the art. Suitable processes include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994 BCPC Mongraph No. 57, and references listed therein.

Compounds of Formula 1 and their compositions, both alone and in combination with other insecticides, nematicides, and fungicides, are particularly useful in seed treatment for crops including, but not limited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats, barley, rye and rice), potatoes, vegetables and oilseed râpe.

Other insecticides with which compounds of Formula 1 can be formulated to provide mixtures useful in seed treatment include abamectin, acetamiprid, acrinathrin, amitraz,

191 avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alphacypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate, formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillus thuringiensis delta-endotoxins, ail strains of Bacillus thuringiensis and ail strains of nucleo polyhedrosis viruses.

Fungicides with which compounds of Formula 1 can be formulated to provide mixtures useful in seed treatment include amisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, fluazinam, fludioxonil, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam, metconazole, myclobutanil, paclobutrazole, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole, thiophanate-methyl, thiram, trifloxystrobin and triticonazole.

Compositions comprising compounds of Formula 1 useful for seed treatment can further comprise bacteria and fungi that hâve the ability to provide protection from the harmful effects of plant pathogenic fungi or bacteria and/or soil born animais such as nematodes. Bacteria exhibiting nematicidal properties may include but are not limited to Bacillus firmus, Bacillus cereus, Bacillius subtiliis and Pasteuria penetrans. A suitable Bacillus firmus strain is strain CNCM 1-1582 (GB-126) which is commercially available as BioNemTM. a suitable Bacillus cereus strain is strain NCMM 1-1592. Both Bacillus strains are disclosed in US 6,406,690. Other suitable bacteria exhibiting nematicidal activity are B. amyloliquefaciens IN937a and B. subtilis strain GB03. Bacteria exhibiting fungicidal properties may include but are not limited to B. pumilus strain GB34. Fungal species exhibiting nematicidal properties may include but are not limited to Myrothecium verrucaria, Paecilomyces lilacinus and Purpureocillium lilacinum.

Seed treatments can also include one or more nematicidal agents of natural origin such as the elicitor protein called harpin which is isolated from certain bacterial plant pathogens such

192 as Erwinia amylovora. An example is the Harpin-N-Tek seed treatment technology available as N-Hibit™ Gold CST.

Seed treatments can also include one or more species of legume-root nodulating bacteria such as the microsymbiotic nitrogen-fixing bacteria Bradyrhizobium Japonicum. These inocculants can optionally include one or more lipo-chitooligosaccharides (LCOs), which are nodulation (Nod) factors produced by rhizobia bacteria during the initiation of nodule formation on the roots of legumes. For example, the Optimize® brand seed treatment technology incorporâtes LCO PromoterTechnologyTM jn combination with an inocculant.

Seed treatments can also include one or more isoflavones which can increase the level of root colonization by mycorrhizal fungi. Mycorrhizal fungi improve plant growth by enhancing the root uptake of nutrients such as water, sulfates, nitrates, phosphates and metals. Examples of isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperetin, naringenin and pratensein. Formononetin is available as an active ingrédient in mycorrhizal inocculant products such as PHC Colonize® AG.

Seed treatments can also include one or more plant activators that induce systemic acquired résistance in plants following contact by a pathogen. An example of a plant activator which induces such protective mechanisms is acibenzolar-S-methyl.

The treated seed typically comprises a compound of the présent invention in an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. from about 0.0001 to 1% by weight of the seed before treatment). A flowable suspension formulated for seed treatment typically comprises from about 0.5 to about 70% of the active ingrédient, from about 0.5 to about 30% of a filmforming adhesive, from about 0.5 to about 20% of a dispersing agent, from 0 to about 5% of a thickener, from 0 to about 5% of a pigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0 to about 1 % of a preservative, and from 0 to about 75% of a volatile liquid diluent.

The compounds of this invention can be incorporated into a bait composition that is consumed by an invertebrate pest or used within a device such as a trap, bait station, and the like. Such a bait composition can be in the form of granules which comprise (a) active ingrédients, namely a biologically effective amount of a compound of Formula 1, an A/-oxide, or sait thereof; (b) one or more food materials; optionally (c) an attractant, and optionally (d) one or more humectants. Of note are granules or bait compositions which comprise between about 0.001-5% active ingrédients, about 40-99% food material and/or attractant; and optionally about 0.05-10% humectants, which are effective in controlling soil invertebrate pests at very low

193 application rates, particularly at doses of active ingrédient that are léthal by ingestion rather than by direct contact. Some food materials can function both as a food source and an attractant. Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids. Examples of attractants are odorants and flavorants, such as fruit or plant extracts, perfume, or other animal or plant component, pheromones or other agents known to attract a target invertebrate pest. Examples of humectants, i.e. moisture retaining agents, are glycols and other polyols, glycérine and sorbitol. Of note is a bait composition (and a method utilizing such a bait composition) used to control at least one invertebrate pest selected from the group consisting of ants, termites and cockroaches. A device for controlling an invertebrate pest can comprise the présent bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.

One embodiment of the présent invention relates to a method for controlling invertebrate pests, comprising diluting the pesticidal composition of the présent invention (a compound of Formula 1 formulated with surfactants, solid diluents and liquid diluents or a formulated mixture of a compound of Formula 1 and at least one other pesticide) with water, and optionally adding an adjuvant to form a diluted composition, and contacting the invertebrate pest or its environment with an effective amount of said diluted composition.

Although a spray composition formed by diluting with water a sufficient concentration of the présent pesticidal composition can provide sufficient efficacy for controlling invertebrate pests, separately formulated adjuvant products can also be added to spray tank mixtures. These additional adjuvants are commonly known as “spray adjuvants” or “tank-mix adjuvants”, and include any substance mixed in a spray tank to improve the performance of a pesticide or alter the physical properties of the spray mixture. Adjuvants can be surfactants, emulsifying agents, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners or defoaming agents. Adjuvants are used to enhancing efficacy (e.g., biological availability, adhesion, pénétration, uniformity of coverage and durability of protection), or minimizing or eliminating spray application problems associated with incompatibility, foaming, drift, évaporation, volatilization and dégradation. To obtain optimal performance, adjuvants are

194 selected with regard to the properties of the active ingrédient, formulation and target (e.g., crops, insect pests).

Among the spray adjuvants, oils including crop oils, crop oil concentrâtes, vegetable oil concentrâtes and methylated seed oil concentrâtes are most commonly used to improve the efficacy of pesticides, possibly by means of promoting more even and uniform spray deposits. In situations where phytotoxicity potentially caused by oils or other water-immiscible liquids are of concern, spray compositions prepared from the composition of the présent invention will generally not contain oil-based spray adjuvants. However, in situations where phytotoxicity caused by oil-based spray adjuvants is commercially insignificant, spray compositions prepared from the composition of the présent composition can also contain oil-based spray adjuvants, which can potentially further increase control of invertebrate pests, as well as rainfastness.

Products identified as “crop oil” typically contain 95 to 98% paraffin or naphtha-based petroleum oil and 1 to 2% of one or more surfactants functioning as emulsifiers. Products identified as “crop oil concentrâtes” typically consist of 80 to 85% of emulsifiable petroleumbased oil and 15 to 20% of nonionic surfactants. Products correctly identified as “vegetable oil concentrâtes” typically consist of 80 to 85% of vegetable oil (i.e. seed or fruit oil, most commonly from cotton, linseed, soybean or sunflower) and 15 to 20% of nonionic surfactants. Adjuvant performance can be improved by replacing the vegetable oil with methyl esters of fatty acids that are typically derived from vegetable oils. Examples of methylated seed oil concentrâtes include MSO® Concentrate (UAP-Loveland Products, Inc.) and Premium MSO Methylated Spray Oil (Helena Chemical Company).

The amount of adjuvants added to spray mixtures generally does not exceed about 2.5% by volume, and more typically the amount is from about 0.1 to about 1% by volume. The application rates of adjuvants added to spray mixtures are typically between about 1 to 5 L per hectare. Représentative examples of spray adjuvants include: Adigor® (Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons, Silwet® (Helena Chemical Company) polyalkyleneoxide modified heptamethyltrisiloxane and Assist® (BASF) 17% surfactant blend in 83% paraffin based minerai oil.

The compounds of this invention can be applied without other adjuvants, but most often application will be of a formulation comprising one or more active ingrédients with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. One method of application involves spraying a water dispersion or refined oil solution of a compound of the présent invention. Combinations with spray oils, spray

195 oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy. For nonagronomic uses such sprays can be applied from spray containers such as a can, a bottle or other container, either by means of a pump or by releasing it from a pressurized container, e.g., a pressurized aérosol spray can. Such spray compositions can take various forms, for example, sprays, mists, foams, fumes or fog. Such spray compositions thus can further comprise propellants, foaming agents, etc. as the case may be. Of note is a spray composition comprising a biologically effective amount of a compound or a composition of the présent invention and a carrier. One embodiment of such a spray composition comprises a biologically effective amount of a compound or a composition of the présent invention and a propellant. Représentative propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing. Of note is a spray composition (and a method utilizing such a spray composition dispensed from a spray container) used to control at least one invertebrate pest selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like, including individually or in combinations.

The following Tests demonstrate the control efficacy of compounds of this invention on spécifie pests. “Control efficacy” represents inhibition of invertebrate pest development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-N for compound descriptions. See Index Table O for ¹H NMR data.

The following abbreviations may be used in the Index Tables which follow: Cmpd means Compound, t is tertiary, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, /-Pr is isopropyl, Bu is butyl, c-Pr is cyclopropyl, c-Pn is cyclopentyl, c-Hx is cyclohexyl, f-Bu is fert/ary-butyl, Ph is phenyl, OMe is methoxy, SMe is methylthio, and SC^Me means methylsulfonyl. A wavy line or in a structure fragment dénotés the attachment point of the fragment to the remainder of the molécule. The abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared.

196

INDEX TABLE A

R

Cmpd. No.	R	£	x!		A	NMR/MS data
1	- C(O)(1 -pyrrolidinyl)	CH	CH	CH	CH	*
2	-C(O)NH(2-pyrimidinyl)	CH	CH	CH	CH	*
3	-C(O)(morpholino)	CH	CH	CH	CH	*
4	-C(O)NH(2-pyridinyl)	CH	CH	CH	CH	★
5	-C(O)NH(phenyl)	CH	CH	CH	CH	*
6	-C(O)NHCH(Me)C(O)NH(t-butyl)	CH	CH	CH	CH	★
7	C(O)NHCH(Me)C(O)NH(isopropy I)	CH	CH	CH	CH	*
8	-C(O)NH(isopropyl)	CH	CH	CH	CH	*
9	-C(O)NHCH₂(2-pyridinyl)	CH	CH	CH	CH	*
10	-C(O)NHCH₂CH(OMe)₂	CH	CH	CH	CH	*
11	-C(O)NHCH₂(2-thiazolyl)	CH	CH	CH	CH	*
12	-C(O)NHCH₂(tetrahydro-2- furanyl)	CH	CH	CH	CH	*
13	-C(O)NHCH₂CH₂SMe	CH	CH	CH	CH	*
14	-C(O)NH(cyclopropyl)	CH	CH	CH	CH	*
15	-C(O)NH(1-piperidinyl)	CH	CH	CH	CH	★
16	-C(O)NH(cyclohexyl)	CH	CH	CH	CH	*
17	3-(trifluoromethyl)-1 -pyrazolyl	CH	CH	CH	CH	*
18	2-pyrimidinyl	CH	CH	CH	CH	*
19	-C(O)NHCH₂CF₃	CH	CH	CH	CH	•k

197

20	6-(2-pyrimidinyl)pyridin-2-yl	CH	CH	CH	CH	*
21	-C(O)NHCH2(2-pyrimidinyl)	CH	CH	CH	CH	★
22	2-(2-pyridinyl)thiazol-4-yl	CH	CH	CH	CH	*
23	2-(2-thiazolyl)thiazol-4-yl	CH	CH	CH	CH	★
24	-C(O)NHCH₂CHF₂	CH	CH	CH	CH	*
129	-C(O)NHCH2(2-pyrimidinyl)	CH	N	CH	CF	*
130	-C(O)NH(isopropyl)	CH	N	CH	CF	★
300	-C(O)NHCH2(2-pyrimidinyl)	CH	CH	CH	CF	it
301	-C(O)NHCH₂CF₃	CH	CH	CH	N	it
302	-C(O)NHCH2(2-pyrimidinyl)	CH	CH	CH	N	*
303	1,2,4-oxadiazol-3-yl	CH	CH	CH	CH	*
304	5 - (t r if I uo rom ethyl )-2- py r i d i nyl	CH	CH	CH	CH	*
305	-C(O)NHCH₂(5-methyl-2- pyrazinyl)	CH	CH	CH	CH	*
306	-C(S)NH(cyclohexyl)	CH	CH	CH	CH	it
307	-C(O)NHCH₂CF₃	CH	CH	CH	CF	it
308	-C(O)NHCH₂(tetrahydro-2- furanyl)	CH	CH	CH	CF	it
309	-C(O)NH(isopropyl)	CH	CH	CH	CF	★
310	-C(O)NHCH₂(2-pyrimidinyl)	CH	N	CH	CH	it
311	-C(O)NH(cyclopropyl)	CH	N	CH	CH	it
312	-C(0)NHCH₂(tetrahydro-2- furanyl)	CH	N	CH	CH	★
313	-C(O)NHCH₂CH(OMe)₂	CH	N	CH	CH	*
314	-C(O)NHCH(Me)(cyclopropyl)	CH	N	CH	CH	*
315	2-thiomethoxy-4-pyrimidinyl	CH	CH	CH	CH	it
316	-C(S)NH(isopropyl)	CH	CH	CH	CH	it
500	-C(O)NH(isopropyl)	CF	CH	CH	CH	299
501	-C(O)NH(isopropyl)	CH	CH	CF	CH	299
502	—C(O)NHCH₂CH₂SMe	CH	CH	CF	CH	331

198

503	—C(O)NHCH₂CH₂SMe	CF	CH	CH	CH	331
504	-C(O)NHCH₂CH(OMe)₂	CH	CH	CH	CF	*

* See Index Table O for H NMR data.

INDEX TABLE B

X⁴ is CH

Cmpd. No.	R	A	NMR/MS data
25	-C(O)(1-pyrrolidinyl)	CH	*
26	-C(O)NH(2-pyrimidinyl)	CH	*
27	1-pyrazolyl	CH	*
28	-C(O)NH(2-pyridinyl)	CH	*
29	-C(O)NH(phenyl)	CH	*
30	-NHC(O)(phenyl)	CH	k
31	-NHC(O)(2-pyridinyl)	CH	k
32	-(R)-C(O)NHCH(Me)C(O)NH(t-butyl)	CH	•k
33	-C(O)NMe₂	CH	•k
34	-C(O)NHCH₂CF₃	CH	*
35	-C(O)NH(isopropyl)	CH	*
36	—C(O)(1-piperidinyl)	CH	*
37	-C(0)NH(cyclopropyl)	CH	*
38	-C(O)NHCH₂CH(-OCH₂CH₂O-)	CH	k
39	-C(O)NHCH₂CH(OMe)₂	CH	*
40	-C(O)NHCH₂(2-thiazolyl)	CH	*
41	-C(O) N H CH₂(tetrahyd ro-2-fu ra ny I )	CH	*
42	-C(O)NHNHCO₂Me	CH	★

199

43	-C(O)(4-methyl-1 -piperazinyl)	CH	k
44	-C(O)(morpholino)	CH	k
45	-C(O)NHOCH₂CH=CH₂	CH	*
46	—C(O)NHCH₂CH₂SEt	CH	*
47	-C(O)NHOCH₂(cyclopropyl)	CH	*
48	-C(O)NHS(O)₂(4-chlorophenyl)	CH	•k
49	-C(O)NHCH₂CN	CH	•k
50	-C(O)N(-CH₂CH(CF₃)CH₂CH₂CH₂-)	CH	k
51	-C(0)NHCH₂(2,2-difluorocyclopropyl)	CH	*
52	-C(O)NHCH₂CH₂CF₃	CH	*
53	-C(O)NHCH₂(cyclopropyl)	CH	*
54	-C(O)NHCH₂C(Me)F₂	CH	•k
55	-C(O)NHCH₂(2-pyrimidinyl)	CH	•k
56	-C(O)NHCH₂(6-bromo-2-pyridinyl)	CH	•k
57	-C(O)NHCH₂CH₂SMe	CH	•k
58	-C(O)N(CH₂CH₂SMe)(CH₂OEt)	CH	k
59	-C(O)NHCH₂CH₂CH₂(1-imidazolyl)	CH	k
60	-C(O)NHCH₂(2-furanyl)	CH	•k
61	-C(O)N(Et)(cyclohexyl)	CH	•k
62	-C(O)NH(3,3-difluorocyclobutyl)	CH	*
63	-C(0)NHCH(isopropyl)C0₂Me	CH	k
64	-C(O)N(Me)CH₂CF₃	CH	k
65	-C(O)NHCH₂(2-thienyl)	CH	•k
66	-C(O)N(CH₂CH₂CN)(CH₂(3-pyridinyl))	CH	k
67	-C(0)N(Me)(cyclopropyl)	CH	★
68	-C(O)NHCH(Me)CH₂OMe	CH	•k
69	-C(O)N(CH₂CCH)₂	CH	•k
70	-C(O)NHCH₂CH₂N(isopropyl)₂	CH	•k
71	-C(O)NHCH₂((3-trifluoromethoxy)phenyl)	CH	•k

200

72	-C(O)N(- CH2CH2N(C(O)(cyclopropyl))CH2CH2-)	CH	*
73	-C(O)NHCH2(2,2-dimethyl-1,3-dioxolan-4-yl)	CH	*
74	-C(O)N(-CH=NC(Me)₂CH₂-)	CH	*
75	-C(O)(thiomorpholino)	CH	*
76	-C(O)NHCH2(5-methyl-2-pyrazinyl)	CH	*
131	-C(O)NHCH2(tetrahydro-2-furanyl)	CF	*
132	-C(O)NHCH₂C(Me)F₂	CF	*
133	-C(O)NHCH₂CH(OMe)2	CF	*
134	0 M	CH	★
320	2-pyrimidinyl	CH	*
321	2-oxazolyl	CH	*
322	5-(3-pyridinyl)-1,2,4-oxadiazol-3-yl	CH	*
323	-C(O)NHCH2CH₂OH	CH	*
324	2-pyrazinyl	CH	*
325	3-pyridinyl	CH	*
326	2-thiomethoxy-4-pyrimidinyl	CH	*
327	6-chloro-2-(SCH2CO2Et)-4-pyrimidinyl	CH	*
328	-C(O)NHCH₂CO₂Me	CH	*
329	-C(0)N(Me)CH2(2,2-difluorocyclopropyl)	CH	343
330	-C(O)N(Me)CH₂CH(OMe)₂	CH	341
331	-C(O)NHCH₂CH₂OMe	CH	297
332	-C(O)NHCH₂CH₂OEt	CH	311
333	-C(O)NHCH₂CH₂O(isopropyl)	CH	325
334	-C(O)NHCH₂CH(Me)OMe	CH	311
335	-C(O)NHCH₂CH₂CH₂OMe	CH	311
336	-C(O)NH(3-methoxycyclobutyl)	CH	323

201

338	-C(O)N(-CH₂CH₂CH₂-)	CH	279
339	-C(O)NHCH₂CH₂N(Me)₂	CH	310
340	1,3,4-oxadiazol-2-yl	CH	•k
341	2-(SCK₂CO₂Et)-4-pyrimidinyl	CH	*
342	-C(O)NHNHCO₂(t-butyl)	CH	•k
343	-C(O)NHCH₂CHF₂	CH	303
344	-C(O)NHCH₂CH₂F	CH	285
345	-C(O)N(Me)Et	CH	281
346	-C(O)N(Me)Pr	CH	295
347	-C(0)NHCH₂(tetrahydro-2-furanyl)	CH	*
348	5-(trifluoromethyl)-2-pyridinyl	CH	•k
349	-C(S)NH₂	CH	*
350	-C(O)NHMe	CH	253
351	-C(O)NHEt	CH	267
352	-C(O)NHPr	CH	281
353	-C(O)N(-CH₂CH2CF₂CH2CH2-)	CH	343
354	-C(O)NHBu	CH	295
355	2-thiazolinyl	CH	•k
356	-NHC(O)(2-furanyl)	CH	*
357	-NHC(O)CH₂SPh	CH	*
358	-NHC(O)(cyclopropyl)	CH	*
359	-NHC(O)CH₂Ph	CH	k
360	-NHC(O)CH(Me)Et	CH	•k
361	-C(O)NHCH₂(5-pyrimidinyl)	CH	*
362	-NHC(O)CH₂CH(Me)₂	CH	•k
363	-C(O)NHNH(cyclohexyl)	CH	k
364	-C(O)NHCK₂(2-pyrimidinyl)	C(OMe)	•k
365	-C(O)NHCH(Me)CF₃	CF	*
366	-C(O)NHCH(Me)(cyclopropyl)	CF	k
367	-C(O)NHCH(CH₂OMe)₂	CF	k

202

368	-C(O)NHCH(isopropyl)CF₃	CF	*
369	-C(O)NHCH₂CO₂Et	CF	★
370	-C(O)NHCH(Me)CH₂OMe	CF	★
371	-C(O)NHCH₂CH₂S(t-butyl)	CH	*
372	-C(O)NHCH(Me)Et	CH	*
373	-C(O)NHNHC(O)(2-thienyl)	CH	*
374	-C(O)NHCH₂(5-pyrimidinyl)	CF	★
375	-C(O)NHNHCO₂Me	CF	k
376	-C(O)NHNHC(O)(t-butyl)	CH	*
377	-C(O)NHNHC(O)(2-furanyl)	CH	*
378	-C(O)NHNHC(O)phenyl	CH	k
379	-C(O)NHNHC(O)CF₃	CH	*
380	-C(O)NHNHCO₂Me	N	k
381	-C(O)NHCH(-C(O)SCH₂CH₂-)	CH	k
382	-C(O)N(-CH₂CH₂CH₂-)	CF	k
383	-C(O)NHCH₂(2-benzimidazole)	CF	k
384	-C(O)NHCH₂CH(-CH₂N(CO₂(tbutyl))CH₂CH₂CH₂-)	CF	k
385	-C(O)NHNHCH₂CF₃	CH	k
386	-C(O)NHCH₂(tetrahydro-2-furanyl)	N	k
387	-C(O)NHCH₂CF₃	N	k
388	-C(O)NH(cyclopropyl)	N	k
389	-C(O)NHCH₂(tetrahydro-2-furanyl)	CCI	k
390	-C(O)NH(cyclopropyl)	CCI	k
391	-C(O)NHCH₂CF₃	CCI	k
392	-NHC(O)CH₂CF₃	CH	k
393	-C(0)NHNH(cyclopropyl)	CH	k
394	-C(O)NHC(Me)₂CECH	CH	k
395	-C(0)NH(cyclobutyl)	CH	k

203

396	-C( Ο ) N H CH2(tetra hyd ro-2-f u ra ny I )	CBr	*
397	-C(O)NHNHCO₂Me	CBr	*
398	-C(O)NHCH₂CF₃	CBr	★
399	-C(O)NH(cyclopropyl)	CBr	*
400	-C(O)NHNHC(O)(3-pyridinyl)	CH	*
401	-C(O)NHCH₂CF₃	CF	*
402	-C(O)NHC(-CH₂CH₂-)CO₂Me	CH	*
403	—C(O)NHCH(Et)CH₂OMe	CH	*
404	-C(O)NHCH₂CsCH	CH	*
405	-C(O)NHCH₂CF₃	C(OMe)	★
406	-C(0)NHCH₂(tetrahydro-2-furanyl)	C(OMe)	★
407	-C(0)NH(cyclopropyl)	C(OMe)	*
408	-C(O)NHNHCO₂Me	C(OMe)	*
409	-C(O)NHCH₂(5-pyrimidinyl)	N	•k
410	-C(O)NH(cyclopropyl)	CF	*
411	-C(O)NHCH(Me)CF₃	CH	*
412	-C(O)NHCH(isopropyl)CF₃	CH	k
413	-C(O)N(Et)₂	CH	*
414	-C(O)NHCH(cyclopropyl)(4-methoxyphenyl)	CH	k
415	-C(O)NHCH(Me)(cyclopropyl)	CH	*
416	-C(O)NHNHC(S)NH(isopropyl)	CH	*
417	-C(O)NHC(Me)₂CF₃	CH	349
418	-C(O)NHC(-CH₂CH₂-)CF₃	CH	347
419	-C(O)NHCH₂(2-pyridinyl)	CH	330
420	-C(O)NHCH₂CH(CI)CH₂CH₂CH₂CI	CH	★
421	-C(0)NHCH₂(tetrahydro-2-furanyl)	C(SMe)	*
422	2-(SCH₂CF₃)pyrimidin-4-yl	CH	•k
423	6-(2-pyrimidinyl)pyridin-2-yl	CH	*
424	5-(trifluoromethyl)pyrazin-2-yl	CH	*

204

425	-C(O)NHCH₂CH₂SCH2CH2CF3	CH	395
426	-C(O)NHCH₂CH₂SCH₂CF3	CH	381
427	-C(O)NHCH2CH₂S(O)2CH2CH2CF3	CH	427

X⁴ is N

Cmpd. No.	R	A	NMR/MS data
173	-C(O)NHCH₂(tetrahydro-2-furanyl)	CH	★

* See Index Table O for 1H NMR data.

INDEX TABLE C

Cmpd. No.	R	A	NMR/MS data
428	-C(O)NHCH₂CF₃	CH	★
429	-C(O)NH(cyclopropyl)	CH	*
430	-C(O)NHCH₂(2-pyrimidinyl)	CH	★
431	-C(O)NHNHCO₂Me	CH	★
432	-C(O)NHCH₂CH₂SMe	CH	*
433	-C(O)NHCH₂CH(OMe)₂	CH	*
434	-C(O)NHCH(Me)CF₃	CH	*
435	-C(O)NHCH₂CHF₂	CH	•k
436	-C(O)NHCH(CH₂OMe)₂	CH	*
437	-C(O)NHCH₂(tetrahydro-2-furanyl)	CH	*

* See Index Table O for 1H NMR data.

205

INDEX TABLE D

Cmpd. No.	R	X	NMR/MS data
135	-C(O)NHNHCO₂Me	Cl	★
136	-C(O)NHCH₂CF₃	Cl	*
137	-C(O)NHCH₂(2-pyrimidinyl)	Cl	*
142	-C(0)NH(cyclopropyl)	H	*
438	-C(O)NHCH₂(tetrahydro-2- furanyl)	Cl	*

* See Index Table O for 1H NMR data.

