US20040102324A1

US20040102324A1 - Heterocyclic diamide invertebrate pest control agents

Info

Publication number: US20040102324A1
Application number: US10/469,263
Authority: US
Inventors: Gary Annis; Bruce Finklestein
Original assignee: Individual
Current assignee: EIDP Inc
Priority date: 2002-02-28
Filing date: 2002-02-28
Publication date: 2004-05-27
Also published as: US7560564B2; US20060205748A1

Abstract

This invention provides compounds of Formula (I), N-oxides and suitable salts thereof, wherein A and B are independently O or S; each J is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 4 R⁵; K is, together with the two contiguous linking carbon atoms, a 5- or 6-membered heteroaromatic ring optionally substituted with 1 to 3 R⁴; and R¹, R², R³, R⁴, R⁵and n are as defined in the disclosure. Also disclosed are methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula (I), an N-oxide thereof or a suitable salt of the compound (e.g., as a composition described herein). This invention also pertains to a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula (I), an N-oxide thereof or a suitable salt of the compound and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

Description

BACKGROUND OF THE INVENTION

This invention relates to certain heterocyclic diamides, their N-oxides, suitable salts and compositions, and a method of their use for controlling invertebrate pests in both agronomic and nonagronomic environments.

The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result 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, 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 have different modes of action.

NL 9202078 discloses N-acyl anthranilic acid derivatives of Formula i as insecticides

wherein, inter alia, X is a direct bond; Y is H or C ₁-C₆alkyl; Z is NH₂, NH(C₁-C₃alkyl) or N(C₁-C₃alkyl)₂; and R¹through R⁹are independently H, halogen, C₁-C₆alkyl, phenyl, hydroxy, C₁-C₆alkoxy or C₁-C₇acyloxy.

WO01/070671 discloses N-acyl anthranilic acid derivatives of Formula i as arthropodicides

wherein, inter alia, A and B are independently O or S; J is an optionally substituted phenyl ring, 5- or 6-membered heteroaromatic ring, naphthyl ring system or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system; R ¹and R³are independently H or optionally substituted C₁-C₆alkyl; R²is H or C₁-C₆alkyl; each R⁴is independently H, C₁-C₆alkyl, C₁-C₆haloalkyl, halogen or CN; and n is 1 to 4.

SUMMARY OF THE INVENTION

This invention pertains to compounds of Formula I, and N-oxides or suitable salts thereof

wherein

A and B are independently O or S;

each J is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 4 R ⁵;

K is, together with the two contiguous linking carbon atoms, a 5- or 6-membered heteroaromatic ring optionally substituted with 1 to 3 R ⁴;

n is 1 to 3;

R ¹is H; or C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₂-C₄alkoxycarbonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino and C₃-C₆cycloalkylamino; or

R ¹is C₂-C₆alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl or C(=A)J;

R ²is H, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₄alkoxy, C₁-C₄alkylamino, C₂-C₅dialkylamino, C₃-C₆cycloalkylamino, C₂-C₆alkoxycarbonyl or C₂-C₆alkylcarbonyl;

R ³is H; G; or C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of G, halogen, CN, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylcarbonyl, C₃-C₆trialkylsilyl, or a phenyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R⁶; or

R ²and R³can be taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, and said ring may be optionally substituted with one to four substituents selected from R¹²; and

G is a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(═O), SO or S(O) ₂and optionally substituted with one to four substituents selected from R¹²;

each R ⁴is independently H, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthib, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₁-C₄alkoxyalkyl, C₁-C₄hydroxyalkyl, C(O)R¹⁰, CO₂R¹⁰, C(O)NR¹⁰R¹¹, NR¹⁰R¹¹, N(R¹¹)CO₂R¹⁰; or

each R ⁴is independently a phenyl, benzyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R⁶;

each R ⁵is independently H, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, CO₂H, CONH₂, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₂-C₆alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl, C₃-C₆trialkylsilyl; or

each R ⁵is independently a phenyl, benzyl, benzoyl, phenoxy, 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each ring or ring system optionally substituted with one to three substituents independently selected from R⁶; or

(R ⁵)₂when attached to adjacent carbon atoms can be taken together as —OCF₂O—, —CF₂CF₂O—, or —OCF₂CF₂O—; and

each R ⁶is independently C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, NO₂, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₃-C₆(alkyl)cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl or C₃-C₆trialkylsilyl;

each R ¹⁰is independently H, C₁-C₄alkyl or C₁-C₄haloalkyl;

each R ¹¹is independently H or C₁-C₄alkyl; and

each R ¹²is independently C₁-C₂alkyl, halogen, CN, NO₂or C₁-C₂alkoxy.

This invention also pertains to 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 I, an N-oxide thereof or a suitable salt of the compound (e.g., as a composition described herein). This invention also relates to such a method wherein the invertebrate pest or its environment is contacted with a biologically effective amount of a compound of Formula I or a composition comprising a compound of Formula I, an N-oxide thereof or a suitable salt of the compound and a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests.

This invention also pertains to a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I, an N-oxide thereof or a suitable salt of the compound and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. This invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I, an N-oxide thereof or a suitable salt of the compound and an effective amount of at least one additional biologically active compound or agent.

DETAILS OF THE INVENTION

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, i-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. “Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH ₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂and CH₃CH₂OCH₂CH₂. “Alkylthio” includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio and butylthio isomers. “Alkylsulfinyl” includes both enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH₃S(O), CH₃CH₂S(O), CH₃CH₂CH₂S(O), (CH₃)₂CHS(O) and the different butylsulfinyl isomers. Examples of “alkylsulfonyl” include CH₃S(O)₂, CH₃CH₂S(O)₂, CH₃CH₂CH₂S(O)₂, (CH₃)₂CHS(O)₂and the different butylsulfonyl isomers. “Alkylamino”, “dialkylamino”, “alkenylthio”, “alkenylsulfinyl”, “alkenylsulfonyl”, “alkynylthio”, “alkynylsulfinyl”, “alkynylsulfonyl”, and the like, are defined analogously to the above examples. “Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

“Aromatic” indicates that each of the ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and in which (4n+2)π electrons, when n is 0 or a positive integer, are associated with the ring to comply with Hückel's rule. The term “aromatic ring system” denotes fully unsaturated carbocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic. The term “aromatic carbocyclic ring or ring system” includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic (e.g. phenyl and naphthyl). The term “nonaromatic carbocyclic ring or ring system” denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the Hückel rule is not satisfied by any of the rings in the ring system. The term “hetero” in connection with rings or ring systems refers to a ring or ring system in which at least one ring atom is not carbon and which can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. The terms “heteroaromatic ring or ring system” and “aromatic fused heterobicyclic ring system” includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Hückel rule is satisfied). The term “nonaromatic heterocyclic ring or ring system” denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Hückel rule is not satisfied by any of the rings in the ring system. The heterocyclic ring or ring system can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

The term “halogen”, either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F ₃C, ClCH₂, CF₃CH₂and CF₃CCl₂. The terms “haloalkenyl”, “haloalkynyl”, “haloalkoxy”, “haloalkylthio”, and the like, are defined analogously to the term “haloalkyl”. Examples of “haloalkenyl” include (Cl)₂C═CHCH₂and CF₃CH₂CH═CHCH₂. Examples of “haloalkynyl” include HC≡CCHCl, CF₃C≡C, CCl₃C≡C and FCH₂C≡CCH₂. Examples of “haloalkoxy” include CF₃O, CCl₃CH₂O, HCF₂CH₂CH₂O and CF₃CH₂O. Examples of “haloalkylthio” include CCl₃S, CF₃S, CCl₃CH₂S and ClCH₂CH₂CH₂S. Examples of “haloalkylsulfinyl” include CF₃S(O), CCl₃S(O), CF₃CH₂S(O) and CF₃CF₂S(O). Examples of “haloalkylsulfonyl” include CF₃S(O)₂, CCl₃S(O)₂, CF₃CH₂S(O)₂and CF₃CF₂S(O)₂.

Examples of “alkylcarbonyl” include C(O)CH ₃, C(O)CH₂CH₂CH₃and C(O)CH(CH₃)₂. Examples of “alkoxycarbonyl” include CH₃OC(═O), CH₃CH₂OC(═O), CH₃CH₂CH₂C(═O), (CH₃)₂CHOC(═O) and the different butoxy- or pentoxycarbonyl isomers. Examples of “alkylaminocarbonyl” include CH₃NHC(═O), CH₃CH₂NHC(═O), CH₃CH₂CH₂NHC(═O), (CH₃)₂CHNHC(═O) and the different butylamino- or pentylaminocarbonyl isomers. Examples of “dialkylaminocarbonyl” include (CH₃)₂NC(═O), (CH₃CH₂)₂NC(═O), CH₃CH₂(CH₃)NC(═O), CH₃CH₂CH₂(CH₃)NC(—O) and (CH₃)₂CHN(CH₃)C(═O).

The total number of carbon atoms in a substituent group is indicated by the “C _i-C_j” prefix where i and j are numbers from 1 to 6. For example, C₁-C₃alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C₂alkoxyalkyl designates CH₃OCH₂; C₃alkoxyalkyl designates, for example, CH₃CH(OCH₃), CH₃OCH₂CH₂or CH₃CH₂OCH₂; and C₄alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH₃CH₂CH₂OCH₂and CH₃CH₂OCH₂CH₂.

In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

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. Further, when the subscript indicates a range, e.g. (R) _i-j, then the number of substituents may be selected from the integers between i and j inclusive.

The term “optionally substituted with one to three substituents” and the like indicates that one to three of the available positions on the group may be substituted. When a group contains a substituent which can be hydrogen, for example R ¹or R⁵, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial 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 prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.

One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-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 N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-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 m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane. These methods for the preparation of N-oxides have 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., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic 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., Academic Press.

The salts of the compounds of the invention 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. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.

As noted above, J is a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 4 R ⁵. The term “optionally substituted” in connection with these J groups refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. An example of phenyl optionally substituted with 1 to 4 R⁵is the ring illustrated as U-1 in Exhibit 1, wherein R^vis R⁵and r is an integer from 1 to 4. An example of a naphthyl group optionally substituted with 1 to 4 R⁵is illustrated as U-85 in Exhibit 1, wherein R^vis R⁵and r is an integer from 1 to 4. Examples of 5- or 6-membered heteroaromatic rings optionally substituted with 1 to 4 R⁵include the rings U-2 through U-53 illustrated in Exhibit 1 wherein R^vis R⁵and r is an integer from 1 to 4. Note that J-1 through J-13 below also denote 5- or 6-membered heteroaromatic rings. Note that U-2 through U-20 are examples of J-1, U-21 through U-35 and U-40 are examples of J-2, U-36 through U-39 are examples of J-3, U-41 through U-48 are examples of J-4 and U-49 through U-53 are examples of J-5. Note that J-6 is a subset of U-11, J-7 or J-10 are a subset of U-26, J-8 is a subset of U-42, J-9 is a subset of U-45, J-11 is a subset of U-4 and J-12 or J-13 are a subset of U-24. Also note that in J-6 through J-13 that R⁷and R⁹are subsets of R⁵. Examples of aromatic 8-, 9- or 10-membered fused heterobicyclic ring systems optionally substituted with 1 to 4 R⁵include U-54 through U-84 illustrated in Exhibit 1 wherein R^vis R⁵and r is an integer from 1 to 4.

Although R ^vgroups are shown in the structures U-1 through U-85, it is noted that they do not need to be present since they are optional substituents. Note that when R^vis 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 some U groups can only be substituted with less than 4 R^vgroups (e.g. U-14, U-15, U-18 through U-21 and U-32 through U-34 can only be substituted with one RV). Note that when the attachment point between (RV)_rand the U group is illustrated as floating, (R^v)_rcan be attached to any available carbon 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 I through any available carbon of the U group by replacement of a hydrogen atom.

As noted above, K is, together with the two contiguous linking carbon atoms, a 5- or 6-membered heteroaromatic ring optionally substituted with 1 to 3 R ⁴. Examples of said K rings wherein said rings are optionally substituted with 1 to 3 R⁴include the ring systems illustrated as K-1 to K-37 in Exhibit 2, wherein n is an integer from 1 to 3 and R⁴is as defined above. The term “optionally substituted” in connection with these K groups refers to K groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As with the carbon atoms in the ring, the nitrogen atoms that require substitution to fill their valence are substituted with hydrogen or with R⁴. Although (R⁴)_ngroups are shown in the structures K-1 to K-37, it is noted that R⁴does not need to be present since it is an optional substituent. Note that some K groups can only be substituted with less than 3 R⁴groups (e.g. K-7 through K-10, K-15, K-16, K-20, K-21, K-23, K-24, K-26 and K-27 can only be substituted with one R⁴). In the exemplified K groups, the upper right bond is attached through the available linking carbon atom to the nitrogen atom of the NR¹(=A)J portion of Formula I and the lower right bond is attached through the available linking carbon atom to the carbon atom of the C(═B)NR²R³portion of Formula I. The wavy line indicates that the K ring is attached to the remainder of Formula I as illustrated below.

Preferred K rings include optionally substituted thiophene, isoxazole, isothiazole, pyrazole, pyridine and pyridine rings. More preferred K rings include K-1, K-14, K-15, K-18, K-23, K-28, K-29, K-30, K-31 and K-33. Most preferred are K-28, K-31 and K-33.

As noted above, R ³can be (among others) C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of a phenyl ring, or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R⁶. Examples of such rings incorporated into said R³groups include the rings illustrated as U-1 through U-53 and U-86 illustrated in Exhibit 1, except that such rings are optionally substituted with 1 to 3 substituents independently selected from R⁶rather than (R^v)_rand are attached to an R³group selected from the list immediately above.

As noted above, R ³can be (among others) G, or C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, each optionally substituted with G; wherein G is a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(═O), SO or S(O)₂and optionally substituted with 1 to 4 substituents selected from R¹². The term “optionally substituted” in connection with these G groups refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. Note that when the attachment point on the G group is illustrated as floating, the G group can be attached to the remainder of Formula I through any available carbon of the G group by replacement of a hydrogen atom. The optional substituents can be attached to any available carbon by replacing a hydrogen atom. Examples of 5- or 65 membered nonaromatic carbocyclic rings as 0 include the rings illustrated as G-I through G-8 of Exhibit 3. Examples of 5- or 6-membered nonaromatic heterocyclic rings as G include the rings illustrated as G-9 through G-48 of Exhibit 3. Note that when G comprises a ring selected from G-31 through G-34, G-37 and G-38, Q¹is selected from O, S or N. Note that when G is G-11, G13, G-14, G16, G-23, G-24, G-30 through G-34, G-37 and G-38 and Q¹is N, the nitrogen atom can complete its valence by substitution with either H or C₁-C₂alkyl.

As noted above, each R ⁴can be independently (among others) a phenyl, benzyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R⁶. Examples of such R⁴groups include the rings or ring systems illustrated as U-1 through U-53, U-86 and U-87 illustrated in Exhibit 1, except that such rings are optionally substituted with 1 to 3 substituents independently selected from R⁶rather than (RV)_r.

As noted above, each R ⁵can be independently (among others) a phenyl, benzyl, benzoyl, phenoxy, 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each ring optionally substituted with one to three substituents independently selected from R⁶. Examples of such R⁵groups include the rings or ring systems illustrated as U-1 through U-88 illustrated in Exhibit 1, except that such rings are optionally substituted with 1 to 3 substituents independently selected from R⁶rather than (R^v)_r.

Preferred compounds for reasons of better activity and/or ease of synthesis are:

Preferred 1. Compounds of Formula I above, and N-oxides and suitable salts thereof, wherein A and B are both 0 and J is a phenyl ring optionally substituted with 1 to 4 R ⁵.

Preferred 2. Compounds of Preferred 1 wherein

each R ⁴is independently C₁-C₄alkyl, C₁-C₄haloalkyl, halogen, CN, NO₂or C₁-C₄alkoxy, and one R⁴group is attached to the K ring at the atom adjacent to either the NR¹C(=A)J moiety or the C(═B)NR²R³moiety; and

each R ⁵is independently H, halogen, C₁-C₄alkyl, C₁-C₂alkoxy, C₁-C₄haloalkyl, CN, NO₂, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl or C₂-C₄alkoxycarbonyl; or

each R ⁵is independently a phenyl or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R⁶; or

(R ⁵)₂when attached to adjacent carbon atoms can be taken together as —OCF₂O—, —CF₂CF₂O— or —OCF₂CF₂O—.

Preferred 3. Compounds of Preferred 2 wherein

R ¹is H;

R ²is H or CH₃;

R ³is C₁-C₄alkyl optionally substituted with one or more substituents independently selected from halogen, CN, OCH₃or S(O)_pCH₃;

each R ⁴is independently CH₃, CF₃, CN or halogen, and one R⁴group is attached to the K ring at the atom adjacent to the NR¹C(=A)J moiety;

each R ⁵is independently H, halogen, methyl, CF₃, OCF₃, OCHF₂, S(O)_pCF₃, S(O)_pCHF₂, OCH₂CF₃, OCF₂CHF₂, S(O)_pCH₂CF₃or S(O)_pCF₂CHF₂;

or a phenyl, pyrazole, imidazole, triazole, pyridine or pyrimidine ring, each ring optionally substituted with one to three substituents independently selected from C ₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN; and

p is 0, 1 or 2.

Preferred 4. Compounds of Preferred 3 wherein R ³is C₁-C₄alkyl.

Preferred 5. Compounds of Formula I wherein

A and B are both 0;

J is a 5- or 6-membered heteroaromatic ring selected from the group consisting of J-1, J-2, J-3, J-4 and J-5, each J optionally substituted with 1 to 3 R ⁵

Q is O, S or NR ⁵; and

W, X, Y and Z are independently N or CR ⁵, provided that in J-4 and J-5 at least one of W, X, Y or Z is N.

Preferred 6. Compounds of Preferred 5 wherein

each R ⁵is independently H, C₁-C₄alkyl, C₁-C₄haloalkyl, halogen, CN, NO₂, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl or C₂-C₄alkoxycarbonyl; or a phenyl or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with R⁶.

Preferred 7. Compounds of Preferred 6 wherein

J substituted with 1 to 3 R ⁵is selected from the group consisting of J-6, J-7, J-8, J-9, J-10, J-11, J-12 and J-13

R ⁵is H, C₁-C₄alkyl, C₁-C₄haloalkyl, or

V is N, CH, CF, CCl, CBr or CI;

each R ⁶and R⁷is independently H, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, CN, C₁-C₄alkoxy, C₁-C₄haloalkoxy or C₁-C₄haloalkylthio; and

R ⁹is H, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl or C₃-C₆haloalkynyl; provided R⁷and R⁹are not both H.

Preferred 8. Compounds of Preferred 7 wherein V is N.

Preferred 9. Compounds of Preferred 7 wherein V is CH, CF, CCl or CBr.

Preferred 10. Compounds of Preferred 8 or Preferred 9 wherein

R ¹is H;

R ²is H or CH₃;

R ⁶is C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN;

R ⁷is H, CH₃, CF₃, OCH₂CF₃, OCHF₂or halogen; and

p is 0, 1 or 2.

Preferred 11. Compounds of Preferred 10 wherein R ³is C₁-C₄alkyl; one R⁴group is independently CH₃, Cl, Br or I and is attached to the K ring at the atom adjacent to the NR¹C(=A)J moiety; and a second optional R⁴is H, F, Cl, Br, I or CF₃.

Preferred 12. Compounds of Preferred 11 wherein J substituted with 1 to 3 R ⁵is J-6; R⁶is Cl or Br; and R⁷is halogen, OCH₂CF₃or CF₃.

Preferred 13. Compounds of Preferred 12 wherein V is N; R ³is methyl, ethyl, isopropyl, tertiary butyl or N(CH₃)₂; and R⁷is Br, Cl, OCH₂CF₃or CF₃.

Preferred 14. Compounds of Preferred 11 wherein J substituted with 1 to 3 R ⁵is J-7; R⁶is Cl or Br; and R⁹is CF₃, CHF₂, CH₂CF₃or CF₂CHF₂.

Preferred 15. Compounds of Preferred 11 wherein J substituted with 1 to 3 R ⁵is J-8; R⁶is Cl or Br; and R⁷is halogen, OCH₂CF₃or CF₃.

Preferred 16. Compounds of Preferred 11 wherein J substituted with 1 to 3 R ⁵is J-9; R⁶is Cl or Br; and R⁷is OCH₂CF₃or CF₃.

Preferred 17. Compounds of Preferred 11 wherein J substituted with 1 to 3 R ⁵is J-10; R⁶is Cl or Br; and R⁹is CF₃, CHF₂, CH₂CF₃or CF₂CHF₂.

Preferred 18. Compounds of Preferred 11 wherein J substituted with 1 to 3 R ⁵is J-11; R⁶is Cl or Br; and R⁷is halogen, OCH₂CF₃, or CF₃.

Preferred 19. Compounds of Preferred 11 wherein J substituted with 1 to 3 R ⁵is J-12; R⁶is Cl or Br; R⁷is H, halogen or CF₃, and R⁹is H, CF₃, CHF₂, CH₂CF₃, or CF₂CHF₂.

Preferred 20. Compounds of Preferred 11 wherein J substituted with 1 to 3 R ⁵is J-13; R⁶is C₁or Br; R⁷is H, halogen or CF₃, and R⁹is H, CF₃, CHF₂, CH₂CF₃or CF₂CHF₂.

Most preferred is the compound of Formula I selected from the group consisting of:

4-[[[1-(2-Chlorophenyl)-3-(trifluoromethyl)-1H-pyrazol-S-yl]carbonyl]amino]-5-methyl-N-1-methylethyl)-3-pyridincarboxamide,

4-Methyl-N-(1-methylethyl)-3-[[2-methyl-4-(trifluoromethyl)benzoyl]amino]-25 thiophencarboxamide,

1-Methyl-N-(1-methylethyl)-5-[[4-(trifluoromethyl)benzoyl]amino]-1H-pyrazole-4-carboxamide;

4-[[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]amino]-5-chloro-N-methyl-3-pyridinecarboxamide;

3-[[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]amino]-2,6-dichloro-N-methyl-4-pyridinecarboxamide;

2,6-dichloro-3-[[[1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl]amino]-N-(1-methylethyl)-4-pyridinecarboxamide;

3-[[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]amino]-6-chloro-N,4-dimethyl-2-pyridinecarboxamide;

3-[[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]amino]-4,6-dichloro-N-methyl-2-pyridinecarboxamide;

5-[[[3-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]amino]-N,6-dimethyl-4-pyrimidinecarboxamide; and

5-[[[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]amino]-N,N,2,6-tetramethyl-4-pyridinecarboxamide.

This invention also pertains to a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I, an N-oxide thereof or a suitable salt thereof and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. This invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I, an N-oxide thereof or a suitable salt thereof and an effective amount of at least one additional biologically active compound or agent. The preferred compositions of the present invention are those which comprise the above preferred compounds.

This invention also pertains to 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 I, an N-oxide t hereof or a suitable salt thereof (e.g., as a composition described herein). This invention also relates to such a method wherein the invertebrate pest or its environment is contacted with a biologically effective amount of a compound of Formula I or a composition comprising a compound of Formula I, an N-oxide thereof or a suitable salt thereof and a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests. The preferred methods of use are those involving the above preferred compounds.