INDEX TABLE E

R^a

R^b is H

Cmpd. No.	FV	X-	A	NMR/MS data
77	-C(O)(1-pyrrolidinyl)	CH	CH	*
78	-C(O)NHCH₂CF₃	CH	CH	★
79	-C(O)N(Me)₂	CH	CH	★

206

80	-C(O)NH(2-pyrimidinyl)	CH	CH	*
81	-C(O)NH(isopropyl)	CH	CH	*
82	-NHC(O)O(t-butyl)	CH	CH	*
83	-NHC(O)(2-pyridinyl)	CH	CH	*
84	-C(O)NHCH₂CH₂SMe	CH	CH	*
85	-C(O)NHCH₂CH₂S(t-butyl)	CH	CH	*
160	-C(O)NH(cyclobutyl)	CH	CH	it
161	-C(O)NHCH₂(tetrahydro-2- furanyl)	CH	CH	*
162	-C(O)NHNHCO₂Me	CH	CH	★
163	-C(O)NH(cyclopropyl)	CH	CH	*

R^a is H

Cmpd. No.			A	NMR/MS data
86	3-(trifluoromethyl)pyrazol-1-yl	CH	CH	*
87	2-fluorophenyl	CH	CH	★
88	-C(O)NH(isopropyl)	CH	CH	*
89	-C(O)NH(1-pyrrolidinyl)	CH	CH	*
90	-C(O)NHCH₂CF₃	CH	CH	★
91	-C(O)N(Me)(isopropyl)	CH	CH	★
92	- (R)-C(O)NHCH(Me)C(O)NH(t-butyl)	CH	CH	*
93	-C(0)NH(cyclopropyl)	CH	CH	★
94	-C(O)NH(cyclopentyl)	CH	CH	*
95	-C(O)NHCH₂Si(Me)₃	CH	CH	*
96	-C(O)NHCH₂CH₂SMe	CH	CH	*
97	-C(O)NHC(Me)₂CH₂SMe	CH	CH	it
98	-C(O)NHCH₂CH(-OCH₂CH₂O-)	CH	CH	it
99	—C(O)NHCH₂CH₂NHC(O)Me	CH	CH	it
100	-C(O)NHCH(- C(O)NHCH₂CH₂CH₂CH₂-)	CH	CH	it

207

101	-C(O)NHC(Me)₂CF₃	CH	CH	*
102	-C(O)NHCH₂C(O)NHCH₂C(O)NHEt	CH	CH	k
103	-C(0)NH(3,3-difluorocyclobutyl)	CH	CH	*
104	-C(O)NHCH(Me)CF₃	CH	CH	*
105	pyrazol-1-yl	CH	CH	*
106	-C(O)NHCH₂(2-pyridinyl)	CH	CH	*
107	-C(O)(2-(trifluoromethyl)pyrrolidin-1-yl)	CH	CH	★
108	—C(0)(2-(2-pyridiny[)pyrrolidin-1-yl)	CH	CH	★
109	-C(0)NHCH2(6-bromo-2-pyridinyl)	CH	CH	*
110	-C(O)NHCH(Me)(3,5-dichloro-2- pyridinyl)	CH	CH	*
111	- (R)-C(O)NHCH(Me)C(O)NH(Et)	CH	CH	*
112	-(R)- C(O)NHCH(Me)C(O)NH(isopropyl)	CH	CH	*
113	-(/?)- C(O)NHCH(Me)C(O)NH(CH₂CF₃)	CH	CH	*
114	3-methyl-1,2,4-oxadiazol-5-yl	CH	CH	•k
115	-NHC(O)O(t-butyl)	CH	CH	*
116	-C(O)NH₂	CH	CH	k
117	-NHC(O)N(Et)₂	CH	CH	*
118	-C(O)NHCH₂(2-pyrimidinyl)	CH	CH	*
119	1,2,4-triazol-1-yl	CH	CH	*
120	CF₃ Ao I! JL 7	CH	CH	•k
121	-C(O)NHCH₂CH₂SMe	CH	CF	*
122	-C(O)NHCH₂(tetrahydro-2-furanyl)	CH	CF	*
123	-C(O)NHCH(Me)CH₂OMe	CH	CF	*
124	-C(O)NH(Et)	CH	CF	•k

208

125	-C(O)(1-pyrrolidinyl)	CH	CF	*
126	-C(O)NH(isopropyl)	CH	CF	*
127	-C(O)NHCH₂CF₃	CH	CF	*
128	Me M/	CH	CH	k

* See Index Table O for 1H NMR data.

INDEX TABLE F çoo

R

Cmpd. No.	R	NMR/MS data
138	-C(O)NHCH2(2-pyrimidinyl)	*
139	-C(O)NHCH2(tetrahydro-2-furanyl)	k
140	-C(O)NHCH₂CF₃	*
141	-C(O)NH(cyclopropyl)	*

* See Index Table O for 1H NMR data.

INDEX TABLE G

209

No.
158	-NHC(O)(cyclobutyl)	★
159	-NHC(O)(cyclopropyl)	*
439	-C(O)NHCH2(2-pyrimidinyl)	*
440	-C(0)NH(tetrahydro-2-furanyl)	*
441	-C(0)NH(isopropyl)	*
442	-C(O)N(Pr)CH2(cyclopropyl)	★
443	-C(O)NHCH₂CF₂CF₃	*
444	-C(O)N(Me)(cyclopropyl)	*
445	-C(O)NHCH₂CH(OMe)₂	*
446	-C(O)NHCH2(cyclopropyl)	*
447	-C(O)NH(cyclopropyl)	*
448	-C(O)NHNHCO₂Me	*
449	-C(O)NHCH₂CH₂CF₃	*

* See Index Table O for NMR data.

INDEX TABLE H

Cmpd. No.	R	NMR/MS data
200	-C(O)(1 -pyrrolidinyl)	★
201	-C(O)NH(isopropyl)	*

* See Index Table O for 1H NMR data.

210

INDEX TABLE I

Cmpd. No.	R	NMR/MS data
450	-C(O)NHCH₂CH₂SMe	★
451	-C(O)NHCH₂CH(OMe)₂	*
452	-C(O)N(Me)₂	★
453	-C(O)NHCH₂CF₃	*
454	-C(O)NH(t-butyl)	*

* See Index Table O for 1H NMR data.

INDEX TABLE J

Cmpd. No.	R	NMR/MS data
455	-C(O)NHCH₂CH(OMe)₂	327
456	-C(O)NHCH₂(tetrahydro-2-furanyl)	323
457	-C(O)NHCH₂CF₃	321
458	-C(O)NHCH₂(2,2-difluorocyclopropyl)	329

See Index Table O for 1H NMR data.

Cmpd. No.	R	MS data
459	-C(O)NHNHCO₂Me	313
460	-C(O)NHCH₂CF₃	322.5

INDEX TABLE L

Cmpd. No.	R	MS data
461	-C(O)NHCH₂CF₃	322.5

INDEX TABLE M

Cmpd. No.	R	MS data
467	-C(0)NHCH₂(tetrahydro-2-furanyl)	★

* See Index Table O for 1H NMR data.

212

INDEX TABLE N

Cmpd.

No.

Structure

NMR/MS data

462

213 * See Index Table O for H NMR data.

INDEX TABLE O

Cmpd. No.	¹H NMRData³
1	¹H NMR (CDCI3) □: 9.23 (s, 1H), 8.74 (d, J=0.9 Hz, 1H), 8.66 (dd, J=4.7, 1.6 Hz, 1H), 8.28 (ddd, J=8.3, 2.6, 1.5 Hz, 1H), 7.85 (dt, J=8.7, 0.9 Hz, 1H), 7.47-7.50 (m, 1H), 7.35 (dd, J=8.7, 6.8 Hz, 1H), 7.28-7.30 (m, 1H), 3.75 (br s, 2H), 3.59 (br s, 2H), 1.97-2.04 (br s, 2H), 1.92 (br s, 2H)
2	¹H NMR (CDCI3) □: 9.27 (d, J=2.2 Hz, 1H), 9.25 (s, 1H), 9.0 (s, 1H), 8.72 (d, J=4.9 Hz, 2H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.28-8.33 (m, 1H), 8.05 (d, J=24.1 Hz, 1H, 7.69 (d, J=6.8 Hz, 1H), 7.52 (m, 1H), 7.44 (dd, J=8.7, 6.9 Hz, 1H), 7.12 (t, J=4.9 Hz, 1H)
3	¹H NMR (CDCI3) □: 9.22 (s, 1H), 8.69 (d, J=3.8 Hz, 1H), 8.61 (s, 1H), 8.25- 8.32 (m, 1H), 7.87 (d, J=8.8 Hz, 1H), 7.50 (dd, J=8.4, 4.7 Hz, 1H), 7.36 (dd, J=8.8, 6.8 Hz, 1H), 7.17 (d, J=6.8, 1H), 3.72-3.82 (m, 4H)
4	¹H NMR (CDCI3) □: 9.28 (d, J=2.5 Hz, 1H), 9.14 (d, J=0.9 Hz, 1H), 8.96-9.00 (m, 1H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.42 (dt, J=8.4, 0.9 Hz, 1H), 8.30-8.33 (m, 1H), 8.01 (dd, J=8.7, 0.7 Hz, 1H), 7.80 (dd, J=1.9, 1.1 Hz, 1H), 7.67 (d, J=6.9 Hz, 1H), 7.49-7.52 (m, 1H), 7.42 (dd, J=8.7, 6.9 Hz, 1H), 7.08-7.12 (m, 1H)
5	¹H NMR (CDCI3) □: 9.27 (d, J=2.5 Hz, 1H), 9.12 (d, J=0.8 Hz, 1H), 8.68 (dd, J=4.7, 1.4 Hz, 1H), 8.28-8.31 (m, 1H), 8.02-8.06 (br s, 1H), 8.00 (d, J=8.7 Hz, 1H), 7.69 (d, J=8.6, Hz, 2H), 7.57 (d, J=6.8 Hz, 1H), 7.48-7.52 (m, 1H), 7.42 (dd, J=8.5, 7.3 Hz, 3H), 7.21 (t, J=24.1 Hz, 1H)
6	¹H NMR (CDCI3) □: 9.26 (d, J=2.5 Hz, 1H), 9.07 (s, 1H), 8.68 (dd, J=4.7, 1.4 Hz, 1 H), 8.29-8.34 (m, 1 H), 7.95 (d, J=8.7 Hz, 1 H), 7.49-7.54 (m, 2H), 7.357.41 (m, 1H), 7.10-7.16 (m, 1H), 4.55-4.66 (m, 1H), 1.52 (d, J=6.9 Hz, 3H), 1.39 (s, 9H)

214

7	¹H NMR (acetone-c/g) □: 9.35 (d, J=2.2 Hz, 1H), 9.32 (d, J=0.9 Hz, 1H), 8.67 (d, J=9.8 Hz, 1H), 8.51-8.57 (m, 1H), 8.48 (d, J=14.3 Hz, 1H), 7.93 (d, J=14.7 Hz, 1H), 7.79 (d, J=7.4 Hz, 1H), 7.77 (d, J=6.5 Hz, 1H), 7.62-7.69 (m, 1H), 7.44 (dd, J=8.7, 6.9 Hz, 1H), 4.49-4.58 (m, 1H), 3.83-3.92 (m, 1H), 1.37 (d, J=7.3 Hz, 3H), 1.06-1.10 (m, 6H)
8	¹H NMR (CDCI₃) □: 9.26 (d, J=2.2 Hz, 1H), 9.09 (d, J=0.9 Hz, 1H), 8.67 (dd, J=4.7, 1.4 Hz, 1H), 8.29 (ddd, J=8.3, 2.6, 1.4 Hz, 1H), 7.92 (dt, J=8.5, 0.9 Hz, 1H), 7.48 (m, 1H), 7.31-7.41 (m, 2H), 6.15 (s, 1H), 4.31-4.41 (m, 1H), 1.33 (d, J=6.6 Hz, 6H)
9	¹H NMR(CDCI₃) □: 9.27 (d, J=10.1 Hz, 1H), 9.17 (s, 1H), 8.68 (dd, J=4.7, 1.4 Hz, 1H), 8.59-8.64 (m, 1H), 8.30-8.35 (m, 1H), 7.96 (d, J=8.7 Hz, 1H), 7.81 (br. s, 1H), 7.72 (t, J=18.8 Hz, 1H), 7.62 (d, J=6.9 Hz, 1H), 7.48-7.52 (m, 1H), 7.40 (dd, J=8.8, 6.9 Hz, 1H), 7.37 (d, J=7.9 Hz, 1H), 4.85 (d, J=4.9 Hz, 2H)
10	¹H NMR (CDCI₃) □: 9.26 (d, J=2.5 Hz, 1H), 9.08 (d, J=0.8 Hz, 1H), 8.68 (dd, J=4.7, 1.4 Hz, 1H), 8.26-8.36 (m, 1H), 7.95 (d, J=8.7 Hz, 1H), 7.50 (dd, J=8.3, 4.8 Hz, 1H), 7.45 (d, J=6.6 Hz, 1H), 7.37 (dd, J=8.7, 6.9 Hz, 1H), 6.51 (br. s„ 1H), 4.55 (t, J=5.2 Hz, 1H), 3.69 (t, J=5.5 Hz, 2H), 3.48 (s, 6H)
11	¹H NMR(CDCI₃) □: 9.25 (d, J=2.5 Hz, 1H), 9.12 (d, J=0.6 Hz, 1H), 8.66 (dd, J=4.7, 1.3 Hz, 1H), 8.30 (d, J=20.3 Hz, 1H), 7.94 (d, J=8.7 Hz, 1H), 7.76 (d, J=3.2 Hz, 1H), 7.54 (d, J=6.9 Hz, 1H), 7.44-7.51 (m, 2H), 7.34 (d, J=3.3 Hz, 2H), 5.03 (d, J=5.5 Hz, 2H)
12	¹H NMR (CDCI3) □: 9.26 (d, J=2.4 Hz, 1H), 9.09 (d, J=0.8 Hz, 1H), 8.67 (dd, J=4.7, 1.3 Hz, 1H), 8.26-8.35 (m, 1H), 7.94 (d, J=8.7 Hz, 1H), 7.47 (dd, J=42.1, 6.8 Hz, 2H), 7.37 (dd, J=32.6, 8.7 Hz, 1H), 6.82 (br. s, 1H), 4.09-4.19 (m, 1H), 3.78-3.99 (m, 3H), 3.35-3.46 (m, 1H), 2.03-2.15 (m, 1H), 1.96 (t, J=7.3 Hz, 2H), 1.66 (ddd, J=59.9, 12.3, 8.2 Hz, 1H)
13	¹H NMR (CDCI3) □: 9.26 (d, J=2.5 Hz, 1H), 9.10 (d, J=0.9 Hz, 1H), 8.68 (dd, J=4.7, 1.6 Hz, 1H), 8.26-8.33 (m, 1H), 7.95 (d, J=21.0 Hz, 1H), 7.45-7.54 (m, 2H), 7.37 (dd, J=8.7, 6.9 Hz, 1H), 6.83 (br. s, 1H), 3.75 (dd, J=39.1, 33.7 Hz, 2H), 2.83 (t, J=27.4 Hz, 2H), 2.18 (s, 3H)

215

14	¹H NMR (CDCI₃) □: 9.26 (d, J=2.0 Hz, 1H), 9.12 (d, J=0.6 Hz, 1H), 8.67 (dd, J=4.7, 1.4 Hz, 1H), 8.29 (ddd, J=8.3, 2.6, 1.5 Hz, 1H), 7.93 (d, J=18.0 Hz, 1H), 7.50 (ddd, J=8.3, 4.8, 0.6 Hz, 1H), 7.29-7.38 (m, 2H), 6.50 (br. s., 1H), 2.91-3.02 (m, 1H), 0.93 (dd, J=32.8, 27.3 Hz, 2H), 0.69 (d, J=27.7 Hz, 2H)
15	¹H NMR (CDCI3) □: 9.21 (d, J=2.4 Hz, 1H), 8.67 (dd, J=4.8, 1.3 Hz, 1H), 8.57 (d, J=0.8 Hz, 1H), 8.27 (d, J=17.5 Hz, 1H), 7.84 (d, J=8.8 Hz, 1H), 7.49 (ddd, J=8.3, 4.8, 0.6 Hz, 1H), 7.35 (dd, J=27.1, 19.9 Hz, 1H), 7.15 (d, J=21.8 Hz, 1H), 3.49 (s, 5H), 1.47-1.71 (m, 5H)
16	¹H NMR (CDCI3) □: 9.26 (d, J=2.2 Hz, 1H), 9.09 (d, J=0.8 Hz, 1H), 8.68 (dd, J=4.7, 1.4 Hz, 1H), 8.27-8.32 (m, 1H), 7.93 (dt, J=8.0, 1.1 Hz, 1H), 7.49 (ddd, J=8.3, 4.8, 0.6 Hz, 1H), 7.33-7.40 (m, 2H), 6.15 (brs, 1H), 4.05 (dd, J=38.3, 8.0 Hz, 1H), 2.10 (dd, J=12.5, 3.5 Hz, 2H), 1.80 (dd, J=26.8, 13.9 Hz, 2H), 1.66-1.74 (m, 1 H), 1.48 (dd, J=47.4, 13.6 Hz, 2H), 1.22-1.38 (m, 3H)
17	¹H NMR (CDCI₃) □: 9.26 (d, J=2.4 Hz, 1H), 9.05 (d, J=0.8 Hz, 1H), 8.71 (dd, J=4.7, 1.4 Hz, 1H), 8.27-8.35 (m, 1H), 8.13 (dd, J=2.4, 0.9 Hz, 1H), 7.80 (d, J=8.7 Hz, 1H), 7.52 (ddd, J=8.2, 4.8, 0.7 Hz, 1H), 7.39 (dd, J=8.7, 7.3 Hz, 1H), 7.22-7.28 (m, 1H), 6.80 (d, J=2.5 Hz, 1H)
18	¹H NMR (CDCI3) □: 9.47 (d, J=0.9 Hz, 1H), 9.31 (d, J=2.5 Hz, 1H), 8.90 (d, J=4.9 Hz, 2H), 8.68 (d, J=20.8 Hz, 1H), 8.44 (d, J=19.4 Hz, 1H), 8.35-8.40 (m, 1H), 7.95 (d, J=27.0 Hz, 1H), 7.51 (t, J=16.6 Hz, 2H), 7.23 (t, J=4.8 Hz, 1H)
19	¹H NMR (CDCI3) □: 9.28 (d, J=19.9 Hz, 1H), 9.06 (d, J=0.8 Hz, 1H), 8.65- 8.75 (m, 1H), 8.25-8.35 (m, 1H), 8.02 (d, J=27.4 Hz, 1H), 7.45-7.56 (m, 2H), 7.36-7.44(m, 1H), 6.56 (brs, 1H), 4.16-4.28 (m, 2H)
20	¹H NMR (CDCI₃) □: 10.44 (d, J=0.9 Hz, 1H), 9.43 (d, J=2.4 Hz, 1H), 9.02 (d, J=4.7 Hz, 2H), 8.67 (d, J=12.0 Hz, 1H), 8.50-8.53 (m, 1H), 8.48 (dd, J=7.7, 0.8 Hz, 1H), 8.09 (d, J=7.4 Hz, 1H), 8.00 (t, J=21.4 Hz, 1H), 8.01 (d, J=18.0 Hz, 1H), 7.76 (d, J=6.9 Hz, 1H), 7.50-7.55 (m, 1H), 7.44-7.49 (m, 1H), 7.39 (t, J=16.9 Hz, 1H)

216

21	¹H NMR (DMSO-d₆) □: 9.39 (d, J=0.8 Hz, 1H), 9.36 (d, J=2.2 Hz, 1H), 9.14 (t, J=5.9 Hz, 1H), 8.79 (d, J=4.9 Hz, 2H), 8.67 (dd, J=4.7, 1.4 Hz, 1H), 8.508.57 (m, 1H), 7.96 (d, J=8.7 Hz, 1H), 7.80 (d, J=6.5 Hz, 1H), 7.64 (ddd, J=8.4, 4.7, 0.8 Hz, 1H), 7.47 (dd, J=8.8, 6.9 Hz, 1H), 7.41 (t, J=4.9 Hz, 1H), 4.76 (d, J=6.0 Hz, 2H)
22	¹H NMR (CDCI₃) □: 9.26-9.33 (m, 1H), 9.23 (s, 1H), 8.62-8.76 (m, 2H), 8.40 (d, J=19.7 Hz, 1H), 8.32 (d, J=18.9 Hz, 1H), 7.90 (t, J=28.4 Hz, 1H), 7.777.85 (m, J=32.5 Hz, 2H), 7.65 (d, J=18.1 Hz, 1H), 7.50-7.59 (m, 1H), 7.45 (t, J=27.3 Hz, 1H), 7.37-7.41 (m, 1H)
23	¹H NMR (CDCI3) □: 9.27 (d, J=10.6 Hz, 1H), 9.23 (d, J=0.9 Hz, 1H), 8.66- 8.72 (m, 2H), 8.39 (d, J=19.4 Hz, 1H), 8.33 (d, J=7.7 Hz, 1H), 7.89 (dd, J=13.6, 1.4 Hz, 1H), 7.83 (d, J=8.8 Hz, 1H), 7.79 (s, 1H), 7.63 (d, J=6.5 Hz, 1H), 7.51-7.56 (m, 1H), 7.45 (dd, J=15.8, 1.7 Hz, 1H), 7.36-7.41 (m, 1H)
24	¹H NMR (CDCI3) □: 9.41 (d, J=2.4 Hz, 1H), 9.26 (d, J=0.8 Hz, 1H), 8.69 (dd, J=4.7, 1.3 Hz, 1H), 8.51-8.58 (m, 1H), 8.24 (br s, 1H), 7.94 (d, J=8.7 Hz, 1H), 7.74 (d, J=6.9 Hz, 1H), 7.62-7.69 (m, 1H), 7.43 (dd, J=8.7, 6.9 Hz, 1H), 6.016.31 (m, J=112.9 Hz, 1H), 3.80-3.96 (m, 2H),
25	¹H NMR (CDCI3) □: 9.20 (d, J=2.5 Hz, 1H), 8.68 (dd, J=4.7, 1.4 Hz, 1H), 8.54 (s, 1H), 8.27-8.32 (m, 1H), 7.93 (s, 1H), 7.79 (d, J=21.8 Hz, 1H), 7.48- 7.54 (m, 2H), 3.69 (t, J=6.8 Hz, 2H), 3.52 (t, J=6.3 Hz, 2H), 1.95-2.03 (t, J=6.2 Hz, 2H), 1.91 (t, J=6.5 Hz, 2H)
26	¹H NMR (CDCI3) □: 9.22 (d, J=2.2 Hz, 1H), 8.79 (s, 1H), 8.72 (dd, J=9.8, 1.0 Hz, 1H), 8.69 (d, J=4.9 Hz, 2H), 8.63 (s, 1H), 8.46 (s, 1H), 8.29-8.34 (m, 1H), 7.88 (d, J=1.3 Hz, 2H), 7.51-7.56 (m, 1H), 7.08 (t, J=4.8 Hz, 1H)
27	¹H NMR(CDCI₃) □: 9.21 (brs, 1H), 8.69 (d, J=4.1 Hz, 1H), 8.51 (s, 1H), 8.30 (d, J=22.1 Hz, 1H), 7.97 (d, J=1.7 Hz, 2H), 7.89 (d, J=9.3 Hz, 1H), 7.78- 7.82 (m, 1H), 7.78-7.82 (m, 2H), 7.51 (dd, J=8.2, 4.7 Hz, 1H), 6.50 (t, J=9.1 Hz, 1 H)
28	¹H NMR (CDCI3) □: 9.23 (d, J=2.4 Hz, 1H), 8.72 (dd, J=4.7, 1.4 Hz, 1H), 8.65 (s, 1 H), 8.44 (t, J=1.3 Hz, 1 H), 8.42 (d, J=10.9 Hz, 1 H), 8.31-8.34 (m, 2H), 7.88-7.90 (m, 2H), 7.75-7.83 (m, 1H), 7.50-7.58 (m, 1H), 7.10 (ddd, J=7.3, 4.9, 1.0 Hz, 1H)

217

29	¹H NMR (CDCI₃) □: 9.22 (d, J=2.2 Hz, 1H), 8.71 (dd, J=4.7, 1.4 Hz, 1H), 8.62 (s, 1H), 8.39 (s, 1H), 8.29-8.35 (m, 1H), 7.88 (d, J=0.8 Hz, 2H), 7.81 (d, J=15.9 Hz, 1H), 7.68 (d, J=18.1 Hz, 2H), 7.54 (dd, J=18.8, 8.4 Hz, 1H), 7.41 (t, J=8.4 Hz, 3H), 7.18 (t, J=20.3 Hz, 2H)
30	¹H NMR (DMSO-c/₆) □: 9.32 (d, J=2.5 Hz, 1H), 9.14 (s, 1H), 9.09 (s, 1H), 8.64 (d, J=7.7 Hz, 1H), 8.44-8.50 (m, 1H), 8.16 (d, J=11.5 Hz, 1H), 8.05 (s, 1H), 7.95 (d, J=10.4 Hz, 1H), 7.82 (t, J=24.7 Hz, 1H), 7.72 (d, J=10.7 Hz, 1H), 7.61-7.68 (m, 2H), 7.51 (d, J=20.2 Hz, 1H), 7.28 (d, J=13.9 Hz, 1H)
31	¹H NMR (DMSO-d₆) □: 9.32 (d, J=2.4 Hz, 1H), 9.29-9.31 (m, 1H), 9.28-9.31 (m, 1H), 9.08 (s, 1H), 8.63 (dd, J=4.7, 1.3 Hz, 1H), 8.45-8.50 (m, 1H), 8.10 (s, 1H), 7.68 (d, J=9.3 Hz, 1H), 7.61-7.66 (m, 2H), 7.34-7.42 (m, 1H), 7.12 (br. s, 2H)
32	¹H NMR (CDCI3) □: 9.26 (d, J=2.5 Hz, 1H), 8.57 (s, 1H), 8.68 (dd, J=4.7, 1.4 Hz, 1H), 8.16 (s, 1H), 7.95 (d, J=8.7 Hz, 1H), 7.49-7.54 (m, 2H), 7.35-7.41 (m, 1H), 7.10-7.16 (m, 1H), 4.55-4.66 (m, 1H), 1.52 (d, J=6.9 Hz, 3H), 1.39 (s, 9H)
33	¹H NMR(CDCI₃) □: 9.21 (brs, 1H), 8.70 (d, J=12.0 Hz, 1H), 8.53 (d, J=0.9 Hz, 1H), 8.27-8.33 (m, 1H), 7.85-7.88 (m, 1H), 7.81 (d, J=15.6 Hz, 1H), 7.50- 7.55 (m, 1H), 7.40 (dd, J=9.0, 1.6 Hz, 1H), 3.03-3.23 (m, 6H)
34	¹H NMR (CDCI3) □: 9.21 (d, J=2.4 Hz, 1H), 8.71 (dd, J=4.8, 1.5 Hz, 1H), 8.60 (s, 1H), 8.32 (dd, J=1.7, 1.0 Hz, 1H), 8.29-8.32 (m, 1H), 8.02 (s, 1H), 7.85 (d, J=9.1 Hz, 1H), 7.72 (dd, J=9.1, 1.7 Hz, 1H), 7.51-7.55 (m, 1H), 6.47 (brs, 1H), 4.12-4.26 (m, 2H)
35	¹H NMR(CDCI₃) □: 9.21 (brs, 1H), 8.70 (d, J=3.6 Hz, 1H), 8.57 (d, J=0.9 Hz, 1H), 8.28-8.33 (m, 1H), 8.26 (s, 1H), 7.81 (dt, J=9.1, 0.9 Hz, 1H), 7.69 (dd, J=9.1, 1.7 Hz, 1H), 7.49-7.56 (m, 1H), 5.98 (brs, 1H), 4.26-4.44 (m, 1H), 1.31 (d, J=6.6 Hz, 6H)
36	¹H NMR (CDCI3) □: 9.20 (d, J=2.4 Hz, 1H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.53 (s, 1H), 8.27-8.32 (m, 1H), 7.83 (dd, J=9.6, 3.3 Hz, 1H), 7.79-7.82 (m, 1H), 7.52 (dd, J=19.7, 4.1 Hz, 1H), 7.37 (dd, J=9.0, 1.6 Hz, 1H), 3.45-3.74 (m, 5H), 1.51-1.70 (m, 5H)

218

37	¹H NMR (acetone-dg) □: 9.35 (d, J=2.7 Hz, 1H), 9.15 (s, 1H), 8.68 (d, J=17.7 Hz, 1 H), 8.47-8.52 (m, 1 H), 8.36 (s, 1 H), 7.84 (d, J=13.4 Hz, 1 H), 7.74 (d, J=11.7 Hz, 1H), 7.61-7.68 (m, 1H), 2.93-3.00 (m, 1H), 0.71-0.80 (m, 2H), 0.61-0.68 (m, 2H)
38	¹H NMR (acetone-dg) □: 9.35 (d, J=2.5 Hz, 1H), 9.16 (d, J=0.9 Hz, 1H), 8.68 (dd, J=4.6, 1.4 Hz, 1H), 8.47-8.52 (m, 1H), 8.44 (dd, J=1.6, 0.9 Hz, 1H), 7.88 (dd, J=9.1, 1.6 Hz, 1H), 7.77 (d, J=9.0 Hz, 1H), 7.61-7.67 (m, 1H), 5.06 (s, 1H), 3.98-4.01 (m, 1H), (m, 2H), 2.8 (brs, 4H)
39	¹H NMR (CDCI₃) □: 9.20 (d, J=2.7 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.58 (d, J=0.9 Hz, 1H), 8.29-8.32 (m, 1H), 8.28 (dd, J=1.7, 1.0 Hz, 1H), 7.82 (dt, J=9.0, 0.9 Hz, 1 H), 7.71 (dd, J=9.1, 1.7 Hz, 1 H), 7.50-7.54 (m, 1 H), 6.406.45 (m, 1H), 4.54 (t, J=5.2 Hz, 1H), 3.66 (t, J=5.5 Hz, 2H), 3.47 (s, 6H)
40	¹H NMR (acetone-dg) □: 9.36 (d, J=2.7 Hz, 1H), 9.19 (d, J=0.9 Hz, 1H), 8.68 (dd, J=4.7, 1.4 Hz, 1 H), 8.61 (br s, 1 H), 8.50-8.52 (m, 1 H), 8.49 (dd, J=2.6, 1.5 Hz, 1H), 7.93 (dd, J=9.1, 1.6 Hz, 1H), 7.80 (dt, J=9.1, 0.9 Hz, 1H), 7.71 (d, J=3.3 Hz, 1H), 7.62-7.66 (m, 1H), 7.51 (d, J=3.2 Hz, 1H), 4.92 (d, J=6.0 Hz, 2H)
41	¹H NMR (CDCI3) □: 9.21 (br s, 1 H), 8.70 (d, J=2.8 Hz, 1 H), 8.57 (d, J=0.9 Hz, 1H), 8.31 (s, 1H), 8.28-8.30 (m, 2H), 7.82 (d, J=12.6 Hz, 1H), 7.73 (dd, J=9.1, 1.7 Hz, 1H), 7.52 (dd, J=8.2, 4.7 Hz, 1H), 6.61 (brs, 1H), 3.92 (dt, J=8.4, 6.7 Hz, 1H), 3.77-3.89 (m, 2H), 3.33-3.44 (m, 1H), 2.05 (d, J=43.0 Hz, 1H), 1.90-2.01 (m, 2H), 1.72-1.79 (m, 1H), 1.60-1.71 (m, 1H)
42	¹H NMR (acetone-dg) □: 9.60 (s, 1H), 9.36 (d, J=2.7 Hz, 1H), 9.20 (d, J=0.8 Hz, 1 H), 8.69 (d, J=11.5 Hz, 1 H), 8.48-8.52 (m, 1 H), 8.47 (s, 1 H), 8.26 (br s, 1H), 7.87 (d, J=16.6 Hz, 1H), 7.81 (d, J=16.6 Hz, 1H), 7.62-7.67 (m, 1H), 3.70 (s, 3H)
43	¹H NMR (CDCI3) □: 9.20 (d, J=2.5 Hz, 1H), 8.69 (dd, J=4.7, 1.3 Hz, 1H), 8.54 (s, 1H), 8.29 (ddd, J=8.3, 2.6, 1.6 Hz, 1H), 7.84-7.87 (m, 1H), 7.81 (d, J=9.0 Hz, 1H), 7.49-7.55 (m, 1H), 7.38 (dd, J=9.0, 1.6 Hz, 1H), 3.66 (brs, 4H), 2.46 (br. s, 4H), 2.35 (s, 3H)

219

44	¹H NMR(CDCI₃) □: 9.20 (d, J=2.4 Hz, 1H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.55 (d, J=0.9 Hz, 1H), 8.29 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 7.86 (s, 1H), 7.82 (dt, J=8.9, 0.9 Hz, 1H), 7.47-7.55 (m, 1H), 7.37 (dd, J=9.0, 1.6 Hz, 1H), 3.84 (brs, 4H)
45	¹H NMR (CDCI₃) □: 9.20 (d, J=2.4 Hz, 1H), 8.71 (dd, J=4.7, 1.3 Hz, 1H), 8.65 (s, 1H), 8.58 (d, J=0.8 Hz, 1H), 8.28-8.33 (m, 1H), 8.25 (s, 1H), 7.83 (d, J=9.0 Hz, 1H), 7.64 (dd, J=9.1, 1.5 Hz, 1H), 7.53 (dd, J=8.0, 4.7 Hz, 1H), 6.02-6.14 (m, 1H), 5.35-5.48 (m, 2H), 4.57 (d, J=6.3 Hz, 2H)
46	¹H NMR (CDCI₃) □: 9.20 (d, J=2.4 Hz, 1 H), 8.70 (dd, J=4.7, 1.4 Hz, 1 H), 8.58 (d, J=0.9 Hz, 1H), 8.31 (dd, J=2.6, 1.5 Hz, 2H), 7.82 (d, J=15.8 Hz, 1H), 7.73 (dd, J=9.1, 1.6 Hz, 1 H), 7.52 (ddd, J=8.2, 4.8, 0.7 Hz, 1 H), 6.71 (br s, 1H), 3.65-3.76 (m, 2H), 2.84 (t, J=18.4 Hz, 2H), 2.62 (q, J=7.4 Hz, 2H), 1.31 (t, J=7.4 Hz, 3H)
47	¹H NMR(CDCI₃) □: 9.17 (d, J=2.4 Hz, 1H), 8.79 (brs, 1H), 8.69 (d, J=18.1 Hz, 1H), 8.55 (s, 1H), 8.26-8.31 (m, 1H), 8.24 (s, 1H), 7.81 (d, J=13.2 Hz, 1H), 7.66 (d, J=21.6 Hz, 1H), 7.49-7.53 (m, 1H), 4.28-4.38 (m, 1H), 1.35 (d, J=6.3 Hz, 6H)
48	¹H NMR (acetone-dg) □: 9.32 (s, 1H), 9.07-9.17 (m, 1H), 8.64-8.70 (m, 1H), 8.55-8.61 (m, 1H), 8.41-8.50 (m, 1H), 8.13 (d, J=8.5 Hz, 3H), 7.88 (d, J=8.2 Hz, 1H), 7.73 (d, J=9.8 Hz, 1H), 7.59-7.67 (m, 3H)
49	¹H NMR (CDCI₃) □: 9.21 (d, J=2.5 Hz, 1H), 8.70-8.75 (m, 1H), 8.62 (d, J=0.9 Hz, 1H), 8.27-8.36 (m, 2H), 7.86 (d, J=12.9 Hz, 1H), 7.69 (dd, J=9.1, 1.7 Hz, 1H), 7.52-7.54 (m, 1H), 6.46 (s, 1H), 4.45 (d, J=5.7 Hz, 2H)
50	¹H NMR (CDCI₃) □: 9.20 (d, J=2.7 Hz, 1H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.55 (d, J=0.9 Hz, 1H), 8.30 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 7.79-7.88 (m, 2H), 7.51 (ddd, J=8.3, 4.7, 0.7 Hz, 1H), 7.35 (dd, J=8.9, 1.5 Hz, 1H), 4.00-4.18 (m, 1H), 2.93-3.10 (m, 2H), 2.30-2.44 (m, 1H), 2.10-2.19 (m, 1H), 1.80-1.92 (m, 1H), 1.71-1.80 (m, 1H), 1.51-1.71 (m, 1H), 0.90-1.04 (m, 1H)

220

51	^ΊΗ NMR (CDCI₃) □: 9.20 (d, J=2.5 Hz, 1H), 8.70 (dd, J=4.7, 1.2 Hz, 1H), 8.58 (d, J=0.9 Hz, 1H), 8.27-8.34 (m, 2H), 7.83 (dt, J=9.1, 0.9 Hz, 1H), 7.71 (dd, J=9.1, 1.7 Hz, 1H), 7.52 (dd, J=8.2, 4.7 Hz, 1H), 6.46 (brs, 1H), 3.894.05 (m, 1H), 3.27-3.38 (m, 1H), 1.95-2.08 (m, 1H), 1.69 (s, 3H), 1.46-1.59 (m, 1H), 1.16-1.31 (m, 2H)
52	¹H NMR (CDCI3) □: 9.20 (d, J=2.4 Hz, 1H), 8.70 (dd, J=4.7, 1.3 Hz, 1H), 8.58 (d, J=0.9 Hz, 1H), 8.28-8.34 (m, 1H), 8.26 (s, 1H), 7.83 (d, J=9.1 Hz, 1 H), 7.69 (d, J=1.6 Hz, 1 H), 7.49-7.57 (m, 1 H), 6.48 (br s, 1 H), 3.78 (q, J=6.3 Hz, 2H), 2.44-2.59 (m, 2H)
53	^ΊΗ NMR (CDCI3) □: 9.19 (brs, 1H), 8.69 (d, J=4.1 Hz, 1H), 8.56 (d, J=0.9 Hz, 1H), 8.25-8.31 (m, 2H), 7.81 (d, J=18.4 Hz, 1H), 7.72 (dd, J=9.1, 1.7 Hz, 1H), 7.51 (dd, J=8.1,4.7Hz, 1H), 6.41 (brs, 1H), 3.36 (dd, J=7.1,5.4Hz, 2H), 1.05-1.17 (m, 1H), 0.58 (d, J=26.2 Hz, 2H), 0.31 (d, J=22.4 Hz, 2H)
54	¹H NMR (acetone-dg) □: 9.35 (d, J=2.7 Hz, 1H), 9.19 (d, J=0.9 Hz, 1H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.46-8.52 (m, 2H), 8.13 (brs, 1H), 7.90 (dd, J=9.1, 1.6 Hz, 1H), 7.79 (d, J=9.1 Hz, 1H), 7.61-7.68 (m, 1H), 3.83-3.95 (m, 2H), 1.68 (t, J=18.8Hz, 3H)
55	¹H NMR (acetone-dg) □: 9.37 (d, J=4.7 Hz, 1H), 9.20 (d, J=0.9 Hz, 1H), 8.78 (d, J=4.9 Hz, 2H), 8.69 (dd, J=4.6, 1.3 Hz, 1H), 8.48-8.54(m, 2H), 8.24(brs, 1H), 7.94 (dd, J=9.1, 1.7 Hz, 1H), 7.81 (d, J=11.3Hz, 1H), 7.62-7.69 (m, 1H), 7.38 (t, J=4.9 Hz, 2H), 4.84 (d, J=5.5 Hz, 3H)
56	¹H NMR(CDCI₃) □: 9.21 (d, J=2.5 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.60 (d, J=0.8 Hz, 1H), 8.35 (d, J=0.9 Hz, 1H), 8.30 (ddd, J=8.3, 2.6, 1.6 Hz, 1H), 7.84 (d, J=23.0 Hz, 1H), 7.79 (d, J=12.5 Hz, 1H), 7.57 (t, J=17.7 Hz, 1H), 7.49-7.54 (m, 1H), 7.43 (d, J=7.4 Hz, 1H), 7.32-7.39 (m, 2H), 4.78 (d, J=5.4 Hz, 2H)
57	¹H NMR(CDCI₃) □: 9.35 (d, J=2.2 Hz, 1H), 9.16 (d, J=0.9 Hz, 1H), 8.68 (dd, J=4.6, 1.3 Hz, 1 H), 8.45-8.54 (m, 1 H), 8.37-8.43 (m, 1 H), 7.93 (br s, 1 H), 7.86 (dd, J=9.1, 1.6 Hz, 1H), 7.77 (d, J=18.6 Hz, 1H), 7.59-7.68 (m, 1H), 3.60-3.69 (m, 2H), 2.73-2.79 (m, 2H), 2.14-2.16 (m, 3H)

221

58	¹H NMR (CDCI₃) □: 9.20 (d, J=2.5 Hz, 1H), 8.70 (d, J=3.5 Hz, 1H), 8.54 (d, J=0.8 Hz, 1H), 8.30 (d, J=9.5 Hz, 1H), 7.96 (brs, 1H), 7.82 (d, J=9.0 Hz, 1H), 7.52 (dd, J=8.1, 4.5 Hz, 2H), 4.77 (br s, 2H), 3.80 (br s, 2H), 3.38 (br s, 2H), 2.87 (brs, 2H), 2.17-2.31 (m, 2H), 1.21 (brs, 1H)
59	¹H NMR (acetone-dg) □: 9.35 (d, J=2.7 Hz, 1H), 9.16 (d, J=0.9 Hz, 1H), 8.68 (d, J=3.3 Hz, 1H), 8.46-8.51 (m, 1H), 8.40 (s, 1H), 7.90 (brs, 1H), 7.86 (dd, J=9.1, 1.7 Hz, 1H), 7.76 (dt, J=9.1, 1.0 Hz, 1H), 7.61-7.66 (m, 2H), 7.17 (t, J=1.3 Hz, 1H), 6.93 (t, J=1.0 Hz, 1H), 4.18 (t, J=6.9 Hz, 2H), 3.47 (dd, J=19.2, 5.8 Hz, 2H), 2.14 (t, J=6.9 Hz, 2H)
60	¹H NMR (CDCI3) □: 9.20 (d, J=2.2 Hz, 1H), 8.70 (dd, J=4.8, 1.5 Hz, 1H), 8.57 (d, J=0.8 Hz, 1H), 8.27-8.34 (m, 2H), 7.82 (dt, J=9.1, 0.9 Hz, 1H), 7.72 (dd, J=9.1, 1.6 Hz, 1H), 7.52 (ddd, J=8.2, 4.7, 0.6 Hz, 1H), 7.41 (dd, J=1.8, 0.9 Hz, 1H), 6.49 (brs, 1H), 6.36 (ddd, J=14.0, 3.2, 1.3 Hz, 2H), 4.69 (d, J=5.4 Hz, 2H)
61	¹H NMR(CDCI₃) □: 9.21 (d, J=2.2 Hz, 1H), 8.67 (dd, J=4.6, 1.0 Hz, 1H), 8.54 (s, 1 H), 8.26-8.33 (m, 1 H), 7.80 (d, J=9.0 Hz, 1 H), 7.75 (s, 1 H), 7.50 (dd, J=8.2, 4.7 Hz, 1H), 7.31 (dd, J=8.9, 1.3 Hz, 1H), 4.03-4.18 (m, 1H), 3.98-4.24 (m, 1 H), 3.47 (br s, 3H), 2.15 (br s, 1 H), 1.77 (br s, 4H), 1.47-1.69 (m, 4H), 1.21-1.36 (m, J=7.1 Hz, 3H), 1.05 (brs, 3H), 0.93 (s, 1H)
62	¹H NMR (CDCI3) □: 9.20 (d, J=2.4 Hz, 1H), 8.71 (dd, J=4.7, 1.4 Hz, 1H), 8.59 (d, J=0.9 Hz, 1H), 8.28-8.33 (m, 1H), 8.10-8.15 (m, 1H), 7.84 (dt, J=9.1, 0.9 Hz, 1H), 7.60 (dd, J=9.0, 1.6 Hz, 1H), 7.53 (ddd, J=8.4, 4.7, 0.6 Hz, 1H), 4.59 (t, J=12.1 Hz, 4H)
63	¹H NMR (CDCI3) □: 9.21 (d, J=2.5 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.59 (d, J=0.8 Hz, 1H), 8.26-8.35 (m, 2H), 7.83 (d, J=9.0 Hz, 1H), 7.75 (dd, J=9.1, 1.7 Hz, 1H), 7.45-7.58 (m, 1H), 4.83 (dd, J=8.7, 4.9 Hz, 1H), 3.80 (s, 3H), 3.48 (q, J=6.9 Hz, 6H), 2.32 (d, J=5.0 Hz, 1H)
64	¹H NMR (CDCI3) □: 9.20 (d, J=2.5 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.56 (d, J=0.9 Hz, 1H), 8.30 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 7.89 (s, 1H), 7.84 (d, J=9.0 Hz, 1H), 7.48-7.57 (m, 1H), 7.39 (d, J=8.7 Hz, 1H), 3.20 (s, 3H), 1.60 (s, 2H), 1.55-1.68 (m, 2H)

222

65	¹H NMR (CDCI₃) □: 9.20 (d, J=2.4 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.58 (d, J=0.9 Hz, 1H), 8.26-8.36 (m, 2H), 7.82 (dt, J=9.1, 0.9 Hz, 1H), 7.71 (dd, J=9.1, 1.7 Hz, 1H), 7.52 (ddd, J=8.3, 4.7, 0.7 Hz, 1H), 7.27 (d, J=16.9 Hz, 3H), 7.09 (dd, J=3.5,1.1 Hz, 1H), 7.00 (dd, J=5.2, 3.5 Hz, 1H), 6.47 (br s, 1H), 4.80-4.97 (m, 2H)
66	¹H NMR (CDCI3) □: 9.19 (d, J=2.5 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.61 (d, J=3.3 Hz, 1H), 8.55 (d, J=0.8 Hz, 2H), 8.26-8.31 (m, 1H), 7.92-7.97 (m, 1H), 7.85 (d, J=9.0 Hz, 1H), 7.56-7.64 (m, 1H), 7.49-7.55 (m, 1H), 7.43 (dd, J=9.0, 1.3 Hz, 1 H), 7.34 (d, J=4.7 Hz, 1 H), 4.84 (s, 2H), 3.68 (s, 1 H), 2.80 (brs, 2H), 1.74(brs, 2H)
67	¹H NMR (CDCI3) □: 9.20 (d, J=2.2 Hz, 3H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.53 (d, J=0.9 Hz, 1H), 8.27-8.34 (m, 1H), 7.95 (s, 1H), 7.77 (d, J=9.1 Hz, 1 H), 7.52 (s, 2H), 3.14 (s, 3H), 2.83-2.96 (m, 1H), 0.46-0.74 (m, 4H)
68	¹H NMR (CDCI3) □: 9.20 (d, J=2.5 Hz, 1H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.57 (d, J=0.8 Hz, 1H), 8.28-8.33 (m, 1H), 8.27 (s, 1H), 7.82 (d, J=9.1 Hz, 1H), 7.71 (dd, J=9.1, 1.6 Hz, 1H), 7.51 (dd, J=8.2, 4.7 Hz, 1H), 6.45 (d, J=7.6 Hz, 1H), 4.36-4.49 (m, 1H), 3.45-3.60 (m, 2H), 3.42 (s, 3H), 1.34 (d, J=6.8 Hz, 3H)
69	¹H NMR(CDCI₃) □: 9.21 (d, J=2.4 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.58 (d, J=0.9 Hz, 1H), 8.28-8.34 (m, 1H), 8.03-8.09 (m, 1H), 7.85 (dt, J=9.0, 0.9 Hz, 1H), 7.49-7.57 (m, 2H), 4.40 (brs, 4H), 2.33-2.45 (m, 2H), 1.65 (brs, 1H), 1.61-1.71 (m, 2H)
70	¹H NMR (CDCI3) □: 9.20 (d, J=2.5 Hz, 1H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.58 (s, 1H), 8.25-8.41 (m, 2H), 7.81 (d, J=9.1 Hz, 1H), 7.69-7.78 (m, 1H), 7.51 (ddd, J=8.3, 4.8, 0.6 Hz, 1H), 3.52 (brs, 1H), 3.14(brs, 1H), 2.79 (brs, 2H), 1.63-1.91 (m, 2H), 1.11 (brs, 8H)
71	¹H NMR(CDCI₃) □: 9.20 (d, J=2.2 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.58 (d, J=0.9 Hz, 1H), 8.32 (dd, J=1.6, 0.9 Hz, 1H), 8.28-8.31 (m, J=5.7 Hz, 1H), 7.83 (dt, J=9.1, 0.9 Hz, 1H), 7.73 (dd, J=7.4, 1.6 Hz, 1H), 7.49-7.55 (m, 1H), 7.37-7.44 (m, J=8.0 Hz, 1H), 7.34 (d, J=7.7 Hz, 1H), 7.24 (s, 1H), 7.17 (d, J=8.2 Hz, 1H), 6.55 (brs, 1H)

223

72	¹H NMR (CDCI₃) □: 9.20 (d, J=2.4 Hz, 1H), 8.70 (d, J=3.3 Hz, 1H), 8.56 (d, J=0.8 Hz, 1H), 8.28-8.34 (m, 1H), 7.88 (s, 1H), 7.84 (d, J=8.8 Hz, 1H), 7.497.56 (m, 1H), 7.38 (d, J=7.4 Hz, 1H), 3.53-3.96 (m, 8H), 1.70-1.79 (m, 1H), 1.03 (dd, J=4.7, 2.9 Hz, 2H), 0.82 (dd, J=7.6, 2.9 Hz, 2H)
73	¹H NMR (CDCI3) □: 9.21 (d, J=2.4 Hz, 1H), 8.71 (d, J=3.5 Hz, 1H), 8.59 (d, J=0.9 Hz, 1H), 8.28-8.34 (m, 2H), 7.83 (d, J=9.1 Hz, 1H), 7.72 (d, J=7.4 Hz, 1H), 7.50-7.56 (m, 1H), 6.56 (brs, 1H), 4.32-4.51 (m, 1H), 4.05-4.19 (m, 1H), 3.68-3.89 (m, 2H), 3.51-3.62 (m, 1H), 1.32-1.72 (m, 9H)
74	¹H NMR (CDCI3) □: 9.21 (d, J=2.4 Hz, 1H), 8.72 (dd, J=4.8, 1.5 Hz, 1H), 8.62 (d, J=0.9 Hz, 1H), 8.28-8.33 (m, 1H), 8.06 (t, J=1.2 Hz, 1H), 7.88 (d, J=9.0 Hz, 1 H), 7.55 (s, 1 H), 7.52-7.54 (m, 1 H), 7.47 (br s, 1 H), 3.71 (s, 2H), 1.70-1.87 (m, 1H), 1.41 (s, 6H)
75	¹H NMR (CDCI3) □: 9.20 (d, J=2.4 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.55 (d, J=0.9 Hz, 1H), 8.30 (ddd, J=8.3, 2.6, 1.4 Hz, 1H), 7.83 (d, J=9.8 Hz, 2H), 7.49-7.56 (m, 1H), 7.34 (d, J=10.6 Hz, 1H), 3.53-4.15 (m, 4H), 2.44-3.03 (m, 4H)
76	¹H NMR (CDCI3) □: 9.20 (d, J=2.2 Hz, 1 H), 8.70 (dd, J=4.8, 1.5 Hz, 1 H), 8.58-8.62 (m, 2H), 8.43 (d, J=0.8 Hz, 1H), 8.36 (t, J=1.3 Hz, 1H), 8.27-8.33 (m, 1H), 7.83 (d, J=9.3 Hz, 1H), 7.78 (d, J=7.6 Hz, 1H), 7.53 (dd, J=4.7, 0.8 Hz, 1H), 7.29-7.40 (m, 1H), 4.82 (d, J=5.0 Hz, 2H), 2.59 (s, 3H),
77	¹H NMR (CDCI3) □: 9.35 (d, J=1.6 Hz, 1H), 8.73 (dd, J=4.8, 1.7 Hz, 1H), 8.40 (dt, J=8.2, 1.8 Hz, 1H), 8.16 (dd, J=8.0, 0.9 Hz, 1H), 7.65 (dd, J=7.6, 0.9 Hz, 1H), 7.56 (t, J=7.8 Hz, 1H), 7.45 (ddd, J=8.0, 4.8, 0.8 Hz, 1H), 3.78 (brs, 2H), 3.68 (br s, 2H), 2.01 (br s, 2H), 1.97 (br s, 2H)
78	¹H NMR (DMSO-cfe) □: 9.56 (t, J=6.2 Hz, 1H), 9.32 (dd, J=2.4, 0.8 Hz, 1H), 8.77 (dd, J=4.8, 1.7 Hz, 1H), 8.51 (ddd, 1H), 8.34 (dd, J=8.0, 0.8 Hz, 1H), 8.23 (dd, J=7.6, 0.9 Hz, 1H), 7.75 (t, J=7.8 Hz, 1H), 7.63 (ddd, J=8.0, 4.8, 0.8 Hz, 1H), 4.21 (m, 2H)
79	¹H NMR (CDCI3) □: 9.33 (s, 1H), 8.74 (d, J=3.5 Hz, 1H), 8.39 (dt, J=8.0, 1.9 Hz, 1H), 8.15 (dd, J=8.0, 1.1 Hz, 1H), 7.58 (t, 1H), 7.49 (dd, 1H), 7.45 (dd, 1H), 3.17 (brs, 6H)