Of note are compounds of Formula 1 (a subset of Formula I) and N-oxides or suitable salts thereof

wherein

A and B are independently O or S;

n is 1 to 3;

R ²is H, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₄alkoxy, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₂-C₆alkoxycarbonyl or C₂-C₆alkylcarbonyl;

R ³is H; G; C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, G, CN, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylcarbonyl, C₃-C₆trialkylsilyl, or a phenyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from the group consisting of C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, NO₂, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₃-C₆(alkyl)cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl or C₃-C₆trialkylsilyl; C₁-C₄alkoxy; C₁-C₄alkylamino; C₂-C₈dialkylamino; C₃-C₆cycloalkylamino; C₂-C₆alkoxycarbonyl or C₂-C₆alkylcarbonyl; or

R ²and R³can be taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring may be optionally substituted with 1 to 4 substituents selected from the group consisting of C₁-C₂alkyl, halogen, CN, NO₂and C₁-C₂alkoxy;

G is a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(═O), SO or S(O) ₂and optionally substituted with 1 to 4 substituents selected from the group consisting of C₁-C₂alkyl, halogen, CN, NO₂and C₁-C₂alkoxy;

each R ⁴is independently H, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, or C₃-C₆trialkylsilyl; or

each R ⁴is independently phenyl, benzyl or phenoxy, each optionally substituted with C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, NO₂, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₃-C₆(alkyl)cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl or C₃-C₆trialkylsilyl;

each R ⁵is independently H, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, CO₂H, CONH₁₂, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₂-C₆alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl, C₃-C₆trialkylsilyl; or

each R ⁵is independently a phenyl, benzyl, benzoyl, phenoxy, 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each ring optionally substituted with one to three substituents independently selected from the group consisting of C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, NO₂, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₃-C₆(alkyl)cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl or C₃-C₆trialkylsilyl; or

(R ⁵)₂when attached to adjacent carbon atoms can be taken together as —OCF₂O—, —CF₂CF₂O—, or —OCF₂CF₂O—.

Also of note are selected compounds for reasons of cost, ease of synthesis and/or biological efficacy:

Selection A. Compounds of Formula 1 wherein K is, together with the two linking atoms, a thiophene, pyrazole, isoxazole, pyridine or pyrimidine optionally substituted with 1 to 3 R ⁴.

Selection B. Compounds of Selection A wherein J is independently a phenyl ring or a 5 or 6-membered heteroaromatic ring wherein each ring is optionally substituted with 1 to 2 R ⁵.

Selection C. Compounds of Selection A wherein

J is a phenyl ring or a 5- or 6-membered heteroaromatic ring selected from the group consisting of J-1, J-2, J-3, J-4 and J-5, each ring optionally substituted with 1 to 3 R ⁵

Q is O, S or NR ⁵; and

Selection D. Compounds of Selection B or Selection C wherein

A and B are both 0;

n is 1 to 2;

R ¹is H, C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, C₂-C₆alkylcarbonyl or C₂-C₆alkoxycarbonyl;

R ²is H, C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, C₂-C₆alkylcarbonyl or C₂-C₆alkoxycarbonyl;

R ³is C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, C₁-C₂alkoxy, C₁-C₂alkylthio, C₁-C₂alkylsulfinyl and C₁-C₂alkylsulfonyl;

one of the R ⁴groups is attached to the heteroaromatic ring at one of the two positions ortho to the two linking atoms, and said R⁴is C₁-C₄alkyl, C₁-C₄haloalkyl, halogen, CN, NO₂, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl or C₁-C₄haloalkylsulfonyl;

each R ⁵is independently H, C₁-C₄alkyl, C₁-C₄haloalkyl, halogen, CN, NO₂, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl or C₂-C₄alkoxycarbonyl; or a phenyl or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, NO₂, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₃-C₆(alkyl)cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl or C₃-C₆trialkylsilyl; or

(R ⁵)₂when attached to adjacent carbon atoms can be taken together as OCF₂O—, —CF₂CF₂O— or —OCF₂CF₂O—.

Selection E. Compounds of Selection D wherein

J is selected from the group consisting of phenyl, pyridine, pyrimidine, pyrazole, imidazole, triazole, thiophene, thiazole and oxazole, furan, isothiazole and isoxazole, each optionally substituted with 1 to 2 R ⁵.

Selection F. Compounds of Selection E wherein

J is selected from the group consisting of phenyl, pyridine, pyrimidine, pyrazole, thiophene and thiazole, each optionally substituted with 1 to 2 R ⁵;

R ¹and R²are both H;

R ³is C₁-C₄alkyl optionally substituted with halogen, CN, OCH₃, S(O)_pCH₃;

each R ⁴is independently CH₃, CF₃, OCF₃, OCHF₂, S(O)_pCF₃, S(O)_pCHF₂, CN or halogen;

each R ⁵is independently H, halogen, CH₃, CF₃, OCHF₂, S(O)_pCF₃, S(O)_pCHF₂, OCH₂CF₃, OCF₂CHF₂, S(O)_pCH₂CF₃, S(O)_pCF₂CHF₂; or phenyl, pyrazole, imidazole, triazole, pyridine or pyrimidine, each ring optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, halogen or CN; and

p is 0, 1 or 2.

Selection G. Compounds of Selection F wherein R ³is C₁-C₄alkyl.

Selection H. Compounds of Selection G wherein J is a phenyl optionally substituted with 1 to 2 R ⁵.

Selection I. Compounds of Selection H wherein one R ⁵is a phenyl optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN.

Selection J. Compounds of Selection H wherein one R ⁵is a pyrazole, imidazole, triazole, pyridine or pyrimidine, each ring optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN.

Selection K. Compounds of Selection I wherein J is a pyridine optionally substituted with 1 to 2 R ⁵.

Selection L. Compounds of Selection K wherein one R ⁵is a phenyl optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN.

Selection M. Compounds of Selection K wherein one R ⁵is a pyrazole, imidazole, triazole, pyridine or pyrimidine, each ring optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN.

Selection N. Compounds of Selection I wherein J is a pyrimidine optionally substituted with 1 to 2 R ⁵.

Selection 0. Compounds of Selection N wherein one R ⁵is a phenyl optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN.

Selection P. Compounds of Selection N wherein one R ⁵is a pyrazole, imidazole, triazole, pyridine or pyrimidine, each ring optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN.

Selection Q. Compounds of Selection I wherein J is a pyrazole optionally substituted with 1 to 2 R ⁵.

Selection R. Compounds of Selection Q wherein one R ⁵is a phenyl optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN.

Selection S. Compounds of Selection Q wherein one R ⁵is a pyrazole, imidazole, triazole, pyridine or pyrimidine, each ring optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN.

Selection T. Compounds of Selection S wherein one R ⁵is a pyridine optionally substituted with C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN.

Most select is the compound of Formula 1 selected from the group consisting of:

4-Methyl-N-(1-methylethyl)-3-[[2-methyl-4-(trifluoromethyl)benzoyl]amino]-2-thiophencarboxamide, and

1-Methyl-N-(1-methylethyl)-5-[[4-(trifluoromethyl)benzoyl]amino]-1H-pyrazole-4-carboxamide.

The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-19. The definitions of A, B, J, K, R ¹, R², R³, R⁴, R⁵and n in the compounds of Formulae I and 2-41 below are as defined above in the Summary of the Invention. Compounds of Ia-c, 2a-b and 4a-g are various subsets of the compounds of Formula I, 2 and 4, respectively. Of note are compounds of Formulae I, 2, 5, 6, 6a, 13, 14, 15, 40 and 41 wherein K is selected from the group consisting of optionally substituted thiophene, isoxazole, isothiazole, pyrazole, pyridine and pyrimidine rings. Also of note are compounds of Formulae I, 2, 5, 6, 6a, 13, 14, 15, 40 and 41 wherein K is K-1, K-14, K-15, K-18, K-23, K-28, K-29, K-30, K-31 and K-33. Of particular note are compounds of Formulae I, 2, 5, 6, 6a, 13, 14, 15, 40 and 41 wherein K is K-28, K-31 and K-33.

Compounds of Formula I can be prepared by procedures outlined in Schemes 1-19. A typical procedure is detailed in Scheme 1 and involves coupling of an ortho amino carboxylic acid amide of Formula 2 with an acid chloride of Formula 3 in the presence of an acid scavenger to provide the compound of Formula Ia. Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine; other scavengers include hydroxides such as sodium and potassium hydroxide and carbonates such as sodium carbonate and potassium carbonate. In certain instances it is useful to use polymer-supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine. In a subsequent step, amides of Formula Ia can be converted to thioamides of Formula Ib using a variety of standard thio transfer reagents including phosphorus pentasulfide and Lawesson's reagent.

An alternate procedure for the preparation of compounds of Formula Ia involves coupling of an amide of Formula 2 with an acid of Formula 4 in the presence of a dehydrating agent such as dicyclohexylcarbodiimide (DCC). Polymer supported reagents are useful here, such as polymer-bound cyclohexylcarbodiimide. Synthetic procedures of Schemes 1 and 2 are only representative examples of useful methods for the preparation of Formula I compounds as the synthetic literature is extensive for this type of reaction.

One skilled in the art will also realize that acid chlorides of Formula 3 may be prepared from acids of Formula 4 by numerous well-known methods.

An alternate procedure for the preparation of compounds of Formula Ia involves coupling of an ortho amino carboxylic acid ester of Formula 5 with an acid chloride of Formula 3 by a method similar to that described in Scheme 1, followed by transformation of the ester group into an amide functionality. This transformation can be achieved by an amination with an amine of Formula 7. A Lewis acid such as trimethylaluminum as shown in Scheme 3 may catalyze this reaction.

Alternatively the ester 6 can be transformed to an amide (6a) as shown in Scheme 4 by saponification with a base such as aqueous sodium hydroxide followed by dehydrative coupling with an amine of Formula 7 by a procedure similar to that described in Scheme 2.

Benzoic acids of Formula 4 (J is optionally substituted phenyl) are generally well known in the art as are procedures for their preparation. One particularly useful subset of benzoic acids of this invention are 2-methyl-4-perfluoroalkyl benzoic acids of Formula 4a (R ⁵(a) equals e.g. CF₃, C₂F₅, C₃F₇). The synthesis for these compounds is outlined in Schemes 5-9. Benzoic acids of Formula 4a may be prepared from the benzonitriles of Formula 8 by hydrolysis. The conditions used may involve the use of a base such as an alkaline metal hydroxide or alkoxide (e.g. potassium or sodium hydroxide) in a solvent such as water, ethanol or ethylene glycol (e.g. J. Chem. Soc. 1948, 1025). Alternatively, the hydrolysis may be carried out using an acid such as sulfuric acid or phosphoric acid in a suitable solvent such as water (e.g. Org. Synth. 1955, Coll. vol. 3, 557). The choice of the conditions is contingent on the stability of R⁵to the reaction conditions and elevated temperatures are usually employed to achieve this transformation.

Nitriles of Formula 8 may be prepared from anilines of Formula 9 by the classical sequence involving diazotization and treatment of the intermediate diazonium salt with a copper cyanide salt (e.g. J. Amer. Chem. Soc. 1902, 24, 1035).

Anilines of Formula 9 may be prepared from compounds of Formula 10. This transformation may be achieved by a well-known procedure that employs Raney Nickel ( Org Synth. Coll. Vol. VI, 581). Alternatively, the same transformation may be effected by the use of a suitable catalyst such as palladium in the presence of hydrogen. The reaction is usually conducted at pressures of 104 to 107 kPa in a suitable organic solvent such as, but not limited to, toluene. Elevated temperatures of 80-110° C. are usually required to achieve the transformation. As one skilled in the art will realize, numerous chemical modifications of the thioether moiety are possible, and may be employed when necessary to facilitate this transformation.

Compounds of Formula 10 may be prepared from iminosulfuranes of Formula 11. The transformation may be achieved in a protic solvent such as methanol or water, in a non-protic solvent such as dichloromethane or toluene in the presence of a suitable base such as triethylamine (e.g. Org. Synth. Coll. Vol. VI, 581) or sodium methoxide, or in a combination of a protic solvent, a protic solvent and a base. The temperature at which the reaction is conducted is usually in the range 40-110° C. As one skilled in the art will realize, suitable salts of compounds of Formula 11 such as, but not limited to a hydrochloride, a sulfate or a bisulfate may also be employed, provided that the appropriate amount of base is first used to generate the free base 11. This may be done as a separate step or as an integral part of the step involving the transformation of compounds of Formula 11 to compounds of Formula 10.

Compounds of Formula 11 may be prepared from anilines of Formula 12 by reaction with dimethyl sulfide and a suitable chlorinating agent such as, but not limited to N-chlorosuccinimide (e.g. Org. Synth. Coll. Vol. VI, 581), chlorine or N-chlorobenzotriazole. Alternatively, anilines of Formula 12 may be treated with dimethyl sulfoxide which has been “activated” by treatment with an agent such as acetic anhydride, trifluoroacetic, anhydride, trifluoromethanesulfonic anhydride, cyclohexylcarbodiimide, sulfur trioxide, or phosphorus pentoxide. The reaction is conducted in a suitable organic solvent such as dichloromethane or dimethyl sulfoxide. The reaction is conducted at a temperature of −70° C. to 25° C. and is dependent on the solvent and reagent used.

Intermediate ortho amino carboxylic acid amides of Formula 2a and 2b may also be prepared from isatoic anhydrides of Formula 13 and 14 (Scheme 10). Typical procedures involve combination of equimolar amounts of the amine 7 with the isatoic anhydride in polar aprotic solvents such as pyridine and dimethylformamide at temperatures ranging from room temperature to 100° C. R ¹substituents such as alkyl and substituted alkyl may be introduced by the base catalyzed alkylation of isatoic anhydride 13 with known alkylating reagents R¹-Lg (wherein Lg is a leaving group such as halogen, alkyl or aryl suphonates or alkyl sulfates) to provide the alkyl substituted intermediates 14. Isatoic anhydrides of Formula 13 may be made by methods described in Coppola, Synthesis 1980, 505 and Fabis et al Tetrahedron, 1998, 10789.

An alternate procedure for the preparation of specific compounds of Formula I (wherein A is 0, B is 0 and R ¹is H) involves reaction of an amine 7 with a heterocyclic fused oxazinone of Formula 15. Typical procedures involve combination of the amine with the oxazinone in solvents such as tetrahydrofuran or pyridine at temperatures ranging from room temperature to the reflux temperature of the solvent. Oxazinones are well documented in the chemical literature and are available via known methods that involve the coupling of either an ortho amino carboxylic acid with an acid chloride. For references to the synthesis and chemistry of heterocyclic fused oxazinones see Jakobsen et al, Biorganic and Medicinal Chemistry, 2000, 8, 2803-2812 and references cited therein.

Heterocyclic acids of Formula 4, wherein J is an optionally substituted heterocycle, can be prepared by procedures outlined in Schemes 12-17. Both general and specific references to a wide variety of heterocyclic acids including thiophenes, furans, pyridines, pyrimidines, triazoles, imidazoles, pyrazoles, thiazoles, oxazoles, isothiazoles, thiadiazoles, oxadiazoles, triazines, pyrazines, pyridazines, and isoxazoles can be found in the following compendia: Rodd's Chemistry of Chemistry of Carbon Compounds, Vol. IVa to IVl., S. Coffey editor, Elsevier Scientific Publishing, New York, 1973; Comprehensive Heterocyclic Chemistry, Vol. 1-7, A. R. Katritzky and C. W. Rees editors, Pergamon Press, New York, 1984; Comprehensive Heterocyclic Chemistry II, Vol. 1-9, A. R. Katritzky, C. W. Rees, and E. F. Scriven editors, Pergamon Press, New York, 1996; and the series, The Chemistry of Heterocyclic Compounds, E. C. Taylor, editor, Wiley, New York. Particularly useful heterocyclic acids of this invention include pyridine acids, pyrimidine acids and pyrazole acids. Procedures for the synthesis of representative examples of each are detailed in Schemes 12-17. A variety of heterocyclic acids and general methods for their synthesis may be found in World Patent Application WO 98/57397.

The synthesis of representative pyridine acids (4b) is depicted in Scheme 12. This procedure involves the known synthesis of pyridines from β-ketoesters and 4aminobutenones (19). Substituent groups R ⁵(a) and R⁵(b) include e.g. alkyl and haloalkyl.

The synthesis of representative pyrimidine acids (4c) is depicted in Scheme 13. This procedure involves the known synthesis of pyrimidines from vinylidene-β-ketoesters (22) and amidines. Substituent groups R ⁵(a) and R⁵(b) include e.g. alkyl and haloalkyl.

The synthesis of representative pyrazole acids (4d-4g) is depicted in Schemes 14-17. Pyrazoles 4d are described in Scheme 14. The synthesis of Scheme 14 involves as the key step introduction of the R ⁵(b) substituent via alkylation of the pyrazole. The alkylating agent R⁵(b)-Lg (wherein Lg is a leaving group such as Cl, Br, I, sulfonates such as p-toluenesulfonate or methanesulfonate or sulfates such as —SO₂OR⁷(b)) includes R⁷(b) groups such as C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, C₂-C₆alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₃-C₈dialkylaminocarbonyl, C₃-C₆trialkylsilyl; or phenyl, benzyl, benzoyl, 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each ring or ring system optionally substituted. Oxidation of the methyl group affords the pyrazole carboxylic acid. Some of the more preferred R⁵(a) groups include haloalkyl.

Pyrazoles 4e are described in Scheme 15. These pyrazole acids may be prepared via metallation and carboxylation of pyrazoles of formula 28 as the key step. The R ⁵(b) group is introduced in a manner similar to that of Scheme 14, i.e. via alkylation with a R⁵(b) alkylating agent. Representative R⁵(a) groups include e.g. cyano, and haloalkyl.

Pyrazoles 4f are described in Scheme 16. These can be prepared via reaction of an optionally substituted phenyl hydrazine 29 with a pyruvate 30 to yield pyrazole esters 31. Hydrolysis of the ester affords the pyrazole acids 4f. This procedure is particularly useful for the preparation of compounds where R ⁵(b) is optionally substituted phenyl and R⁵(a) is haloalkyl.

Pyrazoles acids of Formula 4g are described in Scheme 17. These can be prepared via 3+2 cycloaddition of an appropriately substituted nitrilimine (32) with either substituted propiolates (33) or acrylates (36). Cycloaddition with acrylates requires additional oxidation of the intermediate pyrazoline to the pyrazole. Hydrolysis of the ester affords the pyrazole acids 4g. Preferred iminohalides for this reaction include the trifluoromethyl iminochloride (38) and the iminodibromide (39). Compounds such as 38 are known ( J. Heterocycl Chem. 1985, 22(2), 565-8). Compounds such as 39 are available by known methods (Tetrahedron Letters 1999, 40, 2605). These procedures are particularly useful for the preparation of compounds where R⁵(b) is optionally substituted phenyl and R⁵(a) is haloalkyl or bromo.

Ortho-amino carboxylic acid esters of Formula 5 wherein R ¹is H can be prepared from monoesters of ortho dicarboxylic acids of Formula 40 via rearrangement of the corresponding acyl azide and hydrolysis of the resulting isocyanate (or alternatively by trapping of the isocyanate with an alcohol and cleaving of the resulting carbamate) as shown in Scheme 18.

Alternatively ortho-amino carboxylic acid esters of Formula 5 can be prepared from ortho carboxamide carboxylic esters of Formula 41 by Hoffman rearrangement with reagents such as sodium hydroxide and bromine as shown in Scheme 19.

Compounds of Formulae 40 and 41 are known in the art or can be readily prepared from compounds known in the art. (For example, see Tetrahedron, 1997, 53, 14497; J. Chem. Soc., Perkin Trans. 1, 1996, 10, 1035; WO92/08724 and EP 418667).

It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present 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 the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. 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 prepare the compounds of Formula I.

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

Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present 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 for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. ¹H NMR spectra are reported in ppm downfield from tetramethylsilane; s is singlet, d is doublet, t is triplet, q is quartet, m is multiplet, dd is doublet of doublets, dt is doublet of triplets, brs is broad singlet.

EXAMPLE 1

Preparation of 5-methyl-N-(1-methylethyl)-4-[[4-trifluoromethoxy)benzoyl]amino]-3-pyridinecarboxamide

Step A: Preparation of ethyl 4-azido-5-methyl-3-pyridinecarboxylate [0198]
A slurry of 14.1 g (78 mmol) of ethyl 1,4-dihydro-5-methyl-4-oxo-3-pyridinecarboxylate (prepared according to Horvath, G.; Dvortsak, P. [0199] J Heterocycl. Chem. 1980, 359) in 30 mL of phosphorous oxychloride was refluxed for 1 hour. After cooling, the volatiles were removed with a rotary evaporator. The residue was poured into cold saturated aqueous sodium bicarbonate. Dichloromethane was added and the mixture was filtered through celite. The layers were separated. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator. The residue was dissolved in 150 mL of dimethylformamide. 15.2 g (234 mmol) of sodium azide was added. The mixture was heated at 95° C. for 1 hour. After cooling, the solvent was removed with a rotary evaporator. The residue was partitioned between ethyl acetate and water. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator. The residue was passed through a plug of silica gel with 25% ethyl acetate in hexanes as eluant to afford 11.9 g of the title compound as a cream colored solid.
[0200] ¹H NMR (CDCl₃) δ 1.41 (t,3H), 2.12 (s,3H), 4.36 (q,2H), 8.12 (s,1H), 8.83 (s,1H).
Step B: Preparation of ethyl 4-amino-5-methyl-3-pyridinecarboxylate [0201]
0.50 g of material prepared in Step A was dissolved in 15 mL of ethanol. 0.15 g of 10% palladium on carbon was added. The reaction mixture was placed under one atmosphere of hydrogen for 2 hours. The catalyst was removed by filtration. The solvent was removed with a rotary evaporator to afford 0.43 g of the title compound as a white solid. [0202]
[0203] ¹H NMR (CDCl₃) δ 1.42 (t,3H), 2.30 (s,3H), 4.45 (q,2H), 8.47 (s,1H), 8.87 (s,1H).
Step C: Preparation of ethyl 5-methyl-4-[[4-trifluoromethoxy)benzoyl]amino]-3-pyridinecarboxylate [0204]
1.0 g (5.6 mmol) of material prepared in Step C was dissolved in 30 mL of dichloromethane. 0.77 mL (5.6 mmol) of triethylamine, a catalytic amount of 4-dimethylaminopyridine and 0.88 mL (5.6 mmol) of 4-(trifluoromethoxy)benzoyl chloride were added. The mixture was stirred overnight. The reaction mixture was washed with water. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator. The residue was purified by medium-pressure liquid chromatography (MPLC) with a gradient of 15-100% ethyl acetate in hexanes as eluant. The bisacylation product eluted first, then 0.42 g of the title compound as white solid. Starting material (0.52 g) was also recovered. [0205]
[0206] ¹H NMR (CDCl₃) δ 1.41 (t,3H), 2.32 (s,3H), 4.39 (q,2H), 7.37 (d,2H), 8.08 (d,2H), 8.63 (brs,1H), 9.04 (brs,1H), 10.78 (brs,1H).
Step D: Preparation of 5-methyl-N-(1-methylethyl)-4-[[4-trifluoromethoxy)benzoyl]amino]-3-pyridinecarboxamide [0207]
To a solution of 0.049 mL (0.57 mmol) of isopropylamine in 20 mL of dichloroethane at 0° C. was added 0.64 mL (1.3 mmol) of a 2M solution of trimethylaluminum in toluene dropwise. A solution of 0.21 g (0.57 mmol) of the material prepared in Step C in 5 mL of dichloroethane was added dropwise. Four days later an additional 0.049 mL of isopropylamine and 0.64 mL of trimethylaluminum were added. The reaction was refluxed for 6 h. After cooling 20 mL of 1N HCl was added. The layers were separated. The aqueous layer was made basic with a saturated sodium bicarbonate solution. Dichloromethane was added and the mixture was filtered through celite. The dichloromethane was separated, combined with the dichloroethane layer from above and dried (sodium sulfate). The solvent was removed with a rotary evaporator. The residue was purified by MPLC with a gradient of 25-50% ethyl acetate in hexanes as eluant to afford 0.047 g of the title compound, a compound of the invention, as a white solid; m.p. 202-204° C. [0208]
[0209] ¹H NMR (CDCl₃) δ 1.27 (d,6H), 2.33 (s,3H), 4.23 (m,1H), 6.46 (br,1H), 7.35 (d,2H), 8.07 (d,2H), 8.56 (brs,1H), 8.69 (brs,1H), 11.15 (brs,1H).

EXAMPLE 2

Preparation of 1-methyl-N-(1-methylethyl)-5-[[4-trifluoromethoxy)benzoyl]amino]-1H-pyrazole-4-carboxamide

Step A: Preparation of 5-amino-1-methyl-N-(1-methylethyl)-1H-pyrazole-4-carboxamide [0210]
1.0 g (8.0 mmol) of 2-cyano-N-(1-methylethyl)acetamide (prepared according to the procedure of Cheikh et al [0211] J. Org. Chem., 1991, 56, 970) was combined with 3.1 mL of triethylorthoformate, 5 mL of acetic anhydride and 0.01 g of anhydrous zinc chloride. The mixture was refluxed for 1 hour. A distillation head was placed on the flask and the reaction was heated at 120° C. for 8 hours. After standing for two days the mixture was heated again for 12 hours at 120° C. for 12 hours. The volatiles were removed with a rotary evaporator. Ethanol was added and the volatiles were again removed with a rotary evaporator. This material was dissolved in 15 mL of ethanol. 0.34 mL (6.4 mmol) of methyl hydrazine was added. The reaction mixture was refluxed for 5 hours and then allowed to stand at room temperature overnight. The solvent was removed with a rotary evaporator. The residue was purified by MPLC (ethyl acetate as eluant) to afford 0.14 g of the title compound as a solid.
[0212] ¹H NMR (CDCl₃) δ 1.23 (d,6H), 3.61 (s,3H), 4.21 (m,1H), 5.17 (br,2H), 5.34 (br,1H), 7.38 (s, 1H).
Step B: Preparation of 1-methyl-N-(1-methylethyl)-5-[[4-trifluoromethoxy)benzoyl]amino]-1H-pyrazole-4-carboxamide [0213]
0.14 g (0.77 mmol) of the material from Step A was dissolved in 20 mL of tetrahydrofuran and 0.12 mL (0.85 mmol) of triethylamine and 0.12 mL (0.77 mmol) of 4-(trifluoromethoxy)benzoyl chloride were added. Three days later 0.12 mL (0.85 mmol) of triethylamine and 0.12 mL (0.77 mmol) of 4-(trifluoromethoxy)benzoyl chloride were added. The reaction mixture was refluxed for two days. After cooling the reaction mixture was partitioned between ethyl acetate and water. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator. The residue was purified by MPLC with 50% ethyl acetate in hexanes as eluant to afford 0.18 g of the title compound, a compound of the invention, as a white solid; m.p. 68-75° C. [0214]
[0215] ¹H NMR (CDCl₃) δ 1.22 (d,6H), 3.91 (s,3H), 4.14 (m,1H), 5.92 (brd,1H), 7.32 (d,2H), 7.62 (s,1H), 8.08 (d,2H), 10.78 (brs,1H).

EXAMPLE 3

Preparation of 4-methyl-N-(1-methylethyl)-3-[[4-trifluoromethyl)benzoyl]amino]-2-thiophenecarboxamide

Step A: Preparation of 7-methyl-2H-thieno[3,2-d][1,3]oxazine-2,4(1H)-dione [0216]
Phosgene in toluene (4.4 g, 20%, 8.88 mmol) was added to the sodium salt of 3-amino-4-methyl-thiophene-2-carbocyclic acid (1 g, 5.58 mmol) in water (17 mL) at 0° C. The mixture was allowed to warm to room temperature and was stirred for 1 hour. The mixture was filtered. After drying in vacuum the product was obtained as a solid 0.49 g (47%). [0217]
IR (Nujol®) 1785, 1696, 1580, 1513, 1236, 988, 918, 848, 826 cm[0218] ⁻¹.
[0219] ¹H NMR (DMSO-d₆) δ 2.20 (s,3H), 7.88 (s,1H).
Step B: Preparation of 7-methyl-2-[4-(trifluoromethyl)phenyl]-4H-thieno[3,2-d][1,3]oxazin-4-one [0220]
4-(Dimethylamino)pyridine (0.66 g, 5.41 mmol) was added to the product from Step A in dioxane (10 mL). 4-(Trifluoromethyl)benzoyl chloride (1.13 g, 5.42 mmol) was added to the mixture and the mixture was boiled for approximately 3 hours. The mixture was allowed to cool to room temperature and was poured into hydrochloric acid (100 mL, 1 N). The mixture was extracted with ethyl acetate (3×50 mL) and the combined extracts were dried and evaporated. Chromatography on silicon gel (eluted with ethyl acetate/hexanes) gave the product as a white solid 1.56 g, (91.7%). [0221]
IR (Nujol®) 2923, 1763, 1600, 1572, 1410, 1312, 1234, 1170, 1125, 1068, 1013, 978, 934, 851, 813 cm[0222] ⁻¹.
[0223] ¹H NMR (CDCl₃) δ 2.47 (s,3H), 7.60 (s,1H), 7.77 (d,2H), 8.45(d,2H).
Step C: Preparation of 4-methyl-N-(1-methylethyl)-3-[[4-trifluoromethyl)benzoyl]amino]-2-thiophenecarboxamide [0224]
A mixture of the product from Step B (0.2 g, 0.043 mmol) and isopropylamine (0.2 g, 3.39 mmol) in THF (5 mL) was stirred for 6 hours. The solvent was removed under reduced pressure to give the product, a compound of the invention, as a solid 0.21 g, (91%). [0225]
IR(Nujol®) 3294, 1664, 1625, 1573, 1524, 1409, 1327, 1207, 1167 1126, 1068, 1018, 954, 885, 857 cm[0226] ⁻¹.
[0227] ¹H NMR (CDCl₃) δ 1.22 (d,6H), 2.30 (s,3H), 4.22-4.11 (m,1H), 5.58 (d,1H), 7.03 (s,1H), 7.75 (d, 2H), 8.13 (d,2H), 10.63 (s,1H).

EXAMPLE 4

Preparation of 5-[[[3-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonylamino]-N,6-dimethyl-4-pyrimidinecarboxamide

Step A: Preparation of 1-(111-dimethylethyl) 4-ethyl-2-acetyl-3-amino-2-butenedioate [0228]
To a mixture of 17.15 g (108 mmol) of t-butyl acetoacetate and 12.8 mL (130 mmol) of ethyl cyanoformate in 25 mL of dichloromethane was added 1.64 g of zinc acetylacetonate hydrate. After stirring overnight the volatiles were removed with a rotary evaporator. The residue was dissolved in ethyl acetate) and filtered through celite. The solvent was removed with a rotary evaporator to afford 29.9 g of the title compound as a white solid as an E/Z isomer mixture. [0229]
[0230] ¹H NMR (CDCl₃) δ 1.33 (t,3H), 1.52 (s,9H), 2.35 (s,3H) [minor isomer 2.40 (s,3H)], 4.33 (m,2H).
Step B: Preparation of 5-(1.1-dimethylethyl)hydrogen 6-methyl-4.5-pyrimidinedicarboxylate To a solution of 11.6 g (45 mmol) of the material from Step A in 55 mL of ethanol was added 10.9 g (135 mmol) of formamidine hydrochloride. The reaction mixture was cooled in an ice bath and 17 mL (135 mmol) of 1,1,3,3-tetramethylguanidine was added dropwise. After the mixture was stirred overnight the solvent was removed with a rotary evaporator. The residue was partitioned between ethyl acetate and water. The aqueous layer was cooled in an ice bath, acidified with concentrated HCl and extracted three times with ethyl acetate. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator to afford 9.12 g of the title compound as a yellow solid. [0231]
[0232] ¹H NMR (CDCl₃) δ 1.65 (s,9H), 2.68 (s,3H), 9.19 (s,1H).
Step C: Preparation of 5-(1,1-dimethylethyl) 4-methyl 6-methyl-4,5-pyrimidinedicarboxylate [0233]
To a solution of 9.12 g (38 mmol) of the material from Step B in 100 mL of N,N-dimethyl formamide (DMF) was added 3.1 mL (50 mmol) of iodomethane and 3.7 g (50 mmol) of lithium carbonate. The reaction mixture was heated at 60° C. for 3 hours. After cooling the reaction mixture was partitioned between dichloromethane and water. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator and then a vacuum pump. The residue was purified by MPLC with a gradient of 20-30% ethyl acetate in hexanes as eluant to afford 7.58 g of the title compound as an off-white solid. [0234]
[0235] ¹H NMR (CDCl₃) δ 1.63 (s,9H), 2.67 (s,3H), 4.01 (s,3H), 9.19 (s, 1H).
Step D: Preparation of methyl 5-[[(1,1-dimethylethoxy)carbonyl]amino]-6-methyl-4-pyrimidinecarboxylate [0236]
7.55 g of the material from Step C was dissolved in 40 mL of dichloromethane. 20 mL of trifluoroacetic acid was added. After two days the reaction mixture was refluxed for 6 hours. After an additional day the volatiles were removed with a rotary evaporator. Toluene was added and the solvent was removed with a rotary evaporator. This material (90.2 g) was dissolved in 100 mL of t-butanol. 9.2 mL (66 mmol) of triethylamine and 14 mL (66 mmol) of diphenylphosphoryl azide were added. The reaction was refluxed 3 hours. After cooling, the solvent was removed with a rotary evaporator. The residue was partitioned between ethyl acetate and water. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator. The residue was purified by MPLC with a gradient of 40-100% ethyl acetate in hexanes as eluant to afford 5.81 g of the title compound as a yellow solid. [0237]
[0238] ¹H NMR (CDCl₃) δ 1.52 (s,9H), 2.60 (s,3H), 4.03 (s,3H), 8.07 (br, 1H),8.98 (s,1H).
Step E: Preparation of methyl 5-amino-6-methyl-4-pyrimidinecarboxylate [0239]
5.8 g of the material from Step D was dissolved in 25 mL of trifluoroacetic acid. After stirring for 90 minutes the solvent was removed with a rotary evaporator. Saturated aqueous sodium bicarbonate was added. The aqueous layer was extracted five times with dichloromethane. The organic layer was dried (sodium sulfate) and the solvent was removed with a rotary evaporator to afford 3.78 g of the title compound with a small amount of an impurity. [0240]
[0241] ¹H NMR (CDCl₃) δ 2.50 (s,3H), 4.00 (s,3H), 5.76 (br,2H),8.56 (s,1H).
Step F: Preparation of 5-amino-6-methyl-4-pyrimidinecarboxylic acid monosodium salt [0242]
2.0 g (12 mmol) of the material from Step E was dissolved in 24 mL of methanol. 12 mL of a 1N solution of sodium hydroxide was added. After 1 hour the solvent was removed with a rotary evaporator. The residue was dried in a vacuum oven overnight to afford 2.39 g of the title compound as a tan solid. [0243]
[0244] ¹H NMR (D₂O) δ 2.45 (s,3H), 8.37 (s,1H).
Step G: Preparation of 3-chloro-N,N-dimethyl-1H-pyrazole-1-sulfonamide [0245]
To a solution of N-dimethylsulfamoylpyrazole (188.0 g, 1.07 mol) in dry tetrahydrofuran (1500 mL) at −78° C. was added dropwise a solution of 2.5 M n-butyl-lithium (472 mL, 1.18 mol) in hexane while maintaining the temperature below −65° C. Upon completion of the addition the reaction mixture was maintained at −78° C. for an additional 45 minutes, after which time a solution of hexachloroethane (279 g, 1.18 mol) in tetrahydrofuran (120 mL) was added dropwise. The reaction mixture was maintained for an hour at −78° C., warmed to −20° C. and then quenched with water (1 L). The reaction mixture was extracted with methylene chloride (4×500 mL); the organic extracts were dried over magnesium sulfate and concentrated. The crude product was further purified by chromatography on silica gel using methylene chloride as eluent to afford the title product compound as a yellow oil (160 g). [0246]
[0247] ¹H NMR (CDCl₃) δ 3.07 (d, 6H), 6.33 (s, 1H), 7.61 (s, 1H).
Step H: Preparation of 3-chloropyrazole [0248]
To trifluoroacetic acid (290 mL) was added dropwise the chloropyrazole product (160 g) from Step G, and the reaction mixture was stirred at room temperature for 1.5 hours and then concentrated at reduced pressure. The residue was taken up in hexane, insoluble solids were filtered off, and the hexane was concentrated to afford the crude product as an oil. The crude product was further purified by chromatography on silica gel using ether/hexane (40:60) as eluent to afford the title product as a yellow oil (64.44 g). [0249]
[0250] ¹H NMR (CDCl₃) δ 6.39 (s, 11H), 7.66 (s, 11H), 9.6 (br s, 11H).
Step I: Preparation of 3-chloro-2-(3-chloro-1H-pyrazol-1-yl)pyridine [0251]
To a mixture of 2,3-dichloropyridine (92.60 g, 0.629 mol) and 3-chloropyrazole (64.44 g, 0.629 mol) in N,N-dimethylformamide (400 mL) was added potassium carbonate (147.78 g, 1.06 mol), and the reaction mixture was then heated to 100° C. for 36 hours. The reaction mixture was cooled to room temperature and slowly poured into ice water. The precipitated solids were filtered and washed with water. The solid filter cake was taken up in ethyl acetate, dried over magnesium sulfate and concentrated. The crude solid was chromatographed on silica gel using 20% ethyl acetate/hexane as eluent to afford the title product as a white solid (39.75 g). [0252]
[0253] ¹H NMR (CDCl₃) δ 6.43 (s, 11H), 7.26 (m, 1H), 7.90 (d, 1H), 8.09 (s, 1H), 8.41 (d, 11H).
Step J: Preparation of 3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid To a solution of the pyrazole product from Step 1 (39.75 g, 186 mmol) in dry tetrahydrofuran (400 mL) at −78° C. was added dropwise a solution of 2.0 M lithium diisopropylamide (93 mL, 186 mmol) in tetrahydrofuran. Carbon dioxide was bubbled through the amber solution for 14 minutes, after which time the solution became pale brownish-yellow. The reaction was made basic with 1N aqueous sodium hydroxide solution and extracted with ether (2×500 mL). The aqueous extracts were acidified with 6N hydrochloric acid and extracted with ethyl acetate (3×500 mL). The ethyl acetate extracts were dried over magnesium sulfate and concentrated to afford the title product as an off-white solid (42.96 g). (Product from another run following similar procedure melted at 198-199° C.) [0254]
[0255] ¹H NMR (DMSO-d₆) δ 6.99 (s, 1H), 7.45 (m, 1H), 7.93 (d, 1H), 8.51 (d, 1H).
Step K: Preparation of 2-[3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-4H-pyrimido[5,4-d][1,3]oxazin-4-one [0256]
To a solution of 0.26 mL (3.3 mmol) of methanesulfonyl chloride in 18 mL of acetonitrile at 0° C. was added 0.77 g (3.0 mmol) of 3-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-carboxylic acid from Step J. 0.42 mL (3.0 mmol) of triethylamine in 9 mL of acetonitrile was added dropwise. After 20 minutes at 0° C., 0.525 g (3.0 mmol) of material from Step F was added. After 15 minutes 0.42 mL (3.0 mmol) of triethylamine was added dropwise. After 2 hours 0.26 mL (3.3 mmol) of methanesulfonyl chloride was added. After stirring overnight. The reaction mixture was poured into water. Filtration afforded 0.27 g of the title compound. [0257]
[0258] ¹H NMR (CDCl₃) δ 2.20 (s,3H), 7.23 (s,1H), 7.54(dd,1H), 8.01 (dd,1H), 8.57(dd,1H), 9.20 (s,1H).
Step L: Preparation of 5-[[[3-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]amino]-N,6-dimethyl-4-pyrimidinecarboxamide [0259]
2 mL of a 2M solution of methylamine in tetrahydrofuran was added to 0.090 g of material from Step K. After stirring overnight the solvent was removed with a rotary evaporator to afford 0.071 g of the title compound, a compound of the invention, as a tan solid; m.p. 205-207° C. [0260]
[0261] ¹H NMR (CDCl₃) δ 2.48 (s,3H), 3.04 (d,3H), 7.06 (s,1H), 7.41(dd,1H), 7.89 (dd,1H), 8.30 (br,1H), 8.48 (dd,1H), 8.85 (s,1H), 11.57 (br,1H).

EXAMPLE 5

Preparation of 2.6-dichloro-3-[[f 1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl]amino]-N-(1-methylethyl)-4-pyridinecarboxamide

Step A: Preparation of ethyl 3-amino-4-pyridinecarboxylate [0262]
To a solution of 1 g (7.25 mmol) of 3-amino-4-pyridinecarboxylic acid in 5 mL of ethyl alcohol was added 2 mL of sulfuric acid. The mixture was warmed under reflux for 2 h. It was cooled and basified with conc. NH[0263] ₄OH solution to pH=8. The resulting solution was extracted with ethyl acetate and the organic layer was washed with brine and water, dried (MgSO₄) and concentrated in vacuo to give 1.04 g of the title compound as a white solid (87%).
[0264] ¹H NMR (CDCl₃) δ 8.19 (s 1H), 7.93 (d 1H, J is 5.1 Hz), 7.60 (d, 1H, J is 5.1 Hz), 5.67 (br s, 2H), 4.36 (q, 2H), 1.40 (t, 3H).
Step B: Preparation of ethyl 3-amino-2.6-dichloro-4-pyridinecarboxylate [0265]
To a solution of 1.04 g (6.27 mmol) of ethyl 3-amino-4-pyridinecarboxylate in 5 mL of DMF was added 1.67 g of N-chlorosuccinimide (12.5 mmol) in a single portion at room temperature. The mixture was then stirred at the same temperature for 24 hours. The resulting mixture was concentrated in vacuo and purified by silica gel column to give 1.40 g of the title compound as a white solid (95%). [0266]
[0267] ¹H NMR (CDCl₃) δ 7.67 (s 1H), 6.18 (br s, 2H), 4.39 (q, 2H), 1.42 (t, 3H).
Step C: Preparation of 3-amino-2,6-dichloro-4-pyridinecarboxylic monopotassium salt [0268]
To a solution of 1.30 g (5.54 mmol) of ethyl 3-amino-2,6-dichloro-4-pyridinecarboxylate in a mixture of 5 mL of water and 20 mL of ethyl alcohol was added 622 mg (11.1 mmol) of potassium hydroxide at room temperature and the reaction mixture was warmed at 90° C. for 1 hour. The mixture was then concentrated in vacuo and evaporated with benzene three times to give 1.63 g of the title compound as a white solid. The crude product was used in the next reaction without any further purification (98%). [0269]
[0270] ¹H NMR (DMSOd-₆) δ 7.31 (s, 1H), 7.14 (br s, 2H).
Step D: Preparation of 6,8-dichloro-2H-pyido[3,4-d][1,3]oxazine-2.4(1H)-dione [0271]
To a solution of 1.64 g (5.54 mmol) of the material from Step C in 20 mL of dioxane was added 2.2 g (11.1 mmol) of diphosgene at 0° C. The mixture was allowed to warm to room temperature and stirred for 24 hours. The mixture was then concentrated in vacuo to give 1.70 g of the title compound as a white solid (quantitative). [0272]
[0273] ¹H NMR (DMSOd-₆) δ 7.99 (s, 11H).
Step E: Preparation of 3-chloro-2-[3-(trifluoromethyl)-1H-pyrazol-1-Yl]pridine [0274]
To a mixture of 2,3-dichloropyridine (99.0 g, 0.67 mol) and 3-trifluoromethyl pyrazole (83 g, 0.61 mol) in dry N,N-dimethylformamide (300 mL) was added potassium carbonate (166.0 g, 1.2 mol) and the reaction was then heated to 10-125° C. over 48 hours. The reaction was cooled to 100° C. and filtered through Celite® diatomaceous filter aid to remove solids. N,N-Dimethylformamide and excess dichloropyridine were removed by distillation at atmospheric pressure. Distillation of the product at reduced pressure (b.p. 139-141° C., 7 mm) afforded the desired intermediate as a clear yellow oil (113.4 g). [0275]
[0276] ¹H NMR (CDCl₃) δ6.78 (s, 1H), 7.36 (t, 1H), 7.93 (d, 1H), 8.15 (s, 1H), 8.45 (d, 1H).
Step F: Preparation of 1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxylic acid [0277]
To a solution of the pyrazole product from Step E (105.0 g, 425 mmol) in dry tetrahydrofuran (700 mL) at −75° C. was added via cannula a −30° C. solution of lithium diisopropylamide (425 mmol) in dry tetrahydrofuran (300 mL). The deep red solution was stirred for 15 minutes, after which time carbon dioxide was bubbled through at 63° C. until the solution became pale yellow and the exothermicity ceased. The reaction was stirred for an additional 20 minutes and then quenched with water (20 mL). The solvent was removed under reduced pressure, and the reaction mixture partitioned between ether and 0.5 N aqueous sodium hydroxide solution. The aqueous extracts were washed with ether (3×), filtered through Celite® diatomaceous filter aid to remove residual solids, and then acidified to a pH of approximately 4, at which point an orange oil formed. The aqueous mixture was stirred vigorously and additional acid was added to lower the pH to 2.5-3. The orange oil congealed into a granular solid, which was filtered, washed successively with water and 1N hydrochloric acid, and dried under vacuum at 50° C. to afford the title product as an off-white solid (130 g). (Product from another run following similar procedure melted at 175-176° C.) [0278]
[0279] ¹H NMR (DMSO-d₆) δ 7.61 (s, 1H), 7.76 (dd, 1H), 8.31 (d, 1H), 8.60 (d, 1H).
Step G: Preparation of 2.6-dichloro-3-[[[1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)1H-pyrazol-5-yl]carbonyl]amino]-N-(1-methylethyl)-4-pyridinecarboxamide [0280]
To a solution of 268 mg (0.92 mmol) of 1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)1H-pyrazole-5-carboxylic acid (from Step F) in 5 mL of dichloromethane was added 160 μL (1.84 mmol) of oxalyl chloride and two drops of DMF in sequence at room temperature. The mixture was then stirred at the same temperature for 1 hour. The crude mixture was then concentrated in vacuo. The resulting mixture was dissolved with 5 mL of acetonitrile followed by additions of 280 mg (0.92 mmol) of the compound prepared in Step D and 298 μL (3.68 mmol) of pyridine in sequence. The reaction mixture was warmed to 70° C. for 2 hours and allowed to cool to room temperature. A solution of 157 μL (1.84 mmol) of isopropylamine in 1 mL of acetonitrile was added to the mixture and it was warmed to 60° C. for 1 hour. The reaction was allowed to cool to room temperature and quenched with water. The aqueous layer was extracted with ethyl acetate and the organic layer was dried with MgSO[0281] ₄and concentrated in vacuo. The resulting mixture was purified with a silica gel column to give 250 mg of the title compound, a compound of the invention, as a white solid (52%). m.p. 240-242° C.
[0282] ¹H NMR (CDCl₃) δ 9.85 (s, 1H), 8.53 (dd, 1H), 7.90 (dd, 1H), 7.56 (s, 1H), 7.42 (dd, 1H), 7.22 (s, 1H), 6.08 (br d, 1H), 4.13 (m, 11H), 1.14 (d, 6H).

By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 32 can be prepared. The following abbreviations are used in the Tables: t is tertiary, s is secondary, n is normal, i is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, t-Bu is tertiary butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is ethylthio, CN is cyano, NO ₂is nitro, TMS is trimethylsilyl, S(O)Me is methylsulfinyl, and S(O)₂Me is methylsulfonyl. Structures of K for Tables 15, 16 and 17 can be found in Exhibit 2.