224

80	¹H NMR (CDCI3) □: 9.40 (s, 1H), 8.91 (s, 1H), 8.73-8.76 (m, 3H), 8.43 (dt, J=8.2, 1.8 Hz, 1H), 8.34 (d, J=8.0 Hz, 1H), 7.91 (d, J=7.1 Hz, 1H), 7.69 (t, 1H), 7.48 (m, 1H), 7.14(t, 1H)
81	¹H NMR (CDCI3) □: 9.39 (d, J=1.6 Hz, 1 H), 8.73 (dd, J=4.8, 1.7 Hz, 1 H), 8.43 (dt, J=8.0, 2.0 Hz, 1H), 8.23 (dd, J=8.0, 0.9 Hz, 1H), 7.64 (dd, J=7.6, 0.9 Hz, 1H), 7.57 (t, J=7.7 Hz, 1H), 7.45 (ddd, J=8.0, 4.8, 0.8 Hz, 1H), 6.27 (d, J=6.8 Hz, 1H), 4.39 (doublet of septets, J=7.6, 6.6 Hz, 1H), 1.34 (d, J=6.6 Hz, 6H)
82	¹H NMR (CDCI3) □: 9.30 (d, J=2.2 Hz, 1 H), 8.73 (dd, J=4.9, 1.6 Hz, 1 H), 8.40 (ddd, 1H), 7.87 (dd, J=8.1, 0.9 Hz, 1H), 7.71 (d, J=7.7 Hz, 1H), 7.50 (t, 1 H), 7.45 (dd, 1 H), 6.54 (br s, 1 H), 1.57 (s, 9H)
83	¹H NMR(CDCI₃) □: 10.24 (brs, 1H), 9.34 (d, J=1.9 Hz, 1H), 8.74 (dd, 1H), 8.71 (ddd, 1H), 8.44 (dt, J=8.3, 1.9 Hz, 1H), 8.37 (dt, J=7.8, 1.0 Hz, 1H), 8.07 (d, J=7.4 Hz, 1H), 7.95-7.99 (m, 2H), 7.59 (t, 1H), 7.56 (ddd, 1H), 7.46 (dd, J=8.0, 4.8 Hz, 1H)
84	¹H NMR(CDCI₃) □: 9.39 (d, J=1.7 Hz, 1H), 8.74 (d, J=3.3 Hz, 1H), 8.40-8.47 (dt, 1H), 8.26 (dd, J=8.0, 0.9 Hz, 1H), 7.71 (dd, J=7.6, 0.9 Hz, 1H), 7.58-7.64 (t, 1H), 7.47 (dd, J=7.2, 5.0 Hz, 1H), 6.94 (brt, 1H), 3.75-3.82 (q, 2H), 2.802.88 (t, 2H), 2.18 (s, 3H)
85	¹H NMR (CDCI3) □: 9.39 (dd, J=2.2, 0.6 Hz, 1H), 8.74 (dd, J=4.9, 1.6 Hz, 1H), 8.39-8.47 (dt, 1H), 8.21-8.28 (dd, 1H), 7.69 (dd, J=7.6, 0.9 Hz, 1H), 7.60 (t, 1H), 7.46 (ddd, J=7.9, 4.8, 0.8 Hz, 1H), 6.93 (brt, 1H), 3.76 (q, 2H), 2.89 (t, J=6.4 Hz, 2H), 1.34-1.41 (s, 9H)
86	¹H NMR (CDCI3) □: 9.32 (d, J=2.4 Hz, 1 H), 8.76 (dd, J=4.8, 1.7 Hz, 1 H), 8.39 (dt, 1H), 8.37 (d, 1H), 8.19 (d, 1H), 8.05 (m, 1H), 7.85 (dd, J=8.8, 2.2 Hz, 1H), 7.47 (dd, 1H), 6.79 (d, J=2.4 Hz, 1H)
87	¹H NMR (CDCI3) □: 9.34 (br s, 1 H), 8.75 (br s, 1 H), 8.41 (dt, J=8.0 Hz, 1 H), 8.16 (d, 1H), 8.13 (t, 1H), 7.72 (dt, J=8.5, 1.6 Hz, 1H), 7.53 (td, 1H), 7.45- 7.49 (m, 1H), 7.35-7.40 (m, 1H), 7.26 (m, 1H), 7.21 (ddd, 1H),

225

88	¹H NMR (CDCI₃) □: 9.33 (br s, 1 H), 8.76 (br s, 1 H), 8.43 (d, J=1.3 Hz, 1 H), 8.37-8.42 (dt, 1H), 8.13 (d, J=8.5 Hz, 1H), 7.86 (dd, J=8.5, 1.9 Hz, 1H), 7.48 (dd, J=7.3, 4.2 Hz, 1H), 6.00 (br d, 1H), 4.35 (m, 1H), 1.32 (d, J=6.6 Hz, 6H)
89	¹H NMR (CDCI3) □: 9.31 (s, 1H), 8.75 (d, J=3.5 Hz, 1H), 8.40 (ddd, 1H), 8.14 (dd, 1H), 8.11 (dd, 1H), 7.69 (dd, J=8.4, 1.6 Hz, 1H), 7.47 (dd, 1H), 3.71 (t, J=7.0 Hz, 2H), 3.51 (t, J=6.6 Hz, 2H), 1.94-2.06 (m, 2H), 1.89-1.94 (m, 2H)
90	¹H NMR (CDCI3) □: 9.32 (brs, 1H), 8.77 (d, J=4.3 Hz, 1H), 8.48 (d, J=1.4 Hz, 1H), 8.40 (dt, J=7.9, 2.0 Hz, 1H), 8.16 (d, J=8.5 Hz, 1H), 7.90 (dd, J=8.5, 1.7 Hz, 1H), 7.48 (dd, J=7.8, 4.7 Hz, 1H), 6.48 (brt, 1H), 4.20 (qd, J=9.0 Hz, 1H)
91	¹H NMR(CDCI₃) □: 9.31 (s, 1H), 8.75 (d, J=3.9 Hz, 1H), 8.39 (dt, J=8.0, 1.9 Hz, 1 H), 8.11 (d, J=8.4 Hz, 1 H), 7.99 (br s, 1 H), 7.52 (d, J=7.1 Hz, 1 H), 7.46 (dd, J=7.8, 4.7 Hz, 1 H), 4.07 + 4.99 (two br s, 1 H), 2.99 + 2.86 (two br s, 3H), 1.14-1.32 (m, 6H)
92	¹H NMR (CDCI3) □: 9.33 (br s, 1 H), 8.76 (d, J=3.9 Hz, 1 H), 8.47 (d, J=1.7 Hz, 1H), 8.40 (dt, J=8.2,1.8 Hz, 1H), 8.13 (dd, J=8.5, 0.6 Hz, 1H), 7.93 (dd, J=8.6, 1.8 Hz, 1H), 7.47 (dd, J=8.0, 4.8 Hz, 1H), 6.92 (d, J=6.9 Hz, 1H), 4.68-4.77 (m, 1H), 1.54 (d, 3H), 1.54 (s, 9H)
93	¹H NMR (CDCI3) □: 9.32 (s, 1H), 8.76 (d, J=4.3 Hz, 1H), 8.43 (d, 1H), 8.40 (ddd, 1H), 8.12 (d, J=8.5 Hz, 1H), 7.83 (dd, J=8.5, 1.7 Hz, 1H), 7.47 (dd, J=7.7, 4.7 Hz, 1 H), 6.32 (br s, 1 H), 2.96 (td, J=7.1, 3.2 Hz, 1 H), 0.93 (m, 2H), 0.68 (m, 2H)
94	¹H NMR (CDCI3) □: 9.32 (brs, 1H), 8.76 (d, J=4.3 Hz, 1H), 8.43 (d, 1H), 8.40 (ddd, 1H), 8.12 (d, J=8.5 Hz, 1H), 7.85 (dd, J=8.5, 1.7 Hz, 1H), 7.47 (dd, J=7.9, 4.7 Hz, 1H), 6.13 (d, 1H), 4.46 (m, 1H), 2.02-2.18 (m, 2H), 1.741.81 (m, 2H), 1.64-1.74 (m, 2H), 1.50-1.62 (m, 2H)
95	¹H NMR (CDCI3) □: 9.32 (br s, 1 H), 8.75 (d, J=4.3 Hz, 1 H), 8.41 (d, 1 H), 8.40 (ddd, 1H), 8.12 (dd, J=8.5, 0.6 Hz, 1H), 7.82 (dd, J=8.5, 1.7 Hz, 1H), 6.06 (t, 1H), 3.03 (d, J=5.8 Hz, 2H), 0.17 (s, 9H)

226

96	^ΊΗ NMR (CDCI₃) □: 9.32 (br. s., 1H), 8.76 (dd, >4.8, 1.7 Hz, 1H), 8.46 (d, >1.7 Hz, 1H), 8.39-8.42 (ddd, 1H), 8.14 (d, >8.5 Hz, 1 H),7.90 (dd, >8.5, 1.7 Hz, 1 H), 7.48 (ddd, >8.0, 4.8, 0.8 Hz, 1 H), 6.72 (br t, 1 H), 3.74 (q, 2H), 2.82 (t, 2H), 2.18 (s, 3H)
97	¹H NMR (CDCI3) □: 9.5-9.2 (br. s, 1H), 8.9-87 (br s, 1H), 8.39-8.43 (m, 2H), 8.12 (d, >8.5 Hz, 1H), 7.86 (dd, >8.5, 1.9 Hz, 1H), 7.6-7.5 (brs, 1H), 6.31 (s, 1H), 3.09 (s, 2H), 2.18 (s, 3H), 1.57 (s, 6H)
98	¹H NMR (DMSO-c/₆) □: 9.30 (dd, >2.4, 0.8 Hz, 1H), 8.76-8.82 (m, 2H), 8.70 (d, >1.3 Hz, 1H), 8.49 (ddd, 1H), 8.17 (d, >9.0 Hz, 1H), 8.05 (dd, >8.5, 1.7 Hz, 1H), 7.64 (ddd, >8.0, 4.7, 0.8 Hz, 1H), 5.02 (t, >4.6 Hz, 1H), 3.93-3.98 (m, 2H), 3.79-3.86 (m, 2H), 3.47 (dd, >5.8, 4.6 Hz, 2H)
99	¹H NMR (DMSO-c7₆) □: 9.31 (dd, >2.4, 0.8 Hz, 1H), 8.79 (dd, >4.8, 1.7 Hz, 1H), 8.70 (t, 1H), 8.67 (s, 1H), 8.50 (ddd, >8.0, 2.3, 1.7 Hz, 1H), 8.18 (d, 1H), 7.99-8.06 (m, 2H), 7.64 (ddd, >8.0, 4.8, 0.9 Hz, 1H), 3.35 (q, >6.4 Hz, 2H), 3.24 (q, >6.3 Hz, 2H), 1.82 (s, 3H)
100	¹H NMR (DMSO-ds) □: 9.31 (dd, >2.3, 0.9 Hz, 1H), 8.79 (dd, >4.7, 1.6 Hz, 1H), 8.74 (dd, 1H), 8.50 (ddd, 1H), 8.45 (d, 1H), 8.18 (d, 1H), 8.05 (dd, J=8.5, 1.7 Hz, 1H), 7.89 (dd, 1H), 7.65 (ddd, >8.0, 4.8, 0.8 Hz, 1H), 4.67 (dd, >10.1, 6.9 Hz, 1H), 3.23-3.30 (m, 1H), 3.07-3.15 (m, 1H), 1.91-1.98 (m, 2H), 1.83-1.68 (m, 2H), 1.55-1.65 (m, 1H), 1.22-1.32 (m, 1H)
101	¹H NMR (CDCI3) □: 9.32 (d, >1.7 Hz, 1 H), 8.76 (dd, >4.7, 1.6 Hz, 1 H), 8.37-8.43 (m, 2H), 8.14 (d, >8.5 Hz, 1H), 7.83 (dd, >8.5, 1.7 Hz, 1H), 7.47 (ddd, >8.0, 4.8, 0.8 Hz, 1H), 6.13 (s, 1H), 1.76 (s, 6H)
102	¹H NMR (DMSO-d₆) □: 9.31 (dd, >2.4, 0.8 Hz, 1H), 8.88 (brs, 1H), 8.79 (dd, >4.7,1.6 Hz, 1H), 8.73 (d, >1.4 Hz, 1H), 8.50 (dt, >8.3, 1.8 Hz, 1H), 8.19 (d, >8.5 Hz, 1H), 8.08 (dd, >8.5, 1.7 Hz, 1H), 7.94 (brt, 1H), 7.64 (ddd, >8.0, 4.8, 0.9 Hz, 1H), 3.88 (brs, 2H), 3.12 (m, 2H), 1.04(t, >7.2 Hz, 2H)
103	¹H NMR (CDCI3) □: 9.33 (s, 1H), 8.77 (d, >3.8 Hz, 1H), 8.41 (d, >7.9 Hz, 1H), 8.31 (s, 1H), 8.14 (d, >8.5 Hz, 1H), 7.76 (dd, >8.5, 1.6 Hz, 1H), 7.48 (dd, >7.6, 4.9 Hz, 1H), 4.61 (t, >11.8 Hz, 4H)

227

104	¹H NMR (CDCI₃) □: 9.33 (s, 1H), 8.76 (d, J=4.1 Hz, 1H), 8.45 (d, 1H), 8.40 , (ddd, 1H), 8.15 (d, J=8.5 Hz, 1H), 7.89 (dd, J=8.5, 1.7 Hz, 1H), 7.48 (dd, J=7.4, 4.9 Hz, 1H), 6.22 (d, J=9.5 Hz, 1H), 5.00 (m, 1H), 1.48 (d, J=6.9 Hz, 3H)
105	¹H NMR (CDCI3) □: 9.31 (s, 1H), 8.74 (d, J=3.3 Hz, 1H), 8.39 (dt, J=7.9, 2.0 Hz, 1H), 8.34 (d, J=1.9Hz, 1H), 8.16 (d, J=8.8 Hz, 1H), 8.02 (d, J=2.5 Hz, 1H), 7.85 (dd, J=8.8, 2.4 Hz, 1H), 7.78 (d, J=1.4 Hz, 1H), 7.47 (dd, J=7.7, 5.4 Hz, 1H), 6.54 (dd, J=2.4, 1.8 Hz, 1H)
106	¹H NMR (CDCI3) □: 9.33 (dd, J=2.2, 0.8 Hz, 1H), 8.76 (dd, J=4.8, 1.7 Hz, 1H), 8.59-8.63 (ddd, 1H), 8.55 (d, J=1.7 Hz, 1H), 8.39-8.44 (ddd, 1H), 8.16 (d, J=8.5 Hz, 1H), 8.02 (dd, J=8.6, 1.8 Hz, 1H), 7.79 (brt, 1H), 7.73 (td, J=7.7, 1.7 Hz, 1H), 7.48 (ddd, J=8.0, 4.8, 0.9 Hz, 1H), 7.37 (d, J=7.7 Hz, 1H), 4.83 (d, J=4.6 Hz, 2H)
107	¹H NMR (CDCI3) □: 9.33 (s, 1H), 8.76 (d, J=3.8 Hz, 1H), 8.38-8.43 (ddd, 1H), 8.19 (s, 1H), 8.14 (d, J=8.4 Hz, 1H), 7.74 (d, J=8.2 Hz, 1H), 7.48 (dd, J=8.0, 4.8 Hz, 1H), 5.19 (br s, 1H), 3.72 (dt, J=10.8, 7.4 Hz, 1H), 3.61 (brs, 1 H), 2.07-2.29 (m, 3H), 1.92 (br s, 1 H)
108	¹H NMR (CDCI3) □: 9.31 and 9.35 (two s, 1H), 8.74 (m, 1H), 8.61 and 8.47 (two d, 1H), ), 8.39 and 8.35 (two d, 1H), 8.21 and 7.70 (two s, 1H), 8.12 and 7.87 (two d, 1H), 7.77 and 6.98 (two d, 1H), 7.67 and 7.53 (two t, 1H), 7.497.43 (m, 1H), 7.41 and 7.31 (two d, 1H), 7.18 and 7.10 (two dd, 1H), 5.40 and 5.01 (two m, 1H), 4.05-3.87 and 3.73-3.67 (m, 2H), 2.51-1.89 (m, 4H)
109	¹H NMR (CDCI3) □: 9.33 (dd, J=2.4, 0.8 Hz, 1H), 8.76 (dd, J=4.8, 1.7 Hz, 1H), 8.51 (d, J=1.7 Hz, 1H), 8.39-8.43 (ddd, 1H), 8.16 (dd, J=8.5, 0.6 Hz, 1H), 7.96 (dd, J=8.5, 1.9 Hz, 1H), 7.55-7.61 (t, 1H), 7.47 (ddd, J=8.0, 4.8, 0.9 Hz, 1H), 7.45 (dd, J=7.8, 0.7 Hz, 1H), 7.35-7.39 (m, 2H), 4.79 (d, J=5.2 Hz, 2H)
110	¹H NMR (CDCI3) □: 9.30-9.36 (m, 1H), 8.76 (dd, J=4.8, 1.7 Hz, 1H), 8.50 (dd, J=9.9, 2.0 Hz, 2H), 8.36-8.44 (ddd, 1H), 8.15 (d, J=8.5 Hz, 1H), 7.97 (dd, J=8.5,1.9 Hz, 1H), 7.71-7.81 (m, 2H), 7.47 (ddd, J=8.0, 4.8, 0.8 Hz, 1H), 5.75-5.84 (pentet, 1H), 1.52-1.60 (m, 3H)

228

111	¹H NMR (acetone-dg) □: 8.88 (dd, J=2.4, 0.8 Hz, 1H), 8.35 (dd, J=4.7, 1.6 Hz, 1H), 8.32 (d, J=1.7 Hz, 1H), 8.19 (d, J=7.6 Hz, 1H), 8.07 (ddd, J=8.0, 2.4, 1.6 Hz, 1H), 7.74 (d, J=8.5 Hz, 1H), 7.66 (dd, J=8.7, 1.7 Hz, 1H), 7.467.53 (t, 1H), 7.21 (ddd, J=8.0, 4.8, 0.8 Hz, 1H), 4.04 (pentet, J=7.3 Hz, 1H), 2.63-2.72 (m, 2H), 0.92 (d, J=7.1 Hz, 3H), 0.60 (t, J=7.2 Hz, 3H)
112	¹H NMR (DMSO-d₆) □: 9.31 (dd, J=2.2, 0.8 Hz, 1H), 8.79 (dd, J=4.7, 1.6 Hz, 1H), 8.73-8.76 (m, 1H), 8.59 (d, J=7.6 Hz, 1H), 8.50 (ddd, J=8.0, 2.4, 1.6 Hz, 1H), 8.18 (d, J=9.0 Hz, 1H), 8.09 (dd, J=8.5, 1.7 Hz, 1H), 7.82 (d, J=7.4 Hz, 1H), 7.65 (ddd, J=8.0, 4.8, 0.8 Hz, 1H), 4.47 (pentet, 1H), 3.79-3.90 (m, 1H), 1.34 (d, J=7.1 Hz, 3H), 1.07 (dd, J=12.8, 6.6 Hz, 6H)
113	¹H NMR (acetone-dg) □: 9.33 (dd, J=2.2, 0.8 Hz, 1H), 8.78 (dd, J=4.8, 1.7 Hz, 1H), 8.70 (dd, J=1.6, 0.8 Hz, 1H), 8.47-8.53 (ddd, 1H), 8.11-8.17 (m, 2H), 8.05 (brd, J=6.8 Hz, 1H), 7.98 (brs, 1H), 7.61 (ddd, J=8.0, 4.8, 0.8 Hz, 1H), 4.75 (quin, J=7.2 Hz, 1H), 3.96-4.09 (m, 2H), 1.51 (d, J=7.1 Hz, 3H)
114	¹H NMR (CDCI3) □: 9.29-9.40 (br s, 1 H), 8.75-8.81 (br s, 1 H), 8.73-8.75 (dd, 1H), 8.40-8.45 (dt, 1H), 8.28 (dd, 1H), 8.19-8.24 (d, 1H), 7.46-7.53 (dd, 1H), 2.51 (s, 3H)
115	¹H NMR (DMSO-d₆) □: 9.70-9.78 (br s, 1H), 9.19-9.26 (dd, 1H), 8.70-8.75 (dd, 1H), 8.38-8.42 (ddd, 1H), 8.35-8.38 (s, 1H), 7.99 (d, 1H), 7.57-7.63 (dd, 1H), 7.49-7.56 (dd, 1H), 1.51 (s, 9H)
116	¹H NMR (DMSO-d₆) □: 9.81 (d, J=1.7 Hz, 1H), 9.25 (dd, J=4.8, 1.7 Hz, 1H), 9.17 (t, J=1.2 Hz, 1H), 8.97 (ddd, J=8.0, 2.4, 1.7 Hz, 1H), 8.61 (m, 2H), 8.09 (ddd, J=8.0, 4.8, 0.8 Hz, 2H), 7.73 (brs, 1H), 7.22-7.30 (brs, 1H)
117	¹H NMR (CDCI3) □: 9.20 (d, J=2.4 Hz, 1H), 8.71 (dd, J=4.7, 1.3 Hz, 1H), 8.65 (s, 1H), 8.58 (d, J=0.8 Hz, 1H), 8.28-8.33 (m, 1H), 8.25 (s, 1H), 7.83 (d, J=9.0 Hz, 1H), 7.64 (dd, J=9.1, 1.5 Hz, 1H), 7.53 (dd, J=8.0, 4.7 Hz, 1H), 6.02-6.14 (m, 1H), 5.35-5.48 (m, 2H), 4.57 (d, J=6.3 Hz, 2H)
118	¹H NMR (CDCI3) □: 9.34 (dd, J=2.2, 0.8 Hz, 1H), 8.79 (d, J=4.9 Hz, 2H), 8.76 (dd, J=4.8, 1.7 Hz, 1H), 8.57 (dd, J=1.7 Hz, 1H), 8.40-8.44 (ddd, 1H), 8.18 (dd, J=8.5 Hz, 1H), 8.04 (dd, J=8.6,1.8 Hz, 1H), 7.70 (brt, 1H), 7.46- 7.50 (ddd, 1H), 7.29 (t, J=4.9 Hz, 1H), 4.97 (d, J=4.6 Hz, 2H).

229

119	¹H NMR (CDCI3) □: 9.33 (dd, J=2.3, 0.7 Hz, 1H), 8.77 (dd, J=4.8, 1.7 Hz, 1H), 8.66 (s, 1H), 8.38-8.43 (dt, 1H), 8.33 (d, J=2.2 Hz, 1H), 8.22 (d, J=8.8 Hz, 1H), 8.17 (s, 1H), 7.84 (dd, J=8.8, 2.2 Hz, 1H), 7.46-7.51 (ddd, 1H)
120	¹H NMR (CDCI3) □: 9.34 (s, 1H), 8.77 (d, 1H), 8.40-8.45 (m, 1H), 8.35-8.49 (m, 1H), 8.25-8.31 (m, 2H), 7.97-8.03 (d, 1H), 7.91 (dd, J=8.7, 2.1 Hz, 1H), 7.54-7.62 (m, 2H), 7.45-7.51 (dd, 1H)
121	¹H NMR (CDCI3) □: 9.11 (s, 1 H), 8.62 (d, J=2.8 Hz, 1 H), 8.47 (d, J=1.4 Hz, 1H), 8.17 (ddd, 1H), 8.15 (d, 1H), 7.91 (dd, J=8.5, 1.7 Hz, 1H), 6.66-6.72 (br t, 1H), 3.74 (q, J=6.6 Hz, 2H), 2.79-2.85 (t, 2H), 2.18 (s, 3H)
122	¹H NMR(CDCI₃) □: 9.08-9.15 (br s, 1H), 8.57-8.66 (brs, 1H), 8.46 (d, J=1.3 Hz, 1H), 8.17 (ddd, 1H), 8.14 (d, J=8.5 Hz, 1H), 7.91 (dd, J=8.5, 1.7 Hz, 1H), 6.62 (br m, 1 H), 4.11 (qd, J=7.3, 3.3 Hz, 1 H), 3.90-3.95 (dt, 1 H), 3.84-3.90 (ddd, 1H), 3.78-3.84 (dt, 1H), 3.37 (ddd, J=13.7, 7.7, 4.6 Hz, 1H), 2.02-2.13 (m, 1H), 1.91-2.00 (m, 2H), 1.60-1.70 (m, 1H)
123	¹H NMR (CDCI3) □: 9.11 (s, 1 H), 8.62 (d, J=2.5 Hz, 1 H), 8.45 (d, J=1.3 Hz, 1H), 8.17 (ddd, 1H), 8.14 (d, 1H), 7.90 (dd, J=8.5,1.7 Hz, 1H), 6.43-6.51 (br d, 1H), 4.37-4.50 (m, 1H), 3.55 (dd, J=3.9 Hz, 1H), 3.46-3.49 (dd, 1H), 3.42 (s, 3H).
124	¹H NMR(CDCI₃) □: 9.11 (s, 1H), 8.62 (d, J=2.7 Hz, 1H), 8.45 (d, J=1.3 Hz, 1H), 8.15-8.18 (ddd, 1H), 8.13 (d, J=8.5 Hz, 1H), 7.87 (dd, J=8.5, 1.9 Hz, 1H), 6.13-6.20 (brs, 1H), 3.57 (dq, J=7.3, 5.6 Hz, 2H), 1.31 (t, J=7.3 Hz, 3H)
125	¹H NMR(CDCI₃) □: 9.06-9.20 (brs, 1H), 8.55-8.70 (brs, 1H), 8.14-8.19 (m, 2H), 8.10-8.13 (d, 1H), 7.70 (dd, J=8.4, 1.7 Hz, 1H), 3.66-3.74 (t, 2H), 3.50 (t, 2H), 2.05-1.97 (m, 2H), 1.96-1.89 (m, 2H)
126	¹H NMR (CDCI₃) □: 9.07-9.15 (brs, 1H), 8.59-8.66 (brs, 1H), 8.44 (d, J=1.4 Hz, 1H), 8.15-8.18 (ddd, 1H), 8.13 (d, J=8.5 Hz, 1H), 7.87 (dd, J=8.5, 1.9 Hz, 1H), 5.96-6.04 (brd, 1H), 4.30-4.40 (m, 1H), 1.32 (d, J=6.6 Hz, 6H).
127	¹H NMR(CDCI₃) □: 9.13 (brs, 1H), 8.64 (brs, 1H), 8.49 (d, J=1.7 Hz, 1H), 8.14-8.20 (m, 2H), 7.92 (dd, J=8.5, 1.7 Hz, 1H), 6.43 (brt, J=6.6 Hz, 1H), 4.20 (qd, J=9.0, 6.5 Hz, 2H)

230

128	¹H NMR (CDCI₃) □: 9.32 (br s, 1 H), 8.75 (br s, 1 H), 8.40 (dt, J=8.2, 1.8 Hz, 1H), 8.27 (d, J=2.2 Hz, 1H), 8.17 (d, J=8.8 Hz, 1H), 7.84 (d, J=3.9 Hz, 1H), 7.79 (dd, J=8.7, 2.1 Hz, 1H), 7.47 (dd, J=7.9, 4.9 Hz, 1H), 7.13-7.18 (dq, 1H), 2.31 (d, J=1.3 Hz, 3H)
129	¹H NMR (CDCI3) □: 9.49 (s, 1H), 9.19 (s, 1H), 9.13 (s, 1H), 8.80 (d, J=4.7 Hz, 2H), 8.73 (s, 1H), 8.60-8.67 (m, 1H), 8.19 (d, J=8.5 Hz, 1H), 7.84 (brs, 1H), 7.29-7.36 (m, J=9.6 Hz, 1H), 5.00 (d, J=4.3 Hz, 2H)
130	¹H NMR (CDCI3) □: 9.44 (s, 1H), 9.12 (d, J=0.8 Hz, 2H), 8.62 (d, J=2.5 Hz, 1H), 8.47 (s, 1H), 8.15 (d, J=8.8 Hz, 1H), 6.15 (brs, 1H), 4.29-4.45 (m, 1H), 1.35 (d, J=6.6 Hz, 6H)
131	¹H NMR (CDCI3) □: 9.03 (s, 1H), 8.60 (d, J=0.6 Hz, 1H), 8.56 (d, J=2.4 Hz, 1H), 8.27 (s, 1H), 8.13 (d, J=9.1 Hz, 1H), 7.79 (d, J=9.0 Hz, 1H), 7.73 (d, J=7.6 Hz, 1 H), 6.64 (br s, 1 H), 4.06-4.22 (m, 1 H), 3.92 (dt, J=8.3, 6.7 Hz, 1H), 3.76-3.88 (m, 2H), 3.37 (ddd, J=13.8, 7.6, 4.6 Hz, 1H), 2.03-2.13 (m, 1H), 1.91-2.00 (m,2H), 1.81 (brs, 1H), 1.65 (dd, J=12.2, 8.1 Hz, 1H)
132	¹H NMR (CDCI3) □: 9.03 (d, J=1.9 Hz, 1 H), 8.61 (d, J=0.9 Hz, 1 H), 8.57 (d, J=2.4 Hz, 1H), 8.27-8.32 (m, J=1.6, 0.9 Hz, 1H), 8.11-8.16 (m, 1H), 7.82 (d, J=9.3 Hz, 1 H), 7.74 (dd, J=7.3, 1.7 Hz, 1 H), 6.50 (br s, 1 H), 3.92 (td, J=13.7, 6.3 Hz, 2H), 1.66-1.79 (m, 3H), 1.71 (t, J=18.6 Hz, 4H)
133	¹H NMR (CDCI3) □: 9.03 (s, 1H), 8.60 (d, J=0.8 Hz, 1H), 8.56 (d, J=2.5 Hz, 1H), 8.27 (s, 1H), 8.13 (d, J=9.0 Hz, 1H), 7.80 (d, J=9.1 Hz, 1H), 7.72 (dd, J=9.1, 1.6 Hz, 1H), 6.50 (t, J=5.3 Hz, 1H), 4.54 (t, J=5.2 Hz, 1H), 3.66 (t, J=5.5 Hz, 2H), 3.47 (s, 6H)
134	¹H NMR (DMSO-c/₆) □: 9.41 (d, J=0.8 Hz, 1H), 9.37 (d, J=2.4 Hz, 1H), 9.01 (s, 1H), 8.66-8.72 (m, 1H), 8.50-8.57 (m, 1H), 8.44 (s, 1H), 7.85 (d, J=4.4 Hz, 2H), 7.78 (d, J=9.3 Hz, 1H), 7.65 (s, 2H), 7.21 (d, J=4.4 Hz, 1H), 4.49 (d, J=5.5 Hz, 2H)
135	¹H NMR (acetone-dg) δ: 10.24 (brs, 1H), 9.13 (d, J=2.5 Hz, 1H), 8.86 (dd, J=4.7, 1.4 Hz, 1H), 8.51 (br. s, 1H), 8.29-8.39 (m, 2H), 8.00 (dd, J=8.4, 1.0 Hz, 1H), 7.76 (ddd, J=8.2, 4.7, 0.8 Hz, 1H), 7.45 (t, J=7.5 Hz, 1H), 3.69 (brs, 3H)

231

136	^ΊΗ NMR (acetone-dg) δ: 9.25 (brs, 1H), 9.11 (d, J=2.2 Hz, 1H), 8.86 (d, J=5.4 Hz, 1H), 8.29-8.39 (m, 2H), 7.99 (d, J=8.3 Hz, 1H), 7.77 (ddd, J=8.2, 4.8, 0.7 Hz, 1H), 7.46 (t, J=7.8 Hz, 1H), 4.36 (qd, J=9.5, 6.5 Hz, 2H)
137	¹H NMR (acetone-dg) δ: 10.06 (brs, 1H), 9.34 (d, J=2.5 Hz, 1H), 8.76-8.88 (m, 3H), 8.44-8.55 (m, 1H), 8.30 (dd, J=6.9, 1.1 Hz, 1H), 7.94 (dd, J=8.5, 1.1 Hz, 1H), 7.79 (ddd, J=8.2, 4.8, 0.8 Hz, 1H), 7.42-7.45 (m, 1H), 7.41 (s, 1H), 4.93 (d, J=4.7 Hz, 2H)
138	1¹H NMR (CDCI₃) δ: 10.25 (brs, 1H), 9.66 (s, 1H), 8.80-8.88 (m, 1H), 8.73 (d, J=4.9 Hz, 1H), 8.60 (dt, J=8.1, 1.9 Hz, 1H), 8.29 (dd, J=7.7, 0.9 Hz, 2H), 7.78 (dd, J=8.2, 0.9 Hz, 1H), 7.46-7.59 (m, 1H), 7.23-7.33 (m, 1H), 5.11 (d, J=4.6 Hz, 2H)
139	¹H NMR (CDCI3) δ: 9.53 (dd, J=2.2, 0.6 Hz, 1 H), 9.35 (br s, 1 H), 8.82 (dd, J=4.9, 1.6 Hz, 1H), 8.56 (dt, J=8.0, 1.9 Hz, 1H), 8.25 (dd, J=7.8, 1.0 Hz, 1H), 7.75 (dd, J=8.1, 1.0 Hz, 1H), 7.46-7.58 (m, 2H), 4.22 (dd, J=6.8, 3.8 Hz, 1H), 4.04 (dt, J=8.2, 6.7 Hz, 1H), 3.81-3.92 (m, 2H), 3.61-3.75 (m, 1H), 2.02-2.18 (m, 1H), 1.86-2.01 (m, 3H), 1.67-1.85 (m, 2H)
140	¹H NMR (CDCI3) δ: 9.51 (dd, J=2.2, 0.9 Hz, 1 H), 9.44 (br s, 1 H), 8.85 (dd, J=4.8, 1.7 Hz, 1H), 8.53 (d, J=7.9 Hz, 1H), 8.27 (d, J=7.8 Hz, 1H), 7.82 (d, J=8.0 Hz, 1H), 7.47-7.63 (m, 2H), 4.30 (qd, J=9.2, 6.2 Hz, 2H), 0.07 (s, 1H), 0.01 (s, 1H), -0.01 (s, 1H)
141	¹H NMR(CDCI₃) δ: 9.49 (s, 1H), 9.07 (br. s, 1H), 8.83 (d, J=5.1 Hz, 1H), 8.51 (d, J=7.9 Hz, 1H), 8.25 (d, J=7.8 Hz, 1H), 8.02 (s, 2H), 7.75 (d, J=8.1 Hz, 1H), 7.46-7.58 (m, 2H), 3.08 (dd, J=7.3, 3.7 Hz, 1H), 0.88-1.03 (m, 2H), 0.70-0.81 (m, 2H),
142	¹H NMR(CDCI3) δ: 9.20 (d, J=2.2 Hz, 1H), 9.14 (brs, 1H), 8.73 (d, J=5.2 Hz, 1H), 8.57 (s, 1H), 8.35 (d, J=7.1 Hz, 1H), 8.20 (d, J=8.3 Hz, 1H), 7.88 (d, J=8.2 Hz, 1H), 7.56 (ddd, J=8.2, 4.8, 0.7 Hz, 1H), 7.30 (t, J=7.7 Hz, 1H), 3.08 (td, J=7.3, 3.5 Hz, 1H), 0.87-1.01 (m, 2H), 0.65-0.80 (m, 2H), 0.01 (brs, 1H), -0.01 (brs, 1H)

232

158	^ΊΗ NMR (CDCI3) δ: 9.46 (s, 1 Η), 8.76 (d, J=3.9 Hz, 1H), 8.49 (dt, J=8.0, 1.9 Hz, 1H), 8.26-8.40 (m, 1H), 7.68 (d, J=8.5 Hz, 1H), 7.47 (dd, J=7.7, 5.0 Hz, 1H), 7.16 (dd, J=8.5, 2.0 Hz, 1H), 3.71-3.83 (m, 1H), 3.55-3.71 (m, 1H), 3.48 (t, J=6.8 Hz, 1H), 3.38 (s, 1H), 3.13-3.30 (m, 1H), 2.85 (s, 1H), 2.17-2.35 (m, 3H)
159	¹H NMR (acetone-dg) δ: 9.39 (d, J=1.6 Hz, 1H), 8.81 (dd, J=4.9, 1.6 Hz, 1H), 8.55-8.73 (m, 1H), 8.45 (d, J=1.7 Hz, 1H), 7.69-7.85 (m, 2H), 7.48 (dd, J=8.6, 2.0 Hz, 1H), 1.78-1.90 (m, 1H), 0.89-1.07 (m, 3H), 0.83 (dt, J=7.9, 3.3 Hz, 2H)
160	¹H NMR (acetone-dg) δ: 9.37 (d, J=1.7 Hz, 1H), 8.75 (d, J=5.2 Hz, 1H), 8.52 (dt, J=8.0, 1.9 Hz, 1H), 8.33 (brs, 1H), 8.22 (d, J=8.0 Hz, 1H), 8.09 (d, J=7.6 Hz, 1H), 7.66 (t, J=7.9 Hz, 1H), 7.58-7.62 (m, 1H), 4.62-4.73 (m, 1H), 2.74- 2.86 (m, 1H), 2.30-2.45 (m, 2H), 2.19 (dq, J=11.9, 9.5 Hz, 2H), 1.73-1.84 (m, 2H)
161	¹H NMR (acetone-dg) δ: 9.36 (s, 1H), 8.75 (d, J=5.0 Hz, 1H), 8.49 (d, J=7.9 Hz, 1H), 8.20-8.22 (m, 1H), 8.20 (s, 1H), 8.11 (d, J=7.6 Hz, 1H), 7.65 (t, J=7.6 Hz, 1H), 7.58 (ddd, J=8.0, 4.8, 0.8 Hz, 1H), 4.11 (dd, J=6.8, 4.9 Hz, 1H), 3.83-3.88 (m, 1H), 3.60-3.72 (m, 2H), 3.51 (ddd, J=13.6, 6.7, 5.8 Hz, 1H), 3.33 (s, 2H), 1.99-2.07 (m, 1H), 1.83-1.96 (m, 2H), 1.66-1.73 (m, 1H)
162	¹H NMR (acetone-dg) δ: 9.37 (d, J=1.7 Hz, 1H), 8.76 (dd, J=4.7, 1.6 Hz, 1H), 8.52 (dt, J=8.0, 1.9 Hz, 1H), 8.25 (d, J=8.0 Hz, 1H), 8.18 (d, J=7.6 Hz, 1H), 7.69 (t, J=7.8 Hz, 1H), 7.60 (dd, J=8.0, 4.8 Hz, 1H), 3.72 (s, 3H)
163	1H NMR (acetone-dg) δ: 9.37 (s, 1H), 8.76 (d, J=5.1 Hz, 1H), 8.52 (d, J=8.0 Hz, 1H), 8.22 (dd, J=8.0, 0.9 Hz, 2H), 8.01 (d, J=7.7 Hz, 1H), 7.58-7.66 (m, 2H), 3.04 (td, J=7.3, 3.9 Hz, 1H), 0.77-0.87 (m, 2H), 0.65-0.75 (m, 2H)
173	¹H NMR (CDCI3) δ: 9.25 (d, J=2.5 Hz, 1H), 9.16 (d, J=6.6 Hz, 1H), 8.73 (dd, J=4.8, 1.3 Hz, 1H), 8.58-8.69 (m, 2H), 8.41 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 7.71 (dd, J=5.7, 3.3 Hz, 1 H), 7.40-7.63 (m, 1 H), 6.64 (br s, 1 H), 4.22 (dd, J=8.6, 6.1 Hz, 1H), 4.12 (qd, J=7.4, 3.2 Hz, 1H), 3.78-3.97 (m, 3H), 3.38 (ddd, J=13.7, 7.8, 4.7 Hz, 1H), 1.88-2.02 (m, 2H)

233

200	¹H NMR(CDCI₃) δ: 11.67-12.28 (m, 1H), 9.26-9.29 (m, 1H), 8.63 (dd, J=4.7, 1.4 Hz, 1H), 8.33 (dt, J=8.0, 1.9 Hz, 1H), 7.81 (brs, 1H), 7.30-7.41 (m, 2H), 7.28 (s, 1H), 7.20 (t, J=7.7 Hz, 1H), 3.72 (d, J=6.8 Hz, 3H), 1.91-2.08 (m, 5H)
201	¹H NMR (CDCI₃) Shift: 9.57 (s, J=8.6 Hz, 1H), 8.64-8.71 (m, 2H), 8.15 (s, 1H), 7.49-7.88 (m, 2H), 7.39 (t, J=6.7 Hz, 1H), 6.17 (brs, 1H), 4.24-4.40 (m, 1 H), 1.26-1.32 (m, 7H)
300	¹H NMR (acetone-d₆) δ: 9.29-9.37 (m, 1H), 8.79 (d, J=4.9 Hz, 2H), 8.62 (d, J=2.5 Hz, 1H), 8.47 (d, J=9.5 Hz, 1H), 7.93 (d, J=8.6 Hz, 1H), 7.81 (dd, J=6.9, 0.6 Hz, 1H), 7.48 (dd, J=8.7, 6.9 Hz, 1H), 7.31-7.43 (m, 1H), 4.87 (d, J=5.5 Hz, 2H)
301	¹H NMR (acetone-dg) δ: 9.61 (s, 1H), 9.36 (d, J=0.9 Hz, 1H), 9.25 (s, 1H), 8.33-8.54 (m, 1H), 7.97 (dt, J=8.8, 0.8 Hz, 1H), 7.80 (d, J=7.0 Hz, 1H), 7.47 (dd, J=7.7 Hz, 1H), 4.27 (dd, J=9.6, 6.5 Hz, 1H)
302	¹H NMR (acetone-dg) δ: 9.60 (s, 2H), 9.38 (s, 1H), 9.24 (s, 1H), 8.79 (d, J=4.9 Hz, 1H), 8.31 (brs, 1H), 7.95 (d, J=8.7 Hz, 1H), 7.82 (d, J=6.9 Hz, 1H), 7.49 (dd, J=8.6, 7.0 Hz, 1H), 7.39 (t, J=4.8 Hz, 1H), 4.87 (d, J=5.5 Hz, 2H)
303	¹HNMR(CDCI₃) δ: 9.31 (d, J=2.7 Hz, 1H), 9.13 (d, J=0.9 Hz, 1H), 8.83 (s, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.26-8.46 (m, 1H), 8.09 (dd, J=6.9, 0.8 Hz, 1H), 7.99 (d, J=8.7 Hz, 1H), 7.38-7.59 (m, 2H),
304	¹H NMR (CDCI₃) δ: 9.33 (s, 1H), 9.29 (d, J=2.2 Hz, 1H), 9.07 (s, 1H), 8.69 (d, J=4.7 Hz, 1H), 8.35 (dd, J=8.4, 1.6 Hz, 1H), 8.05 (s, 2H), 7.94 (d, J=8.5 Hz, 1H), 7.71 (d, J=6.9 Hz, 1H), 7.44-7.61 (m, 2H)
305	¹H NMR (CDCI₃) δ: 9.27 (d, J=2.4 Hz, 1H), 9.08-9.14 (m, 1H), 8.68 (dd, J=4.7, 1.3 Hz, 1H), 8.61 (s, 1H), 8.44 (s, 1H), 8.21-8.38 (m, 1H), 7.97 (d, J=8.7 Hz, 1H), 7.45-7.59 (m, 2H), 7.40 (dd, J=8.7, 6.9 Hz, 2H), 4.85 (d, J=5.0 Hz, 3H) 2.53-2.67 (s, 3H)
306	¹H NMR(CDCI₃) δ: 9.08 (brs, 1H), 8.41 (brs, 1H), 7.85 (d, J=7.6 Hz, 3H), 7.58 (br s, 2H), 7.34 (br s, 1 H), 6.94 (br s, 2H), 4.64 (br s, 1 H), 3.56-3.74 (m, 3H), 2.25 (br s, 2H), 1.80 (br s, 2H), 1.73 (s, 1 H), 1.70 (s, 1 H), 1.50 (s, 1 H), 1.40 (brs, 1H)

234

307	^ΊΗ NMR (CDCI₃) δ: 9.05-9.15 (m, 2H), 8.56 (d, J=2.5 Hz, 1H), 8.13 (dt, J=9.1, 2.3 Hz, 1 H), 7.90-8.06 (m, 1 H), 7.49 (d, J=6.5 Hz, 1 H), 7.41 (dd, J=8.7, 6.9 Hz, 1H), 6.50 (brs, 1H), 4.21 (qd, J=9.0, 6.5 Hz, 2H)
308	¹H NMR (CDCI3) δ: 9.04-9.15 (m, 2H), 8.54 (d, J=2.5 Hz, 1H), 8.13 (dt, J=9.1, 2.3 Hz, 1H), 7.92 (d, J=8.7 Hz, 1H), 7.46 (d, J=6.5 Hz, 1H), 7.38 (dd, J=8.7, 6.9 Hz, 1 H), 6.69 (br s, 1 H), 4.13 (qd, J=7.2, 3.2 Hz, 1 H), 3.76-3.96 (m, 3H), 3.40 (ddd, J=13.8, 7.7, 4.7 Hz, 1H), 2.02-2.18 (m, 1H), 1.90-2.02 (m, 2H), 1.51-1.71 (m, 2H)
309	¹H NMR(CDCI₃) δ: 9.13 (s, 1H), 9.09 (s, 1H), 8.54 (d, J=2.2 Hz, 1H), 8.13 (dt, J=9.1, 2.3 Hz, 1H), 7.92 (ddd, J=7.2, 2.3, 0.9 Hz, 1H), 7.32-7.43 (m, 2H), 6.08 (d, J=6.5 Hz, 1H), 4.36 (dt, J=7.7, 6.6 Hz, 1H), 1.33 (d, J=6.5 Hz, 5H)
310	¹H NMR (acetone-c/g) δ: 9.39-9.55 (m, 2H), 9.35 (d, J=18.6 Hz, 1H), 8.72- 8.86 (m, 4H), 8.62 (dt, J=8.3, 1.3 Hz, 1H), 8.49 (br. s, 1H), 7.69 (ddd, J=8.4, 4.7, 0.6 Hz, 1H), 7.39 (t, J=4.9 Hz, 1H), 4.89 (d, J=5.7 Hz, 2H)
311	¹H NMR(CDCI₃) δ: 9.45 (s, 1H), 9.29 (d, J=2.4 Hz, 1H), 9.13 (s, 1H), 8.75 (dd, J=4.7, 1.4 Hz, 1H), 8.44 (s, 1H), 8.29-8.36 (m, 1H), 7.55 (ddd, J=8.3, 4.8, 0.6 Hz, 1 H), 6.54 (br s, 1 H), 2.87-3.06 (m, 1 H), 0.96 (dd, J=7.0, 1.2 Hz, 2H), 0.73 (td, J=2.5, 1.3 Hz, 2H)
312	¹H NMR (CDCI3) δ: 9.46 (s, 1H), 9.28 (d, J=2.4 Hz, 1H), 9.08 (s, 1H), 8.75 (d, J=5.2 Hz, 1H), 8.54 (s, 1H), 8.33 (d, J=8.2 Hz, 1H), 7.54 (ddd, J=8.3, 4.8, 0.6 Hz, 1H), 6.79 (brs, 1H), 4.14 (dd, J=7.2, 3.2 Hz, 1H), 3.79-3.98 (m, 4H), 3.40-3.55 (m, 1H), 2.17 (s, 1H), 2.03-2.13 (m, 1H), 1.90-2.02 (m, 2H)
313	¹H NMR (CDCI3) δ: 9.47 (s, 1H), 9.28 (d, J=2.4 Hz, 1H), 9.08 (d, J=0.8 Hz, 1H), 8.75 (dd, J=4.7, 1.4 Hz, 1H), 8.53 (s, 1H), 8.33 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 7.55 (ddd, J=8.4, 4.7, 0.6 Hz, 1H), 6.56 (brs, 1H), 4.56 (t, J=5.1 Hz, 1H), 3.62-3.79 (m, 2H), 3.48 (s, 6H)
314	¹H NMR (CDCI3) δ: 9.46 (s, 1H), 9.29 (d, J=2.4 Hz, 1H), 9.09 (s, 1H), 8.75 (dd, J=4.7, 1.4 Hz, 1 H), 8.52 (s, 1 H), 8.30-8.37 (m, 1 H), 7.54 (dd, J=8.4, 4.7 Hz, 1H), 7.26 (s, 1H), 6.45 (brs, 1H), 3.41 (d, J=7.1 Hz, 1H), 3.42 (d, J=7.3 Hz, 1H), 1.09 (s, 3H), 0.56-0.68 (m, 2H), 0.27-0.40 (m, 2H)

235

315	¹H NMR (acetone-dg) δ: 9.61 (brs, 1H), 9.38 (d, J=6.1 Hz, 1H), 9.22 (s, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.46-8.56 (m, 2H), 8.28 (br. S, 1H), 7.80-7.97 (m, 2H), 7.66 (ddd, J=8.4, 4.7, 0.6 Hz, 1H), 3.71 (s, 3H)
316	¹H NMR(CDCI₃)5: 9.10 (brs, 1H), 8.40 (brs, 1H), 7.75 (brs, 2H), 7.58 (br s, 1 H), 7.31 (d, J=9.3 Hz, 1 H), 6.94 (br s, 1 H), 1.77 (br s, 1 H), 1.08 (br s, 2H), 0.84 (br s, 2H)
320	¹H NMR (acetone-dg) δ: 9.38 (d, J=2.4 Hz, 1H), 9.18 (d, J=0.9 Hz, 1H), 8.959.07 (m, 1H), 8.89 (d, J=5.1 Hz, 2H), 8.68 (dd, J=4.7, 1.4 Hz, 1H), 8.51 (d, J=8.9 Hz, 2H), 7.83 (d, J=9.1 Hz, 1H), 7.65 (ddd, J=8.3, 4.7, 0.7 Hz, 1H), 7.37 (t, J=4.8 Hz, 1H)
321	¹H NMR (CDCI₃) δ: 9.37 (d, J=2.5 Hz, 1H), 9.18 (d, J=0.9 Hz, 1H), 8.69 (dd, J=4.6, 1.3 Hz, 1H), 8.44-8.57 (m, 2H), 8.02-8.09 (m, 1H), 7.77-7.96 (m, 1H), 7.65 (dd, J=8.4, 4.7 Hz, 1H), 7.32 (d, J=0.8 Hz, 1H)
322	¹H NMR (CDCI₃) δ: 9.49 (d, J=2.0 Hz, 1H), 9.24 (d, J=2.5 Hz, 1H), 8.87 (dd, J=4.8, 1.5 Hz, 1H), 8.66-8.74 (m, 1H), 8.64 (s, 1H), 8.52 (dt, J=8.0, 1.9 Hz, 1H), 8.23-8.42 (m, 1H), 8.13 (dd, J=9.2,1.5 Hz, 1H), 7.92 (d, J=9.1 Hz, 1H), 7.40-7.57 (m, 2H)
323	¹H NMR (acetone-dg) δ: 9.35 (d, J=2.7 Hz, 1H), 9.15 (d, J=0.9 Hz, 1H), 8.68 (dd, J=4.7, 1.4 Hz, 1H), 8.49 (ddd, J=8.4, 2.7, 1.4 Hz, 1H), 8.40-8.46 (m, 1H), 7.88 (dd, J=9.1, 1.7 Hz, 2H), 7.76 (dt, J=9.1, 0.9 Hz, 1H), 7.64 (ddd, J=8.3, 4.7, 0.7 Hz, 1H), 3.72 (t, J=5.6 Hz, 2H), 3.55 (q, J=5.7 Hz, 2H)
324	¹H NMR (acetone-dg) δ: 9.10 (s, 1H), 8.45 (s, 2H), 8.09-8.15 (m, 3H), 7.75- 7.85 (m, 3H), 7.62 (t, J=7.7 Hz, 3H), 7.49 (t, J=7.5 Hz, 2H)
325	¹H NMR (CDCI₃) δ: 9.22 (s, 1H), 8.93 (dd, J=7.1 Hz, 1H), 8.69 (d, J=5.1 Hz, 1H), 8.62 (d, J=5.2 Hz, 1H), 8.55 (s, 1H), 8.32 (d, J=8.2 Hz, 1H), 7.89-7.97 (m, 3H), 7.60 (d, J=8.8 Hz, 1H), 7.52 (ddd, J=8.3, 4.8, 0.6 Hz, 1H), 7.40 (ddd, J=7.9, 4.8, 0.9 Hz, 1H)
326	¹H NMR (acetone-dg) δ: 9.37 (d, J=2.4 Hz, 1H), 9.19 (s, 1H), 8.77 (dd, J=1.7, 0.9 Hz, 1H), 8.69 (d, J=5.1 Hz, 1H), 8.63 (d, J=5.0 Hz, 1H), 8.51 (d, J=8.2 Hz, 1H), 8.21 (dd, J=5.0 Hz, 1H), 7.87 (dt, J=9.3, 0.9 Hz, 1H), 7.75 (d, J=5.5 Hz, 1H), 7.65 (ddd, J=8.3, 4.7, 0.7 Hz, 1H), 2.65 (s, 3H)