TABLE 1

R⁴	(R⁵)_m	R⁴	(R⁵)_m	R⁴	(R⁵)_m

Me	2-CF₃	Me	3-CF₃	Me	4-CF₃
Me	2-OCF₃	Me	3-OCF₃	Me	4-OCF₃
Me	2-OCF₂H	Me	3-OCF₂H	Me	4-OCF₂H
Me	2-OCF₂CF₂H	Me	3-OCF₂CF₂H	Me	4-OCF₂CF₂H
Me	2-OCH₂CF₃	Me	3-OCH₂CF₃	Me	4-OCH₂CF₃
Me	2-SCF₃	Me	3-SCF₃	Me	4-SCF₃
Me	2-SOCF₃	Me	3-SOCF₃	Me	4-SOCF₃
Me	2-SO₂CF₃	Me	3-SO₂CF₃	Me	4-SO₂CF₃
Me	2-SCF₂H	Me	3-SCF₂H	Me	4-SCF₂H
Me	2-SOCF₂H	Me	3-SOCF₂H	Me	4-SOCF₂H
Me	2-SO₂CF₂H	Me	3-SO₂CF₂H	Me	4-SO₂CF₂H
Cl	2-CF₃	Cl	3-CF₃	Cl	4-CF₃
Cl	2-OCF₃	Cl	3-OCF₃	Cl	4-OCF₃
Cl	2-OCF₂H	Cl	3-OCF₂H	Cl	4-OCF₂H
Cl	2-OCF₂CF₂H	Cl	3-OCF₂CF₂H	Cl	4-OCF₂CF₂H
Cl	2-OCH₂CF₃	Cl	3-OCH₂CF₃	Cl	4-OCH₂CF₃
Cl	2-SCF₃	Cl	3-SCF₃	Cl	4-SCF₃
Cl	2-SOCF₃	Cl	3-SOCF₃	Cl	4-SOCF₃
Cl	2-SO₂CF₃	Cl	3-SO₂CF₃	Cl	4-SO₂CF₃
Cl	2-SCF₂H	Cl	3-SCF₂H	Cl	4-SCF₂H
Cl	2-SOCF₂H	Cl	3-SOCF₂H	Cl	4-SOCF₂H
Cl	2-SO₂CF₂H	Cl	3-SO₂CF₂H	Cl	4-SO₂CF₂H
F	2-CF₃	F	3-CF₃	F	4-CF₃
F	2-OCF₃	F	3-OCF₃	F	4-OCF₃
F	2-OCF₂H	F	3-OCF₂H	F	4-OCF₂H
F	2-OCF₂CF₂H	F	3-OCF₂CF₂H	F	4-OCF₂CF₂H
F	2-OCH₂CF₃	F	3-OCH₂CF₃	F	4-OCH₂CF₃
F	2-SCF₃	F	3-SCF₃	F	4-SCF₃
F	2-SOCF₃	F	3-SOCF₃	F	4-SOCF₃
F	2-SO₂CF₃	F	3-SO₂CF₃	F	4-SO₂CF₃
F	2-SCF₂H	F	3-SCF₂H	F	4-SCF₂H
F	2-SOCF₂H	F	3-SOCF₂H	F	4-SOCF₂H
F	2-SO₂CF₂H	F	3-SO₂CF₂H	F	4-SO₂CF₂H
Br	2-CF₃	Br	3-CF₃	Br	4-CF₃
Br	2-OCF₃	Br	3-OCF₃	Br	4-OCF₃
Br	2-OCF₂H	Br	3-OCF₂H	Br	4-OCF₂H
Br	2-OCF₂CF₂H	Br	3-OCF₂CF₂H	Br	4-OCF₂CF₂H
Br	2-OCH₂CF₃	Br	3-OCH₂CF₃	Br	4-OCH₂CF₃
Br	2-SCF₃	Br	3-SCF₃	Br	4-SCF₃
Br	2-SOCF₃	Br	3-SOCF₃	Br	4-SOCF₃
Br	2-SO₂CF₃	Br	3-SO₂CF₃	Br	4-SO₂CF₃
Br	2-SCF₂H	Br	3-SCF₂H	Br	4-SCF₂H
Br	2-SOCF₂H	Br	3-SOCF₂H	Br	4-SOCF₂H
Br	2-SO₂CF₂H	Br	3-SO₂CF₂H	Br	4-SO₂CF₂H
I	2-CF₃	I	3-CF₃	I	4-CF₃
I	2-OCF₃	I	3-OCF₃	I	4-OCF₃
I	2-OCF₂H	I	3-OCF₂H	I	4-OCF₂H
I	2-OCF₂CF₂H	I	3-OCF₂CF₂H	I	4-OCF₂CF₂H
I	2-OCH₂CF₃	I	3-OCH₂CF₃	I	4-OCH₂CF₃
I	2-SCF₃	I	3-SCF₃	I	4-SCF₃
I	2-SOCF₃	I	3-SOCF₃	I	4-SOCF₃
I	2-SO₂CF₃	I	3-SO₂CF₃	I	4-SO₂CF₃
I	2-SCF₂H	I	3-SCF₂H	I	4-SCF₂H
I	2-SOCF₂H	I	3-SOCF₂H	I	4-SOCF₂H
I	2-SO₂CF₂H	I	3-SO₂CF₂H	I	4-SO₂CF₂H
OMe	2-CF₃	OMe	3-CF₃	OMe	4-CF₃
OMe	2-OCF₃	OMe	3-OCF₃	OMe	4-OCF₃
OMe	2-OCF₂H	OMe	3-OCF₂H	OMe	4-OCF₂H
OMe	2-OCF₂CF₂H	OMe	3-OCF₂CF₂H	OMe	4-OCF₂CF₂H
OMe	2-OCH₂CF₃	OMe	3-OCH₂CF₃	OMe	4-OCH₂CF₃
OMe	2-SCF₃	OMe	3-SCF₃	OMe	4-SCF₃
OMe	2-SOCF₃	OMe	3-SOCF₃	OMe	4-SOCF₃
OMe	2-SO₂CF₃	OMe	3-SO₂CF₃	OMe	4-SO₂CF₃
OMe	2-SCF₂H	OMe	3-SCF₂H	OMe	4-SCF₂H
OMe	2-SOCF₂H	OMe	3-SOCF₂H	OMe	4-SOCF₂H
OMe	2-SO₂CF₂H	OMe	3-SO₂CF₂H	OMe	4-SO₂CF₂H
CF₃	2-CF₃	CF₃	3-CF₃	CF₃	4-CF₃
CF₃	2-OCF₃	CF₃	3-OCF₃	CF₃	4-OCF₃
CF₃	2-OCF₂H	CF₃	3-OCF₂H	CF₃	4-OCF₂H
CF₃	2-OCF₂CF₂H	CF₃	3-OCF₂CF₂H	CF₃	4-OCF₂CF₂H
CF₃	2-OCH₂CF₃	CF₃	3-OCH₂CF₃	CF₃	4-OCH₂CF₃
CF₃	2-SCF₃	CF₃	3-SCF₃	CF₃	4-SCF₃
CF₃	2-SOCF₃	CF₃	3-SOCF₃	CF₃	4-SOCF₃
CF₃	2-SO₂CF₃	CF₃	3-SO₂CF₃	CF₃	4-SO₂CF₃
CF₃	2-SCF₂H	CF₃	3-SCF₂H	CF₃	4-SCF₂H
CF₃	2-SOCF₂H	CF₃	3-SOCF₂H	CF₃	4-SOCF₂H
CF₃	2-SO₂CF₂H	CF₃	3-SO₂CF₂H	CF₃	4-SO₂CF₂H
OCF₂H	2-CF₃	OCF₂H	3-CF₃	OCF₂H	4-CF₃
OCF₂H	2-OCF₃	OCF₂H	3-OCF₃	OCF₂H	4-OCF₃
OCF₂H	2-OCF₂H	OCF₂H	3-OCF₂H	OCF₂H	4-OCF₂H
OCF₂H	2-OCF₂CF₂H	OCF₂H	3-OCF₂CF₂H	OCF₂H	4-OCF₂CF₂H
OCF₂H	2-OCH₂CF₃	OCF₂H	3-OCH₂CF₃	OCF₂H	4-OCH₂CF₃
OCF₂H	2-SCF₃	OCF₂H	3-SCF₃	OCF₂H	4-SCF₃
OCF₂H	2-SOCF₃	OCF₂H	3-SOCF₃	OCF₂H	4-SOCF₃
OCF₂H	2-SO₂CF₃	OCF₂H	3-SO₂CF₃	OCF₂H	4-SO₂CF₃
OCF₂H	2-SCF₂H	OCF₂H	3-SCF₂H	OCF₂H	4-SCF₂H
OCF₂H	2-SOCF₂H	OCF₂H	3-SOCF₂H	OCF₂H	4-SOCF₂H
OCF₂H	2-SO₂CF₂H	OCF₂H	3-SO₂CF₂H	OCF₂H	4-SO₂CF₂H
Me	2-Me-4-CF₃	F	2-Me-4-CF₃	Cl	2-Me-4-CF₃
Me	2-Me-4-OCF₃	F	2-Me-4-OCF₃	Cl	2-Me-4-OCF₃
Me	2-Me-4-OCF₂H	F	2-Me-4-OCF₂H	Cl	2-Me-4-OCF₂H
Me	2-Me-4-OCH₂CF₃	F	2-Me-4-OCH₂CF₃	Cl	2-Me-4-OCH₂CF₃
Me	2-Me-4-SCF₃	F	2-Me-4-SCF₃	Cl	2-Me-4-SCF₃
Me	2-Me-4-SOCF₃	F	2-Me-4-SOCF₃	Cl	2-Me-4-SOCF₃
Me	2-Me-4-SO₂CF₃	F	2-Me-4-SO₂CF₃	Cl	2-Me-4-SO₂CF₃
Me	2-Me-4-SCF₂H	F	2-Me-4-SCF₂H	Cl	2-Me-4-SCF₂H
Me	2-Me-4-SOCF₂H	F	2-Me-4-SOCF₂H	Cl	2-Me-4-SOCF₂H
Me	2-Me-4-SO₂CF₂H	F	2-Me-4-SO₂CF₂H	Cl	2-Me-4-SO₂CF₂H
Br	2-Me-4-CF₃	I	2-Me-4-CF₃	OMe	2-Me-4-CF₃
Br	2-Me-4-OCF₃	I	2-Me-4-OCF₃	OMe	2-Me-4-OCF₃
Br	2-Me-4-OCF₂H	I	2-Me-4-OCF₂H	OMe	2-Me-4-OCF₂H
Br	2-Me-4-OCH₂CF₃	I	2-Me-4-OCH₂CF₃	OMe	2-Me-4-OCH₂CF₃
Br	2-Me-4-SCF₃	I	2-Me-4-SCF₃	OMe	2-Me-4-SCF₃
Br	2-Me-4-SOCF₃	I	2-Me-4-SOCF₃	OMe	2-Me-4-SOCF₃
Br	2-Me-4-SO₂CF₃	I	2-Me-4-SO₂CF₃	OMe	2-Me-4-SO₂CF₃
Br	2-Me-4-SCF₂H	I	2-Me-4-SCF₂H	OMe	2-Me-4-SCF₂H
Br	2-Me-4-SOCF₂H	I	2-Me-4-SOCF₂H	OMe	2-Me-4-SOCF₂H
Br	2-Me-4-SO₂CF₂H	I	2-Me-4-SO₂CF₂H	OMe	2-Me-4-SO₂CF₂H
CF₃	2-Me-4-CF₃	NO₂	2-Me-4-CF₃	SMe	2-Me-4-CF₃
CF₃	2-Me-4-OCF₃	NO₂	2-Me-4-OCF₃	SMe	2-Me-4-OCF₃
CF₃	2-Me-4-OCF₂H	NO₂	2-Me-4-OCF₂H	SMe	2-Me-4-OCF₂H
CF₃	2-Me-4-OCH₂CF₃	NO₂	2-Me-4-OCH₂CF₃	SMe	2-Me-4-OCH₂CF₃
CF₃	2-Me-4-SCF₃	NO₂	2-Me-4-SCF₃	SMe	2-Me-4-SCF₃
CF₃	2-Me-4-SOCF₃	NO₂	2-Me-4-SOCF₃	SMe	2-Me-4-SOCF₃
CF₃	2-Me-4-SO₂CF₃	NO₂	2-Me-4-SO₂CF₃	SMe	2-Me-4-SO₂CF₃
CF₃	2-Me-4-SCF₂H	NO₂	2-Me-4-SCF₂H	SMe	2-Me-4-SCF₂H
CF₃	2-Me-4-SOCF₂H	NO₂	2-Me-4-SOCF₂H	SMe	2-Me-4-SOCF₂H
CF₃	2-Me-4-SO₂CF₂H	NO₂	2-Me-4-SO₂CF₂H	SMe	2-Me-4-SO₂CF₂H

TABLE 2

TABLE 3

TABLE 4

TABLE 5

R⁴	(R⁵)_m	R⁴	(R⁵)_m	R⁴	(R⁵)_m

Me	2-CF₃	Me	3-CF₃	Me	4-CF₃
Me	2-OCF₃	Me	3-OCF₃	Me	4-OCF₃
Me	2-OCF₂H	Me	3-OCF₂H	Me	4-OCF₂H
Me	2-OCF₂CF₂H	Me	3-OCF₂CF₂H	Me	4-OCF₂CF₂H
Me	2-OCH₂CF₃	Me	3-OCH₂CF₃	Me	4-OCH₂CF₃
Me	2-SCF₃	Me	3-SCF₃	Me	4-SCF₃
Me	2-SOCF₃	Me	3-SOCF₃	Me	4-SOCF₃
Me	2-SO₂CF₃	Me	3-SO₂CF₃	Me	4-SO₂CF₃
Me	2-SCF₂H	Me	3-SCF₂H	Me	4-SCF₂H
Me	2-SOCF₂H	Me	3-SOCF₂H	Me	4-SOCF₂H
Me	2-SO₂CF₂H	Me	3-SO₂CF₂H	Me	4-SO₂CF₂H
CF₃	2-Me-4-CF₃	CF₂H	2-Me-4-CF₃	CH₂CF₃	2-Me-4-CF₃
CF₃	2-Me-4-OCF₃	CF₂H	2-Me-4-OCF₃	CH₂CF₃	2-Me-4-OCF₃
CF₃	2-Me-4-OCF₂H	CF₂H	2-Me-4-OCF₂H	CH₂CF₃	2-Me-4-OCF₂H
CF₃	2-Me-4-OCH₂CF₃	CF₂H	2-Me-4-OCH₂CF₃	CH₂CF₃	2-Me-4-OCH₂CF₃
CF₃	2-Me-4-SCF₃	CF₂H	2-Me-4-SCF₃	CH₂CF₃	2-Me-4-SCF₃
CF₃	2-Me-4-SOCF₃	CF₂H	2-Me-4-SOCF₃	CH₂CF₃	2-Me-4-SOCF₃
CF₃	2-Me-4-SO₂CF₃	CF₂H	2-Me-4-SO₂CF₃	CH₂CF₃	2-Me-4-SO₂CF₃
CF₃	2-Me-4-SCF₂H	CF₂H	2-Me-4-SCF₂H	CH₂CF₃	2-Me-4-SCF₂H
CF₃	2-Me-4-SOCF₂H	CF₂H	2-Me-4-SOCF₂H	CH₂CF₃	2-Me-4-SOCF₂H
CF₃	2-Me-4-SO₂CF₂H	CF₂H	2-Me-4-SO₂CF₂H	CH₂CF₃	2-Me-4-SO₂CF₂H

TABLE 6

TABLE 7

TABLE 8

TABLE 9

TABLE 10

TABLE 11

TABLE 12

TABLE 13

TABLE 14

TABLE 15

K	R³	(R⁴)_n	R⁵	W	X	Y	Z

K-1	i-Pr	4-Me	CF₃	CMe	N	CH	CH
K-1	i-Pr	4-Cl	CF₃	CMe	N	CH	CH
K-18	i-Pr	4-Me	CF₃	CMe	N	CH	CH
K-18	i-Pr	4-Cl	CF₃	CMe	N	CH	CH
K-14	i-Pr	1-Me	CF₃	CMe	N	CH	CH
K-28	i-Pr	4-Me	CF₃	CMe	N	CH	CH
K-28	i-Pr	4-Cl	CF₃	CMe	N	CH	CH
K-30	i-Pr	5-Me	CF₃	CMe	N	CH	CH
K-30	i-Pr	5-Cl	CF₃	CMe	N	CH	CH
K-31	i-Pr	2-Me	CF₃	CMe	N	CH	CH
K-31	i-Pr	2-Cl	CF₃	CMe	N	CH	CH
K-33	i-Pr	6-Me	CF₃	CMe	N	CH	CH
K-33	i-Pr	6-Cl	CF₃	CMe	N	CH	CH
K-1	i-Pr	4-Me	CF₃	CMe	CH	N	CH
K-1	i-Pr	4-Cl	CF₃	CMe	CH	N	CH
K-18	i-Pr	4-Me	CF₃	CMe	CH	N	CH
K-18	i-Pr	4-Cl	CF₃	CMe	CH	N	CH
K-14	i-Pr	1-Me	CF₃	CMe	CH	N	CH
K-28	i-Pr	4-Me	CF₃	CMe	CH	N	CH
K-28	i-Pr	4-Cl	CF₃	CMe	CH	N	CH
K-30	i-Pr	5-Me	CF₃	CMe	CH	N	CH
K-30	i-Pr	5-Cl	CF₃	CMe	CH	N	CH
K-31	i-Pr	2-Me	CF₃	CMe	CH	N	CH
K-31	i-Pr	2-Cl	CF₃	CMe	CH	N	CH
K-33	i-Pr	6-Me	CF₃	CMe	CH	N	CH
K-33	i-Pr	6-Cl	CF₃	CMe	CH	N	CH
K-1	i-Pr	4-Me	CF₃	CMe	CH	N	CH
K-1	i-Pr	4-Cl	CF₃	CMe	CH	N	CH
K-18	i-Pr	4-Me	CF₃	CMe	CH	N	CH
K-18	i-Pr	4-Cl	CF₃	CMe	CH	N	CH
K-14	i-Pr	1-Me	CF₃	CMe	CH	N	CH
K-28	i-Pr	4-Me	CF₃	CMe	CH	CH	N
K-28	i-Pr	4-Cl	CF₃	CMe	CH	CH	N
K-30	i-Pr	5-Me	CF₃	CMe	CH	CH	N
K-30	i-Pr	5-Cl	CF₃	CMe	CH	CH	N
K-31	i-Pr	2-Me	CF₃	CMe	CH	CH	N
K-31	i-Pr	2-Cl	CF₃	CMe	CH	CH	N
K-33	i-Pr	6-Me	CF₃	CMe	CH	CH	N
K-33	i-Pr	6-Cl	CF₃	CMe	CH	CH	N
K-1	t-Bu	4-Me	CF₃	CMe	N	CH	CH
K-1	t-Bu	4-Cl	CF₃	CMe	N	CH	CH
K-18	t-Bu	4-Me	CF₃	CMe	N	CH	CH
K-18	t-Bu	4-Cl	CF₃	CMe	N	CH	CH
K-14	t-Bu	1-Me	CF₃	CMe	N	CH	CH
K-28	t-Bu	4-Me	CF₃	CMe	N	CH	CH
K-28	t-Bu	4-Cl	CF₃	CMe	N	CH	CH
K-30	t-Bu	5-Me	CF₃	CMe	N	CH	CH
K-30	t-Bu	5-Cl	CF₃	CMe	N	CH	CH
K-31	t-Bu	2-Me	CF₃	CMe	N	CH	CH
K-31	t-Bu	2-Cl	CF₃	CMe	N	CH	CH
K-33	t-Bu	6-Me	CF₃	CMe	N	CH	CH
K-33	t-Bu	6-Cl	CF₃	CMe	N	CH	CH
K-1	t-Bu	4-Me	CF₃	CMe	CH	N	CH
K-1	t-Bu	4-Cl	CF₃	CMe	CH	N	CH
K-18	t-Bu	4-Me	CF₃	CMe	CH	N	CH
K-18	t-Bu	4-Cl	CF₃	CMe	CH	N	CH
K-14	t-Bu	1-Me	CF₃	CMe	CH	N	CH
K-28	t-Bu	4-Me	CF₃	CMe	CH	N	CH
K-28	t-Bu	4-Cl	CF₃	CMe	CH	N	CH
K-30	t-Bu	5-Me	CF₃	CMe	CH	N	CH
K-30	t-Bu	5-Cl	CF₃	CMe	CH	N	CH
K-31	t-Bu	2-Me	CF₃	CMe	CH	N	CH
K-31	t-Bu	2-Cl	CF₃	CMe	CH	N	CH
K-33	t-Bu	6-Me	CF₃	CMe	CH	N	CH
K-33	t-Bu	6-Cl	CF₃	CMe	CH	N	CH
K-1	t-Bu	4-Me	CF₃	CMe	CH	N	CH
K-1	t-Bu	4-Cl	CF₃	CMe	CH	N	CH
K-18	t-Bu	4-Me	CF₃	CMe	CH	N	CH
K-18	t-Bu	4-Cl	CF₃	CMe	CH	N	CH
K-14	t-Bu	1-Me	CF₃	CMe	CH	N	CH
K-28	t-Bu	4-Me	CF₃	CMe	CH	CH	N
K-28	t-Bu	4-Cl	CF₃	CMe	CH	CH	N
K-30	t-Bu	5-Me	CF₃	CMe	CH	CH	N
K-30	t-Bu	5-Cl	CF₃	CMe	CH	CH	N
K-31	t-Bu	2-Me	CF₃	CMe	CH	CH	N
K-31	t-Bu	2-Cl	CF₃	CMe	CH	CH	N
K-33	t-Bu	6-Me	CF₃	CMe	CH	CH	N
K-33	t-Bu	6-Cl	CF₃	CMe	CH	CH	N
K-1	i-Pr	4-Me	OCF₃	CMe	N	CH	CH
K-1	i-Pr	4-Cl	OCF₃	CMe	N	CH	CH
K-18	i-Pr	4-Me	OCF₃	CMe	N	CH	CH
K-18	i-Pr	4-Cl	OCF₃	CMe	N	CH	CH
K-14	i-Pr	1-Me	OCF₃	CMe	N	CH	CH
K-28	i-Pr	4-Me	OCF₃	CMe	N	CH	CH
K-28	i-Pr	4-Cl	OCF₃	CMe	N	CH	CH
K-30	i-Pr	5-Me	OCF₃	CMe	N	CH	CH
K-30	i-Pr	5-Cl	OCF₃	CMe	N	CH	CH
K-31	i-Pr	2-Me	OCF₃	CMe	N	CH	CH
K-31	i-Pr	2-Cl	OCF₃	CMe	N	CH	CH
K-33	i-Pr	6-Me	OCF₃	CMe	N	CH	CH
K-33	i-Pr	6-Cl	OCF₃	CMe	N	CH	CH
K-1	i-Pr	4-Me	OCF₃	CH	N	CH	CH
K-1	i-Pr	4-Cl	OCF₃	CH	N	CH	CH
K-18	i-Pr	4-Me	OCF₃	CH	N	CH	CH
K-18	i-Pr	4-Cl	OCF₃	CH	N	CH	CH
K-14	i-Pr	1-Me	OCF₃	CH	N	CH	CH
K-28	i-Pr	4-Me	OCF₃	CH	N	CH	CH
K-28	i-Pr	4-Cl	OCF₃	CH	N	CH	CH
K-30	i-Pr	5-Me	OCF₃	CH	N	CH	CH
K-30	i-Pr	5-Cl	OCF₃	CH	N	CH	CH
K-31	i-Pr	2-Me	OCF₃	CH	N	CH	CH
K-31	i-Pr	2-Cl	OCF₃	CH	N	CH	CH
K-33	i-Pr	6-Me	OCF₃	CH	N	CH	CH
K-33	i-Pr	6-Cl	OCF₃	CH	N	CH	CH
K-1	i-Pr	4-Me	Cl	CMe	CH	CH	N
K-1	i-Pr	4-Cl	Cl	CMe	CH	CH	N
K-18	i-Pr	4-Me	Cl	CMe	CH	CH	N
K-18	i-Pr	4-Cl	Cl	CMe	CH	CH	N
K-14	i-Pr	1-Me	Cl	CMe	CH	CH	N
K-28	i-Pr	4-Me	Cl	CMe	CH	CH	N
K-28	i-Pr	4-Cl	Cl	CMe	CH	CH	N
K-30	i-Pr	5-Me	Cl	CMe	CH	CH	N
K-30	i-Pr	5-Cl	Cl	CMe	CH	CH	N
K-31	i-Pr	2-Me	Cl	CMe	CH	CH	N
K-31	i-Pr	2-Cl	Cl	CMe	CH	CH	N
K-33	i-Pr	6-Me	Cl	CMe	CH	CH	N
K-33	i-Pr	6-Cl	Cl	CMe	CH	CH	N

TABLE 16

	K	(R⁴)_n	Q	X	Y	Z

R³is i-Pr

K-1	4-Me	NCHF₂	CMe	N	CH
K-1	4-Cl	NCHF₂	CMe	N	CH
K-18	4-Me	NCHF₂	CMe	N	CH
K-18	4-Cl	NCHF₂	CMe	N	CH
K-14	1-Me	NCHF₂	CMe	N	CH
K-28	4-Me	NCHF₂	CMe	N	CH
K-28	4-Cl	NCHF₂	CMe	N	CH
K-30	5-Me	NCHF₂	CMe	N	CH
K-30	5-Cl	NCHF₂	CMe	N	CH
K-31	2-Me	NCHF₂	CMe	N	CH
K-31	2-Cl	NCHF₂	CMe	N	CH
K-33	6-Me	NCHF₂	CMe	N	CH
K-33	6-Cl	NCHF₂	CMe	N	CH
K-1	4-Me	NCHF₂	CH	N	CMe
K-1	4-Cl	NCHF₂	CH	N	CMe
K-18	4-Me	NCHF₂	CH	N	CMe
K-18	4-Cl	NCHF₂	CH	N	CMe
K-14	1-Me	NCHF₂	CH	N	CMe
K-28	4-Me	NCHF₂	CH	N	CMe
K-28	4-Cl	NCHF₂	CH	N	CMe
K-30	5-Me	NCHF₂	CH	N	CMe
K-30	5-Cl	NCHF₂	CH	N	CMe
K-31	2-Me	NCHF₂	CH	N	CMe
K-31	2-Cl	NCHF₂	CH	N	CMe
K-33	6-Me	NCHF₂	CH	N	CMe
K-33	6-Cl	NCHF₂	CH	N	CMe
K-1	4-Me	NCF₂CHF₂	CMe	N	CH
K-1	4-Cl	NCF₂CHF₂	CMe	N	CH
K-18	4-Me	NCF₂CHF₂	CMe	N	CH
K-18	4-Cl	NCF₂CHF₂	CMe	N	CH
K-14	1-Me	NCF₂CHF₂	CMe	N	CH
K-28	4-Me	NCF₂CHF₂	CMe	N	CH
K-28	4-Cl	NCF₂CHF₂	CMe	N	CH
K-30	5-Me	NCF₂CHF₂	CMe	N	CH
K-30	5-Cl	NCF₂CHF₂	CMe	N	CH
K-31	2-Me	NCF₂CHF₂	CMe	N	CH
K-31	2-Cl	NCF₂CHF₂	CMe	N	CH
K-33	6-Me	NCF₂CHF₂	CMe	N	CH
K-33	6-Cl	NCF₂CHF₂	CMe	N	CH
K-1	4-Me	NCH₂CF₃	CMe	N	CH
K-1	4-Cl	NCH₂CF₃	CMe	N	CH
K-18	4-Me	NCH₂CF₃	CMe	N	CH
K-18	4-Cl	NCH₂CF₃	CMe	N	CH
K-14	1-Me	NCH₂CF₃	CMe	N	CH
K-28	4-Me	NCH₂CF₃	CMe	N	CH
K-28	4-Cl	NCH₂CF₃	CMe	N	CH
K-30	5-Me	NCH₂CF₃	CMe	N	CH
K-30	5-Cl	NCH₂CF₃	CMe	N	CH
K-31	2-Me	NCH₂CF₃	CMe	N	CH
K-31	2-Cl	NCH₂CF₃	CMe	N	CH
K-33	6-Me	NCH₂CF₃	CMe	N	CH
K-33	6-Cl	NCH₂CF₃	CMe	N	CH
K-1	4-Me	NCH₂CF₃	CH	N	CMe
K-1	4-Cl	NCH₂CF₃	CH	N	CMe
K-18	4-Me	NCH₂CF₃	CH	N	CMe
K-18	4-Cl	NCH₂CF₃	CH	N	CMe
K-14	1-Me	NCH₂CF₃	CH	N	CMe
K-28	4-Me	NCH₂CF₃	CH	N	CMe
K-28	4-Cl	NCH₂CF₃	CH	N	CMe
K-30	5-Me	NCH₂CF₃	CH	N	CMe
K-30	5-Cl	NCH₂CF₃	CH	N	CMe
K-31	2-Me	NCH₂CF₃	CH	N	CMe
K-31	2-Cl	NCH₂CF₃	CH	N	CMe
K-33	6-Me	NCH₂CF₃	CH	N	CMe
K-33	6-Cl	NCH₂CF₃	CH	N	CMe
K-1	4-Me	NCF₂CHF₂	N	CH	CMe
K-1	4-Cl	NCF₂CHF₂	N	CH	CMe
K-18	4-Me	NCF₂CHF₂	N	CH	CMe
K-18	4-Cl	NCF₂CHF₂	N	CH	CMe
K-14	1-Me	NCF₂CHF₂	N	CH	CMe
K-28	4-Me	NCF₂CHF₂	N	CH	CMe
K-28	4-Cl	NCF₂CHF₂	N	CH	CMe
K-30	5-Me	NCF₂CHF₂	N	CH	CMe
K-30	5-Cl	NCF₂CHF₂	N	CH	CMe
K-31	2-Me	NCF₂CHF₂	N	CH	CMe
K-31	2-Cl	NCF₂CHF₂	N	CH	CMe
K-33	6-Me	NCF₂CHF₂	N	CH	CMe
K-33	6-Cl	NCF₂CHF₂	N	CH	CMe

R³is t-Bu

TABLE 17

K	W	X	Y	Z	R³	(R⁴)_n	R⁵	R⁶

K-1	CH	CH	CH	CH	i-Pr	4-Me	CF₃	Me
K-1	CH	CH	CH	CH	t-Bu	4-Me	CF₃	Me
K-1	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	Me
K-1	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	Me
K-1	CH	CH	CH	CH	i-Pr	4-Me	CF₃	F
K-1	CH	CH	CH	CH	t-Bu	4-Me	CF₃	F
K-1	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	F
K-1	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	F
K-1	CH	CH	CH	CH	i-Pr	4-Me	CF₃	Cl
K-1	CH	CH	CH	CH	t-Bu	4-Me	CF₃	Cl
K-1	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	Cl
K-1	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	Cl
K-1	CH	CH	CH	CH	i-Pr	4-Me	CF₃	Br
K-1	CH	CH	CH	CH	t-Bu	4-Me	CF₃	Br
K-1	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	Br
K-1	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	Br
K-1	CH	CH	CH	CH	i-Pr	4-Me	CF₃	CN
K-1	CH	CH	CH	CH	t-Bu	4-Me	CF₃	CN
K-1	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	CN
K-1	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	CN
K-1	CH	CH	CH	N	i-Pr	4-Me	CF₃	Me
K-1	CH	CH	CH	N	t-Bu	4-Me	CF₃	Me
K-1	CH	CH	CH	N	i-Pr	4-Cl	CF₃	Me
K-1	CH	CH	CH	N	t-Bu	4-Cl	CF₃	Me
K-1	CH	CH	CH	N	i-Pr	4-Me	CF₃	F
K-1	CH	CH	CH	N	t-Bu	4-Me	CF₃	F
K-1	CH	CH	CH	N	i-Pr	4-Cl	CF₃	F
K-1	CH	CH	CH	N	t-Bu	4-Cl	CF₃	F
K-1	CH	CH	CH	N	i-Pr	4-Me	CF₃	Cl
K-1	CH	CH	CH	N	t-Bu	4-Me	CF₃	Cl
K-1	CH	CH	CH	N	i-Pr	4-Cl	CF₃	Cl
K-1	CH	CH	CH	N	t-Bu	4-Cl	CF₃	Cl
K-1	CH	CH	CH	N	i-Pr	4-Me	CF₃	Br
K-1	CH	CH	CH	N	t-Bu	4-Me	CF₃	Br
K-1	CH	CH	CH	N	i-Pr	4-Cl	CF₃	Br
K-1	CH	CH	CH	N	t-Bu	4-Cl	CF₃	Br
K-1	CH	CH	CH	N	i-Pr	4-Me	CF₃	CN
K-1	CH	CH	CH	N	t-Bu	4-Me	CF₃	CN
K-1	CH	CH	CH	N	i-Pr	4-Cl	CF₃	CN
K-1	CH	CH	CH	N	t-Bu	4-Cl	CF₃	CN
K-18	CH	CH	CH	CH	i-Pr	4-Me	CF₃	Me
K-18	CH	CH	CH	CH	t-Bu	4-Me	CF₃	Me
K-18	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	Me
K-18	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	Me
K-18	CH	CH	CH	CH	i-Pr	4-Me	CF₃	F
K-18	CH	CH	CH	CH	t-Bu	4-Me	CF₃	F
K-18	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	F
K-18	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	F
K-18	CH	CH	CH	CH	i-Pr	4-Me	CF₃	Cl
K-18	CH	CH	CH	CH	t-Bu	4-Me	CF₃	Cl
K-18	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	Cl
K-18	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	Cl
K-18	CH	CH	CH	CH	i-Pr	4-Me	CF₃	Br
K-18	CH	CH	CH	CH	t-Bu	4-Me	CF₃	Br
K-18	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	Br
K-18	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	Br
K-18	CH	CH	CH	CH	i-Pr	4-Me	CF₃	CN
K-18	CH	CH	CH	CH	t-Bu	4-Me	CF₃	CN
K-18	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	CN
K-18	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	CN
K-18	CH	CH	CH	N	i-Pr	4-Me	CF₃	Me
K-18	CH	CH	CH	N	t-Bu	4-Me	CF₃	Me
K-18	CH	CH	CH	N	i-Pr	4-Cl	CF₃	Me
K-18	CH	CH	CH	N	t-Bu	4-Cl	CF₃	Me
K-18	CH	CH	CH	N	i-Pr	4-Me	CF₃	F
K-18	CH	CH	CH	N	t-Bu	4-Me	CF₃	F
K-18	CH	CH	CH	N	i-Pr	4-Cl	CF₃	F
K-18	CH	CH	CH	N	t-Bu	4-Cl	CF₃	F
K-18	CH	CH	CH	N	i-Pr	4-Me	CF₃	Cl
K-18	CH	CH	CH	N	t-Bu	4-Me	CF₃	Cl
K-18	CH	CH	CH	N	i-Pr	4-Cl	CF₃	Cl
K-18	CH	CH	CH	N	t-Bu	4-Cl	CF₃	Cl
K-18	CH	CH	CH	N	i-Pr	4-Me	CF₃	Br
K-18	CH	CH	CH	N	t-Bu	4-Me	CF₃	Br
K-18	CH	CH	CH	N	i-Pr	4-Cl	CF₃	Br
K-18	CH	CH	CH	N	t-Bu	4-Cl	CF₃	Br
K-18	CH	CH	CH	N	i-Pr	4-Me	CF₃	CN
K-18	CH	CH	CH	N	t-Bu	4-Me	CF₃	CN
K-18	CH	CH	CH	N	i-Pr	4-Cl	CF₃	CN
K-18	CH	CH	CH	N	t-Bu	4-Cl	CF₃	CN
K-14	CH	CH	CH	CH	i-Pr	1-Me	CF₃	Me
K-14	CH	CH	CH	CH	t-Bu	1-Me	CF₃	Me
K-14	CH	CH	CH	CH	i-Pr	1-Me	CF₃	F
K-14	CH	CH	CH	CH	t-Bu	1-Me	CF₃	F
K-14	CH	CH	CH	CH	i-Pr	1-Me	CF₃	Cl
K-14	CH	CH	CH	CH	t-Bu	1-Me	CF₃	Cl
K-14	CH	CH	CH	CH	i-Pr	1-Me	CF₃	Br
K-14	CH	CH	CH	CH	t-Bu	1-Me	CF₃	Br
K-14	CH	CH	CH	CH	i-Pr	1-Me	CF₃	CN
K-14	CH	CH	CH	CH	t-Bu	1-Me	CF₃	CN
K-14	CH	CH	CH	N	i-Pr	1-Me	CF₃	Me
K-14	CH	CH	CH	N	t-Bu	1-Me	CF₃	Me
K-14	CH	CH	CH	N	i-Pr	1-Me	CF₃	F
K-14	CH	CH	CH	N	t-Bu	1-Me	CF₃	F
K-14	CH	CH	CH	N	i-Pr	1-Me	CF₃	Cl
K-14	CH	CH	CH	N	t-Bu	1-Me	CF₃	Cl
K-14	CH	CH	CH	N	i-Pr	1-Me	CF₃	Br
K-14	CH	CH	CH	N	t-Bu	1-Me	CF₃	Br
K-14	CH	CH	CH	N	i-Pr	1-Me	CF₃	CN
K-14	CH	CH	CH	N	t-Bu	1-Me	CF₃	CN
K-28	CH	CH	CH	CH	i-Pr	4-Me	CF₃	Me
K-28	CH	CH	CH	CH	t-Bu	4-Me	CF₃	Me
K-28	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	Me
K-28	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	Me
K-28	CH	CH	CH	CH	i-Pr	4-Me	CF₃	F
K-28	CH	CH	CH	CH	t-Bu	4-Me	CF₃	F
K-28	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	F
K-28	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	F
K-28	CH	CH	CH	CH	i-Pr	4-Me	CF₃	Cl
K-28	CH	CH	CH	CH	t-Bu	4-Me	CF₃	Cl
K-28	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	Cl
K-28	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	Cl
K-28	CH	CH	CH	CH	i-Pr	4-Me	CF₃	Br
K-28	CH	CH	CH	CH	t-Bu	4-Me	CF₃	Br
K-28	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	Br
K-28	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	Br
K-28	CH	CH	CH	CH	i-Pr	4-Me	CF₃	CN
K-28	CH	CH	CH	CH	t-Bu	4-Me	CF₃	CN
K-28	CH	CH	CH	CH	i-Pr	4-Cl	CF₃	CN
K-28	CH	CH	CH	CH	t-Bu	4-Cl	CF₃	CN
K-28	CH	CH	CH	N	i-Pr	4-Me	CF₃	Me
K-28	CH	CH	CH	N	t-Bu	4-Me	CF₃	Me
K-28	CH	CH	CH	N	i-Pr	4-Cl	CF₃	Me
K-28	CH	CH	CH	N	t-Bu	4-Cl	CF₃	Me
K-28	CH	CH	CH	N	i-Pr	4-Me	CF₃	F
K-28	CH	CH	CH	N	t-Bu	4-Me	CF₃	F
K-28	CH	CH	CH	N	i-Pr	4-Cl	CF₃	F
K-28	CH	CH	CH	N	t-Bu	4-Cl	CF₃	F
K-28	CH	CH	CH	N	i-Pr	4-Me	CF₃	Cl
K-28	CH	CH	CH	N	t-Bu	4-Me	CF₃	Cl
K-28	CH	CH	CH	N	i-Pr	4-Cl	CF₃	Cl
K-28	CH	CH	CH	N	t-Bu	4-Cl	CF₃	Cl
K-28	CH	CH	CH	N	i-Pr	4-Me	CF₃	Br
K-28	CH	CH	CH	N	t-Bu	4-Me	CF₃	Br
K-28	CH	CH	CH	N	i-Pr	4-Cl	CF₃	Br
K-28	CH	CH	CH	N	t-Bu	4-Cl	CF₃	Br
K-28	CH	CH	CH	N	i-Pr	4-Me	CF₃	CN
K-28	CH	CH	CH	N	t-Bu	4-Me	CF₃	CN
K-28	CH	CH	CH	N	i-Pr	4-Cl	CF₃	CN
K-28	CH	CH	CH	N	t-Bu	4-Cl	CF₃	CN
K-30	CH	CH	CH	CH	i-Pr	Me	CF₃	Me
K-30	CH	CH	CH	CH	t-Bu	Me	CF₃	Me
K-30	CH	CH	CH	CH	i-Pr	5-Cl	CF₃	Me
K-30	CH	CH	CH	CH	t-Bu	5-Cl	CF₃	Me
K-30	CH	CH	CH	CH	i-Pr	Me	CF₃	F
K-30	CH	CH	CH	CH	t-Bu	Me	CF₃	F
K-30	CH	CH	CH	CH	i-Pr	5-Cl	CF₃	F
K-30	CH	CH	CH	CH	t-Bu	5-Cl	CF₃	F
K-30	CH	CH	CH	CH	i-Pr	Me	CF₃	Cl
K-30	CH	CH	CH	CH	t-Bu	Me	CF₃	Cl
K-30	CH	CH	CH	CH	i-Pr	5-Cl	CF₃	Cl
K-30	CH	CH	CH	CH	t-Bu	5-Cl	CF₃	Cl
K-30	CH	CH	CH	CH	i-Pr	Me	CF₃	Br
K-30	CH	CH	CH	CH	t-Bu	Me	CF₃	Br
K-30	CH	CH	CH	CH	i-Pr	5-Cl	CF₃	Br
K-30	CH	CH	CH	CH	t-Bu	5-Cl	CF₃	Br
K-30	CH	CH	CH	CH	i-Pr	Me	CF₃	CN
K-30	CH	CH	CH	CH	t-Bu	Me	CF₃	CN
K-30	CH	CH	CH	CH	i-Pr	5-Cl	CF₃	CN
K-30	CH	CH	CH	CH	t-Bu	5-Cl	CF₃	CN
K-30	CH	CH	CH	N	i-Pr	Me	CF₃	Me
K-30	CH	CH	CH	N	t-Bu	Me	CF₃	Me
K-30	CH	CH	CH	N	i-Pr	5-Cl	CF₃	Me
K-30	CH	CH	CH	N	t-Bu	5-Cl	CF₃	Me
K-30	CH	CH	CH	N	i-Pr	Me	CF₃	F
K-30	CH	CH	CH	N	t-Bu	Me	CF₃	F
K-30	CH	CH	CH	N	i-Pr	5-Cl	CF₃	F
K-30	CH	CH	CH	N	t-Bu	5-Cl	CF₃	F
K-30	CH	CH	CH	N	i-Pr	Me	CF₃	Cl
K-30	CH	CH	CH	N	t-Bu	Me	CF₃	Cl
K-30	CH	CH	CH	N	i-Pr	5-Cl	CF₃	Cl
K-30	CH	CH	CH	N	t-Bu	5-Cl	CF₃	Cl
K-30	CH	CH	CH	N	i-Pr	Me	CF₃	Br
K-30	CH	CH	CH	N	t-Bu	Me	CF₃	Br
K-30	CH	CH	CH	N	i-Pr	5-Cl	CF₃	Br
K-30	CH	CH	CH	N	t-Bu	5-Cl	CF₃	Br
K-30	CH	CH	CH	N	i-Pr	Me	CF₃	CN
K-30	CH	CH	CH	N	t-Bu	Me	CF₃	CN
K-30	CH	CH	CH	N	i-Pr	5-Cl	CF₃	CN
K-30	CH	CH	CH	N	t-Bu	5-Cl	CF₃	CN
K-30	CH	CH	CH	CH	i-Pr	Me	CF₃	Me
K-30	CH	CH	CH	CH	t-Bu	Me	CF₃	Me
K-30	CH	CH	CH	CH	i-Pr	5-Cl	CF₃	Me
K-30	CH	CH	CH	CH	t-Bu	5-Cl	CF₃	Me
K-30	CH	CH	CH	CH	i-Pr	Me	CF₃	F
K-30	CH	CH	CH	CH	t-Bu	Me	CF₃	F
K-30	CH	CH	CH	CH	i-Pr	5-Cl	CF₃	F
K-30	CH	CH	CH	CH	t-Bu	5-Cl	CF₃	F
K-30	CH	CH	CH	CH	i-Pr	Me	CF₃	Cl
K-30	CH	CH	CH	CH	t-Bu	Me	CF₃	Cl
K-30	CH	CH	CH	CH	i-Pr	5-Cl	CF₃	Cl
K-30	CH	CH	CH	CH	t-Bu	5-Cl	CF₃	Cl
K-30	CH	CH	CH	CH	i-Pr	Me	CF₃	Br
K-30	CH	CH	CH	CH	t-Bu	Me	CF₃	Br
K-30	CH	CH	CH	CH	i-Pr	5-Cl	CF₃	Br
K-30	CH	CH	CH	CH	t-Bu	5-Cl	CF₃	Br
K-30	CH	CH	CH	CH	i-Pr	Me	CF₃	CN
K-30	CH	CH	CH	CH	t-Bu	Me	CF₃	CN
K-30	CH	CH	CH	CH	i-Pr	5-Cl	CF₃	CN
K-30	CH	CH	CH	CH	t-Bu	5-Cl	CF₃	CN
K-30	CH	CH	CH	N	i-Pr	Me	CF₃	Me
K-30	CH	CH	CH	N	t-Bu	Me	CF₃	Me
K-30	CH	CH	CH	N	i-Pr	5-Cl	CF₃	Me
K-30	CH	CH	CH	N	t-Bu	5-Cl	CF₃	Me
K-30	CH	CH	CH	N	i-Pr	Me	CF₃	F
K-30	CH	CH	CH	N	t-Bu	Me	CF₃	F
K-30	CH	CH	CH	N	i-Pr	5-Cl	CF₃	F
K-30	CH	CH	CH	N	t-Bu	5-Cl	CF₃	F
K-30	CH	CH	CH	N	i-Pr	Me	CF₃	Cl
K-30	CH	CH	CH	N	t-Bu	Me	CF₃	Cl
K-30	CH	CH	CH	N	i-Pr	5-Cl	CF₃	Cl
K-30	CH	CH	CH	N	t-Bu	5-Cl	CF₃	Cl
K-30	CH	CH	CH	N	i-Pr	Me	CF₃	Br
K-30	CH	CH	CH	N	t-Bu	Me	CF₃	Br
K-30	CH	CH	CH	N	i-Pr	5-Cl	CF₃	Br
K-30	CH	CH	CH	N	t-Bu	5-Cl	CF₃	Br
K-30	CH	CH	CH	N	i-Pr	Me	CF₃	CN
K-30	CH	CH	CH	N	t-Bu	Me	CF₃	CN
K-30	CH	CH	CH	N	i-Pr	5-Cl	CF₃	CN
K-30	CH	CH	CH	N	t-Bu	5-Cl	CF₃	CN
K-31	CH	CH	CH	CH	i-Pr	2-Me	CF₃	Me
K-31	CH	CH	CH	CH	t-Bu	2-Me	CF₃	Me
K-31	CH	CH	CH	CH	i-Pr	2-Cl	CF₃	Me
K-31	CH	CH	CH	CH	t-Bu	2-Cl	CF₃	Me
K-31	CH	CH	CH	CH	i-Pr	2-Me	CF₃	F
K-31	CH	CH	CH	CH	t-Bu	2-Me	CF₃	F
K-31	CH	CH	CH	CH	i-Pr	2-Cl	CF₃	F
K-31	CH	CH	CH	CH	t-Bu	2-Cl	CF₃	F
K-31	CH	CH	CH	CH	i-Pr	2-Me	CF₃	Cl
K-31	CH	CH	CH	CH	t-Bu	2-Me	CF₃	Cl
K-31	CH	CH	CH	CH	i-Pr	2-Cl	CF₃	Cl
K-31	CH	CH	CH	CH	t-Bu	2-Cl	CF₃	Cl
K-31	CH	CH	CH	CH	i-Pr	2-Me	CF₃	Br
K-31	CH	CH	CH	CH	t-Bu	2-Me	CF₃	Br
K-31	CH	CH	CH	CH	i-Pr	2-Cl	CF₃	Br
K-31	CH	CH	CH	CH	t-Bu	2-Cl	CF₃	Br
K-31	CH	CH	CH	CH	i-Pr	2-Me	CF₃	CN
K-31	CH	CH	CH	CH	i-Bu	2-Me	CF₃	CN
K-31	CH	CH	CH	CH	i-Pr	2-Cl	CF₃	CN
K-31	CH	CH	CH	CH	t-Bu	2-Cl	CF₃	CN
K-31	CH	CH	CH	N	i-Pr	2-Me	CF₃	Me
K-31	CH	CH	CH	N	t-Bu	2-Me	CF₃	Me
K-31	CH	CH	CH	N	i-Pr	2-Cl	CF₃	Me
K-31	CH	CH	CH	N	t-Bu	2-Cl	CF₃	Me
K-31	CH	CH	CH	N	i-Pr	2-Me	CF₃	F
K-31	CH	CH	CH	N	t-Bu	2-Me	CF₃	F
K-31	CH	CH	CH	N	i-Pr	2-Cl	CF₃	F
K-31	CH	CH	CH	N	t-Bu	2-Cl	CF₃	F
K-31	CH	CH	CH	N	i-Pr	2-Me	CF₃	Cl
K-31	CH	CH	CH	N	t-Bu	2-Me	CF₃	Cl
K-31	CH	CH	CH	N	i-Pr	2-Cl	CF₃	Cl
K-31	CH	CH	CH	N	t-Bu	2-Cl	CF₃	Cl
K-31	CH	CH	CH	N	i-Pr	2-Me	CF₃	Br
K-31	CH	CH	CH	N	t-Bu	2-Me	CF₃	Br
K-31	CH	CH	CH	N	i-Pr	2-Cl	CF₃	Br
K-31	CH	CH	CH	N	t-Bu	2-Cl	CF₃	Br
K-31	CH	CH	CH	N	i-Pr	2-Me	CF₃	CN
K-31	CH	CH	CH	N	t-Bu	2-Me	CF₃	CN
K-31	CH	CH	CH	N	i-Pr	2-Cl	CF₃	CN
K-31	CH	CH	CH	N	t-Bu	2-Cl	CF₃	CN
K-31	CH	CH	CH	CH	i-Pr	2-Me	CF₃	Me
K-31	CH	CH	CH	CH	t-Bu	2-Me	CF₃	Me
K-31	CH	CH	CH	CH	i-Pr	2-Cl	CF₃	Me
K-31	CH	CH	CH	CH	t-Bu	2-Cl	CF₃	Me
K-31	CH	CH	CH	CH	i-Pr	2-Me	CF₃	F
K-31	CH	CH	CH	CH	t-Bu	2-Me	CF₃	F
K-31	CH	CH	CH	CH	i-Pr	2-Cl	CF₃	F
K-31	CH	CH	CH	CH	t-Bu	2-Cl	CF₃	F
K-31	CH	CH	CH	CH	i-Pr	2-Me	CF₃	Cl
K-31	CH	CH	CH	CH	t-Bu	2-Me	CF₃	Cl
K-31	CH	CH	CH	CH	i-Pr	2-Cl	CF₃	Cl
K-31	CH	CH	CH	CH	t-Bu	2-Cl	CF₃	Cl
K-31	CH	CH	CH	CH	i-Pr	2-Me	CF₃	Br
K-31	CH	CH	CH	CH	t-Bu	2-Me	CF₃	Br
K-31	CH	CH	CH	CH	i-Pr	2-Cl	CF₃	Br
K-31	CH	CH	CH	CH	t-Bu	2-Cl	CF₃	Br
K-31	CH	CH	CH	CH	i-Pr	2-Me	CF₃	CN
K-31	CH	CH	CH	CH	t-Bu	2-Me	CF₃	CN
K-31	CH	CH	CH	CH	i-Pr	2-Cl	CF₃	CN
K-31	CH	CH	CH	CH	t-Bu	2-Cl	CF₃	CN
K-31	CH	CH	CH	N	i-Pr	2-Me	CF₃	Me
K-31	CH	CH	CH	N	t-Bu	2-Me	CF₃	Me
K-31	CH	CH	CH	N	i-Pr	2-Cl	CF₃	Me
K-31	CH	CH	CH	N	t-Bu	2-Cl	CF₃	Me
K-31	CH	CH	CH	N	i-Pr	2-Me	CF₃	F
K-31	CH	CH	CH	N	t-Bu	2-Me	CF₃	F
K-31	CH	CH	CH	N	i-Pr	2-Cl	CF₃	F
K-31	CH	CH	CH	N	t-Bu	2-Cl	CF₃	F
K-31	CH	CH	CH	N	i-Pr	2-Me	CF₃	Cl
K-31	CH	CH	CH	N	t-Bu	2-Me	CF₃	Cl
K-31	CH	CH	CH	N	i-Pr	2-Cl	CF₃	Cl
K-31	CH	CH	CH	N	t-Bu	2-Cl	CF₃	Cl
K-31	CH	CH	CH	N	i-Pr	2-Me	CF₃	Br
K-31	CH	CH	CH	N	t-Bu	2-Me	CF₃	Br
K-31	CH	CH	CH	N	i-Pr	2-Cl	CF₃	Br
K-31	CH	CH	CH	N	t-Bu	2-Cl	CF₃	Br
K-31	CH	CH	CH	N	i-Pr	2-Me	CF₃	CN
K-31	CH	CH	CH	N	t-Bu	2-Me	CF₃	CN
K-31	CH	CH	CH	N	i-Pr	2-Cl	CF₃	CN
K-31	CH	CH	CH	N	t-Bu	2-Cl	CF₃	CN
K-33	CH	CH	CH	CH	i-Pr	6-Me	CF₃	Me
K-33	CH	CH	CH	CH	t-Bu	6-Me	CF₃	Me
K-33	CH	CH	CH	CH	i-Pr	6-Cl	CF₃	Me
K-33	CH	CH	CH	CH	t-Bu	6-Cl	CF₃	Me
K-33	CH	CH	CH	CH	i-Pr	6-Me	CF₃	F
K-33	CH	CH	CH	CH	t-Bu	6-Me	CF₃	F
K-33	CH	CH	CH	CH	i-Pr	6-Cl	CF₃	F
K-33	CH	CH	CH	CH	t-Bu	6-Cl	CF₃	F
K-33	CH	CH	CH	CH	i-Pr	6-Me	CF₃	Cl
K-33	CH	CH	CH	CH	t-Bu	6-Me	CF₃	Cl
K-33	CH	CH	CH	CH	i-Pr	6-Cl	CF₃	Cl
K-33	CH	CH	CH	CH	t-Bu	6-Cl	CF₃	Cl
K-33	CH	CH	CH	CH	i-Pr	6-Me	CF₃	Br
K-33	CH	CH	CH	CH	t-Bu	6-Me	CF₃	Br
K-33	CH	CH	CH	CH	i-Pr	6-Cl	CF₃	Br
K-33	CH	CH	CH	CH	t-Bu	6-Cl	CF₃	Br
K-33	CH	CH	CH	CH	i-Pr	6-Me	CF₃	CN
K-33	CH	CH	CH	CH	t-Bu	6-Me	CF₃	CN
K-33	CH	CH	CH	CH	i-Pr	6-Cl	CF₃	CN
K-33	CH	CH	CH	CH	t-Bu	6-Cl	CF₃	CN
K-33	CH	CH	CH	N	i-Pr	6-Me	CF₃	Me
K-33	CH	CH	CH	N	t-Bu	6-Me	CF₃	Me
K-33	CH	CH	CH	N	i-Pr	6-Cl	CF₃	Me
K-33	CH	CH	CH	N	t-Bu	6-Cl	CF₃	Me
K-33	CH	CH	CH	N	i-Pr	6-Me	CF₃	F
K-33	CH	CH	CH	N	t-Bu	6-Me	CF₃	F
K-33	CH	CH	CH	N	i-Pr	6-Cl	CF₃	F
K-33	CH	CH	CH	N	t-Bu	6-Cl	CF₃	F
K-33	CH	CH	CH	N	i-Pr	6-Me	CF₃	Cl
K-33	CH	CH	CH	N	t-Bu	6-Me	CF₃	Cl
K-33	CH	CH	CH	N	i-Pr	6-Cl	CF₃	Cl
K-33	CH	CH	CH	N	t-Bu	6-Cl	CF₃	Cl
K-33	CH	CH	CH	N	i-Pr	6-Me	CF₃	Br
K-33	CH	CH	CH	N	t-Bu	6-Me	CF₃	Br
K-33	CH	CH	CH	N	i-Pr	6-Cl	CF₃	Br
K-33	CH	CH	CH	N	t-Bu	6-Cl	CF₃	Br
K-33	CH	CH	CH	N	i-Pr	6-Me	CF₃	CN
K-33	CH	CH	CH	N	t-Bu	6-Me	CF₃	CN
K-33	CH	CH	CH	N	i-Pr	6-Cl	CF₃	CN
K-33	CH	CH	CH	N	t-Bu	6-Cl	CF₃	CN
K-33	CH	CH	CH	CH	i-Pr	6-Me	CF₃	Me
K-33	CH	CH	CH	CH	t-Bu	6-Me	CF₃	Me
K-33	CH	CH	CH	CH	i-Pr	6-Cl	CF₃	Me
K-33	CH	CH	CH	Cl-i	t-Bu	6-Cl	CF₃	Me
K-33	CH	CH	CH	CH	i-Pr	6-Me	CF₃	F
K-33	CH	CH	CH	CH	t-Bu	6-Me	CF₃	F
K-33	CH	CH	CH	CH	i-Pr	6-Cl	CF₃	F
K-33	CH	CH	CH	CH	t-Bu	6-Cl	CF₃	F
K-33	CH	CH	CH	CH	i-Pr	6-Me	CF₃	Cl
K-33	CH	CH	CH	CH	i-Bu	6-Me	CF₃	Cl
K-33	CH	CH	CH	CH	i-Pr	6-Cl	CF₃	Cl
K-33	CH	CH	CH	CH	t-Bu	6-Cl	CF₃	Cl
K-33	CH	CH	CH	CH	i-Pr	6-Me	CF₃	Br
K-33	CH	CH	CH	CH	t-Bu	6-Me	CF₃	Br
K-33	CH	CH	CH	CH	i-Pr	6-Cl	CF₃	Br
K-33	CH	CH	CH	CH	t-Bu	6-Cl	CF₃	Br
K-33	CH	CH	CH	CH	i-Pr	6-Me	CF₃	CN
K-33	CH	CH	CH	CH	t-Bu	6-Me	CF₃	CN
K-33	CH	CH	CH	CH	i-Pr	6-Cl	CF₃	CN
K-33	CH	CH	CH	CH	i-By	6-Cl	CF₃	CN
K-33	CH	CH	CH	N	i-Pr	6-Me	CF₃	Me
K-33	CH	CH	CH	N	t-Bu	6-Me	CF₃	Me
K-33	CH	CH	CH	N	i-Pr	6-Cl	CF₃	Me
K-33	CH	CH	CH	N	t-Bu	6-Cl	CF₃	Me
K-33	CH	CH	CH	N	i-Pr	6-Me	CF₃	F
K-33	CH	CH	CH	N	t-Bu	6-Me	CF₃	F
K-33	CH	CH	CH	N	i-Pr	6-Cl	CF₃	F
K-33	CH	CH	CH	N	t-Bu	6-Cl	CF₃	F
K-33	CH	CH	CH	N	i-Pr	6-Me	CF₃	Cl
K-33	CH	CH	CH	N	t-Bu	6-Me	CF₃	Cl
K-33	CH	CH	CH	N	i-Pr	6-Cl	CF₃	Cl
K-33	CH	CH	CH	N	t-Bu	6-Cl	CF₃	Cl
K-33	CH	CH	CH	N	i-Pr	6-Me	CF₃	Br
K-33	CH	CH	CH	N	t-Bu	6-Me	CF₃	Br
K-33	CH	CH	CH	N	i-Pr	6-Cl	CF₃	Br
K-33	CH	CH	CH	N	t-Bu	6-Cl	CF₃	Br
K-33	CH	CH	CH	N	i-Pr	6-Me	CF₃	CN
K-33	CH	CH	CH	N	t-Bu	6-Me	CF₃	CN
K-33	CH	CH	CH	N	i-Pr	6-Cl	CF₃	CN
K-33	CH	CH	CH	N	t-Bu	6-Cl	CF₃	CN