236

327	¹H NMR (acetone-dg) δ: 9.37 (d, J=6.3 Hz, 1H), 9.21 (s, 1H), 8.78-8.85 (m, 1H), 8.69 (dd, J=7.5 Hz, 1H), 8.51 (d, J=8.2 Hz, 1H), 8.18 (d, J=9.0 Hz, 1H), 7.82-7.92 (m, 2H), 7.65 (dd, J=8.2, 4.7 Hz, 1H), 4.16-4.28 (m, 2H), 4.12 (s, 2H), 1.22-1.31 (m, 3H)
328	¹H NMR (acetone-dg) δ: 9.36 (d, J=2.5 Hz, 1H), 9.19 (s, 1H), 8.69 (dd, J=4.7, 1.3 Hz, 1H), 8.50 (d, J=8.3 Hz, 1H), 8.46 (s, 1 H), 8.11-8.19 (m, 1H), 7.88 (d, J=8.8 Hz, 1H), 7.79 (d, J=9.1 Hz, 1H), 7.64 (t, J=6.8 Hz, 1H), 4.18 (d, J=6.0 Hz, 2H), 3.70-3.74 (m, 3H)
340	¹H NMR (acetone-dg) δ: 9.38 (d, J=2.5 Hz, 1H), 9.25 (s, 1H), 9.00 (s, 1H), 8.65-8.84 (m, 1 H), 8.58 (s, 1 H), 8.38-8.56 (m, 1 H), 8.05 (dd, J=9.1, 1.6 Hz, 1H), 7.94 (d, J=9.1 Hz, 1H), 7.67 (dd, J=8.3, 4.7 Hz, 1H)
341	¹H NMR (acetone-dg) δ: 9.37 (d, J=2.2 Hz, 1H), 9.19 (d, J=0.9 Hz, 1H), 8.76 (dd, J=1.7, 0.9 Hz, 1H), 8.69 (dd, J=4.7,1.4 Hz, 1H), 8.62 (d, J=5.4 Hz, 1H), 8.51 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 8.19 (dd, J=9.2, 1.7 Hz, 1H), 7.86 (dt, J=9.1, 0.9 Hz, 1H), 7.77 (d, J=5.4 Hz, 1H), 7.64 (ddd, J=8.3, 4.7, 0.7 Hz, 1H), 4.14-4.26 (m, 1H), 4.20 (d, J=7.1 Hz, 2H), 4.10 (s, 2H), 1.20-1.27 (m, 3H)
342	¹H NMR (acetone-dg) δ: 9.36 (d, J=2.7 Hz, 1H), 9.20 (s, 1H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.43-8.59 (m, 2H), 7.86 (d, J=9.0 Hz, 1H), 7.80 (d, J=9.0 Hz, 1H), 7.58-7.72 (m, 1H) 2.01-2.09 (m, 10H)
347	¹H NMR (acetone-dg) δ: 9.38 (brs, 2H), 9.17 (brs, 1H), 8.70 (brs, 1H), 8.54 (d, J=8.0 Hz, 1H), 8.26 (s, 1H), 7.94 (dd, J=9.1, 1.4 Hz, 2H), 7.76-7.90 (m, 2H), 7.61-7.76 (m, 3H), 6.97-7.16 (m, 2H), 6.75-6.97 (m, 3H), 4.32 (qd, J=7.0, 4.5 Hz, 1H), 3.98-4.19 (m, 2H), 3.70-3.91 (m, 2H), 1.82-2.00 (m, 3H), 1.73 (ddt, 3H)
348	¹H NMR (CDCI3) δ: 9.22 (d, J=2.4 Hz, 1H), 8.97 (s, 1H), 8.70 (d, J=3.8 Hz, 1H), 8.59 (s, 1H), 8.48 (s, 1H), 8.23-8.41 (m, 1H), 7.96-8.12 (m, 2H), 7.85- 7.96 (m, 2H), 7.52 (dd, J=8.2, 4.7 Hz, 1H), 7.26 (s, 1H)
349	¹H NMR (DMSO-d₆) δ: 9.34 (d, J=2.4 Hz, 1H), 9.13 (d, J=6.9 Hz, 1H), 8.64 (d, J=5.3 Hz, 1H), 8.46-8.55 (m, 1H), 8.17 (d, J=6.6 Hz, 1H), 7.72 (dd, J=8.7, 1.0 Hz, 1H), 7.60-7.67 (m, 2H), 1.60 (s, 3H)

237

355	¹H NMR (CDCl₃) δ: 9.21 (d, J=2.2 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.59 (d, J=0.9 Hz, 1H), 8.34 (s, 1H), 8.30 (d, J=8.1 Hz, 1H), 7.80-7.91 (m, 1H), 7.76 (dd, J=8.8 Hz, 1H), 7.52 (ddd, J=8.2, 4.8, 0.7 Hz, 1H), 7.11 (br. s, 1H), 4.43-4.50 (m, 2H), 4.23-4.35 (m, 2H), 3.41 (t, J=8.4 Hz, 2H)
356	¹H NMR (acetone-dg) δ: 9.47 (brs, 1H), 9.35 (d, J=2.7 Hz, 1H), 8.97 (s, 1H), 8.65 (d, J=5.0 Hz, 1H), 8.41-8.54 (m, 2H), 7.78 (s, 1H), 7.72 (d, J=9.1 Hz, 1H), 7.59-7.67 (m, 2H), 7.24 (d, J=3.5 Hz, 1H), 6.67 (dd, J=2.1 Hz, 1H)
357	¹H NMR (acetone-dg) δ: 9.43 (brs, 1H), 9.32 (d, J=2.5 Hz, 1H), 8.93 (d, J=0.8 Hz, 1H), 8.64 (dd, J=4.7, 1.3 Hz, 1H), 8.45 (ddd, J=8.4, 2.7, 1.4 Hz, 1 H), 8.34 (d, J=1.3 Hz, 1 H), 7.67 (d, J=9.0 Hz, 1 H), 7.59-7.63 (m, 1 H), 7.49 (d, J=7.4 Hz, 2H), 7.29-7.39 (m, 3H), 7.06-7.28 (m, 1H), 3.88 (s, 2H)
358	¹H NMR (acetone-dg) δ: 9.44 (brs, 1H), 9.32 (d, J=2.7 Hz, 1H), 8.89 (d, J=0.8 Hz, 1H), 8.63 (dd, J=4.6, 1.4 Hz, 1H), 8.44 (d, J=8.2 Hz, 1H), 8.37 (s, 1H), 7.66 (d, J=9.1 Hz, 1H), 7.58-7.62 (m, 1H), 7.38 (dd, J=9.3, 1.9 Hz, 1H), 1.79 (tt, J=7.9, 4.6 Hz, 1H), 0.86-0.99 (m, 2H), 0.73-0.86 (m, 2H)
359	¹H NMR (CDCI₃) δ: 9.14-9.21 (m, 1H), 9.15 (d, J=2.4 Hz, 1H), 8.64 (dd, J=4.7, 1.6 Hz, 1H), 8.30-8.45 (m, 1H), 8.18-8.28 (m, 1H), 7.66 (d, J=9.1 Hz, 1H), 7.32-7.50 (m, 6H), 7.17-7.23 (m, 1H), 6.90-7.02 (m, 1H), 3.78 (s, 2H)
360	¹H NMR (acetone-dg) δ: 9.33 (d, J=2.5 Hz, 1H), 9.11 (brs, 1H), 8.91 (d, J=0.9 Hz, 1H), 8.63 (dd, J=4.7, 1.4 Hz, 1H), 8.41-8.53 (m, 1H), 7.59-7.77 (m, 2H), 7.37 (dd, J=8.6 Hz, 1H), 2.44 (dd, J=14.1, 6.9 Hz, 1H), 1.75 (dt, J=13.4, 7.8 Hz, 1H), 1.47 (ddd, J=13.4, 7.4, 6.0 Hz, 1H), 1.18 (d, J=6.8 Hz, 2H), 0.94 (t, J=7.4 Hz, 2H)
361	¹H NMR (CDCI3) δ: 9.13 (d, J=2.2 Hz, 1H), 8.71-8.91 (m, 2H), 8.61 (s, 1H), 8.55 (d, J=2.0 Hz, 1H), 8.41 (s, 1H), 7.85 (s, 2H), 4.96 (d, J=4.6 Hz, 2H)
362	¹H NMR (CDCI3) δ: 9.13 (d, J=2.2 Hz, 1H), 8.71-8.91 (m, 2H), 8.61 (s, 1H), 8.55 (d, J=2.0 Hz, 1H), 8.41 (s, 1H), 7.85 (s, 2H), 4.96 (d, J=4.6 Hz, 2H)
363	¹H NMR (CDCI3) δ: 9.20 (d, J=2.2 Hz, 1H), 8.69 (d, J=3.8 Hz, 1H), 8.55 (s, 1H), 8.30 (d, J=8.3 Hz, 1H), 7.78-7.94 (m, 2H), 7.52 (dd, J=8.1, 4.8 Hz, 1H), 7.37 (d, J=8.4 Hz, 1H), 3.95-4.49 (m, 2H), 3.41-3.93 (m, 1H), 1.67-1.97 (m, 6H), 1.11 (brs, 3H)

238

364	ⁿH NMR (CDCI3) δ: 8.74-8.82 (m, 2Η), 8.62 (s, 1H), 8.35-8.48 (m, 1H), 7.83- 7.94 (m, 2H), 7.59-7.67 (m, 1H), 7.25-7.29 (m, 3H), 4.96 (d, J=4.4 Hz, 2H), 4.00 (s, 2H)
365	¹H NMR (acetone-dg) δ: 9.24-9.27 (m, 2H), 8.63 (s, 1H), 8.45 (s, 1H), 8.38 (d, J=10.0 Hz, 1H), 8.07-8.18 (m, 1H), 7.89 (dd, J=5.0 Hz, 1H), 7.79 (d, J=9.0 Hz, 1H), 5.02 (d, J=8.5 Hz, 1H), 1.48 (d, J=7.1 Hz, 3H)
366	¹H NMR (acetone-dg) δ: 9.26 (brs, 1H), 9.21 (s, 1H), 8.62 (brs, 1H), 8.348.44 (m, 2H), 7.88 (d, J=9.1 Hz, 1H), 7.66-7.81 (m, 2H), 3.56-3.77 (m, 1H), 2.82 (d, J=16.7 Hz, 1H), 1.33 (d, J=6.5 Hz, 3H), 1.05 (d, J=6.1 Hz, 1H), 0.51 (br s, 1 H), 0.37-0.48 (m, 2H), 0.28 (br s, 1 H)
367	¹H NMR (acetone-dg) δ: 9.25 (s, 1H), 9.20 (s, 1H), 8.62 (s, 1H), 8.39 (s, J=7.1, 7.1 Hz, 2H), 7.85 (d, J=8.8 Hz, 1H), 7.75 (d, J=8.8 Hz, 1H), 7.49-7.60 (m, 1H), 4.38-4.51 (m, 1H), 3.48-3.62 (m, 4H), 3.34 (s, 6H),
368	¹H NMR (acetone-dg) δ: 9.26 (s, 2H), 8.63 (s, 1H), 8.47 (s, 1H), 8.38 (d, J=9.4 Hz, 1H), 8.01 (d, J=9.6 Hz, 1H), 7.89 (d, J=8.8 Hz, 1H), 7.79 (d, J=8.9 Hz, 1H), 4.82 (ddd, J=9.8, 8.9, 6.5 Hz, 1H), 2.25-2.36 (m, 1H), 1.12 (d, J=6.6 Hz, 6H),
369	¹H NMR (acetone-dg) δ: 9.28 (s, 1H), 9.25 (d, J=9.5 Hz, 1H), 8.63 (d, J=2.8 Hz, 1H), 8.45 (s, 1H), 8.39 (d, J=9.5 Hz, 1H), 8.11-8.19 (m, 1H), 7.89 (d, J=8.9 Hz, 1H), 7.79 (d, J=9.0 Hz, 1H), 4.15-4.20 (m, 4H), 2.79-2.84 (m, 1H), 1.26 (t, J=7.1 Hz, 3H)
370	¹H NMR (acetone-dg) δ: 9.26 (s, 1H), 9.21 (s, 1H), 8.62 (s, 1H), 8.32-8.43 (m, 2H), 7.87 (d, J=8.9 Hz, 1H), 7.75 (d, J=9.0 Hz, 1H), 7.49-7.59 (m, 1H), 4.29-4.44 (m, 1H), 3.52 (dd, J=9.3, 5.7 Hz, 1H), 3.40 (dd, J=9.5, 5.8 Hz, 1H), 3.34 (s, 3H), 1.26 (d, J=6.8 Hz, 3H)
371	¹H NMR (acetone-dg) δ: 9.35 (s, 1H), 9.17 (s, 1H), 8.68 (d, J=5.0 Hz, 1H), 8.49 (d, J=8.2 Hz, 1H), 8.40 (s, 1H), 7.99 (brs, 1H), 7.86 (d, J=9.0 Hz, 1H), 7.77 (d, J=9.0 Hz, 1H), 7.64 (ddd, J=8.3, 4.7, 0.7 Hz, 1H), 3.54-3.62 (m, 2H), 2.78-2.86 (m, 3H), 1.31-1.38 (m, 9H),

239

372	¹H NMR (acetone-dg) δ: 9.35 (dd, J=2.9, 0.7 Hz, 1H), 9.14 (d, J=1.0 Hz, 1H), 8.68 (dd, J=4.7, 1.5 Hz, 1H), 8.49 (ddd, J=8.3, 2.9, 1.6 Hz, 1H), 8.37-8.40 (m, 1 H), 7.86 (dd, J=9.1, 1.8 Hz, 1 H), 7.75 (dt, J=9.1, 1.3 Hz, 1 H), 7.64 (ddd, J=8.4, 4.7, 0.9 Hz, 1H), 7.48 (d, J=7.0 Hz, 1H), 4.05-4.15 (m, 1H), 1.55-1.70 (m, 2H), 1.24 (d, J=6.6 Hz, 3H), 0.97 (t, J=7.4 Hz, 3H)
373	¹H NMR (acetone-dg) δ: 9.78 (brs, 1H), 9.37 (d, J=2.4 Hz, 1H), 9.22 (s, 1H), 8.69 (dd, J=4.7, 1.2 Hz, 1H), 8.43-8.61 (m, 2H), 7.86-7.99 (m, 2H), 7.74-7.85 (m, 2H), 7.65 (dd, J=8.3, 4.7 Hz, 1H), 7.21 (t, J=4.2 Hz, 1H)
374	¹H NMR (acetone-dg) δ: 9.04 (s, 1H), 8.87 (s, 1H), 8.73 (s, 1H), 8.35 (d, J=4.9 Hz, 2H), 8.29 (d, J=2.5 Hz, 1H), 8.08-8.20 (m, 1H), 8.04 (s, 1H), 7.40- 7.50 (m, 1H), 7.37 (d, J=9.3 Hz, 1H), 6.97 (t, J=4.8 Hz, 1H), 4.26 (d, J=5.8 Hz, 2H)
375	¹H NMR (acetone-dg) δ: 9.28 (s, 2H), 8.64 (d, J=2.5 Hz, 1H), 8.47 (s, 1H), 8.40 (d, J=9.8 Hz, 2H), 7.86 (d, J=1.4 Hz, 1H), 7.78-7.84 (m, 1H), 3.70 (s, 3H)
376	¹H NMR (acetone-dg) δ: 9.37 (d, J=2.5 Hz, 2H), 9.20 (s, 2H), 8.85 (br. s, 1H), 8.69 (dd, J=4.7, 1.3 Hz, 1H), 8.40-8.58 (m, 3H), 7.87 (d, J=8.8 Hz, 1H), 7.79 (d, J=9.1 Hz, 1H), 7.65 (dd, J=8.2, 4.9 Hz, 1H), 1.29 (s, 10H)
377	¹H NMR (acetone-dg) δ: 9.68 (br. s, 1H), 9.37 (d, J=2.2 Hz, 1H), 9.23 (s, 1H), 8.69 (dd, J=4.7, 1.3 Hz, 1H), 8.44-8.61 (m, 2H), 7.86-8.07 (m, 1H), 7.74-7.86 (m, 2H), 7.65 (dd, J=8.4, 4.3 Hz, 1H), 7.23 (d, J=3.3 Hz, 1H), 6.66 (dd, J=3.3, 1.6 Hz, 1H)
378	¹H NMR (acetone-dg) δ: 9.74 (br. s, 1H), 9.38 (d, J=2.5 Hz, 1H), 9.23 (s, 1H), 8.70 (dd, J=4.7, 1.3 Hz, 1H), 8.45-8.61 (m, 2H), 8.02 (d, J=7.3 Hz, 2H), 7.92 (d, J=9.1 Hz, 1H), 7.83 (d, J=9.1 Hz, 1H), 7.57-7.73 (m, 2H), 7.53 (t, J=7.2 Hz, 2H)
379	¹H NMR (acetone-dg) δ: 9.36 (d, J=2.4 Hz, 1H), 9.17 (s, 1H), 8.96-9.03 (m, 1H), 8.68 (dd, J=4.6, 1.4 Hz, 1H), 8.45-8.59 (m, 1H), 8.36-8.43 (m, 1H), 7.85 (dd, J=9.1, 1.6 Hz, 1H), 7.78 (d, J=9.3 Hz, 1H), 7.65 (dd, J=8.3, 4.5 Hz, 1H)

240

380	¹H NMR (acetone-dg) δ: 9.55 (s, J=8.1 Hz, 2H), 9.34 (d, J=0.9 Hz, 1H), 9.26 (s, 1H), 8.60-8.66 (m, 1H), 7.94 (dd, J=9.1, 1.6 Hz, 1H), 7.74-7.88 (m, 1H), 3.93 (s, 3H)
381	¹H NMR (acetone-dg) δ: 9.36 (d, J=2.2 Hz, 1H), 9.19 (d, J=0.9 Hz, 1H), 8.69 (dd, J=4.7,1.3 Hz, 1H), 8.38-8.57 (m, 2H), 8.02 (d, J=8.4 Hz, 1H), 7.87 (dd, J=9.1, 1.6 Hz, 1H), 7.79 (dt, J=9.1, 0.9 Hz, 1H), 7.65 (ddd, J=8.3, 4.7, 0.7 Hz, 1H), 5.00 (ddd, J=12.9, 8.2, 7.0 Hz, 1H), 3.56 (ddd, J=12.0, 11.2, 5.4 Hz, 1H), 3.39 (ddd, J=11.2, 7.0, 1.0 Hz, 1H), 2.73 (dddd, J=12.3, 6.9, 5.4, 1.4 Hz, 1H), 2.29-2.48 (m, 1H)
382	¹H NMR (CDCI₃) δ: 8.97-9.11 (m, 1H), 8.52-8.63 (m, 2H), 8.13 (dt, J=9.0, 2.4 Hz, 1H), 8.00-8.09 (m, 1H), 7.78 (dt, J=9.1, 0.9 Hz, 1H), 7.63 (dd, J=9.1, 1.6 Hz, 1 H), 7.26 (s, 2H), 4.38 (br s, 2H), 4.28 (br s, 2H), 2.39 (t, J=7.7 Hz, 2H)
383	¹H NMR (DMSO-d₆) δ: 9.49 (s, 1H), 9.31 (s, 2H), 8.73 (d, J=2.4 Hz, 1H), 8.46-8.62 (m, 2H), 7.91 (d, J=9.1 Hz, 1H), 7.82 (d, J=9.1 Hz, 1H), 7.42-7.59 (m, 2H), 7.10-7.18 (m, 2H), 4.74 (d, J=3.6 Hz, 2H)
384	¹H NMR (acetone-dg) δ: 9.24-9.29 (m, 1H), 9.22 (d, J=1.0 Hz, 1H), 8.62 (d, J=2.4 Hz, 1H), 8.38 (d, J=9.8 Hz, 2H), 7.93-8.05 (m, 1H), 7.85-7.93 (m, 1H), 7.76 (d, J=9.1 Hz, 1H), 3.39-3.59 (m, 4H), 3.22-3.34 (m, 1H), 3.07-3.15 (m, 1H), 2.51-2.66 (m, 1H), 1.66-1.82 (m, 1H), 1.43 (s, 8H)
385	¹H NMR (acetone-dg) δ: 9.60 (brs, 1H), 9.36 (d, J=2.4 Hz, 1H), 9.21 (d, J=15.9 Hz, 1H), 8.69 (dd, J=4.8 Hz, 1H), 8.49-8.52 (m, 1H), 8.46 (s, 1H), 7.86 (dd, J=9.1, 1.6 Hz, 1H), 7.80 (dt, J=8.9 Hz, 1H), 7.65 (ddd, J=8.4, 4.7, 0.8 Hz, 1H), 5.49 (d, J=4.4 Hz, 1H), 3.59-3.75 (m, 2H),
386	¹H NMR (CDCI3) δ: 9.36-9.38 (m, 2H), 9.28 (s, 1H), 8.60 (s, 1H), 8.29 (s, 1H), 7.82 (d, J=8.8 Hz, 1H), 7.75 (d, J=9.2 Hz, 1H), 6.65 (brs, 1H), 4.12 (dd, J=7.3, 3.1 Hz, 1H), 3.78-3.95 (m, 3H), 3.37 (ddd, J=13.7, 7.7, 4.7 Hz, 1H), 2.02-2.21 (m, 2H), 1.88-2.02 (m, 2H), 1.65 (dd, J=12.2, 8.1 Hz, 1H)
387	¹H NMR (CDCI3) δ: 9.35-9.39 (m, 2H), 9.27-9.33 (m, 1H), 8.63 (s, 1H), 8.23- 8.43 (m, 1 H), 7.87 (dt, J=9.1, 0.9 Hz, 1 H), 7.74 (dd, J=9.1, 1.6 Hz, 1 H), 6.40 (brs, 1H), 4.19 (qd, J=9.0, 6.5 Hz, 2H)

241

388	¹H NMR (CDCI₃) δ: 9.37 (s, 2H), 9.29 (s, 1H), 8.60 (s, 1H), 8.26 (s, 1H), 7.82 (d, J=9.1 Hz, 1H), 7.68 (dd, J=9.1, 1.6 Hz, 1H), 6.30 (brs, 1H), 2.96 (dd, J=7.0, 3.9 Hz, 1H), 0.80-1.01 (m, 3H), 0.62-0.79 (m, 2H)
389	¹H NMR (CDCI3) δ: 9.08 (s, 1H), 8.64 (s, 1H), 8.58 (s, 1H), 8.38 (s, 1H), 8.27 (s, 1 H), 7.80 (dt, J=10.2 Hz, 1 H), 7.73 (dd, J=8.9 Hz, 1 H), 6.61 (br s, 1 H), 4.03-4.19 (m, 2H), 3.78-3.95 (m, 3H), 3.37 (ddd, J=13.8, 7.6, 4.7 Hz, 1H), 2.02-2.13 (m, 2H), 1.83-2.02 (m, 3H),
390	¹H NMR (CDCI3) δ: 9.32 (d, J=2.2 Hz, 1H), 9.21 (d, J=0.9 Hz, 1H), 8.67 (d, J=2.2 Hz, 1H), 8.59 (t, J=2.2 Hz, 1H), 8.33-8.41 (m, 1H), 7.85 (dd, J=9.1, 1.6 Hz, 1H), 7.60-7.79 (m, 2H), 2.72-2.85 (m, 10H), 2.13-2.20 (m, 1H), 0.70-0.81 (m, 2H), 0.49-0.69 (m, 2H)
391	¹H NMR (CDCI3) δ: 9.08 (d, J=2.0 Hz, 1H), 8.59-8.75 (m, 2H), 8.48-8.59 (m, 1H), 8.38 (t, J=2.2 Hz, 1H), 7.97 (dd, J=9.2, 1.5 Hz, 1H), 7.79 (d, J=9.1 Hz, 1H), 3.97 (s, 2H)
392	¹H NMR (CDCI3) δ: 9.19 (d, J=2.2 Hz, 1H), 8.55-8.74 (m, 1H), 8.43 (d, J=0.8 Hz, 1H), 8.17-8.32 (m, 1H), 7.77 (d, J=9.3 Hz, 1H), 7.50 (dd, J=8.2, 4.7 Hz, 1H), 7.40 (brs, 1H), 7.13 (d, J=9.0 Hz, 1H), 3.30 (q, J=10.5 Hz, 2H)
393	¹H NMR (CDCI3) δ: 9.20 (d, J=2.5 Hz, 1H), 8.62-8.79 (m, 1H), 8.47-8.62 (m, 1H), 8.30 (ddd, J=8.3, 2.6, 1.6 Hz, 1H), 7.90 (brs, 1H), 7.81 (d, J=8.8 Hz, 1H), 7.52 (dd, J=8.3, 4.8 Hz, 1H), 7.43 (brs, 1H), 0.98-1.17 (m, 1H), 0.420.63 (m, 2H), 0.19 (br s, 2H)
394	¹H NMR (CDCI3) δ: 9.21 (br s, 1 H), 8.70 (d, J=3.9 Hz, 1 H), 8.58 (s, 1 H), 8.24-8.36 (m, 2H), 7.81 (d, J=9.0 Hz, 1H), 7.69 (d, J=9.1 Hz, 1H), 7.53 (dd, J=8.0, 4.7 Hz, 1 H), 6.28 (br s, 1 H), 2.42 (s, 1 H), 1.81 (s, 6H)
395	¹H NMR (CDCI3) δ: 9.20 (d, J=2.4 Hz, 1H), 8.67-8.85 (m, 2H), 8.57 (s, 1H), 8.22-8.44 (m, 2H), 7.76-7.93 (m, J=9.1 Hz, 1H), 7.61-7.75 (m, J=9.0 Hz, 1H), 7.52 (dd, J=8.1, 4.7 Hz, 2H), 6.27 (d, J=6.6 Hz, 2H), 4.60-4.72 (m, 1H), 2.43- 2.55 (m, 2H), 1.91-2.08 (m, 2H), 1.68-1.90 (m, 2H)

242

396	¹H NMR (CDCI₃) δ: 9.12 (d, J=2.2 Hz, 1H), 8.74 (d, J=2.0 Hz, 1H), 8.46-8.64 (m, 2H), 8.27 (s, 1H), 7.80 (d, J=8.9 Hz, 1H), 7.73 (d, J=8.9 Hz, 1H), 6.56 (br s, 1H), 4.11 (dd, J=7.2, 3.1 Hz, 1H), 3.77-3.98 (m, 3H), 3.37 (ddd, J=13.8, 7.6, 4.6 Hz, 1H), 2.01-2.21 (m, 1H), 1.89-2.01 (m, 2H), 1.60-1.78 (m, 1H)
397	¹H NMR (acetone-dg) δ: 9.37 (d, J=2.2 Hz, 1H), 9.32 (s, 1H), 8.75-8.83 (m, 2H), 8.56-8.65 (m, 1H), 7.93 (dd, J=9.1, 1.6 Hz, 1H), 7.81 (d, J=9.0 Hz, 1H), 3.92 (s, 3H)
398	¹HNMR(CDCI₃) δ: 9.12 (d, J=1.9Hz, 1H), 8.76 (d, J=1.6 Hz, 1H), 8.61 (d, J=0.9 Hz, 1H), 8.53 (t, J=2.2 Hz, 1H), 8.31 (dd, J=1.6, 0.9 Hz, 1H), 7.80-7.93 (m, 1H), 7.72 (dd, J=9.1, 1.7 Hz, 1H), 4.19 (dd, J=9.1, 6.4 Hz, 2H)
399	¹H NMR(CDCI₃) δ: 9.11 (d, J=2.4 Hz, 1H), 8.74 (d, J=2.0 Hz, 1H), 8.46-8.61 (m, 2H), 8.12-8.31 (m, 1H), 7.79 (d, J=9.1 Hz, 1H), 7.66 (dd, J=9.1, 1.7 Hz, 1H), 6.26 (br. S, 1H), 2.95 (d, J=3.2 Hz, 1H), 0.91 (d, J=5.7 Hz, 2H), 0.610.77 (m, 2H)
400	¹H NMR (acetone-dg) δ: 9.92-10.04 (m, 1H), 9.81-9.92 (m, 1H), 9.37 (d, J=2.5 Hz, 1H), 9.20-9.26 (m, 1H), 9.03-9.20 (m, 1H), 8.78 (dd, J=4.8, 1.5 Hz, 1H), 8.69 (dd, J=4.7, 1.3 Hz, 1H), 8.45-8.62 (m, 2H), 8.32 (d, J=7.9 Hz, 1H), 7.87-7.99 (m, 1H), 7.83 (d, J=8.8 Hz, 1H), 7.61-7.74 (m, 1H), 7.55 (s, 1H)
401	¹H NMR (acetone-dg) δ: 9.25 (s, 1H), 9.23-9.28 (m, 1H), 9.21-9.32 (m, 1H), 8.63 (d, J=2.2 Hz, 1H), 8.48 (dd, J=1.6, 0.9 Hz, 1H), 8.31-8.44 (m, 1H), 7.90 (dd, J=9.1, 1.7 Hz, 1H), 7.80 (dt, J=9.1, 0.9 Hz, 1H), 4.23 (q, J=9.5 Hz, 1H), 4.22 (q, J=9.5 Hz, 2H)
402	¹H NMR (acetone-dg) δ: 9.37 (brs, 1H), 9.18 (s, 1H), 8.61-8.83 (m, 1H), 8.51 (d, J=7.7 Hz, 1H), 8.42 (s, 1H), 8.35 (brs, 1H), 7.87 (dd, J=9.1, 1.6 Hz, 1H), 7.77 (d, J=8.9 Hz, 1H), 7.66 (t, J=7.1 Hz, 1H), 3.65 (s, 3H) 1.45-1.59 (m, 2H), 1.19-1.35 (m, 2H)
403	¹H NMR (CDCI3) δ: 9.21 (d, J=2.5 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.58 (d, J=0.9 Hz, 1H), 8.29-8.32 (m, 1H), 8.28 (s, 1H), 7.83 (d, J=8.9 Hz, 1H), 7.72 (d, J=8.9 Hz, 1H), 7.52 (ddd, J=8.4, 4.7, 0.6 Hz, 1H), 6.36-6.45 (m, 1H), 4.18-4.31 (m, 1H), 3.55 (dd, J=9.9, 3.5 Hz, 2H), 3.41 (s, 3H), 1.65-1.81 (m, 2H), 1.02 (t, J=7.5 Hz, 3H)

243

404	ⁿH NMR (CDCI3) δ: 9.21 (d, J=2.5 Hz, 1 H), 8.70 (dd, J=4.7, 1.3 Hz, 1 H), 8.51-8.64 (m, 1H), 8.28-8.36 (m, 2H), 7.84 (d, J=9.1 Hz, 1H), 7.71 (dd, J=9.1, 1.7 Hz, 1H), 7.52 (dd, J=8.3, 4.8 Hz, 1H), 6.31 (brs, 1H), 4.31 (dd, J=5.1, 2.6 Hz, 2H)
405	¹H NMR (CDCI3) δ: 8.74 (d, J=2.0 Hz, 1H), 8.60 (d, J=0.9 Hz, 1H), 8.40 (d, J=2.7 Hz, 1H), 8.31 (dd, J=1.6, 0.9 Hz, 1H), 7.81-7.92 (m, 2H), 7.72 (dd, J=9.1, 1.6 Hz, 1H), 4.19 (dd, J=9.1,6.4 Hz, 2H), 4.00 (s, 3H)
406	¹H NMR (CDCI3) δ: 8.74 (s, 1H), 8.57 (d, J=0.8 Hz, 1H), 8.38 (d, J=2.8 Hz, 1H), 8.27 (s, 1H), 7.87 (s, 1H), 7.80 (d, J=8.7 Hz, 1H), 7.73 (d, J=9.0 Hz, 1H), 6.66 (brs, 1H), 4.05-4.19 (m, 1H), 3.91-4.00 (m, 4H), 3.78-3.87 (m, 2H), 3.38 (ddd, J=13.8, 7.6, 4.8 Hz, 1H), 2.01-2.12 (m, 2H), 1.89-2.01 (m, 2H), 1.65 (dd, J=12.2, 8.3 Hz, 1H)
407	¹H NMR (CDCI3) δ: 8.74 (d, J=2.0 Hz, 1H), 8.57 (d, J=0.8 Hz, 1H), 8.39 (d, J=2.7 Hz, 1H), 8.24 (d, J=0.9 Hz, 1H), 7.87 (t, J=2.4 Hz, 1H), 7.80 (d, J=9.1 Hz, 1 H), 7.66 (dd, J=9.1, 1.7 Hz, 1 H), 6.28 (br s, 1 H), 3.99 (s, 3H), 2.95 (dd, J=6.9, 3.8 Hz, 1H), 0.91 (d, J=5.7 Hz, 2H), 0.56-0.75 (m, 2H)
408	¹H NMR (CDCI3) δ: 8.75 (d, J=2.0 Hz, 1H), 8.60 (s, 1H), 8.40 (d, J=2.7 Hz, 1H), 8.34 (s, 1H), 7.79-7.98 (m, 2H), 7.72 (dd, J=9.1, 1.7 Hz, 1H), 4.00 (s, 3H), 3.83 (s, 3H)
409	¹H NMR (CDCI3) δ: 9.38 (s, 2H), 9.30 (s, 1H), 8.78 (d, J=4.9 Hz, 2H), 8.64 (s, 1H), 8.43 (s, 2H), 7.87 (d, J=1.1 Hz, 2H), 7.64 (br. S, 1H), 4.97 (d, J=4.4 Hz, 2H)
410	¹H NMR (acetone-dg) δ: 9.26 (s, 1H), 9.21 (s, 1H), 8.62 (d, J=8.3 Hz, 1H), 8.34-8.42 (m, 2H), 7.85 (dd, J=9.1, 1.6 Hz, 2H), 7.74 (dt, J=9.1, 0.9 Hz, 2H), 2.89-3.06 (m, 1H), 0.70-0.81 (m, 2H), 0.58-0.69 (m, 2H)
411	¹H NMR(CDCl₃) δ: 9.20 (brs, 1H), 8.71 (d, J=4.3 Hz, 1H), 8.58 (s, 1H), 8.25-8.35 (m, 2H), 7.84 (d, J=9.0 Hz, 1H), 7.71 (dd, J=9.1, 1.7 Hz, 1H), 7.53 (dd, J=8.2, 4.7 Hz, 1H), 7.27 (s, 1H), 6.25 (d, J=9.5 Hz, 1H), 4.92-5.08 (m, 1H), 1.47 (d, J=7.1 Hz, 3H)

244

412	¹H NMR (CDCI₃) δ: 9.21 (br s, 1 H), 8.72 (d, J=3.8 Hz, 1 H), 8.62 (d, J=0.9 Hz, 1 H), 8.26-8.36 (m, 2H), 7.87 (dt, J=9.1, 0.9 Hz, 1 H), 7.72 (dd, J=9.1, 1.7 Hz, 1 H), 7.53 (dd, J=8.2, 4.7 Hz, 1 H), 6.22 (s, 1 H), 4.84 (ddd, J=10.2, 8.5, 4.7 Hz, 1H) 1.10 (dd, J=9.3, 7.1 Hz, 6H)
413	¹H NMR (CDCI3) δ: 9.20 (d, J=2.4 Hz, 1H), 8.68 (d, J=5.1 Hz, 1H), 8.53 (s, 1H), 8.30 (d, J=8.2 Hz, 1H), 7.78-7.82 (m, 2H), 7.51 (ddd, J=8.3, 4.8, 0.6 Hz, 1H), 7.35 (d, J=8.7 Hz, 1H), 7.28 (s, 1H), 3.48 (q, J=7.1 Hz, 5H), 1.21-1.36 (m, 5H)
414	¹H NMR (CDCI3) δ: 9.19 (s, 1H), 9.20 (d, J=5.2 Hz, 1H), 8.69 (dt, J=4.7, 1.7 Hz, 1H), 8.56 (dd, J=6.9, 0.8 Hz, 1H), 8.24-8.34 (m, 2H), 7.77-7.89 (m, 1H), 7.62-7.77 (m, 1H), 7.46-7.58 (m, 1H), 7.41-7.43 (m, 1H), 7.40 (d, J=7.8 Hz, 1H), 7.33 (d, J=7.7 Hz, 1H), 6.87-6.96 (m, 2H), 6.52 (d, J=7.7 Hz, 1H), 5.17 (d, J=7.7 Hz, 1H), 3.80 (s, 3H), 3.48 (q, J=7.1 Hz, 1H), 1.24-1.47 (m, 2H), 0.67 (d, J=8.7 Hz, 2H)
415	¹H NMR (CDCI3) δ: 9.20 (d, J=2.5 Hz, 1H), 8.70 (dd, J=4.7, 1.4 Hz, 1H), 8.57 (d, J=0.8 Hz, 1H), 8.25-8.33 (m, 2H), 7.82 (d, J=9.0 Hz, 1H), 7.71 (dd, J=9.1, 1.6 Hz, 1H), 7.52 (dd, J=8.2, 4.7 Hz, 1H), 6.16 (d, J=7.6 Hz, 1H), 3.60-3.72 (m, 1H), 1.35 (d, J=6.6 Hz, 3H), 0.87-1.05 (m, 1H), 0.42-0.62 (m, 3H), 0.34 (dt, J=9.8, 4.7 Hz, 1H)
416	¹H NMR (acetone-^) δ: 9.37 (d, J=2.2 Hz, 1H), 9.18-9.31 (m, 1H), 8.69 (dd, J=4.7, 1.4 Hz, 1H), 8.36-8.56 (m, 3H), 7.88 (d, J=9.0 Hz, 1H), 7.80 (d, J=9.1 Hz, 1H), 7.65 (ddd, J=8.4, 4.7, 0.6 Hz, 2H), 4.63 (d, J=6.6 Hz, 1H), 1.19 (d, J=6.6 Hz, 6H)
420	¹H NMR (CDCI3) δ: 9.21 (d, J=2.4 Hz, 1H), 8.70 (d, J=5.1 Hz, 1H), 8.59 (s, 1H), 8.25-8.35 (m, 2H), 7.84 (d, J=8.9 Hz, 1H), 7.72 (d, J=8.9 Hz, 1H), 7.52 (ddd, J=8.3, 4.8, 0.6 Hz, 1H), 6.64 (br s, 1H), 4.15-4.27 (m, 1H), 4.05 (ddd, J=14.2, 6.8, 3.5 Hz, 1 H), 3.52-3.66 (m, 3H), 2.02-2.17 (m, 2H), 1.87-2.02 (m, 2H)

245

421	¹H NMR (CDCI₃) δ: 8.88 (d, J=2.2 Hz, 1H), 8.50-8.59 (m, 2H),.8.23-8.33 (m, 1H), 8.17 (t, J=2.2 Hz, 1H), 7.81 (dt, J=9.1, 0.9 Hz, 1H), 7.73 (dd, J=9.1, 1.7 Hz, 1H) 6.59 (brs, 1H), 4.03-4.19 (m, 1H), 3.77-3.95 (m, 3H), 3.38 (ddd, J=13.7, 7.6, 4.7 Hz, 1H), 2.62 (s, 3H), 2.01-2.17 (m, 1H), 1.89-2.01 (m, 2H), 1.56-1.74 (m, 3H)
422	¹H NMR (CDCI3) δ: 9.22 (s, 1H), 8.71 (d, J=5.2 Hz, 1H), 8.55-8.64 (m, 3H), 8.32 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 8.03 (d, J=9.0 Hz, 1H), 7.90 (dt, J=9.1, 0.9 Hz, 1H), 7.45-7.57 (m, 2H), 4.09 (q, J=9.9 Hz, 2H)
423	¹H NMR (CDCI3) δ: 9.23 (d, J=2.4 Hz, 1H), 8.98 (d, J=5.2 Hz, 2H), 8.62-8.75 (m, 1H), 8.56 (d, J=8.0 Hz, 2H), 8.44 (d, J=6.9 Hz, 1H), 8.26-8.38 (m, 1H), 8.16 (dd, J=9.1, 1.6 Hz, 1H), 7.84-8.01 (m, 3H), 7.51 (dd, J=8.2, 4.7 Hz, 1H), 7.35 (t, J=4.8 Hz, 1H)
424	¹H NMR (CDCI3) δ: 9.19-9.27 (m, 8H), 8.90-9.09 (m, 5H), 8.72 (dd, J=4.7, 1.4 Hz, 5H), 8.64 (d, J=6.4 Hz, 4H), 8.49-8.58 (m, 4H), 8.33 (ddd, J=8.2, 2.6, 1.4 Hz, 6H), 8.10 (dd, J=9.2, 1.7 Hz, 5H), 7.96 (dt, J=9.1, 0.9 Hz, 5H), 7.54 (ddd, J=8.2, 4.8, 0.7 Hz, 5H)
428	¹H NMR (acetone-dg) δ: 9.36 (d, J=2.7 Hz, 1H), 9.10 (d, J=0.9 Hz, 1H), 8.70 (dd, J=4.7,1.3 Hz, 1H), 8.42-8.56 (m, 2H), 8.38 (d, J=1.3 Hz, 1H), 7.90 (dd, J=8.8, 0.9 Hz, 1H), 7.63-7.71 (m, 2H), 5.63 (s, 1H), 4.25 (qd, J=9.6, 6.5 Hz, 2H)
429	¹H NMR (acetone-dg) δ: 9.34 (d, J=2.5 Hz, 1H), 9.03 (s, 1H), 8.68 (d, J=5.3 Hz, 1 H), 8.48 (ddd, J=8.4, 2.7, 1.4 Hz, 1 H), 8.24 (d, J=1.1 Hz, 1 H), 7.83 (dd, J=8.8, 0.9 Hz, 2H), 7.58-7.65 (m, 2H), 2.99 (d, J=3.9 Hz, 1H), 0.72-0.93 (m, 3H), 0.53-0.72 (m, 2H)
430	¹H NMR (CDCI3) δ: 9.22 (s, 1H), 8.77 (d, J=5.1 Hz, 2H), 8.70 (d, J=4.6 Hz, 1H), 8.52 (s, 1H), 8.38 (s, 1H), 8.31 (d, J=8.2 Hz, 1H), 7.82 (dd, J=17.3 Hz, 1H), 7.73-7.76 (m, 1H), 7.70 (d, J=8.7 Hz, 1H), 7.52 (ddd, J=8.3, 4.8, 0.8 Hz, 1H), 7.22-7.32 (m, 1H), 4.97 (d, J=4.4 Hz, 2H)
431	¹H NMR (CDCI3) δ: 9.21 (d, J=2.2 Hz, 1H), 8.71 (dd, J=7.1 Hz, 1H), 8.52 (d, J=0.9 Hz, 1H), 8.12-8.34 (m, 2H), 7.82 (d, J=8.7 Hz, 2H), 7.49-7.61 (m, 2H), 3.83 (s, 3H)

246

432	¹H NMR (acetone-dg) δ: 9.35 (s, 1H), 9.05 (s, 1H), 8.68 (d, J=4.9 Hz, 1H), 8.49 (d, J=8.3 Hz, 1H), 8.30 (s, 1H), 8.02 (brs, 1H), 7.85 (d, J=8.7 Hz, 1H), 7.59-7.69 (m, 2H), 3.62-3.69 (m, 2H), 2.74-2.83 (m, 3H), 2.16 (s, 3H)
433	¹H NMR (acetone-dg) δ: 9.36 (s, 1H), 9.06 (s, 1H), 8.68 (d, J=5.1 Hz, 1H), 8.49 (d, J=8.2 Hz, 1H), 8.31 (s, 1H), 7.85 (dd, J=8.7, 0.9 Hz, 2H), 7.62-7.67 (m, 2H), 4.61 (t, J=5.5 Hz, 1H), 3.55 (t, J=5.8 Hz, 2H), 3.38-3.40 (m, 6H)
434	¹H NMR (acetone-dg) δ: 9.36 (s, 1H), 9.08 (s, 1H), 8.69 (d, J=5.0 Hz, 1H), 8.49 (d, J=8.2 Hz, 1H), 8.36 (s, 1H), 8.18 (d, J=8.8 Hz, 1H), 7.88 (d, J=8.8 Hz, 1H), 7.63-7.68 (m, 2H), 4.96-5.14 (m, 1H), 1.51 (d, J=7.1 Hz, 3H)
435	¹H NMR (acetone-dg) δ: 9.36 (d, J=7.1 Hz, 1H), 9.08 (s, 1H), 8.69 (d, J=5.2 Hz, 1 H), 8.50 (ddd, J=8.4, 2.7, 1.4 Hz, 1 H), 8.31-8.41 (m, 1 H), 8.25 (br s, 1H), 7.88 (d, J=8.7 Hz, 1H), 7.63-7.69 (m, 2H), 6.14 (t, J=4.3 Hz, 1H), 3.84 (tdd, 2H)
436	¹H NMR (acetone-dg) δ: 9.36 (d, J=7.1 Hz, 1H), 9.08 (s, 1H), 8.69 (d, J=5.2 Hz, 1H), 8.50 (ddd, J=8.4, 2.7, 1.4 Hz, 1H), 8.31-8.41 (m, 1H), 8.25 (brs, 1H), 7.88 (d, J=8.7 Hz, 1H), 7.63-7.69 (m, 2H), 6.14 (t, J=4.3 Hz, 1H), 3.84 (tdd, 2H)
437	¹H NMR (acetone-dg) δ: 9.35 (s, 1H), 9.05 (s, 1H), 8.68 (d, J=5.0 Hz, 1H), 8.50 (s, 1H), 8.48 (d, J=8.2 Hz, 1H), 8.31 (s, 1H), 7.85 (dd, J=8.8, 0.9 Hz, 2H), 7.56-7.74 (m, 2H), 4.08 (dd, J=6.6, 5.2 Hz, 1H), 3.86 (ddd, J=8.1, 7.2, 6.1 Hz, 1H), 3.69 (td, J=7.7, 6.5 Hz, 1H), 3.40-3.58 (m, 2H), 2.00-2.08 (m, 5H), 1.83-1.94 (m, 2H), 1.70 (dd, J=12.1, 8.7 Hz, 1H)
438	¹H NMR (CDCl₃) δ: 9.04-9.20 (m, 2H), 8.79 (dd, J=4.7, 1.4 Hz, 1H), 8.36 (dd, J=7.1, 1.1 Hz, 1H), 8.16 (ddd, J=8.2, 2.6, 1.5 Hz, 1H), 7.79 (dd, J=8.4, 1.1 Hz, 1H), 7.57 (ddd, J=8.2, 4.8, 0.8 Hz, 1H), 7.33 (dd, J=8.4, 7.0 Hz, 1H), 4.15 (dd, J=6.4, 3.9 Hz, 1H), 3.72-3.91 (m, 3H), 3.62 (dt, J=13.9, 6.0 Hz, 1H), 1.95-2.11 (m, 1H), 1.84-1.95 (m, 2H), 1.69 (dd, J=12.2, 8.7 Hz, 2H)
439	¹H NMR (CDCI3) δ: 9.51 (s, 1H), 8.74-8.84 (m, 3H), 8.55 (dt, J=7.9, 2.0 Hz, 1 H), 8.25 (s, 1 H), 7.96 (d, J=8.5 Hz, 1 H), 7.87 (d, J=8.4 Hz, 1 H), 7.72 (br s, 1H), 7.51 (ddd, J=6.4 Hz, 1H), 7.26-7.31 (m, 2H), 4.97 (d, J=4.4 Hz, 2H)

247

440	'Ή NMR (CDCI3) δ: 9.50 (dd, J=2.1, 0.9 Hz, 1H), 8.80 (dd, J=4.8, 1.7 Hz, 1H), 8.53 (dt, J=8.0, 2.0 Hz, 1H), 8.12-8.17 (m, 1H), 7.77-7.87 (m, 2H), 7.50 (ddd, J=8.0, 4.8, 0.9 Hz, 1H), 6.64(brs, 1H), 4.11 (dd, J=7.3, 3.2 Hz, 1H), 3.77-3.95 (m, 4H), 3.38 (ddd, J=13.8, 7.6, 4.7 Hz, 1H), 2.02-2.12 (m, 2H), 1.87-2.01 (m, 3H), 1.56-1.76 (m, 4H)
441	¹H NMR (CDCI3) δ: 9.49 (d, J=1.6 Hz, 1H), 8.80 (dd, J=4.9, 1.6 Hz, 1H), 8.53 (d, J=7.9 Hz, 1H), 8.10 (s, 1H), 7.74-7.84 (m, 2H), 7.50 (ddd, J=6.6 Hz, 1H), 6.06 (d, J=7.3 Hz, 1H), 4.34 (dt, J=7.7, 6.6 Hz, 1H), 1.28-1.33 (m, 6H)
442	¹H NMR (CDCI3) δ: 8.74 (d, J=2.0 Hz, 1H), 8.47 (dd, J=4.7, 1.2 Hz, 1H), 7.96-8.18 (m, 3H), 7.78-7.94 (m, 4H), 7.67 (d, J=8.2 Hz, 2H), 7.54-7.63 (m, 2H), 7.42-7.53 (m, 3H), 7.35 (ddd, J=8.2, 4.8, 0.7 Hz, 1H), 3.91-4.00 (m, 9H), 1.72 (brs, 8H)
443	¹H NMR (CDCI3) δ: 9.50 (d, J=1.6 Hz, 1H), 8.82 (dd, J=4.7, 1.6 Hz, 1H), 8.54 (d, J=8.0 Hz, 1H), 8.14 (dd, J=1.6, 0.6 Hz, 1H), 7.77-7.90 (m, 2H), 7.51 (t, J=6.5 Hz, 1H), 6.47 (brs, 1H), 4.18-4.31 (m, 2H)
444	¹H NMR(CDCI₃) δ: 9.20 (d, J=2.2 Hz, 1H), 9.14 (brs, 1H), 8.73 (d, J=5.2 Hz, 1H), 8.57 (s, 1H), 8.35 (d, J=7.1 Hz, 1H), 8.20 (d, J=8.3 Hz, 1H), 7.88 (d, J=8.2 Hz, 1H), 7.56 (ddd, J=8.2, 4.8, 0.7 Hz, 1H), 7.29 (t, J=7.5 Hz, 1H), 3.08 (dt, J=7.3, 3.6 Hz, 1H), 0.87-1.01 (m, 2H), 0.65-0.80 (m, 5H),
445	¹H NMR (CDCI3) δ: 9.51 (s, 1H), 8.81 (d, J=3.5 Hz, 1H), 8.54 (d, J=7.9 Hz, 1 H), 8.13 (s, 1 H), 7.77-7.87 (m, 2H), 7.51 (t, J=6.6 Hz, 1 H), 6.42 (br s, 1 H), 4.54 (t, J=5.1 Hz, 1H), 3.67 (t, J=5.4 Hz, 2H), 3.47 (s, 6H)
446	¹H NMR (CDCI3) δ: 9.50 (s, 1H), 8.81 (d, J=3.9 Hz, 1H), 8.53 (d, J=7.9 Hz, 1H), 8.14 (s, 1H), 7.78-7.86 (m, 2H), 7.50 (dd, J=7.7, 4.7 Hz, 1H), 7.26 (s, 1H), 6.32 (brs, 1H), 3.38 (dd, J=7.3, 5.4 Hz, 2H), 1.04-1.18 (m, 1H), 0.540.65 (m, 2H), 0.27-0.37 (m, 2H)
447	¹H NMR (CDCI3) δ: 9.49 (d, J=1.6 Hz, 1H), 8.80 (dd, J=4.7, 1.6 Hz, 1H), 8.53 (dt, J=8.0, 1.9 Hz, 1H), 8.10 (d, J=1.6 Hz, 1H), 7.77-7.85 (m, 1H), 7.73 (dd, J=8.4, 1.6 Hz, 1 H), 7.50 (ddd, J=8.0, 4.9, 0.8 Hz, 1 H), 6.35 (br s, 1 H), 2.96 (dd, J=7.0, 3.9 Hz, 1H), 0.84-1.00 (m, 2H), 0.62-0.74 (m, 2H)

248

448	¹H NMR (CDCi₃)5: 9.50 (d, J=1.4 Hz, 1H), 8.81 (dd, J=4X 1.7 Hz, 1 H), 8.53 (dt, J=8.0, 1.9 Hz, 1H), 8.14 (s, 1H), 7.81-7.99 (m, 2H), 7.39-7.56 (m, 1H), 7.26 (s, 3H), 3.83 (s, 2H)
449	¹H NMR (acetone-dg) δ: 9.39-9.47 (m, 1H), 8.83 (dd, J=4.8, 1.7 Hz, 1H), 8.59 (d, J=7.8 Hz, 1H), 8.25 (d, J=1.6 Hz, 1H), 8.16 (brs, 1H), 8.00 (d, J=8.2 Hz, 1H), 7.86 (d, J=8.1 Hz, 1H), 7.65 (t, J=6.7 Hz, 1H), 3.72 (td, J=7.0, 5.8 Hz, 2H), 2.64 (tdd, 2H)
450	¹H NMR (CDCI₃) δ: 10.09-10.35 (m, 1H), 9.53 (dd, J=8.8 Hz, 1H), 8.74 (dd, J=4.8, 1.7 Hz, 1H), 8.67 (dd, J=11.3 Hz, 1H), 8.06 (dd, J=7.6, 1.1 Hz, 1H), 7.75 (dd, J=8.0, 1.1 Hz, 1H), 7.60 (ddd, J=8.0, 4.8, 0.8 Hz, 1H), 7.40 (t, J=7.7 Hz, 1H), 3.81 (td, J=6.7, 5.8 Hz, 2H), 2.86 (t, J=6.7 Hz, 2H), 2.22 (s, 2H)
451	¹HNMR(CDCI₃) δ: 12.46 (brs, 1H), 10.36 (brs, 1H), 9.44(brs, 1H), 8.71 (d, J=3.9 Hz, 1H), 8.53 (brs, 1H), 8.03 (brs, 1H), 7.44-7.58 (m, 2H), 7.21 (br s, 1 H), 4.66 (br s, 1 H), 3.82 (br s, 2H), 3.50 (s, 5H)
452	¹H NMR (CDCI3) δ: 9.12-9.24 (m, 1H), 8.58 (d, J=3.6 Hz, 1H), 8.23 (d, J=8.0 Hz, 1H), 7.66 (brs, 1H), 7.21-7.34(m, 2H), 7.17 (d, J=7.4 Hz, 1H), 7.06-7.14 (m, 1H), 3.17 (brs, 6H),
453	¹H NMR(CDCI₃) δ: 10.32-10.42 (m, 1H), 9.81-9.95 (m, 1H), 9.24-9.34 (m, 1H), 8.68-8.82 (m, 1H), 8.41 (d, J=8.6 Hz, 1H), 8.15-8.29 (m, 1H), 7.65-7.76 (m, 1H), 7.49-7.59 (m, 1H), 7.47 (s, 1H), 4.30 (s, 2H)
454	¹HNMR(CDCI₃) δ: 13.25 (brs, 1H), 10.39 (s, 1H), 9.54 (s, 1H), 8.70 (d, J=3.8 Hz, 1H), 8.63 (d, J=7.9 Hz, 1H), 8.04 (d, J=7.4 Hz, 1H), 7.39-7.51 (m, 2H), 7.16 (t, J=7.8 Hz, 1H), 1.63 (s, 9H)
462	¹H NMR (DMSO-d₆) δ: 9.41 (d, J=0.9 Hz, 1H), 9.10 (t, J=1.7 Hz, 1H), 8.62 (t, J=5.8 Hz, 1H), 8.35-8.40 (m, 1H), 8.31 (ddd, J=6.5, 1.6, 0.8 Hz, 1H), 8.11 (ddd, J=8.5, 1.9, 0.8 Hz, 1H), 7.82 (dd, J=9.1, 1.6 Hz, 1H), 7.76 (dt, J=9.1, 0.9 Hz, 1H), 7.64 (dd, J=8.5, 6.5 Hz, 1H), 4.01 (t, J=6.3 Hz, 1H), 3.80 (ddd, J=8.1, 7.1, 6.1 Hz, 1H), 3.58-3.70 (m, 1H), 3.28-3.39 (m, 3H), 1.78-1.97 (m, 3H), 1.57-1.67 (m, 1H)
463	¹H NMR (DMSO-d₆) δ: 9.49 (s, 1H), 9.46 (s, 1H), 8.88 (t, J=5.5 Hz, 1H), 8.76 (d, J=5.2 Hz, 1H), 8.70-8.74 (m, 1H), 8.43 (s, 1H), 7.78-7.86 (m, 3H), 3.723.83 (m, 2H), 3.62 (q, J=6.2 Hz, 2H)

249

464	¹H NMR (CDCI3) δ: 9.08 (S, 1H), 9.00 (t, J=1.7 Hz, 1H), 8.12-8:28 (m, 1H); · 7.85-8.06 (m, 1H), 7.80 (dd, J=8.4, 1.1 Hz, 1H), 7.4’1 (dd, J=8.4, 6.5 Hz, 1H), 7.31-7.36 (m, 1H), 6.48 (brs, 1H), 2.96 (dd, J=7.1, 3.9 Hz, 1H), 0.84-0.99 (m, 2H), 0.61-0.76 (m, 2H)
465	¹H NMR (CDCI3) δ: 8.99-9.09 (m, 3H), 8.21 (d, J=6.6 Hz, 2H), 7.84-7.96 (m, 2H), 7.80 (dt, J=8.4, 0.9 Hz, 2H), 7.30-7.47 (m, 5H), 6.17 (d, J=7.7 Hz, 2H), 3.98-4.19 (m, 2H), 2.09 (dd, J=12.5, 3.2 Hz, 4H), 1.80 (dt, J=13.8, 3.7 Hz, 4H), 1.69 (dt, J=13.0, 3.7 Hz, 2H), 1.41-1.55 (m, 4H), 1.23-1.36 (m, 5H)
466	¹H NMR (CDCI3) δ: 8.91-9.08 (m, 2H), 8.23 (d, J=6.8 Hz, 1H), 7.95 (d, J=8.7 Hz, 2H), 7.81 (dd, J=8.4, 1.1 Hz, 2H), 7.34-7.56 (m, 4H), 6.61 (brs, 1H), 4.16-4.36 (m, 2H)
467	¹H NMR (CDCI3) δ: 9.19 (d, 1H), 8.63 (dd, 1H), 8.51 (d, 1H), 8.26 (dt, 1H), 8.03 (s, 1H), 7.39 (dd, 1H), 7.16 (dd, 1H), 7.00 (s, 1H), 6.60 (brs, 1H), 4.10 (qd, 1H), 3.93 (dt, 1H), 3.89-3.76 (m, 2H), 3.38-3.29 (m, 1H), 2.11-2.02 (m, 1H), 2.00-1.83 (m, 3H)
504	¹H NMR (acetone-dg) δ: 9.29-9.35 (m, 2H), 8.62 (d, J=2.4 Hz, 1H), 8.46 (d, J=9.8 Hz, 1H), 7.89 (d, J=8.8 Hz, 2H), 7.68 (d, J=6.6 Hz, 1H), 7.42 (dd, J=7.5 Hz, 1H), 4.62 (t, J=5.5 Hz, 1H), 3.57 (t, J=5.8 Hz, 2H), 3.39 (s, 6H)

^{a 1}H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br)-broad.

BIOLOGICAL EXAMPLES OFTHE INVENTION

Formulation and Spray Methodoloqy for Tests A-F

Test compounds were formulated using a solution containing 10% acetone, 90% water and 300 ppm X-77® Spreader Lo-Foam Formula non-ionic surfactant containing alkylarylpolyoxyethylene, free fatty acids, glycols and isopropanol (Loveland Industries, Inc. Greeley, Colorado, USA). The formulated compounds were applied in 1 mL of liquid through a 10 SUJ2 atomizer nozzle with 1/8 JJ custom body (Spraying Systems Co. Wheaton, Illinois, USA) positioned 1.27 cm (0.5 inches) above the top of each test unit. Test compounds were sprayed at the rates indicated, and each test was replicated three times.

250

Test A

For evaluating control of diamondback moth (Plutella xylostella (L.)) the test unit consisted of a small open container with a 12-14-day-old mustard plant inside. This was pre-infested with ~50 neonate larvae that were dispensed into the test unit via corn cob grits using an inoculator. The larvae moved onto the test plant after being dispensed into the test unit.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. After spraying of the formulated test compound, each test unit was allowed to dry for 1 hour and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 25 °C and 70% relative humidity. Plant feeding damage was then visually assessed based on foliage consumed, and larvae were assessed for mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following provided very good to excellent levels of control efficacy (40% or less feeding damage and/or 100% mortality): 309, 501, 502, 344, 431 and 466.

Test B

For evaluating control of potato leafhopper (Empoasca fabae (Harris)) through contact and/or systemic means, the test unit consisted of a small open container with a 5-6-day-old Soleil bean plant (primary leaves emerged) inside. White sand was added to the top of the soil, and one of the primary leaves was excised priorto application of the test compound.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. After spraying of the formulated test compound, the test units were allowed to dry for 1 hour before they were post-infested with 5 potato leafhoppers (18-to-21-day-old adults). A black, screened cap was placed on the top of the test unit, and the test units were held for 6 days in a growth chamber at 24 °C and 70% relative humidity. Each test unit was then visually assessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 21, 130, 131, 133, 300, 301, 309, 366, 367, 368, 370, 375, 380, 382, 386, 387, 388, 409 and 466.

Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 301, 309, 375, 380, 382, 386, 387 and 388.

Teste

For evaluating control of green peach aphid (Myzus persicae (Sulzer)) through contact and/or systemic means, the test unit consisted of a small open container with a 12-15-day-old radish plant inside. This was pre-infested by placing on a leaf of the test plant 30-40 aphids on a piece of leaf excised from a culture plant (cut-leaf method). The aphids moved onto the test

251 plant as the leaf piece desiccated. After pre-infestation, the soil of the test unit was covered with a layer of sand.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. After spraying of the formulated test compound, each test unit was allowed to dry for 1 hour and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 19-21 °C and 50-70% relative humidity. Each test unit was then visually assessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1, 6, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 28, 34, 35, 36, 37, 39, 41, 42, 44, 46, 49, 51, 52, 53, 54, 55, 56, 57, 58, 60, 61, 62, 63, 64, 66, 67, 68, 69, 70, 72, 73, 74, 75, 76, 78, 79, 81, 84, 85, 86, 92, 96, 97, 98, 100, 102, 106, 111, 114, 117, 118, 121, 122, 124, 125, 131, 132, 133, 160, 161, 162, 163, 173, 300, 301, 308, 309, 320, 321, 322,

323, 324, 326, 329, 330, 331, 332, 333, 334, 335, 336, 338, 340, 341, 342, 343, 344, 345,346,

348, 350, 351, 352, 353, 354, 363, 364, 366, 370, 372, 374, 375, 376, 377, 378, 380, 381,382,

387, 388, 393, 400, 401, 402, 403, 404, 409, 410, 411, 412, 413, 415, 416, 419, 439, 440,442,

443, 444, 445, 446, 447, 448, 449, 455, 456, 462, 463, 464, 500, 501, 502 and 503.

Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 6, 7, 8, 10, 11, 12, 13, 14, 16, 17, 18, 19, 21, 24, 25, 26, 27, 28, 34, 35, 36, 37, 39, 41, 42, 46, 49, 51, 52, 53, 54, 55, 56, 57, 58, 60, 62, 63, 64, 66, 67, 68, 69, 73, 75, 76, 78, 81, 84, 85, 86, 96, 121, 122, 124, 125, 131, 132, 133, 160, 161, 162, 163, 300, 308, 309, 320, 322, 323, 324, 325, 326, 329, 330, 331, 332, 333, 334, 335, 336, 338, 340, 342, 343, 344, 345, 346,

348, 350, 351, 352, 353, 354, 366, 374, 375, 376, 378, 380, 382, 387, 388, 401, 402, 403, 404,

409, 410, 411, 412, 413, 415, 419, 440, 443, 444, 445, 446, 447, 448, 455, 462, 463, 464, 500,

501, 502 and 503.

TestD

For evaluating control of cotton melon aphid (Aphis gossypii (Glover)) through contact and/or systemic means, the test unit consisted of a small open container with a 6-7-day-old cotton plant inside. This was pre-infested with 30-40 insects on a piece of leaf according to the cut-leaf method, and the soil of the test unit was covered with a layer of sand.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. After spraying, the test units were maintained in a growth chamber for 6 days at 19 °C and 70% relative humidity. Each test unit was then visually assessed for insect mortality.

252

Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 6, 7, 8, 11, 12, 14, 16, 19, 21, 24, 25, 37, 39, 40, 41, 51, 52, 54, 55, 58, 62, 63, 64, 66, 67, 68, 69, 70, 79, 96, 131, 133, 160, 161, 309, 323, 336, 342, 345, 348, 350, 351, 353, 366, 401, 403, 412, 419, 440, 444, 447, 455, 462, 464, 500, 501 and 503.

Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 6, 8, 14, 16, 19, 21, 24, 39, 41, 42, 51, 52, 54, 55, 58, 67, 76, 131, 133, 323, 348, 351, 401 and 403.

Test E

For evaluating control of the Western Flower Thrips (Frankliniellla occidentalis (Pergande)) through contact and/or systemic means, the test unit consisted of a small open container with a 5-7-day-old Soleil bean plant inside.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. After spraying, the test units were allowed to dry for 1 hour, and then 22-27 adult thrips were added to each unit. A black, screened cap was placed on top, and the test units were held for 6 days at 25 °C and 45-55% relative humidity.

Of the compounds of Formula 1 tested at 250 ppm, the following provided very good to excellent levels of control efficacy (30% or less plant damage and/or 100% mortality): 13, 64, 68, 70, 72, 131, 132, 133, 314, 340, 348, 367, 409, 410, 415, 464 and 504.

Test F

For evaluating control of the sweetpotato whitefly (Bemisia tabaci (Gennadius)) through contact and/or systemic means, the test unit consisted of a small open container with a 12-14day-old cotton plant inside. Prior to the spray application, both cotylédons were removed from the plant, leaving one true leaf for the assay. Adult whiteflies were allowed to lay eggs on the plant and then were removed from the test unit. Cotton plants infested with at least 15 eggs were submitted to the test for spraying.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. After spraying, the test units were allowed to dry for 1 hour. The cylinders were then removed, and the units were taken to a growth chamber and held for 13 days at 28 °C and 50-70% relative humidity. Each test unit was then visually assessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 50% mortality: 8, 42, 58, 63, 64, 68, 72, 321, 324, 326, 330, 334, 339, 340, 348, 349, 360, 366, 368, 402, 403, 412,456 and 463.

253

Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 50% mortality: 326.

Claims

What is claimed is:

1. A compound selected from Formula 1, an /V-oxide or sait thereof, i

wherein

Q is

Q-1

Q-2

A is CH, CR¹ or N;

each R¹ is independently halogen, cyano, nitro, Ci-C₄ alkyl, Ct-^ haloalkyl, C1-C4 alkoxy, Cï-CU haloalkoxy, C!-C₄ alkylthio or Ci-C₄ haloalkylthio;

m is 0,1, 2 or 3;

X¹, X², X³ and X⁴ are each independently CR², CR³ or N, provided that (i) one of X¹, X², X³and X⁴ is CR², and (ii) no more than one of X¹, X², X³ and X⁴ is N;

R² is C(=Z)NR⁶R⁷, N(R⁸)C(=Z)R⁹, C(=NR¹⁰)R¹¹ or Q^a;

each Z is independently O or S;

each R³ is independently H, halogen, cyano, nitro, C₁-C₄ alkyl, C-|-C₄ haloalkyl, C₁-C₄alkoxy or C-|-C₄ haloalkoxy;

Y¹ is O, S or N R⁴;

Y² is N or CR^5a;

Y³ is N or CR^5b;

255

R⁴ is H or C-|—C₄ alkyl;

R^5a is H, halogen, cyano, nitro, C^-C^ alkyl, C₃-C₆ cycloalkyl, C-i-C₄ haloalkyl, C-f-C₄alkoxy or C-|-C₄ haloalkoxy;

R^5b is H, halogen, cyano, nitro, C-i-C₄ alkyl, C₃-C₆ cycloalkyl, Ci-C₄ haloalkyl, Ο·|-Ο₄alkoxy or C-|-C₄ haloalkoxy;

R⁶ is H, NR¹⁵R¹⁶, OR¹⁷, C(=NR¹⁰)R¹¹, C(O)OR²¹, C(O)NR¹⁵R¹⁶, C(O)R²², S(O)nR²³ orQ^b; or Ci-C6 alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted or substituted with at least one R^x;

R⁷ is H or Q^b; or Ci-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted or substituted with at least one R^x; or

R⁶ and R⁷ are taken together with the nitrogen atom to which they are attached to form a 3- to 10-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2> said ring being unsubstituted or substituted with up to 4 R^x; or

R⁶ and R⁷ are taken together as =S(O)_PR¹⁸R¹⁹ or =S(=NR²⁰)R¹⁸R¹⁹;

each R^x is independently halogen, cyano, nitro, hydroxy, Ο-ι-Ο6 alkyl, C^-Cs haloalkyl, C3C6 cycloalkyl, CrC6 alkoxy, C^Ce haloalkoxy, C3-C6 cycloalkoxy, C(=NR'10)R''\ C(O)OR²¹, C(O)NR¹⁵R¹⁶, OC(O)R²², NR²⁵R²⁶, NR²⁴C(O)R²², C(O)R²², S(O)nR²³, Si(R²⁸)3, OSi(R²⁸)3 or Q^b;

R⁸ is H, C(O)OR²¹, C(O)NR¹⁵R¹⁶, C(O)R²², S(O)nR²³ or Q^b; or C^Ce alkyl, C3-C₆cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted or substituted with at least one R^x;

R⁹ is H, C(=NR¹⁰)R¹¹, OR²¹ or NR¹⁵R¹⁶; or C^Ce alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl or C2-C6 alkynyl, each unsubstituted or substituted with at least one R^x; or phenyl, phenoxy or a 5- or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, Cr-C^ alkyl, C3-C₆ cycloalkyl, (^-(¼ haloalkyl, C!-C₄ alkoxy and Ci-C₄ haloalkoxy; or a 3- to 6-membered heterocyclic nonaromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom,

256 and up to 2 nitrogen atoms, wherein up to 1 carbon atom ring member is independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, each ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C,-C₄ alkyl, C₃-C₆ cycloalkyl, C,-C₄ haloalkyl, Ο,-Ο₄ alkoxy and C1-C4 haloalkoxy;

each R¹⁰ is independently OR¹², S(O)_nR¹³ or NHR¹⁴;

each R¹¹ is independently H; or C,-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl or C2-C6 alkynyl, each unsubstituted or substituted with at least one R^x; or C,-C6 alkoxy, C1C₆ haloalkoxy, C₃-C₆ cycloalkoxy, C(O)OR²¹, C(O)NR¹⁵R¹⁶, NR²⁵R²⁶, NR²⁴C(O)R²², C(O)R²² or Q^b;

each R¹² is independently 0,-04 alkyl, C₃-C₆ cycloalkyl, C,-C₄ haloalkyl, 0(0^22, S(O)_nR¹³ or Q^b;

each R¹³ is independently C1-C4 alkyl or C,-C₄ haloalkyl;

R¹⁴ is C,-C4 alkyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C(O)R²² or C(O)OR²¹; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C3-C₆ cycloalkyl, Ci-C₄ haloalkyl, C-1-C4 alkoxy and C1-C4 haloalkoxy;

each R¹⁵ is independently H, C,-C6 alkyl, C-1-C4 haloalkyl, C(O)R²⁷ or S(O)2r27; or phenyl or a 5- or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C₃-C₆ cycloalkyl, C1-C4 haloalkyl, C,—C₄ alkoxy and 0,-04 haloalkoxy;

each R¹⁶ is independently H, Ci-C₆ alkyl or C1-C4 haloalkyl; or

R¹⁵ and R¹⁶ are taken together with the nitrogen atom to which they are attached to form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=0) and C(=S) and the sulfur atom ring member is selected from S, S(0) or S(0)₂, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C,-C₄ alkyl, C₃-C₆ cycloalkyl, C,-C₄ haloalkyl, C,-C₄ alkoxy and C,-C₄haloalkoxy;

257

R¹⁷ is C1-C4 alkyl, C₃-C₆ cycloalkyl or C1-C4 haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C₃-C₆ cycloalkyl, CYC4 haloalkyl, C!-C₄ alkoxy and U-C4 haloalkoxy;

each R¹⁸ is independently C1-C4 alkyl or C1-C4 haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, CT-C4 alkyl, C₃-C₆ cycloalkyl, C1-C4 haloalkyl, C-(—C₄ alkoxy and C-1-C4 haloalkoxy;

each R¹⁹ is independently C1-C4 alkyl or C-J-C4 haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-i-C₄ alkyl, C₃-C₆ cycloalkyl, C1-C4 haloalkyl, C-|—C4 alkoxy and C1-C4 haloalkoxy; or

R¹⁸ and R¹⁹ are taken together with the sulfur atom to which they are attached to form a ring;

R²⁰ is H, cyano, C-i-GU alkyl, C-1-C4 haloalkyl or C(O)R²²; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-1-C4 alkyl, C₃-C₆ cycloalkyl, C1-C4 haloalkyl, Cb-04 alkoxy and C-1-C4 haloalkoxy;

each R²¹ is independently alkyl, C1-C4 haloalkyl, C₃-C₆ cycloalkyl or C₃-C₆halocycloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, Ct-C₄alkyl, C₃-C₆ cycloalkyl, C-J-C4 haloalkyl, C-1-C4 alkoxy and Ο-!-Ο₄ haloalkoxy;

each R²² is independently C1-C4 alkyl, C1-C4 haloalkyl, C₃-C₆ cycloalkyl or C₃-C₆halocycloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C₃-C₆ cycloalkyl, θ!-θ₄ haloalkyl, C-|-C₄ alkoxy and U-C4 haloalkoxy;

each R²³ is independently C1-C4 alkyl, 0^04 haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₃-C₆ cycloalkylalkyl or C₃-C₆ halocycloalkylalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C₃-C₆ cycloalkyl, C1-C4 haloalkyl, C^-C₄ alkoxy and C1-C4 haloalkoxy;

each R²⁴ is independently θ!-θ₄ alkyl;

258 each R²⁵ is independently H, C-1-C4 alkyl or C-1-C4 haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-1-C4 alkyl, C₃-C₆ cycloalkyl, C^-CU haloalkyl, Ci-C₄ alkoxy and C1-C4 haloalkoxy;

each R²⁶ is independently C1-C4 alkyl or C1-C4 haloalkyl; or phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C!-C₄ alkyl, C₃-C₆ cycloalkyl, C-|-C4 haloalkyl, C1-C4 alkoxy and C-I-C4 haloalkoxy; or

R²⁵ and R²⁶ are independently taken together with the nitrogen atom to which they are attached to form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-|-C₄ alkyl, C₃-C₆ cycloalkyl, C!-C₄ haloalkyl, C·,—C₄ alkoxy and C1-C4 haloalkoxy;

each R²⁷ is independently Ct-Ce alkyl, Ο-ι-Ο₆ haloalkyl, Ci-C₆ alkoxy, Ci-C₆ haloalkoxy or _nr29r30_; or phenyl or a 5- or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, θ!-θ₄ alkyl, C₃-C₆ cycloalkyl, C1-C4 haloalkyl, ¢^-04 alkoxy and C!-C₄ haloalkoxy;

each R²⁸ is independently C-|-C₆ alkyl, C₃-C₆ cycloalkyl or phenyl;

each R²⁹ is independently H or Q^b; or C!-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂C₆ alkynyl, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C₃-C₆ cycloalkyl, C^-04 haloalkyl, C-|-C₄ alkoxy and C^-04 haloalkoxy;

each R³⁰ is independently H or Q^fa; or Ο·ι-Ο₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂C₆ alkynyl, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C1-C4 alkyl, C₃-C₆ cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy; or

R²⁹ and R³⁰ are taken together with the nitrogen atom to which they are attached to form a 3- to 10-membered ring containing ring members selected from carbon atoms and

259 up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, said ring being unsubstituted or substituted with up to 4 substituents independently selected from the group consisting of halogen, cyano, nitro, C-J-C4 alkyl, C₃-C₆ cycloalkyl, C-1-C4 haloalkyl, C1-C4 alkoxy and C-|-C₄haloalkoxy;

Q^a is a 5- to 10-membered aromatic ring or ring System, each ring or ring System containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 3 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, each ring or ring System being unsubstituted or substituted with at least one R^x; or a 3- to 6-membered partially saturated ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)2, each ring unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-|-C₄ alkyl, C₃-C₆ cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C-i-C₄ haloalkoxy;

each Q^b is independently phenyl, a 5- or 6-membered heterocyclic aromatic ring or a 3- to 6-membered heterocyclic non-aromatic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S) and the sulfur atom ring member is selected from S, S(O) or S(O)₂, each ring unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C-|-C₄ alkyl, C₃-C₆ cycloalkyl, C-1-C4 haloalkyl, C-|-C₄ alkoxy and U-C4 haloalkoxy;

each n is independently 0, 1 or 2; and p is 1 or 2.
2. The compound of Claim 1 wherein

260 is CR², and X², X² and χ4 are each independently CR²; or X² is CR², and , X²and χ4 are each independently CR².
3. The compound of Claim 2 wherein

Q is Q-1 or Q-2.
4. The compound of Claim 3 wherein

Q is Q-1; and

Y¹ is O or S.
5. The compound of Claim 3 wherein

Q is Q-2; and

Y² is CR^5a.
6. The compound of any one of Claims 2 through 5 wherein

A is CH or CF; and m is 0.
7. The compound of Claim 1 that is selected from the group consisting of: /V-(1-methylethyl)-2-(3-pyridinyl)-2/7-indazole-4-carboxamide; /V-cyclopropyl-2-(3-pyridiny!)-2/-/-indazole-4-carboxamide;

A/-cyclohexy!-2-(3-pyridinyl)-2/7-indazole-4-carboxamide; 2-(3-pyridinyl)-/V-(2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide;

2-(3-pyridinyl)-A/-[(tetrahydro-2-furanyl)methyl]-2/-/-indazole-5-carboxamide;

methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate; /V-[(2,2-difluorocyclopropyl)methylI-2-(3-pyridinyl)-2A/-indazole-5-carboxamide; /V-(2,2-difluoropropyl)-2-(3-pyridinyl)-2/7-indazole-5-carboxamide;

2-(3-pyridinyl)-/\/-(2-pyrimidinylmethyl)-2F/-indazole-5-carboxamide; and A/-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2/7-indazole-5-carboxamide.
8. A composition comprising a compound of Claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising at least one additional biologically active compound or agent.
9. The composition of Claim 8 wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen, amidoflumet, amitraz, avermectin, azadirachtin,

261 azinphos-methyl, benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cycloxaprid, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin, fluensulfone, fluopyram, flupyradifurone, fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, heptafluthrin, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone, metaldehyde, methamidophos, methidathion, methiodicarb, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, monocrotophos, monofluorothrin, nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide, pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin, pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen, toifenpyrad, tralomethrin, triazamate, trichlorfon, triflumezopyrim, triflumuron, Bacillus thuringiensis delta-endotoxins, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi.
10. The composition of Claim 9 wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gammacyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin,

262 flufensulfone, flupiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide, metofluthrin, monofluorothrin, nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine,

5 pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumezopyrim, triflumuron, Bacillus thuringiensis delta-endotoxins, ail strains of Bacillus thuringiensis and ail strains of nucleo polyhedrosis viruses.

10
11. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Claim 1.
12. The method of Claim 11 wherein the environment is a plant.
13. The method of Claim 11 wherein the environment is an animal.
14. The method of Claim 11 wherein the environment is a seed.
15. The method of Claim 14 wherein the seed is coated with the compound of Claim 1 formulated as a composition comprising a film former or adhesive agent.
16. A treated seed comprising a compound of Claim 1 in an amount of from about

0.0001 to 1 % by weight of the seed before treatment.