TABLE 18

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶

R⁵is Cl

CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl
CH₃	H	Br	CH₃	H	Br	CH₃	H	Br	CH₃	H	Br
CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl
CH₃	I	Br	CH₃	I	Br	CH₃	I	Br	CH₃	I	Br
CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl
CH₃	F	Br	CH₃	F	Br	CH₃	F	Br	CH₃	F	Br
CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl
CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br
CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl
CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br
CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl
CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br
Cl	H	Cl	Cl	H	Cl	Cl	H	Cl	Cl	H	Cl
Cl	H	Br	Cl	H	Br	Cl	H	Br	Cl	H	Br
Cl	I	Cl	Cl	I	Cl	Cl	I	Cl	Cl	I	Cl
Cl	I	Br	Cl	I	Br	Cl	I	Br	Cl	I	Br
Cl	F	Cl	Cl	F	Cl	Cl	F	Cl	Cl	F	Cl
Cl	F	Br	Cl	F	Br	Cl	F	Br	Cl	F	Br
Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl
Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br
Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl
Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br
Br	H	Cl	Br	H	Cl	Br	H	Cl	Br	H	Cl
Br	H	Br	Br	H	Br	Br	H	Br	Br	H	Br
Br	I	Cl	Br	I	Cl	Br	I	Cl	Br	I	Cl
Br	I	Br	Br	I	Br	Br	I	Br	Br	I	Br
Br	F	Cl	Br	F	Cl	Br	F	Cl	Br	F	Cl
Br	F	Br	Br	F	Br	Br	F	Br	Br	F	Br
Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl
Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br
Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br
Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl
Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br

R⁵is Br

R⁵is CF₃

R⁵is OCH₂CF₃

TABLE 19

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶

R⁵is CHF₂

R⁵is CH₂CF₃

R⁵is CF₂CHF₂

TABLE 20

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶

R⁵is Cl

R⁵is Br

R⁵is CF₃

R⁵is OCH₂CF₃

TABLE 21

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶

R⁵is CHF₂

R⁵is CH₂CF₃

R⁵is CF₂CHF₂

CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl
CH₃	H	Br	CH₃	H	Br	CH₃	H	Br	CH₃	H	Br
CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl
CH₃	I	Br	CH₃	I	Br	CH₃	I	Br	CH₃	I	Br
CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl
CH₃	F	Br	CH₃	F	Br	CH₃	F	Br	CH₃	F	Br
CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl	CF₃	CF₃	Cl
CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br	CF₃	CF₃	Br
CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl
CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br
CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl
CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br
Cl	H	Cl	Cl	H	Cl	Cl	H	Cl	Cl	H	Cl
Cl	H	Br	Cl	H	Br	Cl	H	Br	Cl	H	Br
Cl	I	Cl	Cl	I	Cl	Cl	I	Cl	Cl	I	Cl
Cl	I	Br	Cl	I	Br	Cl	I	Br	Cl	I	Br
Cl	F	Cl	Cl	F	Cl	Cl	F	Cl	Cl	F	Cl
Cl	F	Br	Cl	F	Br	Cl	F	Br	Cl	F	Br
Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl
Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br
Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl
Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br
Br	H	Cl	Br	H	Cl	Br	H	Cl	Br	H	Cl
Br	H	Br	Br	H	Br	Br	H	Br	Br	H	Br
Br	I	Cl	Br	I	Cl	Br	I	Cl	Br	I	Cl
Br	I	Br	Br	I	Br	Br	I	Br	Br	I	Br
Br	F	Cl	Br	F	Cl	Br	F	Cl	Br	F	Cl
Br	F	Br	Br	F	Br	Br	F	Br	Br	F	Br
Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl
Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br
Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br
Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl
Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br

TABLE 22

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶

R⁵is Cl

R⁵is Br

R⁵is CF₃

R⁵is OCH₂CF₃

TABLE 23

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶

R⁵is CHF₂

R⁵is CH₂CF₃

R⁵is CF₂CHF₂

TABLE 24

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶

R⁵is Cl

R⁵is Br

R⁵is CF₃

R⁵is OCH₂CF₃

TABLE 25

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R⁴	R⁵	R⁶	R⁴	R⁵	R⁶	R⁴	R⁵	R⁶	R⁴	R⁵	R⁶

V is CH

Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl
Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br
Cl	Br	CN	Cl	Br	CN	Cl	Br	CN	Cl	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br
Cl	Cl	CN	Cl	Cl	CN	Cl	Cl	CN	Cl	Cl	CN
Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl
Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br
Cl	CF₃	CN	Cl	CF₃	CN	Cl	CF₃	CN	Cl	CF₃	CN
Cl	OCH₂CF₃	Cl	Cl	OCH₂CF₃	Cl	Cl	OCH₂CF₃	Cl	Cl	OCH₂CF₃	Cl
Cl	OCH₂CF₃	Br	Cl	OCH₂CF₃	Br	Cl	OCH₂CF₃	Br	Cl	OCH₂CF₃	Br
Cl	OCH₂CF₃	CN	Cl	OCH₂CF₃	CN	Cl	OCH₂CF₃	CN	Cl	OCH₂CF₃	CN
Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br
Br	Br	CN	Br	Br	CN	Br	Br	CN	Br	Br	CN
Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl
Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br
Br	Cl	CN	Br	Cl	CN	Br	Cl	CN	Br	Cl	CN
Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl
Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br
Br	CF₃	CN	Br	CF₃	CN	Br	CF₃	CN	Br	CF₃	CN
Br	OCH₂CF₃	Cl	Br	OCH₂CF₃	Cl	Br	OCH₂CF₃	Cl	Br	OCH₂CF₃	Cl
Br	OCH₂CF₃	Br	Br	OCH₂CF₃	Br	Br	OCH₂CF₃	Br	Br	OCH₂CF₃	Br
Br	OCH₂CF₃	CN	Br	OCH₂CF₃	CN	Br	OCH₂CF₃	CN	Br	OCH₂CF₃	CN
CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl
CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br
CH₃	Br	CN	CH₃	Br	CN	CH₃	Br	CN	CH₃	Br	CN
CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl
CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br
CH₃	Cl	CN	CH₃	Cl	CN	CH₃	Cl	CN	CH₃	Cl	CN
CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl
CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br
CH₃	CF₃	CN	CH₃	CF₃	CN	CH₃	CF₃	CN	CH₃	CF₃	CN
CH₃	OCH₂CF₃	Cl	CH₃	OCH₂CF₃	Cl	CH₃	OCH₂CF₃	Cl	CH₃	OCH₂CF₃	Cl
CH₃	OCH₂CF₃	Br	CH₃	OCH₂CF₃	Br	CH₃	OCH₂CF₃	Br	CH₃	OCH₂CF₃	Br
CH₃	OCH₂CF₃	CN	CH₃	OCH₂CF₃	CN	CH₃	OCH₂CF₃	CN	CH₃	OCH₂CF₃	CN
CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br	Cl
CF₃	Br	Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br	Br
CF₃	Br	CN	CF₃	Br	CN	CF₃	Br	CN	CF₃	Br	CN
CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl	Cl
CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl	Br
CF₃	Cl	CN	CF₃	Cl	CN	CF₃	Cl	CN	CF₃	Cl	CN
CF₃	CF₃	Cl	CF₃	CF₃	Cl	CF₃	CF₃	Cl	CF₃	CF₃	Cl
CF₃	CF₃	Br	CF₃	CF₃	Br	CF₃	CF₃	Br	CF₃	CF₃	Br
CF₃	CF₃	CN	CF₃	CF₃	CN	CF₃	CF₃	CN	CF₃	CF₃	CN
CF₃	OCH₂CF₃	Cl	CF₃	OCH₂CF₃	Cl	CF₃	OCH₂CF₃	Cl	CF₃	OCH₂CF₃	Cl
CF₃	OCH₂CF₃	Br	CF₃	OCH₂CF₃	Br	CF₃	OCH₂CF₃	Br	CF₃	OCH₂CF₃	Br
CF₃	OCH₂CF₃	CN	CF₃	OCH₂CF₃	CN	CF₃	OCH₂CF₃	CN	CF₃	OCH₂CF₃	CN

V is N

TABLE 26

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R⁴	R⁵	R⁶	R⁴	R⁵	R⁶	R⁴	R⁵	R⁶	R⁴	R⁵	R⁶

V is CH

V is N

TABLE 27

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R⁴	R⁵	R⁶	R⁴	R⁵	R⁶	R⁴	R⁵	R⁶	R⁴	R⁵	R⁶

V is CH

V is N

TABLE 28

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R⁴	R⁵	R⁶	R⁴	R⁵	R⁶	R⁴	R⁵	R⁶	R⁴	R⁵	R⁶

V is CH

V is N

TABLE 29

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R⁵	R⁶	R⁵	R⁶	R⁵	R⁶	R⁵	R⁶

R4 is CHF₂

Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN
Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN
Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	QCH2CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN
Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN

R⁴is CH₃

Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN
Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN
Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN
Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	ON	CF₃	ON	CF₃	ON
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN

R4 is CF₃

Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN
Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN
Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN
Br	Cl	Br	Cl	Br	Cl	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br
Br	CN	Br	CN	Br	CN	Br	CN
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Br	Cl	Br	Cl	Br	Cl	Br
Cl	CN	Cl	CN	Cl	CN	Cl	CN
CF₃	Cl	CF₃	Cl	CF₃	Cl	CF₃	Cl
CF₃	Br	CF₃	Br	CF₃	Br	CF₃	Br
CF₃	CN	CF₃	CN	CF₃	CN	CF₃	CN
OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl	OCH₂CF₃	Cl
OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br	OCH₂CF₃	Br
OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN	OCH₂CF₃	CN

R⁴is CH₂CF₃

TABLE 30

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	R^4b	R⁶

R^5bis Cl

R5 is OCF₃

R⁵is CF₃

CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl
CH₃	H	Br	CH₃	H	Br	CH₃	H	Br	CH₃	H	Br
CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl
CH₃	I	Br	CH₃	I	Br	CH₃	I	Br	CH₃	I	Br
CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl
CH₃	F	Br	CH₃	F	Br	CH₃	F	Br	CH₃	F	Br
CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl
CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br
CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br.	Cl	CH₃	Br	Cl
CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br
CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl
CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br
Cl	H	Cl	Cl	H	Cl	Cl	H	Cl	Cl	H	Cl
Cl	H	Br	Cl	H	Br	Cl	H	Br	Cl	H	Br
Cl	I	Cl	Cl	I	Cl	Cl	I	Cl	Cl	I	Cl
Cl	I	Br	Cl	I	Br	Cl	I	Br	Cl	I	Br
Cl	F	Cl	Cl	F	Cl	Cl	F	Cl	Cl	F	Cl
Cl	F	Br	Cl	F	Br	Cl	F	Br	Cl	F	Br
Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl
Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br
Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl
Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br
Br	H	Cl	Br	H	Cl	Br	H	Cl	Br	H	Cl
Br	H	Br	Br	H	Br	Br	H	Br	Br	H	Br
Br	I	Cl	Br	I	Cl	Br	I	Cl	Br	I	Cl
Br	I	Br	Br	I	Br	Br	I	Br	Br	I	Br
Br	F	Cl	Br	F	Cl	Br	F	Cl	Br	F	Cl
Br	F	Br	Br	F	Br	Br	F	Br	Br	F	Br
Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl
Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br
Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br
Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl
Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br

R^5bis CF(CF₃)₂

CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl
CH₃	H	Br	CH₃	H	Br	CH₃	H	Br	CH₃	H	Br
CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl
CH₃	I	Br	CH₃	I	Br	CH₃	I	Br	CH₃	I	Br
CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl
CH₃	F	Br	CH₃	F	Br	CH₃	F	Br	CH₃	F	Br
CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl
CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br
CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl
CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br
CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl
CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br
Cl	H	Cl	Cl	H	Cl	Cl	H	Cl	Cl	H	Cl
Cl	H	Br	Cl	H	Br	Cl	H	Br	Cl	H	Br
Cl	I	Cl	Cl	I	Cl	Cl	I	Cl	Cl	I	Cl
Cl	I	Br	Cl	I	Br	Cl	I	Br	Cl	I	Br
Cl	F	Cl	Cl	F	Cl	Cl	F	Cl	Cl	F	Cl
Cl	F	Br	Cl	F	Br	Cl	F	Br	Cl	F	Br
Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl
Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br
Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl
Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br
Br	H	Cl	Br	H	Cl	Br	H	Cl	Br	H	Cl
Br	H	Br	Br	H	Br	Br	H	Br	Br	H	Br
Br	I	Cl	Br	1	Cl	Br	I	Cl	Br	1	Cl
Br	I	Br	Br	I	Br	Br	I	Br	Br	I	Br
Br	F	Cl	Br	F	Cl	Br	F	Cl	Br	F	Cl
Br	F	Br	Br	F	Br	Br	F	Br	Br	F	Br
Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl
Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br
Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br
Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl
Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br

TABLE 31

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R^4a	4^4b	R⁶	R^4a	4^4b	R⁶	R^4a	4^4b	R⁶	R^4a	4^4b	R⁶

R^5bis CHF₂

R^5bis CH₂CF₃

R^5bis CF₃

CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl
CH₃	H	Br	CH₃	H	Br	CH₃	H	Br	CH₃	H	Br
CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl
CH₃	I	Br	CH₃	1	Br	CH₃	I	Br	CH₃	I	Br
CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl
CH₃	F	Br	CH₃	F	Br	CH₃	F	Br	CH₃	F	Br
CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl
CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br
CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl
CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br
CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl
CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br
Cl	H	Cl	Cl	H	Cl	Cl	H	Cl	Cl	H	Cl
Cl	H	Br	Cl	H	Br	Cl	H	Br	Cl	H	Br
Cl	I	Cl	Cl	I	Cl	Cl	I	Cl	Cl	I	Cl
Cl	I	Br	Cl	I	Br	Cl	I	Br	Cl	I	Br
Cl	F	Cl	Cl	F	Cl	Cl	F	Cl	Cl	F	Cl
Cl	F	Br	Cl	F	Br	Cl	F	Br	Cl	F	Br
Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl
Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br
Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl
Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br
Br	H	Cl	Br	H	Cl	Br	H	Cl	Br	H	Cl
Br	H	Br	Br	H	Br	Br	H	Br	Br	H	Br
Br	I	Cl	Br	I	Cl	Br	I	Cl	Br	I	Cl
Br	I	Br	Br	I	Br	Br	I	Br	Br	I	Br
Br	F	Cl	Br	F	Cl	Br	F	Cl	Br	F	Cl
Br	F	Br	Br	F	Br	Br	F	Br	Br	F	Br
Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl
Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br
Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br
Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl
Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br

R^5bis CF₂CHF₂

TABLE 32

R²is H, R³is Me

R²is H, R³is Et

R²is H, R³is i-Pr

R²is Me, R³is Me

R^4a	R^4b	R⁶	R^4a	R^4b	R⁶	R^4a	4^4b	R⁶	R^4a	4^4b	R⁶

R^5bis CHF₂

R^5bis CH₂CF₃

CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl	CH₃	H	Cl
CH₃	H	Br	CH₃	H	Br	CH₃	H	Br	CH₃	H	Br
CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl	CH₃	I	Cl
CH₃	I	Br	CH₃	I	Br	CH₃	I	Br	CH₃	I	Br
CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl	CH₃	F	Cl
CH₃	F	Br	CH₃	F	Br	CH₃	F	Br	CH₃	F	Br
CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl	CH₃	CF₃	Cl
CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br	CH₃	CF₃	Br
CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl	CH₃	Br	Cl
CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br	CH₃	Br	Br
CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl	CH₃	Cl	Cl
CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br	CH₃	Cl	Br
Cl	H	Cl	Cl	H	Cl	Cl	H	Cl	Cl	H	Cl
Cl	H	Br	Cl	H	Br	Cl	H	Br	Cl	H	Br
Cl	I	Cl	Cl	I	Cl	Cl	I	Cl	Cl	I	Cl
Cl	I	Br	Cl	I	Br	Cl	I	Br	Cl	I	Br
Cl	F	Cl	Cl	F	Cl	Cl	F	Cl	Cl	F	Cl
Cl	F	Br	Cl	F	Br	Cl	F	Br	Cl	F	Br
Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl	Cl	CF₃	Cl
Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br	Cl	CF₃	Br
Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl
Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br
Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl	Cl
Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br
Br	H	Cl	Br	H	Cl	Br	H	Cl	Br	H	Cl
Br	H	Br	Br	H	Br	Br	H	Br	Br	H	Br
Br	I	Cl	Br	I	Cl	Br	I	Cl	Br	I	Cl
Br	1	Br	Br	I	Br	Br	I	Br	Br	I	Br
Br	F	Cl	Br	F	Cl	Br	F	Cl	Br	F	Cl
Br	F	Br	Br	F	Br	Br	F	Br	Br	F	Br
Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl	Br	CF₃	Cl
Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br	Br	CF₃	Br
Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl
Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br	Br
Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl	Br	Cl	Cl
Br	Cl	Br	Br	Cl	Br	Br	Cl	Br	Br	Cl	Br

R^5bis CF₃

R^5bis CF₂CHF₂

Formulation/Utility [0315]
Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible (“wettable”) or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation. [0316]

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



	Weight Percent

Active
Ingre-		Surfac-
dient	Diluent	tant

Water-Dispersible and Water-	5-90	0-94	1-15
soluble Granules, Tablets
and Powders.
Suspensions, Emulsions,	5-50	40-95	0-15
Solutions (including
Emulsifiable Concentrates)
Dusts	1-25	70-99	0-5
Granules and Pellets	0.01-99	5-99.99	0-15
High Strength Compositions	90-99	0-10	0-2

Typical solid diluents are described in Watkins, et al., [0318] Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, N.J. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, N.J., as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montinorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol. [0319]
Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. Pat. No. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, “Agglomeration”, [0320] Chemical Engineering, Dec. 4, 197, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and PCT Publication WO 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701 and U.S. Pat. No. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.
For further information regarding the art of formulation, see T. S. Woods, “The Formulator's Toolbox —Product Forms for Modern Agriculture” in [0321] 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 Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 1041; U.S. Pat. No. 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. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Table A. [0322]

Example A

[0323]

Wettable Powder

Compound 1 65.0%

dodecylphenol polyethylene glycol ether 2.0%

sodium ligninsulfonate 4.0%

sodium silicoaluminate 6.0%

montmorillonite (calcined) 23.0%.

Example B

[0324]

Granule

Compound 1 10.0%

attapulgite granules (low volatile matter, 90.0%.

0.71/0.30 mm; U.S.S. No. 25-50 sieves)

Example C

[0325]

Extruded Pellet

Compound 1 25.0%

anhydrous sodium sulfate 10.0%

crude calcium ligninsulfonate 5.0%

sodium alkylnaphthalenesulfonate 1.0%

calcium/magnesium bentonite 59.0%.

Example D

[0326]

Emulsifiable Concentrate

Compound 1 20.0%

blend of oil soluble sulfonates 10.0%

and polyoxyethylene ethers

isophorone 70.0%.

Example E

[0327]

Granule

Compound 1 0.5%

cellulose 2.5%

lactose 4.0%

cornmeal 93.0%.
Compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and nonagronomic invertebrate pests. (In the context of this disclosure “invertebrate pest control” means inhibition of invertebrate pest development (including mortality) that causes significant reduction in feeding or other injury or damage caused by the pest; related expressions are defined analogously.) As referred to in this disclosure, the term “invertebrate pest” includes arthropods, gastropods and nematodes of economic 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 all of the helminths, such as: roundworrns, heartworms, and phytophagous nematodes (Nematoda), flukes (Tematoda), Acanthocephala, and tapeworms (Cestoda). Those skilled in the art will recognize that not all compounds are equally effective against all pests. Compounds of this invention display activity against economically important agronomic and nonagronomic pests. The term “agronomic” refers to the production of field crops such as for food and fiber and includes the growth of cereal crops (e.g., wheat, oats, barley, rye, rice, maize), soybeans, vegetable crops (e.g., lettuce, cabbage, tomatoes, beans), potatoes, sweet potatoes, grapes, cotton, and tree fruits (e.g., pome fruits, stone fruits and citrus fruits). The term “nonagronomic” refers to other horticultural (e.g., forest, greenhouse, nursery or ornamental plants not grown in a field), public (human) and animal health, domestic and commercial structure, household, and stored product applications or pests. For reason of invertebrate pest control spectrum and economic importance, protection (from damage or injury caused by invertebrate pests) of agronomic crops of cotton, maize, soybeans, rice, vegetable crops, potato, sweet potato, grapes and tree fruit by controlling invertebrate pests are preferred embodiments of the invention. Agronomic or nonagronomic pests include larvae of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., fall armyworm ([0328] Spodoptera fugiperda J. E. Smith), beet armyworm (Spodoptera exigua Hübner), black cutworm (Agrotis ipsilon Hufnagel), 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 webworm (Herpetogramma licarsisalis Walker)); 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)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus)); nymphs 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 (Supelta longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)); foliar 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)); 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 Scaribaeidae (e.g., Japanese beetle (Popillia japonica Newman) 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 agronomic and nonagronomic pests include: 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)); 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, planthoppers from the families Fulgoroidae and Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera 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, cinch bugs (e.g., Blissus spp.) 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. Also included are adults and larvae of the 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 mcdanieli McGregor)), flat mites in the family Tenuipalpidae (e.g., citrus flat 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 order Ixodidae (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 scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; 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), house cricket (Acheta domesticus Linnaeus), mole crickets (Gryllotalpa spp.)); adults and immatures of the order Diptera including leafminers, 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., Gastrophilus spp., Oestrus spp.), cattle grubs (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; adults and immatures of the order Thysanoptera including onion thrips (Thrips tabaci Lindeman) and other foliar feeding thrips; insect pests of the order Hymenoptera including ants (e.g., red carpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), 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 Förster), odorous house ant (Tapinoma sessile Say)), bees (including carpenter bees), hornets, yellow jackets and wasps; insect pests of the order Isoptera including 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) and other termites of economic 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 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 animals; insect pests of the order Siphonoptera including the oriental rat flea (Xenopsylla cheopis Rothschild), 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). Compounds of the present invention also have 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, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e. all economically important flukes, tapeworms, and roundworms, such as Strongvlus 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 show particularly high activity against pests in the order Lepidoptera (e.g., [0329] 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 Guenee (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), 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 also have commercially significant activity on members from the order Homoptera including: Acyrthisiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphisfabae 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), Macrosipum 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); Phylloxera devastatrix Pergande (pecan phylloxera); 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 Stal (rice leafhopper), Nilaparvata lugens Stal (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 Jose scale); Planococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla). These compounds also have activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp. (complex of seed bugs), 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 thrip), Scirthothrips citri Moulton (citrus thrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaci Lindeman (onion thrip); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius).
Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators such as 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 agricultural utility. Thus compositions of the present invention can further comprise a biologically effective amount of at least one additional biologically active compound or agent. Examples of such biologically active compounds or agents with which compounds of this invention can be formulated are: insecticides such as abarnectin, acephate, acetamiprid, avermectin, azadirachtin, azinphos-methyl, bifenthrin, binfenazate, buprofezin, carbofuran, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothicarb, fenoxycarb, fenpropathrin, fenproximate, fenvalerate, fipronil, flonicamid, flucythrinate, tau-fluvalinate, flufenoxuron, fonophos, halofenozide, hexaflumuron, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, methoxyfenozide, nithiazin, novaluron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, pymetrozine, pyridalyl, pyriproxyfen, rotenone, spinosad, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, trichlorfon and triflumuron; fungicides such as acibenzolar, azoxystrobin, benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cyflufenarnid, cymoxanil, cyproconazole, cyprodinil, (S)-3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide (RH 7281), diclocymet (S-2900), diclomezine, dicloran, difenoconazole, (S)-3,5-dihydro-5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one (RP 407213), dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dodine, edifenphos, epoxiconazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramid (SZX0722), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, fluazinam, fludioxonil, flumetover (RPA 403397), fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, furametapyr (S-82658), hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mepronil, metalaxyl, metconazole, metominostrobin/fenominostrobin (SSF-126), myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propamocarb, propiconazole, pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon, quinoxyfen, spiroxamine, sulfur, tebuconazole, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, triadimefon, triadimenol, tricyclazole, trifloxystrobin, triticonazole, validamycin and vinclozolin; nematocides such as aldicarb, oxamyl and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as [0330] Bacillus thuringiensis including ssp. aizawai and kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi. Compounds of this invention and compositions thereof may be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin). The effect of the exogenous invertebrate pest control compounds and compositions may be synergistic with the expressed toxin proteins.
A general reference for these agricultural protectants is The Pesticide Manual, 12th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Fanham, Surrey, U.K., 2000. [0331]
Preferred insecticides and acaricides for mixing with compounds of this invention include pyrethroids such as cypermethrin, cyhalothrin, cyfluthrin, beta-cyfluthrin, esfenvalerate, fenvalerate and tralomethrin; carbamates such as fenothicarb, methomyl, oxamyl and thiodicarb; neonicotinoids such as clothianidin, imidacloprid and thiacloprid; neuronal sodium channel blockers such as indoxacarb; insecticidal macrocyclic lactones such as spinosad, abamectin, avermectin and emamectin; γ-aminobutyric acid (GABA) antagonists such as endosulfan, ethiprole and fipronil; insecticidal ureas such as flufenoxuron and triflumuron; juvenile hormone mimics such as diofenolan and pyriproxyfen; pymetrozine; and amitraz. Preferred biological agents for mixing with compounds of this invention include [0332] Bacillus thuringiensis and Bacillus thuringiensis delta endotoxin as well as naturally occurring and genetically modified viral insecticides including members of the family Baculoviridae as well as entomophagous fungi.
Most preferred mixtures include a mixture of a compound of this invention with cyhalothrin; a mixture of a compound of this invention with beta-cyfluthrin; a mixture of a compound of this invention with esfenvalerate; a mixture of a compound of this invention with methomyl; a mixture of a compound of this invention with imidacloprid; a mixture of a compound of this invention with thiacloprid; a mixture of a compound of this invention with indoxacarb; a mixture of a compound of this invention with abamectin; a mixture of a compound of this invention with endosulfan; a mixture of a compound of this invention with ethiprole; a mixture of a compound of this invention with fipronil; a mixture of a compound of this invention with flufenoxuron; a mixture of a compound of this invention with pyriproxyfen; a mixture of a compound of this invention with pymetrozine; a mixture of a compound of this invention with amitraz; a mixture of a compound of this invention with [0333] Bacillus thuringiensis and a mixture of a compound of this invention with Bacillus thuringiensis delta endotoxin.
In certain instances, combinations with other invertebrate pest control compounds or agents having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management. Thus, compositions of the present invention can further comprise a biologically effective amount of at least one additional invertebrate pest control compound or agent having a similar spectrum of control but a different mode of action. Contacting a plant genetically modified to express a plant protection compound (e.g., protein) or the locus of the plant with a biologically effective amount of a compound of invention can also provide a broader spectrum of plant protection and be advantageous for resistance management. [0334]
Invertebrate pests are controlled in agronomic and nonagronomic applications by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus, the present invention further comprises a method for the control of invertebrates in agronomic and/or nonagronomic applications, comprising contacting the invertebrates or their 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 an effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a compound of the invention and an effective amount of at least one additional biologically active compound or agent include granular compositions wherein the additional biologically active compound is present on the same granule as the compound of the invention or on granules separate from those of the compound of this invention. [0335]
A preferred 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 are also 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. Compounds are also effective by topical application of a composition comprising a compound of this invention 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, eartags, boluses, foggers, fumigants, aerosols, dusts and many others. The compounds of this invention may also be impregnated into materials for fabricating invertebrate control devices (e.g. insect netting). [0336]
The compounds of this invention can be incorporated into baits that are consumed by the invertebrates or within devices such as traps and the like. Granules or baits comprising between 0.01-5% active ingredient, 0.05-10% moisture retaining agent(s) and 40-99% vegetable flour are effective in controlling soil insects at very low application rates, particularly at doses of active ingredient that are lethal by ingestion rather than by direct contact. [0337]
The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy. [0338]
The rate of application required for effective control (i.e. “biologically effective amount”) will depend on such factors as the species of invertebrate to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg/hectare may be sufficient or as much as 8 kg/hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required. One Skilled in the art can easily determine the biologically effective amount necessary for the desired level of invertebrate pest control. [0339]

The following TESTS demonstrates the control efficacy of compounds of this invention on specific 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 through K and L for compound descriptions. The following abbreviations are used in the Index Tables which follow: t is tertiary, n is normal, i is iso, c is cyclo, s is secondary, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, c-Pr is cyclopropyl, Bu is butyl, s-Bu is secondary butyl, Pent is pentyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is ethylthio, CN is cyano, and NO ₂is nitro. The abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared.

INDEX TABLE A

Compound	R²	R³	(R⁴)_n	J	m.p. ° C.

1 (Ex. 3)	H	i-Pr	4-Me	4-CF₃-Ph	*
2	H	t-Bu	4-Me	4-CF₃-Ph	*
3	H	i-Pr	4-Me	4-OCF₃-Ph	*
4	H	i-Pr	4-Me	2-Me,4-SCHF₂-Ph	*
5	H	t-Bu	4-Me	2-Me,4-SCHF₂-Ph	*
6	H	t-Bu	4-Me	4-OCF₃-Ph	*
7	H	i-Pr	4-Me	2-Me,4-SO₂CHF₂-Ph	*
8	H	i-Pr	4-Me	2-Me,4-SOCF₃-Ph	*
9	H	t-Bu	4-Me	2-Me,4-SO₂CHF₂-Ph	*
10	H	t-Bu	4-Me	2-Me,4-SOCHF₂-Ph	*
11	H	i-Pr	4-Me	4-SCHF₂-Ph	*
12	H	t-Bu	4-Me	4-SCHF₂-Ph	*
13	H	i-Pr	4-Me	2-Me,4-CF₃-Ph	*
14	H	i-Pr	4-Me	2-Me,4-OCF₃-Ph	*
15	H	t-Bu	4-Me	2-Me,4-CF₃-Ph	*
16	H	t-Bu	4-Me	2-Me,4-OCF₃-Ph	*
17	H	i-Pr	4-Me	2-Me,4-Cl-Ph	222.5-225
18	H	t-Bu	4-Me	2-Me,4-Cl-Ph	214-215
19	H	i-Pr	4-Me	2-Me-6-CF₃-3-pyridinyl	*
20	H	t-Bu	4-Me	2-Me-6-CF₃-3-pyridinyl	*
21	H	i-Pr	4-Me	1-Ph-3-Me-5-pyrazolyl	*
22	H	t-Bu	4-Me	1-Ph-3-Me-5-pyrazolyl	*
23	H	i-Pr	4-Me	2-Me-6-Cl-3-pyridinyl	*
24	H	t-Bu	4-Me	2-Me-6-Cl-3-pyridinyl	*
25	H	CH₂CH₂NMe₂	4,5-Me₂	Ph

26

—CH₂CH₂CH₂CH₂—

H

Ph

27	H	c-hexyl	H	Ph
28	H	c-propyl	H	Ph
29	H	H	4-t-Bu-Ph	3,5-Cl₂-Ph
30	H	Me	4-Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	214-215
31	H	i-Pr	4-Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	159-161
32	H	i-Pr	4-Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	198-202
33	H	Me	4-Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	188-190
34	H	i-Pr	4-Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	170-174
35	H	Me	4-Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	201-203
36	H	Me	4,5-Cl₂	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	238-240
37	H	i-Pr	4,5-Cl₂	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	240
38	H	i-Pr	4,5-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	208-210
39	H	Me	4,5-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	208
40	H	i-Pr	4-Me-S-Cl	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	234-236
41	H	Me	4-Me-S-Cl	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	229-231
42	H	i-Pr	4-Me-S-Cl	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	222-223
43	H	Me	4-Me-S-Cl	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	226-228

INDEX TABLE B

Com-
pound	R³	J	m.p. ° C.

B1	i-Pr	2-Me,4-SCHF₂-Ph	178.5-180.5
B2	i-Pr	2-Me,4-SO₂CHF₂-Ph	207-210
B3	i-Pr	2-Me,4-SOCF₃-Ph	175-180
B4	i-Pr	2-Me,4-CF₃-Ph	201-203
B5	i-Pr	2-Me-6-CF₃-3-pyridinyl	221.5-222.5
B6	i-Pr	1-Ph-3-Me-5-pyrazolyl	*
B7	t-Bu	1-Ph-3-Me-5-pyrazolyl	*
B8	t-Bu	2-Me-6-CF₃-3-pyridinyl	*
B9	i-Pr	2-Me-5-Cl-3-thienyl	*
B10	Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	266-270
B11	i-Pr	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	232-236
B12	Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	233-236
B13	i-Pr	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	220-222
B14	Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	235-238
B15	i-Pr	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	198-200

INDEX TABLE C

Compound	R²	R³	R⁴	J	m.p. ° C.

C1	H	i-Pr	Me	4-F-Ph	*
C2	H	i-Pr	Me	4-Br-Ph	*
C3	H	i-Pr	Me	4-Cl-Pb	*
C4	H	i-Pr	Me	2-NO₂-Ph	*
C5	H	i-Pr	Me	3-Cl-Ph	*
C6	H	i-Pr	Me	4-CN-Ph	*
C7	H	i-Pr	Me	4-CF₃-Ph	*
C8	H	i-Pr	Me	2-Me-4-SOCF₃-Ph	*
C9 Ex. 2)	H	i-Pr	Me	4-OCF₃-Ph	68-75
C10	H	i-Pr	Me	2-Me-4-Br-Ph	*
C11	Pr	Pr	Ph	3-F-Ph

C12	—(CH₂)₅—	Ph	2-thienyl
C13	—(CH₂)₂NMe(CH₂)₂—	Ph	4-NO₂-Ph

C14	H	i-Pr	Me	3-pyridinyl
C15	H	c-hexyl	Ph	2-thienyl
C16	allyl	allyl	Ph	2-Me-Ph
C17	Et	Et	Pb	Ph
C18	H	allyl	Ph	Ph
C19	H	(CH₂)₂Ph	Ph	Ph
C20	Me	Me	Ph	4-Me-Ph

C21	—(CH₂)₂NMe(CH₂)₂—	Ph	4-Br-Ph
C22	—(CH₂)₂O(CH₂)₂—	Ph	Ph

C23	H	Et	Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	253-255
C24	H	i-Pr	Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	214-216
C25	H	Me	Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	230-232
C26	H	Me	Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	234-236
C27	H	i-Pr	Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	218-220
C28	H	i-Pr	Me	1-(2-Cl-Ph)-3-Br-5-pyrazolyl	170-173
C29	H	CH₂-2-furanyl	Ph	3-Me-Ph
C30	H	Et	CH₂CF₃	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	236-238
C31	H	i-Pr	CH₂CF₃	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	216-218
C32	H	Me	Et	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	238-240
C33	H	Et	Et	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	216-218
C34	H	i-Pr	Et	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	198-201
C35	H	Me	CH₂CF₃	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	260-262
C36	H	Me	CH₂CF₃	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	253-256
C37	H	Et	CH₂CF₃	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	220-223
C38	H	i-Pr	CH₂CF₃	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	188-190
C39	H	Me	Et	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	221-223
C40	H	Et	Et	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	182-184
C41	H	i-Pr	Et	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	172-175

C42	—(CH₂)₆—	Ph	4-Br-Ph
C43	—(CH₂)₄—	Ph	4-Me-Ph
C44	—(CH₂)₅—	Ph	3-F-Ph
C45	—(CH₂)₄—	Ph	3-F-Ph

C46	H	CH₂Ph	Ph	2-F-Ph
C47	H	CH₂-2-furanyl	Ph	3-F-Ph

C48	—(CH₂)₆—	Ph	4-Me-Ph
C49	—(CH₂)₂O(CH₂)₂—	Ph	2-Me-Ph

INDEX TABLE D

Compound	R²	R³	R⁴	J	m.p. ° C.

D1	H	i-Pr	2-Me	4-CF₃-Ph	223-225
D2	H	i-Bu	2-Me	4-CF₃-Ph	260-261
D3 (Ex. 1)	H	i-Pr	2-Me	4-OCF₃-Ph	202-204
D4	H	i-Pr	2-Me	2-Me,4-CF₃-Ph	235-236
D5	H	i-Pr	2-Me	2-Me,4-OCF₃-Ph	198-200
D6	H	i-Pr	2-Me	2-Me-6-CF₃-3-pyridinyl	240-243
D7	H	i-Pr	2-Me	1-Ph-3-CF₃-5-pyrazolyl	215-220 (dec.)
D8	H	i-Pr	2-Me	I-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	140-144
D9	H	i-Pr	2-Me	2-Me-3-Cl-Ph	260-261
D10	H	i-Pr	2-Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	207-209*
D11	Me	Me	2-Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	172-175
D12	H	Me	2-Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	193-195
D13	H	i-Pr	2-Cl	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	175-179
D14	H	i-Pr	2-Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	156-158
D15	H	i-Pr	2-Cl	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	160-165
D16	H	Me	2-Cl	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	178-180
D17	H	Me	2-Cl	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	118-125
D18	H	Me	2-Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	207-209
D19	H	Me	2-Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	216-218
D20	H	allyl	Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	187
D21	H	allyl	Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	199-201

INDEX TABLE E

Compound	R²	R³	(R⁴)_n	J	m.p. ° C.

E1	H	i-Pr	H	4-CF₃-Ph	*
E2	H	i-Pr	H	4-OCF₃-Ph	*
E3	H	i-Pr	2-Cl	4-CF₃-Ph	*
E4	H	i-Pr	H	2-Me,3-Cl-Ph	*
E5	H	i-Pr	2-Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	138-140
E6	H	i-Pr	2-Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	170-173
E7	H	i-Pr	2-Me	1-(2-Cl-Ph)-3-Br-5-pyrazolyl	*
E8	H	i-Pr	2-Me	1-(2-Cl-3-pyridinyl)-3-CN-5-pyrazolyl	*
E9	H	i-Pr	2-Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	112-115
E10	H	Et	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	147-150
E11	H	Me	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	223-224
E12	H	i-Pr	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	142-145
E13	H	Me	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	238-240
E14	H	Et	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	207-209
E15 (Ex. 5)	H	i-Pr	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	240-242
E16	Me	Me	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	153-155
E17	Me	Me	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl	224-226
E18	Me	Me	2,6-Br₂	2,6-Br₂-3-NH₂-4-pyridinyl	208-210
E19	H	Et	2,6-Br₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	223-225
E20	H	i-Pr	2,6-Br₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	>240
E21	Et	Et	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	231-233
E22	H	i-Pr	2-Cl-6-Br	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	224-226
E23	H	NMe₂	2,6-Br₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl	*
E24	H	H	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	*
E25	H	NMe₂	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	*
E26	Me	Me	2-Cl-6-NMe₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	*
E27	H	Me	2,6-Br₂	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	*
E28	H	Et	2,6-Br₂	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	*
E29	H	Me	2,6-Br₂	1-(2-Cl-3-pyrzdinyl)-3-CF₃-5-pyrazolyl	*
E30	H	Et	2,6-Br₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl	*
E31	H	Me	2,6-Br₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl	*
E32	H	i-Pr	2,6-Br₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl	*
E33	H	NMe₂	2,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	*
E34	H	i-Pr	2,6-Br₂	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	*
E35	H	NMe₂	2,6-Cl₂	2,6-Cl₂-3-NH₂-4-pyridinyl	*
E36	Et	Et	2,6-Cl₂	2,6-Cl₂-3-NH₂-4-pyridinyl	*

INDEX TABLE F

Compound	R³	(R⁴)_n	J	m.p. ° C.

F1	i-Pr	H	4-CF₃-Ph
F2	t-Bu	H	4-CF₃-Ph	199-200
F3	i-Pr	6-Me	4-CF₃-Ph	218-220
F4	i-Pr	4,6-Me₂	4-CF₃-Ph	235-237
F5	i-Pr	6-Me	2-Me-4-Cl-Ph	172-174
F6	t-Bu	H	2-Me-3-Cl-Ph	218-220
F7	i-Pr	H	2-Me-3-Cl-Ph

INDEX TABLE G

Compound	R²	R³	(R⁴)_n	J	m.p. ° C.

G1	H	i-Pr	4-Me	4-CF₃-Ph	121-123*
G2	H	i-Pr	4-Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	183-184
G3	H	S—CH(Ph)Me	H	3-pyridinyl
G4	H	i-Pr	4-Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	172-175
G5	H	i-Pr	4-Me	1-(2-Cl-3-Ph)-3-Br-5-pyrazolyl
G6	H	i-Pr	4-Me-6-Cl	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	175-177
G7	H	Me	4-Me-6-Cl	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	230-235
G8	Me	Me	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	225-227
G9	H	NMe₂	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	125-130
G10	H	H	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	130-135
G11	H	Me	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	214-216
G12	H	Et	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	210-212
G13	H	i-Pr	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	208-210
G14	H	NMe₂	4,6-Cl₂	4,6-Cl₂-3-NH₂-2-pyridinyl	192-194
G15	Me	Me	4,6-Cl₂	4,6-Cl₂-3-NH₂-2-pyridinyl	171-172
G16	H	H	4,6-Br₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl	>240
G17	H	Me	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl
G18	H	Et	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl
G19	H	i-Pr	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl
G20	H	H	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl
G21	Et	Et	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl
G22	H	Me	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl
G23	H	Et	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl
G24	H	i-Pr	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl
G25	H	NMe₂	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl
G26	Me	Me	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl
G27	Me	Me	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl
G28	H	H	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl
G29	H	NMe₂	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl
G30	Et	Et	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl
G31	H	Me	4,5,6-Cl₃	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazalyl
G32	H	Et	4,5,6-Cl₃	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl
G33	H	CH₂CH₂SMe	4,6-Cl₂	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl

[0347]

INDEX TABLE H

Compound J m.p. ° C.

H1 2-Me-4-Br-Ph *

INDEX TABLE I

Compound	R²	R³	(R⁴)_n	J	m.p. ° C.

I1	Me	Me	4,6-Me₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	244-245*
I2	H	i-Pr	4,6-Me₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl
I3	H	Me	4,6-Me₂	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	195-197
I4	Me	Me	4,6-Me₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	243-244
I5	H	Me	4,6-Me₂	1-(2-Cl-3-pyridiny1)-3-Br-5-pyrazolyl	202-204
I6 (Ex. 4)	Me	Me	4-Me	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl	232-236
I7	H	i-Pr	4-Me	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl	87-90
I8	H	i-Pr	4,6-Me₂	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	81-83
I9	H	Me	4-Me	1-(2-Cl-3-pyridinyl)-3-Cl-5-pyrazolyl	205-207

INDEX TABLE J

Compound	R²	R³	R⁴	J	m.p. ° C.

J1	H	i-Pr	Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	174-176*
J2	H	i-Pr	Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	206-208
J3	H	Me	Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	166-168
J4	H	Me	Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	176-178
J5	H	Me	Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	227-229
J8	H	i-Pr	Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	172-174

INDEX TABLE K

Compound	R²	R³	R⁴	J	m.p. ° C.

K1	H	Me	Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	224-226*
K2	H	i-Pr	Me	1-(2-Cl-3-pyridinyl)-3-Br-5-pyrazolyl	168-172
K3	H	Me	Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	185-190
K4	H	i-Pr	Me	1-(2-Cl-Ph)-3-CF₃-5-pyrazolyl	160-162
K5	H	Me	Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	176-179
K6	H	i-Pr	Me	1-(2-Cl-3-pyridinyl)-3-CF₃-5-pyrazolyl	180-182

INDEX TABLE L

		¹H NMR Partial Spectrum Data (CDCl₃
	Compd. No.	solution unless indicated otherwise)^a

	1	10.63 (s, 1H), 5.58 (d, 1H)
	2	10.55 (s, 1H), 5.60 (s, 1H)
	3	10.55 (s, 1H), 5.58 (d, 1H)
	4	9.80 (s, 1H), 5.60 (d, 1H)
	5	9.68 (s, 1H), 5.60 (s, 1H)
	6	10.45 (s, 1H), 5.60 (d, 1H)
	7	9.93 (s, 1H), 5.60 (d, 1H)
	8	9.90 (s, 1H), 5.59 (d, 1H)
	9	9.83 (s, 1H), 5.60 (s, 1H)
	10	9.78 (s, 1H), 5.60 (s, 1H)
	11	10.57 (s, 1H), 5.58 (d, 1H)
	12	10.46 (s, 1H), 5.60 (s, 1H)
	13	9.85 (s, 1H), 5.60 (d, 1H)
	14	9.82 (s, 1H), 5.58 (d, 1H)
	15	9.76 (s, 1H), 5.62 (s, 1H)
	16	9.68 (s, 1H), 5.60 (s, 1H)
	C1	10.19 (s, 1H), 5.72 (d, 1H)
	C2	10.23 (s, 1H), 5.71 (d, 1H)
	C3	10.23 (s, 1H), 5.66 (s, 1H)
	C4	9.50 (s, 1H), 5.62 (d, 1H)
	C5	10.18 (s, 1H), 5.67 (s, 1H)
	C6	10.41 (s, 1H), 5.62 (s, 1H)
	C7	10.36 (s, 1H), 5.66 (s, 1H)
	C8	9.56 (s, 1H), 5.54 (d, 1H)
	C10	9.56 (s, 1H), 5.53 (d, 1H)
	D10	12.2 (brs, 1H), 6.0 (s, 1H)
	E1	10.10 (s, 1H), 6.24 (s, 1H)
	E2	10.08 (s, 1H), 6.30 (s, 1H)
	E3	8.36 (m, 3H), 7.94 (d, 1H), 7.79 (d, 2H),
		4.36 (m, 1H), 1.32 (d, 6H)
	E4	10.05, 1H), 6.16 (d, 1H)
	E7	7.75 (d, 1H), 7.67 (s, 1H)
	E8	8.23 (s, 1H), 7.77 (d, 1H)
	E23	(DMSO-d₆) 10.8 (m, 1H), 9.5 (s, 1H)
	E24	(DMSO-d₆) 10.5 (s, 1H)
	E25	(DMSO-d₆) 10.9 (s, 1H)
	E26	(DMSO-d₆) 13.4 (brs, 1H)
	E27	9.0 (s, 1H), 6.2 (m, 1H)
	E28	9.25 (s, 1H), 6.18 (m, 1H)
	E29	(DMSO-d₆) 10.9 (s, 1H), 8.55 (m, 1H)
	E30	9.3 (s, 1H), 6.25 (t, 1H)
	E31	(DMSO-d₆) 10.75 (s, 1H), 8.55 (m, 1H)
	E32	(DMSO-d₆) 13.5 (brs, 1H)
	E33	(DMSO-d₆) 10.9 (m, 1H), 9.6 (s, 1H)
	E34	9.5 (brs, 1H), 6.05 (d, 1H)
	E35	(DMSO-d₆) 10.9 (s, 1H), 6.66 (m, 1H)
	E36	10.3 (s, 1H)
	F1	11.56 (s, 1H), 8.41 (d, 1H)
	G1	11.97 (s, 1H)
	H1	5.56 (d, 1H)

BIOLOGICAL EXAMPLES OF THE INVENTION

Test A

For evaluating control of diamondback moth ([0352] Plutella xylostella) the test unit consisted of a small open container with a 12-14-day-old radish plant inside. This was pre-infested with 10-15 neonate larvae on a piece of insect diet by use of a core sampler to remove a plug from a sheet of hardened insect diet having many larvae growing on it and transfer the plug containing larvae and diet to the test unit. The larvae moved onto the test plant as the diet plug dried out.
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.), unless otherwise indicated. The formulated compounds were applied in 1 mL of liquid through a SUJ2 atomizer nozzle with 1/8 JJ custom body (Spraying Systems Co.) positioned 1.27 cm (0.5 inches) above the top of each test unit. All experimental compounds in these tests were sprayed at 250 ppm and replicated three times. 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. [0353]
Of the compounds tested the following provided very good to excellent levels of plant protection (ratings of 0-1, 10% or less feeding damage): 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 30, 31, 32, 33, 34, 36, 37, 38, B1, B3, B5, B11, B12, B15, C1, C2, C3, C7, C9, C24, D1, D3, D4, D5, D6, D7, D8, D10, D11, D12, D13, D14, D18, D19, D20, D21, E5, E6, E7, E8, E9, E10, E11, E12, E13, E14, E15, E16, E17, E19, E20, E21, E22, G1, G2, G4, G5, G6, G7, G8, G9, G10, G11, G12, G13, J6, K1 and K2. [0354]

Test B

For evaluating control of fall armyworm ([0355] Spodoptera frugiperda) the test unit consisted of a small open container with a 4-5-day-old corn (maize) plant inside. This was pre-infested (using a core sampler) with 10-15-1-day-old larvae on a piece of insect diet.
Test compounds were formulated and sprayed at 250 ppm as described for Test A. The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test A. [0356]
Of the compounds tested, the following provided excellent levels of plant protection (10% or less feeding damage): 30, 31, 32, 33, 34, 35, 36, B10, B11, B12, B13, B14, D1, D3, D7, D8, D10, D11, D14, D15, E5, E6, E7, E9, E10, E11, E12, E13, E22, G2, G4, G5, G6, G7, G9, G10, G11, G12, G13, J6 and K2. [0357]

Test C

For evaluating control of tobacco budworm ([0358] Heliothis virescens) the test unit consisted of a small open container with a 6-7 day old cotton plant inside. This was pre-infested (using a core sampler) with 8-2-day-old larvae on a piece of insect diet.
Test compounds were formulated and sprayed at 250 ppm as described for Test A. The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test A. [0359]
Of the compounds tested, the following provided very good to excellent levels of plant protection (20% or less feeding damage): 31, 32, 33, 34, 35, 36, 37, B12, B13, B14, B15, D1, D4, D5, D6, D8, D10, D11, D12, D13, D14, D15, D18, D19, D20, D21, E5, E6, E7, E9, E0, E12, E15, E20, E21, E22, G2, G5, G6, G7, G8, G9, G10, G1, G12, and G13. [0360]

Test D

For evaluating control of beet armyworm ([0361] Spodoptera exigua) the test unit consisted of a small open container with a 4-5-day-old corn plant inside. This was pre-infested (using a core sampler) with 10-15-1-day-old larvae on a piece of insect diet.
Test compounds were formulated and sprayed at 250 ppm as described for Test A. The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test A. [0362]
Of the compounds tested, the following provided very good to excellent levels of plant protection (20% or less feeding damage): 31, 32, 34, B13, B15, D1, D3, D4, D7, D8, D10, D11, D14, D19, E5, E6, E7, E9, E10, El5, E22, G1, G2, G4, G5, G6, G7, G9, G10, G 1, G12, G13, D20, J6 and K2. [0363]

Test E

For evaluating control of green peach aphid ([0364] Myzus persicae) 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 (using the cut leaf method) with 30-40 insects on each piece of leaf, and the soil was covered with a layer of sand.
Test compounds were formulated and sprayed at 250 ppm as described for Test A. The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually assessed for insect mortality. [0365]
Of the compounds tested, the following resulted in at least 80% mortality: C48, E13, E14, E16, G4, G9, G10, G11 and G13. [0366]

Test F

For evaluating control of cotton melon aphid ([0367] Aphis gossypii) 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 (using the cut leaf method) with 30-40 insects on each piece of leaf, and the soil was covered with a layer of sand.
Test compounds were formulated and sprayed at 250 ppm as described for Test A. The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test E. [0368]
Of the compounds tested, the following resulted in at least 80% mortality: E9. [0369]

Claims

What is claimed is:

1. A compound of Formula I, an N-oxide thereof or suitable salt thereof

wherein

A and B are independently O or S;

each J is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 4 R⁵;

K is, together with the two contiguous linking carbon atoms, a 5- or 6-membered heteroaromatic ring optionally substituted with 1 to 3 R⁴;

n is 1 to 3;

R¹is H; or C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₂-C₄alkoxycarbonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino and C₃-C₆cycloalkylamino; or

R¹is C₂-C₆alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl or C(=A)J;

R²is H, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₄alkoxy, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₂-C₆alkoxycarbonyl or C₂-C₆alkylcarbonyl;

R³is H; G; or C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of G, halogen, CN, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylcarbonyl, C₃-C₆trialkylsilyl, or a phenyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R⁶; or

R²and R³can be taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, and said ring may be optionally substituted with one to four substituents selected from R¹²; and

G is a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(═O), SO or S(O)₂and optionally substituted with one to four substituents selected from R¹²;

each R⁴is independently H, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₁-C₄alkoxyalkyl, C₁-C₄hydroxyalkyl, C(O)R¹⁰, CO₂R¹⁰, C(O)NR¹⁰R¹¹, NR¹⁰R¹¹, N(R¹¹)CO₂R¹⁰; or

each R⁴is independently a phenyl, benzyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R⁶;

each R⁵is independently H, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, CO₂H, CONH₂, NO₂, hydroxy, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₂-C₆alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl, C₃-C₆trialkylsilyl; or

each R⁵is independently a phenyl, benzyl, benzoyl, phenoxy, 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each ring or ring system optionally substituted with one to three substituents independently selected from R⁶; or

(R⁵)₂when attached to adjacent carbon atoms can be taken together as —OCF₂O—, —CF₂CF₂O—, or —OCF₂CF₂O—; and

each R⁶is independently C₁-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C₃-C₆cycloalkyl, C₁-C₄haloalkyl, C₂-C₄haloalkenyl, C₂-C₄haloalkynyl, C₃-C₆halocycloalkyl, halogen, CN, NO₂, C₁-C₄alkoxy, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylamino, C₂-C₈dialkylamino, C₃-C₆cycloalkylamino, C₃-C₆(alkyl)cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, C₃-C₈dialkylaminocarbonyl or C₃-C₆trialkylsilyl;

each R¹⁰is independently H, C_1-4alkyl or C₁-C₄haloalkyl;

each R¹¹is independently H or C₁-C₄alkyl; and

each R¹²is independently C₁-C₂alkyl, halogen, CN, NO₂or C₁-C₂alkoxy.

2. The compound of claim 1 wherein A and B are both 0 and J is a phenyl ring optionally substituted with 1 to 4 R⁵.

3. The compound of claim 2 wherein

each R⁴is independently C₁-C₄alkyl, C₁-C₄haloalkyl, halogen, CN, NO₂or C₁-C₄alkoxy, and one R⁴group is attached to the K ring at the atom adjacent to either the NR¹C(=A)J moiety or the C(═B)NR²R³moiety; and

each R⁵is independently H, halogen, C₁-C₄alkyl, C₁-C₂alkoxy, C₁-C₄haloalkyl, CN, NO₂, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl or C₂-C₄alkoxycarbonyl; or

each R⁵is independently a phenyl or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R⁶; or

(R⁵)₂when attached to adjacent carbon atoms can be taken together as —OCF₂O—, —CF₂CF₂O— or —OCF₂CF₂O—.

4. The compound of claim 3 wherein

R¹is H;

R²is H or CH₃;

R³is C₁-C₄alkyl optionally substituted with one or more substituents independently selected from halogen, CN, OCH₃or S(O)_pCH₃;

each R⁴is independently CH₃, CF₃, CN or halogen, and one R⁴group is attached to the K ring at the atom adjacent to the NR¹C(=A)J moiety;

each R⁵is independently H, halogen, methyl, CF₃, OCF₃, OCHF₂, S(O)_pCF₃, S(O)_pCHF₂, OCH₂CF₃, OCF₂CHF₂, S(O)_pCH₂CF₃or S(O)_pCF₂CHF₂; or a phenyl, pyrazole, imidazole, triazole, pyridine or pyrimidine ring, each ring optionally substituted with one to three substituents independently selected from C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN; and

p is 0, 1 or 2.

5. The compound of claim 4 wherein R³is C₁-C₄alkyl.

6. The compound of claim 1 wherein

A and B are both 0;

J is a 5- or 6-membered heteroaromatic ring selected from the group consisting of J-1, J-2, J-3, J-4 and J-5, each J optionally substituted with 1 to 3 R⁵

Q is O, S or NR⁵; and

W, X, Y and Z are independently N or CR⁵, provided that in J-4 and J-5 at least one of W, X, Y or Z is N.

7. The compound of claim 6 wherein

each R⁵is independently H, C₁-C₄alkyl, C₁-C₄haloalkyl, halogen, CN, NO₂, C₁-C₄haloalkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄haloalkylthio, C₁-C₄haloalkylsulfinyl, C₁-C₄haloalkylsulfonyl or C₂-C₄alkoxycarbonyl; or a phenyl or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with R⁶.

8. The compound of claim 7 wherein

J substituted with 1 to 3 R⁵is selected from the group consisting of J-6, J-7, J-8, J-9, J-10, J-11, J-12 and J-13

R⁵is H, C₁-C₄alkyl, C₁-C₄haloalkyl, or

V is N, CH, CF, CCl, CBr or CI;

each R⁶and R⁷is independently H, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆haloalkyl, halogen, CN, C₁-C₄alkoxy, C₁-C₄haloalkoxy or C₁-C₄haloalkylthio; and

R⁹is H, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆haloalkenyl, C₃-C₆alkynyl or C₃-C₆haloalkynyl; provided R⁷and R⁹are not both H.

9. The compound of claim 8 wherein V is N.

10. The compound of claim 8 wherein V is CH, CF, CCl or CBr.

11. The compound of claim 9 or claim 10 wherein

R¹is H;

R²is H or CH₃;

R⁶is C₁-C₄alkyl, C₁-C₄haloalkyl, halogen or CN;

R⁷is H, CH₃, CF₃, OCH₂CF₃, OCHF₂or halogen; and

p is 0, 1 or 2.

12. The compound of claim 11 wherein R³is C₁-C₄alkyl; one R⁴group is independently CH₃, Cl, Br or I and is attached to the K ring at the atom adjacent to the NR¹C(=A)J moiety; and a second optional R⁴is H, F, Cl, Br, I or CF₃.

13. The compound of claim 12 wherein J substituted with 1 to 3 R⁵is J-6; R⁶is Cl or Br; and R⁷is halogen, OCH₂CF₃or CF₃.

14. The compound of claim 13 wherein V is N; R³is methyl, ethyl, isopropyl, tertiary butyl or N(CH₃)₂; and R⁷is Br, Cl, OCH₂CF₃, or CF₃.

15. The compound of claim 12 wherein J substituted with 1 to 3 R⁵is J-7; R⁶is Cl or Br; and R⁹is CF₃, CHF₂, CH₂CF₃or CF₂CHF₂.

16. The compound of claim 12 wherein J substituted with 1 to 3 R⁵is J-8; R⁶is Cl or Br; and R⁷is halogen, OCH₂CF₃or CF₃.

17. The compound of claim 12 wherein J substituted with 1 to 3 R⁵is J-9; R⁶is Cl or Br; and R⁷is OCH₂CF₃or CF₃.

18. The compound of claim 12 wherein J substituted with 1 to 3 R⁵is J-10; R⁶is Cl or Br; and R⁹is CF₃, CHF₂, CH₂CF₃or CF₂CHF₂.

19. The compound of claim 12 wherein J substituted with 1 to 3 R⁵is J-11; R⁶is Cl or Br; and R⁷is halogen, OCH₂CF₃or CF₃.

20. The compound of claim 12 wherein J substituted with 1 to 3 R⁵is J-12; R⁶is Cl or Br; R⁷is H, halogen or CF₃, and R⁹is H, CF₃, CHF₂, CH₂CF₃, or CF₂CHF₂.

21. The compound of claim 12 wherein J substituted with 1 to 3 R⁵is J-13; R⁶is Cl or Br; R⁷is H, halogen or CF₃, and R⁹is H, CF₃, CHF₂, CH₂CF₃or CF₂CHF₂.

22. The compound of claim 1 selected from the group consisting of:

4-[[[1-(2-Chlorophenyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]carbonyl]amino]-5-methyl-N-1-methylethyl)-3-pyridincarboxamide,

4-Methyl-N-(1-methylethyl)-3-[[2-methyl-4-(trifluoromethyl)benzoyl]amino]-2-thiophencarboxamide,

5-[[[3-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]carbonyl]amino]-N,625 dimethyl-4-pyrimidinecarboxamide; and

23. 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.

24. The method of claim 23 further comprising a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests.

25. A composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

26. The composition of claim 25 further comprising a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests.