KR20090005201A - Pyrazoline for invertebrate pest control - Google Patents

Abstract

The present invention discloses compounds of formula (I), N-oxides and salts thereof, including all geometric isomers and stereoisomers.

<Formula 1>

(In the meal,

Z is N or CR ² ;

R ¹ is cyano or C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ optionally substituted with one or more substituents independently selected from R ¹⁷ Cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl;

R ³ is H, cyano or —CHO or C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, optionally substituted with one or more substituents independently selected from R ¹⁸ , C ₃ -C ₆ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl, C ₄ -C ₇ cycloalkylalkyl, phenyl, C ₂ -C ₆ alkylcarbonyl, C ₂ -C ₆ alkoxycarbonyl, C ₂ -C ₆ alkylaminocarbonyl or C ₃ -C ₉ dialkylaminocarbonyl;

Q is an optionally substituted 5- or 6-membered saturated or unsaturated heterocycle; Or Q is C (O) NR ¹² R ¹³ , C (S) NR ¹² R ¹³ , S (O) ₂ NR ¹⁴ R ¹⁵ or R ¹⁶ .

The present invention also discloses a composition containing a compound of formula 1 and a method for controlling invertebrate pests, comprising contacting the invertebrate pest or environment thereof with a biologically effective amount of the compound or composition of the invention.

Description

Pyrazoline for invertebrate pest control {PYRAZOLINES FOR CONTROLLING INVERTEBRATE PESTS}

The present invention relates to certain pyrazolines, N-oxides, salts and compositions thereof suitable for agronomic and nonagronomic uses, including those listed below, and to invertebrate pests such as arthropods in both agronomic and nonagronomic environments. It relates to a method of using these for the control.

Control of invertebrate pests is of great importance in achieving high crop efficiency. Damage to invertebrate pests on the crops being grown and on the stored crops can significantly lower the production rate, thus pushing prices up to consumers. Control of invertebrate pests is also important in forests, greenhouse crops, ornamental water, seedling crops, stored food and fiber products, livestock, housekeeping, grass, wood products, and public and animal health. While many products are commercially available for this purpose, there is a continuing need for new compounds that are more effective, cheaper, less toxic and environmentally more stable or new compounds with different modes of action.

PCT Patent Publication WO 05/085216 discloses isoxazolin derivatives of formula i as pesticides.

Wherein, in particular, each A ¹ , A ² and A ³ is independently C or N; G is a benzene ring; W is O or S; X is halogen or C ₁ -C ₆ haloalkyl

Summary of the Invention

The present invention relates to compounds of formula (I), including N-oxides and salts thereof, compositions containing them, and their use for invertebrate pest control, including all geometric isomers and stereoisomers:

In the formula,

Z is N or CR ² ;

A ¹ is CR ⁴ or N;

A ² is CR ⁵ or N;

A ³ is CR ⁶ or N;

A ⁴ is CR ⁷ or N;

Q is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy , C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano, nitro, C (O) NR ⁸ R ⁹ , C (O) OR ¹⁰ , phenyl and pyridinyl (each Phenyl and pyridinyl of is optionally substituted with one or more substituents independently selected from R ¹¹ ) or 5- or 6-membered saturated or unsaturated heterocycle optionally substituted with one or more substituents independently selected from; or

Q is C (O) NR ¹² R ¹³ , C (S) NR ¹² R ¹³ , S (O) ₂ NR ¹⁴ R ¹⁵ or R ¹⁶ ;

R ¹ is cyano or C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ optionally substituted with one or more substituents independently selected from R ¹⁷ Cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl;

Each R ² is independently H, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, C ₂ -C ₄ alkoxycarbonyl, C ₂ -C ₄ alkylaminocarbonyl, C ₃ -C ₉ dialkylaminocarbonyl, cyano or nitro;

R ³ is H, cyano or —CHO or C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, optionally substituted with one or more substituents independently selected from R ¹⁸ , C ₃ -C ₆ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl, C ₄ -C ₇ cycloalkylalkyl, phenyl, C ₂ -C ₆ alkylcarbonyl, C ₂ -C ₆ alkoxycarbonyl, C ₂ -C ₆ alkylaminocarbonyl or C ₃ -C ₉ dialkylaminocarbonyl;

R ⁴ , R ⁵ , R ⁶ and R ⁷ are H, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano, and independently of the other, is selected from nitro; or

R ⁶ and R ⁷ are taken together, with 1 or 2 carbon atoms, 0 or 2 nitrogen atoms, 0 or 1 oxygen atom and 0 or 1 sulfur as ring members in addition to A ³ and A ⁴ bridgehead atoms To form a fused aromatic ring containing three atoms selected from atoms, or four atoms selected from 2 to 4 carbon atoms and 0 to 2 nitrogen atoms;

Each R ⁸ , R ¹² and R ¹⁴ is independently H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl, C ₄ -C ₇ cycloalkylalkyl, C ₂ -C ₇ alkylcarbonyl, C ₂ -C ₆ alkoxyalkyl or C ₂ -C ₇ alkoxycarbonyl;

Each R ⁹ , R ¹⁰ , R ¹³ and R ¹⁵ is independently H or C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C optionally substituted with one or more substituents independently selected from R ¹⁹ ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl;

Each of R ¹¹ , R ²³ and R ²⁴ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylaminosulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, C ₂ -C ₄ alkoxycarbonyl, cyano or nitro;

R ¹⁶ is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ halo Alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C _1- C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano or nitro;

Each R ¹⁷ and R ¹⁸ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulphur Phonyl, cyano or nitro;

Each R ¹⁹ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₂ -C ₆ alkylcarbonyl, C ₂ -C ₆ alkoxycarbonyl, C ₃ -C ₆ trialkylsilyl, cyano, nitro or Q ¹ ;

Each Q ¹ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C _1- C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsul Ponyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano, nitro, C (O) NR ²⁰ R ²¹ , C (O) OR ²² , Phenyl or 5- or 6-membered saturated or unsaturated hetero optionally substituted with one or more substituents independently selected from phenyl and pyridinyl (each phenyl and pyridinyl is optionally substituted with one or more substituents independently selected from R ²³ ) Cycle;

Each R ²⁰ is independently H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl, C ₄ -C ₇ cycloalkylalkyl, C ₂ -C ₆ alkoxyalkyl, C ₂ -C ₇ alkylcarbonyl or C ₂ -C ₇ alkoxycarbonyl;

Each R ²¹ and R ²² is independently H or C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ Cycloalkyl, C ₄ -C ₇ alkylcycloalkyl, C ₄ -C ₇ cycloalkylalkyl, phenyl or pyridinyl, each phenyl and pyridinyl optionally substituted with one or more substituents independently selected from R ²⁴ ;

n is 1, 2, 3 or 4.

The invention also provides a composition comprising a compound of Formula 1, or an N-oxide or salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. In one embodiment, the invention also includes a biologically effective amount of a compound of Formula 1, or an N-oxide or salt thereof, and one or more additional components selected from the group consisting of surfactants, solid diluents and liquid diluents, optionally Provided is a composition for controlling invertebrate pests, further comprising a biologically effective amount of at least one additional biologically active compound or agent.

The present invention further provides a spray composition for invertebrate pest control comprising a biologically effective amount of a compound of formula 1 or an N-oxide or salt thereof, or a composition described above, and a propellant. The invention also provides a bait composition for invertebrate pest control comprising a biologically effective amount of a compound of Formula 1 or an N-oxide or salt thereof, or a composition described in the above embodiments, one or more foods, optionally attractants and optionally wetting agents. to provide.

The present invention further includes a bait composition and a housing suitable for receiving the bait composition, wherein the housing is one or more sized to allow invertebrate pests to pass through to access the bait composition from a location outside the housing. It provides a trap device for invertebrate pest control having an opening and further suitable for placement at or near the site of potential or known activity of the invertebrate pest.

The present invention provides a method of controlling an invertebrate pest comprising contacting the invertebrate pest or environment thereof with a biologically effective amount of a compound of Formula 1 or an N-oxide or salt thereof (eg, as a composition described herein). do. The invention also comprises an invertebrate pest or environment thereof, comprising at least one additional component selected from the group consisting of a biologically effective amount of a compound of formula 1 or an N-oxide or salt thereof, and a surfactant, a solid diluent and a liquid diluent, A method of contacting a composition optionally further comprising a biologically effective amount of one or more additional biologically active compounds or agents.

The invention also provides a method of protecting a seed from invertebrate pests comprising contacting the seed with a biologically effective amount of a compound of Formula 1, or an N-oxide or salt thereof (eg, as a composition described herein). to provide. The invention also relates to treated seeds. The invention further provides a method of protecting an animal from invertebrate parasites comprising administering to the animal a pesticidal effective amount of a compound of Formula 1, or an N-oxide or salt thereof (eg, as a composition described herein). To provide.

As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “haves”, “haves”, “contains” or “contains”, or any other derivative thereof is exclusive. It is intended to cover categories that are not. For example, a composition, mixture, process, method, article, or device comprising the listed elements need not be limited to these elements, and other than those specifically listed for such composition, mixture, process, method, article, or device. Elements or unique elements thereof. In addition, unless explicitly stated otherwise, "or" means inclusive "or" and does not mean exclusive "or". For example, condition A or B satisfies any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is True (or present), and both A and B are true (or present).

Also, the indefinite article before an element or component of the present invention is meant to be non-limiting with respect to the number of instances (ie occurrences) of the element or component. Thus, an indefinite article should be construed to include more than one, and the singular word forms of the element or component also include the plural unless the number is obviously meant to be one.

The term “invertebrate pest” referred to in this disclosure includes arthropods, gastropods and nematodes that are economically important as pests. The term “arthropod” includes insects, mites, spiders, scorpions, centipedes, millipedes, rattles, and conjunctiva. The term "gastropod" includes snails, slugs and other Stylommatophora. The term “nematode” includes worms belonging to linear, cubic and oral worms such as roundworms, filaments, and herbivorous nematodes (nematodes), tapeworms (worms), tapeworms (worms) and spiny headed worms.

In the present disclosure, "invertebrate pest control" means the inhibition (including mortality, reduced feed intake and / or mating interference) of invertebrate pest development, and the related expressions are similarly defined.

The term “agronomic” refers to the production of crops such as food and fiber, and includes corn, soybeans and other legumes, rice, grains (eg, wheat, oats, barley, rye, rice, maize), leafy vegetables. (E.g. lettuce, cabbage and other rapeseed crops), orchard vegetables (e.g. tomatoes, peppers, eggplant, cruciferous and calabash), potatoes, sweet potatoes, grapes, cotton, acorns (e.g. And citrus fruits), small fruits (berry, cherries) and other special crops (eg canola, sunflower, olives). The term "non-agronomic" refers to other horticultural crops (eg, greenhouse plants, seedlings or ornamental plants not grown in fields), residential and commercial structures in urban and industrial facilities, grass (eg, lawn farms, Pastures, golf courses, residential lawns, recreational sports fields, etc.), wood products, storage products, agro-forestry and vegetation management, public health (human) and animal health (e.g., pets, livestock and poultry Same domesticated animal, and untamed animal such as wildlife).

In the above description, the term "alkyl", used alone or in compound words such as "alkylthio" or "haloalkyl", refers to a straight or branched alkyl such as methyl, ethyl, n-propyl, i-propyl, or different Butyl, pentyl or hexyl isomers. “Alkenyl” includes straight or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and 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 different butynyl, pentynyl and hexynyl isomers. "Alkynyl" may also include residues consisting of multiple triple bonds, such as 2,5-hexadiynyl.

"Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, and different butoxy, pentoxy and hexyloxy isomers. The term "alkoxyalkyl" denotes an alkoxy substitution on an alkyl moiety. Examples of "alkoxyalkyl" include methoxymethyl, 1-ethoxyethyl, ethoxymethyl and t-butoxymethyl. "Alkylthio" includes branched or straight chain alkylthio moieties such as methylthio, ethylthio, and different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylsulfinyl" includes all of the enantiomers of the alkylsulfinyl group. Examples of “alkylsulfinyl” include CH ₃ S (O) —, CH ₃ CH ₂ S (O) —, CH ₃ CH ₂ CH ₂ S (O) —, (CH ₃ ) ₂ CHS (O) —, and Different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers are included. Examples of "alkylsulfonyl" include CH ₃ S (O) _2- , CH ₃ CH ₂ S (O) _2- , CH ₃ CH ₂ CH ₂ S (O) _2- , (CH ₃ ) ₂ CHS (O) _2- , and different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkylamino", "dialkylamino" and the like are defined similarly to the above examples. Examples of "alkylaminosulfonyl" include CH ₃ NHS (O) _2- , CH ₃ CH ₂ NHS (O) _2- , CH ₃ CH ₂ CH ₂ NHS (O) _2- , (CH ₃ ) ₂ CHNHS (O ) ₂ - is included, or pentyl-amino-sulfonyl-isomer -, and the different butylamino. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "alkylcycloalkyl" denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term "cycloalkylalkyl" denotes cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bound to straight or branched alkyl groups. When used alone or in compound words such as "haloalkyl" or in descriptions such as "alkyl substituted with halogen", the term "halogen" includes fluorine, chlorine, bromine or iodine. In addition, when used in compound words such as "haloalkyl" or in descriptions such as "alkyl substituted with halogen", said alkyl may be partially or completely substituted with halogen atoms, which may be the same or different. Examples of "haloalkyl" or "alkyl substituted with halogen" include F ₃ C-, ClCH _2- , CF ₃ CH ₂ -and CF ₃ CCl _2- . The terms "halocycloalkyl", "haloalkoxy", "haloalkylthio" and the like are defined similarly to the term "haloalkyl". Examples of “haloalkoxy” include CF ₃ O—, CCl ₃ CH ₂ O—, HCF ₂ CH ₂ CH ₂ O— and CF ₃ CH ₂ O—. Examples of "haloalkylthio" include CCl ₃ S-, CF ₃ S-, CCl ₃ CH ₂ S-, and ClCH ₂ CH ₂ CH ₂ S-. Examples of "haloalkylsulfinyl" include CF ₃ S (O)-, CCl ₃ S (O)-, CF ₃ CH ₂ S (O)-, and CF ₃ CF ₂ S (O)-. Examples of "haloalkylsulfonyl" include CF ₃ S (O) _2- , CCl ₃ S (O) _2- , CF ₃ CH ₂ S (O) ₂ -and CF ₃ CF ₂ S (O) _2-. do.

"Alkylcarbonyl" refers to a straight or branched alkyl moiety bound to a C (O) moiety. Examples of "alkylcarbonyl" include CH ₃ C (O)-, CH ₃ CH ₂ CH ₂ C (O)-and (CH ₃ ) ₂ CHC (O)-. Examples of “alkoxycarbonyl” include CH ₃ OC (O) —, CH ₃ CH ₂ OC (O) —, CH ₃ CH ₂ CH ₂ OC (O) —, (CH ₃ ) ₂ CHOC (O) — and different Butoxy- or pentoxycarbonyl isomers are included. Examples of “alkylaminocarbonyl” include CH ₃ NHC (O) —, CH ₃ CH ₂ NHC (O) —, CH ₃ CH ₂ CH ₂ NHC (O) —, (CH ₃ ) ₂ CHNHC (O) — and Different butylamino- or pentylaminocarbonyl isomers are included. Examples of "dialkylaminocarbonyl" include (CH ₃ ) ₂ NC (O)-, (CH ₃ CH ₂ ) ₂ NC (O)-, CH ₃ CH ₂ (CH ₃ ) NC (O)-, (CH ₃ ) ₂ CHN (CH ₃ ) C (O) — and CH ₃ CH ₂ CH ₂ (CH ₃ ) NC (O) —.

“Trialkylsilyl” includes three branched and / or straight chain alkyl radicals such as trimethylsilyl, triethylsilyl and t-butyl-dimethylsilyl attached to and connected to a silicon atom.

The number of total carbon atoms in the substituents is given by the prefix "C _i -C _j ", where i and j are numbers from 1 to 9. For example, C ₁ -C ₄ alkylsulfonyl represents methylsulfonyl to butylsulfonyl; C ₂ alkoxyalkyl represents CH ₃ OCH ₂ ; C ₃ alkoxyalkyl represents, for example, CH ₃ CH (OCH ₃ ), CH ₃ OCH ₂ CH ₂ or CH ₃ CH ₂ OCH ₂ ; C ₄ alkoxyalkyl refers to various isomers of alkyl groups substituted with alkoxy groups containing a total of four carbon atoms, examples include CH ₃ CH ₂ CH ₂ OCH ₂ and CH ₃ CH ₂ OCH ₂ CH ₂ .

When the compound is substituted with a substituent having a subscript that indicates that the number of substituents may be greater than one (eg, (R ² ) _n , where n is 1, 2, 3 or 4) (If more than one) are independently selected from the group of defined substituents. In the case of R ² which contains a substituent which may be hydrogen, for example R ² , it is recognized that if this substituent is taken as hydrogen, it is equivalent to the above unsubstituted group.

The term "heterocycle", "heterocyclic ring" or "heterocyclic ring system" denotes a ring or ring system in which at least one ring atom is not carbon, for example nitrogen, oxygen or sulfur. Typically, the heterocyclic ring does not contain at least 4 nitrogens, at least 2 oxygens and at least 2 sulfurs. Heterocyclic rings may be attached through the carbon or nitrogen by replacing hydrogen on any available carbon or nitrogen. The heterocyclic ring may be a saturated, partially unsaturated or fully unsaturated ring. If a fully unsaturated heterocyclic ring meets the Hueckel rule, such a ring is also referred to as a "heteroaromatic ring" or an "aromatic heterocyclic ring".

The term “aromatic ring” or “aromatic ring system” refers to fully unsaturated carbocycles and heterocycles in which at least one ring of the polycyclic ring system is aromatic, where aromatic indicates that the ring system meets the Whikel law. . The term "fused bicyclic ring system" refers to a ring system containing two fused rings in which one of the rings may be saturated, partially unsaturated or fully unsaturated. The term “fused heterobicyclic ring system” refers to a ring system containing at least one ring atom that is not carbon and contains two fused rings, which may be aromatic or non-aromatic as defined above.

The term “optionally substituted” associated with an aromatic ring refers to a group having one or more substituents other than hydrogen, which are unsubstituted or do not destroy the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or the term "(un) substituted". Unless otherwise indicated, optionally substituted groups may have a substituent at each substitutable position of the group, and each substitution is independent of each other.

Q ¹ mentioned above may be (particularly) phenyl optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary of the Invention. Examples of phenyl optionally substituted with one or more substituents include U-1 in Formula 1 below, wherein R ^v is any substituent as defined in <Summary of Invention> for Q ¹ , and r is 0 to 5 As an integer).

The above-mentioned Q or Q ¹ may be a (particularly) 5- or 6-membered saturated or unsaturated heterocycle, optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary of the Invention. Examples of 5- or 6-membered unsaturated aromatic heterocycles optionally substituted with one or more substituents include the rings U-2 to U-61 illustrated in the following presentation (wherein R ^v is <invented for Q or Q ¹⁾ Any substituent as defined in &lt;Summary>, and r is an integer of 0 to 4). Note that some U groups can only be substituted with fewer than 4 R ^v groups (eg, U-2 to U-5, U-7 to U-48, and U-52 to U-61).

If Q is a 5-membered nitrogen-containing heterocycle, it may be attached to the remainder of Formula 1 via any available carbon or nitrogen ring atom unless otherwise noted. Similarly, when Q ¹ is a 5-membered nitrogen-containing heterocycle, it may be attached via any available carbon or nitrogen ring atom unless otherwise noted.

<Presentation 1>

When Q or Q ¹ is a 5- or 6-membered saturated or unsaturated non-aromatic heterocycle optionally substituted with one or more substituents selected from the group of substituents as defined in <Summary of the Invention> for Q or Q ¹ , Note that one or two carbon ring members of the heterocycle may optionally be an oxidized form of carbonyl moiety.

Examples of 5- or 6-membered saturated or non-aromatic unsaturated heterocycles include the rings G-1 to G-35 as exemplified in presentation 2 below. If the point of attachment on the Q or Q ¹ group is illustrated as fluid, the Q or Q ¹ group will be attached to the remainder of Formula 1 through any available carbon or nitrogen of the Q or Q ¹ group by replacement of a hydrogen atom. Note that you can. Any substituent may be attached to any available carbon or nitrogen by replacement of a hydrogen atom.

Note that when Q or Q ¹ comprises a ring selected from G-28 to G-35, G ² is selected from O, S or N. Note that when G ² is N, the nitrogen atom may be complete in its valency by substitution with a substituent as defined in H, or Q or Q ¹ in the Summary of the Invention.

<Presentation 2>

Note that when the point of attachment on the G group is illustrated as fluid, the G group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the G group by replacement of a hydrogen atom. When the point of attachment between (R ^v ) _r and a G (or U) group is illustrated as fluid, (R ^v ) _r may be attached to any available carbon atom or nitrogen atom of the G (or U) group. Note that there is. Note that although the R ^v groups are represented in the structures U-1 to U-61 and G-1 to G-35, they do not necessarily need to be present because they are optional substituents. Note that when R ^v is H and attached to one atom, this is the same as when the atom is unsubstituted. In addition, the nitrogen atom for which substitution is required to satisfy the valence is substituted with H or R ^v .

Compounds of the invention may exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Those skilled in the art will appreciate that one stereoisomer may be more active and / or have a beneficial effect when enriched relative to other stereoisomer (s) or when separated from other stereoisomer (s). In addition, those skilled in the art know how to separate and / or enrich and / or selectively prepare such stereoisomers. Accordingly, the present invention includes compounds selected from compounds of Formula 1, their N-oxides and salts. The compounds of the present invention may exist as mixtures of stereoisomers, as individual stereoisomers, or as optically active forms.

Those skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides, since nitrogen requires an isolated pair of electrons available for oxidation to oxide, which will form N-oxides. It will be appreciated that it can contain nitrogen-containing heterocycles. Those skilled in the art will also recognize that tertiary amines can form N-oxides. Peroxy acids (eg peracetic acid and m-chloroperbenzoic acid (MCPBA)), hydrogen peroxide, alkyl hydroperoxides (eg t-butyl hydroperoxide), sodium perborate and dioxirane (eg dimethyldioxirane) Synthetic methods for preparing N-oxides of heterocycles and tertiary amines, including the oxidation of heterocycles and tertiary amines), are well known by those skilled in the art. Such methods of making N-oxides are extensively described and reviewed in the literature. See, eg, 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.

Salts of the compounds of the present invention are inorganic or organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid Or acid-addition salts with valeric acid. Salts of the compounds of the present invention also include organic bases (eg, pyridine or triethylamine) when the compound contains an acidic moiety, such as when Q is substituted with C (O) OR ¹⁰ and R ¹⁰ is H Or salts formed with inorganic bases (eg, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium).

Accordingly, the present invention includes compounds selected from compounds of Formula 1, their N-oxides and salts.

Embodiments of the invention as described in the Summary of the Invention include:

Embodiment 1. A compound of Formula 1 wherein R ¹ is C ₁ -C ₃ alkyl optionally substituted with one or more substituents independently selected from R ¹⁷ .

Embodiment 2. A compound of Embodiment _{1 wherein} R ¹ is C ₁ -C ₃ alkyl optionally substituted with one or more halogens.

Embodiment 3. A compound of Embodiment 2 wherein R ¹ is CF ₃ .

Embodiment 4. A compound of Formula 1 wherein Z is CR ² .

Embodiment 5. A compound of Formula 1 wherein each R ² is independently hydrogen, halogen or C ₁ -C ₂ haloalkyl.

Embodiment 6. A compound of Embodiment 5 wherein R ² is hydrogen, halogen or CF ₃ .

Embodiment 7. A compound of Formula 1 wherein n is 1 or 2.

Embodiment 8. R ³ is H or cyano; Or C ₁ -C ₄ alkyl optionally substituted with one or more halogens.

Embodiment 9. A compound of Embodiment 8 wherein R ³ is methyl, ethyl or CH ₂ CF ₃ .

Embodiment 10. A compound of Formula 1 wherein up to 3 of A ¹ , A ² , A ³ and A ⁴ are N.

Embodiment 11. A compound of Formula 1 wherein up to two of A ¹ , A ² , A ³ and A ⁴ are N.

Embodiment 12 A compound of Formula 1 wherein at least one of A ¹ , A ² , A ³ and A ⁴ is N.

Embodiment 13. A compound of Formula 1 wherein A ¹ , A ² , A ³ and A ⁴ are not N.

Embodiment 14. A compound of Formula 1 wherein A ¹ is CR ⁴ .

Embodiment 15. A compound of Formula 1 wherein A ² is CR ⁵ .

Embodiment 16. A compound of Formula 1 wherein A ³ is CR ⁶ .

Embodiment 17. A compound of Formula 1 wherein A ⁴ is CR ⁷ .

Embodiment 18. A compound of Formula 1 wherein R ⁴ and R ⁵ are independently selected from H, halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano and nitro.

Embodiment 19 A compound of Formula 1 wherein R ⁶ and R ⁷ are independently selected from H, halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano and nitro.

Embodiment 20. A fused aromatic ring wherein R ⁶ and R ⁷ are taken together and contain 4 atoms selected from 3 or 4 carbon atoms and 0 or 1 nitrogen atom as ring members in addition to A ³ and A ⁴ leg atoms Compound of Formula 1 to form.

Embodiment 21 A compound of Embodiment 20 wherein R ⁶ and R ⁷ are taken together to form a fused aromatic ring containing 4 carbon atoms as ring member in addition to A ³ and A ⁴ leg atoms.

Embodiment 22. Q is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C _1- C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano, nitro, C (O) NR ⁸ R ⁹ , C (O) OR ¹⁰ , phenyl and Pyridinyl, pyrimidinyl, triazinyl, pyrazolyl, tria, optionally substituted with one or more substituents independently selected from pyridinyl, each phenyl and pyridinyl, optionally substituted with one or more substituents independently selected from R ¹¹ 5- or 6-membered unsaturated heterocycle selected from zolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl and isothiazolyl; Or Q is C (O) NR ¹² R ¹³ , S (O) ₂ NR ¹⁴ R ¹⁵ or R ¹⁶ .

Embodiment 23. A compound of Embodiment 22 wherein Q is C (O) NR ¹² R ¹³ or R ¹⁶ .

Embodiment 24 A compound of Embodiment 23 wherein Q is C (O) NR ¹² R ¹³ .

Embodiment 25 A compound of Embodiment 22 wherein Q is S (O) ₂ NR ¹⁴ R ¹⁵ .

Embodiment 26 A compound of Embodiment 23 wherein Q is R ¹⁶ .

Embodiment 27. A compound of Formula 1 wherein Q is not R ¹⁶ .

Embodiment 28. Q is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C _1- C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano, nitro, C (O) NR ⁸ R ⁹ , C (O) OR ¹⁰ , phenyl and Pyridinyl, pyrimidinyl, triazinyl, pyrazolyl, tria, optionally substituted with one or more substituents independently selected from pyridinyl, each phenyl and pyridinyl, optionally substituted with one or more substituents independently selected from R ¹¹ The compound of embodiment 22 which is a 5- or 6-membered unsaturated heterocycle selected from zolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl and isothiazolyl.

Embodiment 29. Q is attached to the remainder of Formula 1 via nitrogen and is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocyclo Alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylamino, C ₂ -C ₄ dialkylamino, cyano, nitro, C (O) NR ⁸ R ⁹ , C ( O) OR ¹⁰ , phenyl and pyridinyl, each phenyl and pyridinyl, each optionally substituted with one or more substituents independently selected from R ¹¹ , pyrazolyl, triazolyl and imido The compound of embodiment 28 which is a 5-membered unsaturated heterocycle selected from dazolyl.

Embodiment 30. Q is attached to the remainder of Formula 1 via nitrogen and is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, 5-membered unsaturated heterocycle selected from pyrazolyl, triazolyl and imidazolyl, optionally substituted with one or more substituents independently selected from cyano, nitro, C (O) NR ⁸ R ⁹ and C (O) OR ¹⁰ The compound of embodiment 29 which is.

Embodiment 31. pyrazolyl, tria, wherein Q is attached to the remainder of Formula 1 via nitrogen and optionally substituted with one or more substituents independently selected from halogen, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl The compound of embodiment 30 which is a 5-membered unsaturated heterocycle selected from zolyl and imidazolyl.

Embodiment 32. Triazolyl and imi, Q is attached via nitrogen to the remainder of Formula 1 and optionally substituted with one or more substituents independently selected from halogen, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl The compound of embodiment 31 which is a 5-membered unsaturated heterocycle selected from dazolyl.

Embodiment 33 A compound of Formula 1 wherein each R ⁸ is independently H, C ₁ -C ₆ alkyl, C ₂ -C ₇ alkylcarbonyl or C ₂ -C ₇ alkoxycarbonyl.

Embodiment 34 A compound of Embodiment 33 wherein each R ⁸ is H. Embodiment 34.

Embodiment 35. C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, each R ⁹ is independently H or optionally substituted with one or more substituents selected from R ¹⁹ , A compound of formula 1 which is C ₃ -C ₄ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl.

Embodiment 36 A compound of Embodiment 35 wherein each R ⁹ is independently C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from R ¹⁹ .

Embodiment 37 Each R ⁹ is independently halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, cyano and one The compound of embodiment 36 being C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from Q ¹ below.

Embodiment 38. C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, wherein each R ¹⁰ is independently H or optionally substituted with one or more substituents selected from R ¹⁹ , A compound of formula 1 which is C ₃ -C ₄ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl.

Embodiment 39 A compound of Embodiment 38 wherein each R ¹⁰ is independently C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from R ¹⁹ .

Embodiment 40 Each R ¹⁰ is, independently, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, cyano and one The compound of embodiment 39 which is C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from Q ¹ below.

Embodiment 41. A compound of Formula 1 wherein R ¹² is H, C ₁ -C ₆ alkyl, C ₂ -C ₇ alkylcarbonyl or C ₂ -C ₇ alkoxycarbonyl.

Embodiment 42 A compound of Embodiment 41 wherein R ¹² is H.

Embodiment 43. C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C, wherein R ¹³ is H or optionally substituted with one or more substituents selected from R ¹⁹ Compound of formula 1 which is ₄ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl.

Embodiment 44 A compound of Embodiment 43 wherein R ¹³ is H or C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from R ¹⁹ .

Embodiment 45. R ¹³ is H, or halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkyl Embodiments that are C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from sulfonyl, C ₂ -C ₄ alkylcarbonyl, C ₂ -C ₄ alkoxycarbonyl, cyano, nitro and up to one Q ¹ . Compound of 44.

Embodiment 46. R ¹³ is H or halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, cyano and up to 1 The compound of embodiment 45 which is C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from Q ¹ .

Embodiment 47 A compound of Embodiment 46 wherein R ¹³ is H or C ₁ -C ₄ alkyl optionally substituted with one or more halogen and up to one Q ¹ .

Embodiment 48 A compound of Embodiment 47 wherein R ¹³ is H or C ₁ -C ₄ alkyl optionally substituted with one or more fluorine and up to one Q ¹ .

Embodiment 49. A compound of Formula 1 wherein R ¹⁴ is H, C ₁ -C ₆ alkyl, C ₂ -C ₇ alkylcarbonyl or C ₂ -C ₇ alkoxycarbonyl.

Embodiment 50 A compound of Embodiment 49 wherein R ¹⁴ is H.

Embodiment 51. C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C, wherein R ¹⁵ is H or optionally substituted with one or more substituents selected from R ¹⁹ Compound of formula 1 which is ₄ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl.

Embodiment 52 A compound of Embodiment 51 wherein R ¹⁵ is H or C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from R ¹⁹ .

Embodiment 53. R ¹⁵ is H, or halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkyl Embodiments that are C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from sulfonyl, C ₂ -C ₄ alkylcarbonyl, C ₂ -C ₄ alkoxycarbonyl, cyano, nitro and up to one Q ¹ . 52 compound.

Embodiment 54. R ¹⁵ is H or halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, cyano and up to 1 The compound of embodiment 53 which is C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from Q ¹ .

Embodiment 55 A compound of Embodiment 54 wherein R ¹⁵ is H or C ₁ -C ₄ alkyl optionally substituted with one or more halogen and up to 1 Q ¹ .

Embodiment 56 A compound of Embodiment 55 wherein R ¹⁵ is H or C ₁ -C ₄ alkyl optionally substituted with one or more fluorine and up to one Q ¹ .

Embodiment 57. A compound of Formula 1 wherein R ¹⁶ is halogen, C ₁ -C ₃ haloalkyl, C ₂ -C ₄ dialkylamino, cyano or nitro.

Embodiment 58. Each R ¹⁹ is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl , C ₂ -C ₄ alkylcarbonyl, C ₂ -C ₄ alkoxycarbonyl, cyano, nitro and Q ¹ .

Embodiment 59 Each R ¹⁹ is independently from halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, cyano and Q ¹ Compound of Formula 1 selected.

Embodiment 60 A compound of Formula 1 wherein each R ¹⁹ is independently selected from halogen and Q ¹ .

Embodiment 61 A compound of Formula 1 wherein each R ¹⁹ is independently selected from fluorine and Q ¹ .

Embodiment 62. Phenyl, pyridinyl, and each Q ¹ is optionally substituted with one or more substituents independently selected from halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano, phenyl and pyridinyl A compound of formula 1 independently selected from thiazolyl.

Embodiment 63 A compound of Embodiment 62 wherein Q ¹ is phenyl, pyridinyl or thiazolyl.

Embodiments of the present invention, including Embodiments 1-63 above and any other embodiment described herein, can be combined in any manner, the description of the variables in the embodiments including the compounds of Formula 1 as well as the starting compounds and It relates to an intermediate compound. In addition, embodiments of the present invention, including Embodiments 1-63 above and any other embodiments described herein, and any combination thereof, relate to the compositions and methods of the present invention.

Combinations of Embodiments 1-63 are illustrated by:

Embodiment A.

Q is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy , C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano, nitro, C (O) NR ⁸ R ⁹ , C (O) OR ¹⁰ , phenyl and pyridinyl (each Phenyl and pyridinyl are optionally substituted with one or more substituents independently selected from R ¹¹ ), pyridinyl, pyrimidinyl, triazinyl, pyrazolyl, triazolyl, imida 5- or 6-membered unsaturated heterocycles selected from zolyl, oxazolyl, isoxazolyl, thiazolyl and isothiazolyl; Or Q is C (O) NR ¹² R ¹³ , S (O) ₂ NR ¹⁴ R ¹⁵ or R ¹⁶ ;

Z is CR ² ;

At most one of A ¹ , A ² , A ³ and A ⁴ is N;

R ¹ is C ₁ -C ₃ alkyl optionally substituted with one or more substituents independently selected from R ¹⁷ ;

Each R ² is independently hydrogen, halogen or C ₁ -C ₂ haloalkyl;

R ³ is H or cyano or C ₁ -C ₄ alkyl optionally substituted with one or more halogens;

R ⁴ and R ⁵ are independently selected from H, halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano and nitro;

R ⁶ and R ⁷ are independently selected from H, halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano and nitro; Or R ⁶ and R ⁷ taken together to form a fused aromatic ring containing 3 or 4 carbon atoms and 4 atoms selected from 0 or 1 nitrogen atom as ring member in addition to A ³ and A ⁴ leg atoms ;

Each R ⁸ is independently H, C ₁ -C ₆ alkyl, C ₂ -C ₇ alkylcarbonyl or C ₂ -C ₇ alkoxycarbonyl;

Each R ⁹ and R ¹⁰ is independently H, or optionally substituted with one or more substituents selected from R ¹⁹ , C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₄ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl;

Each of R ¹² and R ¹⁴ is independently H, C ₁ -C ₆ alkyl, C ₂ -C ₇ alkylcarbonyl or C ₂ -C ₇ alkoxycarbonyl;

Each R ¹³ and R ¹⁵ is independently H, or optionally substituted with one or more substituents selected from R ¹⁹ , C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₄ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl;

R ¹⁶ is halogen, C ₁ -C ₃ haloalkyl, C ₂ -C ₄ dialkylamino, cyano or nitro;

Each R ¹⁹ is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C _2- Independently selected from C ₄ alkylcarbonyl, C ₂ -C ₄ alkoxycarbonyl, cyano, nitro and Q ¹ ;

Each Q ¹ is independent from phenyl, pyridinyl and thiazolyl, optionally substituted with one or more substituents independently selected from halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano, phenyl and pyridinyl Is selected;

A compound of formula 1, wherein n is 1 or 2.

Embodiment B.

The compound of embodiment A, wherein R ¹ is C ₁ -C ₃ alkyl optionally substituted with one or more halogens.

Embodiment C.

Q is attached to the remainder of Formula 1 via nitrogen and is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, cyano, nitro Or a 5-membered unsaturated heterocycle selected from pyrazolyl, triazolyl and imidazolyl, optionally substituted with one or more substituents independently selected from C (O) NR ⁸ R ⁹ and C (O) OR ¹⁰ ; Or Q is C (O) NR ¹² R ¹³ ;

R ¹ is CF ₃ ;

R ⁶ and R ⁷ are independently selected from H, halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano and nitro; Or R ⁶ and R ⁷ are taken together to form a fused aromatic ring containing four carbon atoms as ring member in addition to A ³ and A ⁴ leg atoms;

Each R ⁸ is H;

Each R ⁹ and R ¹⁰ is independently halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, cyano and one or less C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from Q ¹ of;

Each of R ¹² and R ¹⁴ is independently H;

Each R ¹³ and R ¹⁵ is independently H or C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from R ¹⁹ ;

The compound of embodiment B, wherein R ¹⁹ is independently selected from halogen and Q ¹ .

Embodiment D.

The compound of embodiment C, wherein R ³ is methyl, ethyl or CH ₂ CF ₃ .

Certain embodiments

4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -2-methyl-N- (2-pyridinylmethyl) benzamide,

4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -N- (2,2 , 2-trifluoroethyl) benzamide,

4- [5- (3,5-Dichlorophenyl) -4,5-dihydro-1- (2,2,2-trifluoroethyl) -5- (trifluoromethyl) -1H-pyrazole- 3-yl] -N- (2-pyridinylmethyl) benzamide and

1- [4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] phenyl] -1H It includes a compound of formula (I) selected from the group consisting of -1,2,4-triazole.

Further particular embodiments include any combination of compounds of Formula 1 selected from the group directly above.

It is noted that the compounds of the present invention are characterized by desirable metabolic and / or soil residual patterns and exhibit activity in controlling a wide range of agronomic and nonagronomic invertebrate pests.

In particular, because of the extent and economic importance of invertebrate pest control, it is noted that it is an embodiment of the present invention to protect crops from damage or damage caused by invertebrate pests by controlling invertebrate pests. In addition, because of the desirable current characteristics or phylogeny in plants, the compounds of the present invention protect houseplants or other plant parts that are not in direct contact with a compound of Formula 1 or a composition comprising a compound of Formula 1.

Also noteworthy as embodiments of the invention are groups of biologically effective amounts of any of the above embodiments and of any other embodiments described herein, and any combination thereof, and surfactants, solid diluents and liquid diluents. A composition for controlling invertebrate pests comprising at least one additional ingredient selected from and optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent. Embodiments of the present invention further include methods of controlling invertebrate pests comprising contacting the invertebrate pest or environment thereof with a biologically effective amount of a compound of any of the above embodiments (eg, as a composition described herein). .

Embodiments of the invention also include compositions comprising a compound of any of the above embodiments in the form of a soil drench liquid formulation. Embodiments of the present invention further include methods of controlling invertebrate pests comprising contacting the soil with a liquid composition as a soil irrigation comprising a biologically effective amount of a compound of any of the above embodiments.

Embodiments of the present invention also include spray compositions for invertebrate pest control comprising a biologically effective amount of a compound of any of the above embodiments and a propellant. Embodiments of the present invention further include bait compositions for invertebrate pest control comprising a biologically effective amount of a compound of any of the above embodiments, one or more foods, optionally attractants and optionally wetting agents. Embodiments of the present invention also include a bait composition and a housing suitable for receiving the bait composition, wherein the housing is one or more openings of a size that allows the invertebrate pest to pass through to access the bait composition from a location outside the housing. And further suitable for placement at or near the site of potential or known activity of invertebrate pests.

Compounds of Formula 1 may be prepared by one or more methods and variations as described in Schemes 1-15 below. The definitions of R ¹ , R ² , R ⁴ , R ⁵ , R ¹² , R ¹³ , A ¹ to A ⁴ , Q, n and Z in the compounds of Formulas 1 to 25 are provided unless otherwise stated. As defined in &gt; Formulas 1a, 6 and 8 are subsets of Formula 1 and Formula 13a is a subset of Formula 13.

Compounds of formula (1) can be prepared by cycloaddition of the ions of formula (2) and hydrazine of formula (3), as outlined in Scheme 1. The reaction is generally believed to proceed through an intermediate stage of the hydrazone which is formed in situ. In conventional procedures, the reagents are combined in polar protic solvents such as ethanol or methanol. It may be advantageous to add an amine base such as pyridine or triethylamine to the reaction mixture. The reaction can be carried out in a variety of solvents, including tetrahydrofuran, diethyl ether, methylene chloride, dioxane and toluene, at an optimal temperature range from room temperature to the reflux temperature of the solvent. General procedures for the cycloaddition of hydrazines and enons are already documented in the chemical literature. For related literature, see Dandia et al., Heterocyclic Communications 1996, 2, 281-286 and Sibi et al., Tetrahedron: Asymmetry 2004, 15, 3353-3356, and references cited therein. . The method of Scheme 1 is illustrated in step C of Example 1.

Alternatively, the compound of formula 1 may be prepared using the method illustrated by Scheme 2, wherein the hydrazone of formula 4 is reacted with styrene of formula 5 under oxidative conditions. The reaction shown in Scheme 2 is an example of a [3 + 2] dipolar cycloaddition reaction involving the oxidative formation of a nitrile-imine dipole derived from a hydrazone of Formula 4, followed by cyclization with styrene of Formula 5 . The reaction is generally believed to proceed through an intermediate step of hydrazonoyl chloride produced in situ. In a conventional procedure, a chlorinating agent such as sodium hypochlorite, N-chlorosuccinimide or N-chloro-p-toluenesulfonamide sodium salt (Chloramine T) is added with hydrazone (4) in the presence of styrene (4). ) It is often advantageous to add amine bases (eg pyridine or triethylamine) or carbonate bases (eg potassium carbonate or sodium bicarbonate), which may be necessary. The reaction can be carried out in a variety of solvents, including tetrahydrofuran, diethyl ether, methylene chloride, dioxane and toluene, at an optimal temperature range from room temperature to the reflux temperature of the solvent. Examples of reactions similar to those shown in Scheme 2 can be found in J. Het. Chem. 2004, 41, 677-680 and Tetrahedron 1994, 50, 7543-7556.

Compounds of formula (1), wherein Q is a 5-membered N-linked heterocyclic ring, are also prepared by directly replacing the aryl halide of formula (6), wherein Y is a halogen atom, with an azole heterocyclic ring of formula (7), as shown in Scheme 3. It can manufacture. Typical azole heterocyclic rings of formula 7 include optionally substituted pyrazoles, imidazoles and triazoles. Bromide of formula 6, wherein Y is Br, can be replaced by the use of copper iodide and palladium catalysts (see, eg, Cristau et al., European Journal of Organic Chemistry 2004, 695-709) . For the substitution of fluoride (Y is F) from Formula 6, the reaction is typically carried out in a polar aprotic solvent such as N, N-dimethylformamide or N, N-dimethylacetamide, such as sodium carbonate or potassium carbonate. It is carried out in the presence of an inorganic base.

Alternative preparation of the compound of Formula 1 includes the well-known Suzuki reaction including Pd-catalyzed crosslinking coupling of aryl iodide or bromide of Formula 8 with aryl or heteroaryl boronic acid of Formula 9 ( Scheme 4). Many palladium catalysts are useful for this type of conversion and a common catalyst is tetrakis (triphenylphosphine) palladium (0). Solvents such as tetrahydrofuran, acetonitrile, diethyl ether and dioxane are suitable. Boronic acid of formula (9) is commercially available or can be prepared by known methods. Other methods, including Heck, Stille, Kudada and Buchwald-Hartwig coupling procedures, provide numerous alternatives to the introduction of heterocyclic groups Q. For main references, see, eg, Zificsak, C. A. and Hlasta, D. J., Tetrahedron, 2004, 60, 8991-9016. For a general review of palladium chemistry that can be applied to the synthesis of heterocyclic groups Q, see Li, J. J .; Gribble, G. W .; Editors; Palladium in Heterocyclic Chemistry: A Guide for the Synthetic Chemist, Elsevier: Oxford, UK, 2000.

Formula 6 is Formula 1 wherein Q is Y, and Formula 8 is Formula 1 wherein Q is X. Thus, the compounds of Formulas 6 and 8 may be prepared by the methods described for the compounds of Formula 1 of Scheme 1.

Various other methods exist for the preparation of the heterocyclic group Q found in formula (1). It can be prepared from well described functional group conversions such as ketones, esters, acids, aldehydes, nitriles and the like. For main references, see Tanaka et al., J. Med Chem, 1998, 41, 2390-2410 and the references cited therein.

Compounds of Formula 1a (Formula 1 wherein Q is CONR ¹² R ¹³ ) can be prepared by coupling the carboxylic acid of Formula 10 with an appropriately substituted amino compound of Formula 11, as shown in Scheme 5. The method of Scheme 5 is illustrated in step E of Example 2.

This reaction is carried out with dehydrating coupling agents such as dicyclohexyl carbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, 1-propane-phosphonic acid cyclic anhydride or carbonyl diimidazole and In the presence of a base such as triethylamine, pyridine, 4- (dimethylamino) pyridine or N, N-diisopropylethylamine, anhydrous aprotic solvents, typically from room temperature to 70 ° C., such as dichloromethane or tetrahydro It is carried out in furan.

Alternatively, the compound of Formula 1a may also be prepared by coupling the halide of Formula 8 with an appropriately substituted amino compound of Formula 11 in the presence of a palladium catalyst under a carbon monoxide atmosphere, as shown in Scheme 6. The method of Scheme 6 is illustrated in step D of Example 1.

The palladium catalyst used in the process of Scheme 6 is typically in the form of compounds comprising palladium in formal oxidation state of 0 (ie Pd (0)) or 2 (ie Pd (II)). A wide variety of these palladium-containing compounds and complexes are useful as catalysts for this process. Examples of palladium-containing compounds and complexes useful as catalysts in the process of Scheme 6 include PdCl ₂ (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ (tetrakis (triphenylphosphine) palladium (0)), Pd (C ₅ H ₇ O ₂ ) ₂ (palladium (II) acetylacetonate) and Pd ₂ (dba) ₃ (tris (dibenzylideneacetone) dipalladium (0)), and [1,1′-bis (diphenylphosphino) ) Ferrocene] dichloropalladium (II). The process of Scheme 6 is generally carried out in the liquid phase, and therefore, preferably having a good solubility in the liquid phase is the most effective palladium catalyst. Useful solvents include, for example, ethers (eg 1,2-dimethoxyethane), amides (eg N, N-dimethylacetamide), and non-halogenated aromatic hydrocarbons (eg toluene).

The method of Scheme 6 can be carried out over a wide range of temperatures, including about 25 to about 150 ° C. It is noted that temperatures of about 60 to about 110 ° C. typically provide fast reaction rates and high product yields. General methods and procedures for aminocarbonylation with aryl bromide and amines are well known in the literature (see, for example, H. Horino et al., Synthesis 1989, 715-718); and JJ Li, GW Gribble, editors, Palladium in Heterocyclic Chemistry: A Guide for the Synthetic Chemist, 2000].

Compounds of formula 10 can be prepared by hydrolyzing esters of formula 12, wherein W is methyl or ethyl, as shown in Scheme 7.

In this process, the ester compound of formula 12 is converted to the corresponding carboxylic acid of formula 10 by acidification after treatment with aqueous lithium hydroxide in, for example, tetrahydrofuran, by general procedures well known in the art. The method of Scheme 7 is illustrated in step D of Example 2.

As shown in Scheme 8, the enons of formula (2) are available from the addition-removal reaction of organometallic reagents such as Grignard reagent of formula (14) with β-enamine or β-haloenone of formula (13). .

The reaction can be carried out in a variety of solvents including tetrahydrofuran, diethyl ether, dioxane or methylene chloride, at an optimum temperature range of -78 ° C to the reflux temperature of the solvent. General procedures for the addition of Grignard reagents to enamines and haloenons are already recorded in the chemical literature (see, eg, Jeong et al., Journal of Fluorine Chemistry 2004, 125, 1629-1638), And references cited therein). The method of Scheme 8 is illustrated in step B of Example 1.

Alternatively, as shown in Scheme 9, condensation of the ketone of Formula 15 with the phosphonate compound of Formula 16 according to the Wadsworth-Emmons variant of the Wittig reaction to form an enon of Formula 2 can do.

In this process, the phosphonate compound of formula 16 is prepared in a solvent such as tetrahydrofuran, diethyl ether, dioxane or methylene chloride with a base such as pyridine, triethylamine, NaH, NaHCO ₃ or lithium diisopropylamide ( Deprotonation with LDA) to form the Ilide intermediate, and the ketone of Formula 15 is added to form the compound of Formula 2. The optimum temperature is from 0 ° C. to the reflux temperature of the solvent. General reaction conditions of the Beatig reaction are already recorded in the chemical literature (see, eg, Dull et al., J. Org. Chem. 1967, 32, 1622-1623).

There are a variety of different methods for the preparation of enons of formula (2). Such enons can be prepared from functional group conversion, addition and removal reactions already recorded.

Β-enamines of Formula 13a (which is a subset of compounds of Formula 13 wherein G is N (CH ₃ ) OCH ₃ ) are alkyne of Formula 17 and Weinreb amide reagent of Formula 19, as shown in Scheme 10; It can be prepared from.

In this process, the alkyne of formula 17 is reacted with a lithium strong base (eg, n-BuLi) at a temperature of -78 to -30 ° C to form a lithiated alkynyl compound of formula 18, followed by Add and warm to 0 ° C. For a main reference to this general method, see Jeong et al., Journal of Fluorine Chemistry 2004, 125, 1629-1638, and references cited therein.

Alternatively, as shown in Scheme 11, the elimination reaction of the bromoalkene compound of formula 20 using a non-nucleophilic strong base may form a lithiated alkynyl compound of formula 18.

In a variation of this method of Scheme 10, the bromoalkene compound of Formula 20 is combined with at least two equivalents of lithium strong bases such as LDA, sec-BuLi or lithium hexamethyldisilazide (LiHMDS) at temperatures from -78 to -30 ° C. After the reaction, the lithiated compound of formula 18 is prepared in situ by adding the Wainleb reagent of formula 19 as shown in Scheme 10. For a major reference on this general method, see Chae et al., Journal of Fluorine Chemistry 2003, 120, 185-193 and Konno et al., Tetrahedron 2003, 59, 7571-7580. The method of Scheme 11 is illustrated in step B of Example 1.

Compounds of formula 13 wherein G is halogen can be prepared by a variety of methods known in the art. For a main reference, see Laurent, A. et al., Tetrahedron Letters 1991, 32, 3071-3074 and Okano, T. et al., Synlett 1990, 403-404.

Wainrep amides of Formula 19 are commercially available or can be prepared from the corresponding acid chlorides of Formula 21 as shown in Scheme 12. Acid chlorides can be prepared by a variety of methods known in the synthetic literature, many of which are known compounds or are commercially available.

Esters of formula 12 may be prepared under oxidative conditions as shown in Scheme 13. The conditions for the method of Scheme 13 are similar to those described for the method of Scheme 2 above. The method of Scheme 13 is illustrated in step C of Example 2.

The conversion of the ester of formula 12 to the amide of formula 1a is described by the combination of the methods of Schemes 7 and 5 above.

As shown in Scheme 14, the hydride of Formula 23 may be reacted with the hydrazine of Formula 24 to prepare the hydrazones of Formulas 4 and 22. In this reaction, either stoichiometric or excess hydrazine 24 is commonly used. Typical solvents include alcohols (eg methanol or ethanol) and ethers (eg tetrahydrofuran or 1,4-dioxane). The reaction is typically carried out at a temperature in the range of 0 ° C. to the reflux temperature of the solvent and is completed in 0.5 to 48 hours. Acid catalysts such as p-toluenesulfonic acid or acetic acid are sometimes used in the process of Scheme 14. Procedures for this method are described in Eur. J. Med. Chem. 2004, 39, 499-505; Bioorg. Med. Chem. 2003, 11, 4161-4169. The method of Scheme 14 is illustrated in step A of Example 2.

Aldehydes of formula 23 may be prepared by a variety of methods known in the art, and some aldehydes are known compounds or are commercially available.

Styrene of Formula 5 may be prepared as shown in Scheme 15. This method comprises a palladium-catalyst coupling of bromoalkene of formula 20 with aryl boronic acid of formula 25. For a review of this general method, reference is made to the references listed for the method of Scheme 4. A typical procedure for this method is illustrated as Step B of Example 2.

Those skilled in the art will appreciate that the compounds of formula 1 and the intermediates described herein may be applied to a variety of electrophilic, nucleophilic, radical, organometallic, oxidation and reduction reactions for the addition of substituents or for modification of substituents present. It is also recognized that some of the reagents and reaction conditions described above for preparing compounds of Formula 1 are not compatible with certain functional groups present in the intermediate. In such cases, the incorporation of a protection / deprotection sequence or functional interconversion into the synthesis will assist in obtaining the desired product. The use and selection of protecting groups will be apparent to those skilled in chemical synthesis (see, e.g., Greene, T. W .; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed .; Wiley: New York, 1991). Those skilled in the art may in some cases, after introducing the reagents shown as shown in any individual schemes, it may be necessary to carry out additional conventional synthetic steps that are not described in detail to complete the synthesis of the compound of Formula 1 It will be recognized. Those skilled in the art will also recognize that it may be necessary to perform the combination of steps illustrated in the above schemes in an order other than as specified in the specific order presented for preparing compounds of Formula 1.

Without further elaboration, it is believed that one skilled in the art can, using the above description, utilize the present invention to its fullest extent. Accordingly, the following examples are to be construed as illustrative only, and not in any way limiting the disclosure. ¹ H NMR spectra are reported in ppm downfield from tetramethylsilane; "s" means singlet, "d" means doublet, "t" means triplet, "m" means multiplet, "dd" means doublet of doublet, "br s" means wide singlet and "br t" means wide triplet.

Example  One

4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -2-methyl-N- Preparation of (2-pyridinylmethyl) benzamide

Step A: Preparation of 4-bromo-N-methoxy-N, 3-dimethylbenzamide

A stirred suspension of 4-bromo-3-methylbenzoic acid (15 g, 69.0 mmol) in thionyl chloride (60 mL) was heated under reflux for 2 hours and then concentrated in vacuo. Residual acyl chloride is dissolved in dichloromethane (300 mL), which is N, O-dimethylhydroxylamine hydrochloride (7.2 g, 72.0 mmol) and pyridine (16.8 mL, 207.0 in dichloromethane (450 mL) at -20 ° C. mmol) to the stirred solution. The reaction mixture was allowed to warm to room temperature overnight and then washed with 1 M aqueous potassium carbonate solution. The aqueous solution was extracted with dichloromethane. The organic extract was concentrated under reduced pressure. The residue was purified by silica gel chromatography using 50% hexanes / ethyl acetate as eluent to afford the title product as light yellow oil (17.81 g, 69.0 mmol, 100% yield).

Step B: (2E / Z) -1- (4-Bromo-3-methylphenyl) -3- (3,5-dichlorophenyl) -4,4,4-trifluoro-2-buten-1-one Manufacture

To a stirred solution of diisopropylamine (11.1 mL, 83.3 mmol) in tetrahydrofuran (100 mL) at −78 ° C. was added 2.5 M n-BuLi (33.31 mL, 83.3 mmol) in hexanes. The reaction mixture was warmed to 0 ° C, stirred for 20 minutes and then cooled to -78 ° C. 2-bromo-3,3,3-trifluoropropene (6.78 g, 38.7 mmol) was added to the reaction mixture and stirred for 30 minutes. Subsequently, a solution of 4-bromo-N-methoxy-N, 3-dimethylbenzamide (ie, the product of Step A) (5.0 g, 19.4 mmol) in tetrahydrofuran (20 mL) was added at -78 ° C. It was added to the reaction mixture and then warmed to 0 ° C. Water (25 mL) was added to the mixture and then stirred at 0 ° C. for 1 hour. The reaction mixture is extracted with ether, concentrated under reduced pressure, and the oily residue is purified by chromatography on silica gel to give (2E / Z) -3- [bis (1-methylethyl) amino] -1 as a pale orange oil. -(4-bromo-3-methylphenyl) -4,4,4-trifluoro-2-buten-1-one and (2E / Z) -1- (4-bromo-3-methylphenyl) -4 A mixture of, 4,4-trifluoro-3- (methoxymethylamino) -2-buten-1-one (ratio of 2.5: 1 by LCMS) (6.55 g, approximately 92% yield) was obtained.

The crude mixture (3 g, approximately 8.5 mmol) was diluted with tetrahydrofuran (40 mL), cooled to -78 ° C and 3,5-dichlorophenyl magnesium bromide (0.5 M in tetrahydrofuran) (51 mL, 25.5 mmol) was added. The reaction mixture was allowed to warm to room temperature and stirred for 2 hours, then quenched with saturated aqueous ammonium chloride solution and extracted with diethyl ether. The organic solution was concentrated under reduced pressure and the residual oil was purified by silica gel chromatography using 10% ethyl acetate / hexanes as eluent to afford the title product as a yellow oil (3.24 g, 87% yield).

Step C: 3- (4-Bromo-3-methylphenyl) -5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyra Preparation of the sol

(2E / Z) -1- (4-Bromo-3-methylphenyl) -3- (3,5-dichlorophenyl) -4,4,4-trifluoro-2-butene- in ethanol (3 mL) Methylhydrazine (55 mg, 1.18 mmol) was added to a solution of 1-one (ie the product of Step B) (400 mg, 0.91 mmol). The reaction mixture was heated at reflux for 2 hours and then cooled to room temperature. The reaction mixture was quenched by addition of water (5 mL) and extracted with diethyl ether. The organic extract was concentrated under reduced pressure and the residue was purified by silica gel chromatography using 10% ethyl acetate / hexanes as eluent to give the title product as light yellow oil (130 mg, 31% yield).

Step D: 4- [5- (3,5-Dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -2-methyl Preparation of -N- (2-pyridinylmethyl) benzamide

3- (4-Bromo-3-methylphenyl) -5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl)-in toluene (5 mL) To a stirred solution of 1H-pyrazole (ie the product of Step C) (110 mg, 0.24 mmol) 2- (aminomethyl) pyridine (38 mg, 0.35 mmol), [1,1'-bis (diphenylphosphino) Ferrocene] dichloropalladium (II) (10 mg, 0.01 mmol) and triethylamine (0.5 mL) were added. The carbon monoxide gas was bubbled into the reaction mixture for 10 minutes, and then the reaction mixture was heated to 90 ° C. overnight under a carbon monoxide atmosphere maintained using a balloon filled with carbon monoxide. The reaction mixture was concentrated and the residual oil was purified by silica gel chromatography using 100% ethyl acetate as eluent to afford the title product as a pale yellow oil (53 mg, 42% yield).

Example  2

4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -N- (2,2 Preparation of, 2-trifluoroethyl) benzamide

Step A: Preparation of Methyl 4-[(E)-(methylhydrazono) methyl)] benzoate

A solution of methyl 4-formylbenzoate (1.0 g, 6.1 mmol), methylhydrazine sulfate (0.88 g, 6.1 mmol), potassium carbonate (0.92 g, 6.7 mmol) and 1,4-dioxane (25 mL) Heated under reflux for 8 hours. The resulting mixture was cooled to room temperature and treated with excess ice water. The crude product was collected by filtration and air dried to afford the title product, which was used in the next step without further purification.

Step B: Preparation of 1,3-dichloro-5- [1- (trifluoromethyl) ethenyl] benzene

In a mixture of tetrahydrofuran (33 mL), ethylene glycol dimethyl ether (33 mL) and aqueous potassium hydroxide (4 N, 33 mL) in a 200 mL Fisher-Porter sealed tube, 3,5-dichloro Phenylboronic acid (8.72 g, 45.7 mmol) and 2-bromo-3,3,3-trifluoropropene (10.0 g, 57.2 mmol) were added followed by tetrakis (triphenylphosphine) palladium (0 ) (264 mg, 0.23 mmol) was added. The mixture was heated to 75 ° C. for 3 hours. The reaction mixture was partitioned between diethyl ether and water. The aqueous extract was extracted with diethyl ether (2 x 20 mL). The organic extracts were combined, dried (MgSO ₄ ) and concentrated under reduced pressure to give a residue. The residue was purified by silica gel chromatography using 10% ethyl acetate / hexanes as eluent to afford the title compound as a clear oil (4.42 g).

Step C: of methyl 4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] benzoate Produce

Methyl 4-[(E)-(methylhydrazono) methyl)] benzoate (ie the product of step A) (0.475 g, 2.49 mmol) and 1,3-dichloro-5 in ethyl acetate (6 mL) at room temperature N-chlorosuccinimide (0.22 g, 1.7 mmol) and potassium carbonate (0.23) in a solution of [[1- (trifluoromethyl) ethenyl] benzene (ie, the product of Step B) (0.20 g, 0.83 mmol) g, 1.7 mmol) were added sequentially. After stirring for 12 hours, the reaction mixture was partitioned between ice water and ethyl acetate. The organic phase was washed with water and brine, dried over anhydrous sodium sulfate and concentrated. Purification by silica gel column chromatography eluting with 2% ethyl acetate in petroleum ether gave the title product as a semisolid (35 mg).

Step D: Preparation of 4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] benzoic acid

Methyl 4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] in ethanol (2 mL) To a solution of benzoate (ie the product of Step C) (50 mg, 0.12 mmol) was added sodium hydroxide (1 mL of 0.24 M aqueous solution, 0.24 mmol) and the resulting mixture was stirred at 60 ° C. for 3 hours. The resulting mixture was concentrated to remove solvent and the residue was acidified to pH 2 and extracted with ethyl acetate. The organic extracts were combined, washed with brine, dried over anhydrous sodium sulfate and concentrated to give the title carboxylic acid (50 mg) which was used in the next step without purification.

Step E: 4- [5- (3,5-Dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -N- ( Preparation of 2,2,2-trifluoroethyl) benzamide

4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazole-3 in tetrahydrofuran (2 mL) at room temperature -Yl] benzoic acid (ie the crude product of step D) (50 mg, 0.12 mmol) and triethylamine (0.026 mL, 0.19 mmol) were treated with methyl chloroformate (0.014 mL, 0.19 mmol) and the reaction The mixture was stirred for 30 minutes. 2,2,2-trifluoroethylamine (0.015 mL, 0.19 mmol) was then added to the reaction mixture at room temperature and stirred for 2 more hours, then poured into ice and quenched. The resulting mixture was extracted with ethyl acetate and the organic extracts were washed with water and brine, dried over anhydrous sodium sulfate and concentrated. Purification by silica gel chromatography eluting with 25% ethyl acetate in petroleum ether gave the title product as a compound of the invention as a solid (40 mg, 70% yield).

By the procedures described herein in conjunction with methods known in the art, the compounds of Tables 1-8 below can be prepared. The following abbreviations were used in the table: CN means cyano, NO ₂ means nitro, Me means methyl, Et means ethyl, Pr means propyl, c-Pr is cyclo Propyl, and OMe means methoxy. The (R ² ) _m shown represents a combination of (R ² ) _n when Z is CR ² .

Formulation / Utility

The compounds of the present invention can generally be used as a formulation or composition with a carrier suitable for agronomic or nonagronomic applications comprising one or more liquid diluents, solid diluents or surfactants. The formulation or composition component is selected to match the physical properties of the active ingredient, the mode of application and environmental factors such as soil type, humidity and temperature.

Useful formulations include liquids, such as solutions (including emulsifiable concentrates) that can optionally be thickened into gels, suspensions, emulsions (microemulsions and / or suspending agents) and the like. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspending agents. Common types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.

Common types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings), and the like, which may be water dispersible (“wettable”) or water soluble. Membranes and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. The active ingredient may be (micro) encapsulated and may also be formed into a suspension or solid preparation; Alternatively, the entire formulation containing the active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules have the advantages of both emulsifiable concentrate formulations and dry granules. High concentration compositions are mainly used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid preparations are formulated for easy dilution in spray media, usually water. Spray volumes can range from about 1 to several thousand liters per hectare, but more typically from about 10 to several hundred liters per hectare. Sprayable formulations may be tank mixed with water or other suitable medium for the treatment of the leaves by air or surface application, or for application to the growth medium of the plant. Liquid and dry preparations can be metered directly in a drip irrigation system or can be metered in the furrow during sowing. Liquid and solid preparations can be applied on the seeds of crops and other preferred plants as seed treatment prior to sowing to protect the growth of roots and other subground vegetation and / or foliage through systemic absorption.

The formulation will typically contain an effective amount of the active ingredient, diluent and surfactant in the following approximate range, which is added up to 100% by weight.

weight% Active ingredient diluent Surfactants Water dispersible and water soluble granules, tablets and powders 0.001-90 0-99.999 0-15 Suspensions, emulsions, solutions (including emulsifiable concentrates) 1-50 40-99 0-50 Dust 1-25 70-99 0-5 Granules and Pellets 0.001-99 5-99.999 0-15 High concentration composition 90-99 0-10 0-2

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

Liquid diluents include, for example, water, N, N-dimethylalkanamide (eg, N, N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (eg, N- Methylpyrrolidinone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffin (e.g., white inorganic oil, common paraffin, isoparaffin) , Alkylbenzenes, alkylnaphthalenes, glycerin, glycerol triacetate, sorbitol, triacetin, aromatic hydrocarbons, dearomatic aliphatic substances, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl- 2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters, Such as alkylated lactate esters, dibasic esters and γ-butyrolactone, and alcohols that may be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol , n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydro Furfuryl alcohol, diacetone alcohol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (usually C ₆ -C ₂₂ ), such as plant seed and fruit oils (eg olive oil, castor oil, linseed oil, tung oil, sesame oil, corn oil (maize) ), Peanut oil, sunflower seed oil, grape seed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil and palm kernel oil), animal-source fats (e.g., tallow, lard, lard, liver oil, fish oil), And mixtures thereof. Liquid diluents also include alkylated (eg methylated, ethylated, butylated) fatty acids that can be obtained by hydrolysis of glycerol esters from plant and animal sources and can be purified by distillation. Conventional liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, lists surfactants and recommended usage.

Solid and liquid compositions of the invention often comprise one or more surfactants. When added to a liquid phase, the surfactant typically deforms, and most often reduces, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, the surfactant may be useful as a wetting agent, dispersing agent, emulsifier or antifoaming agent.

Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the compositions of the present invention include alcohol alkoxylates such as natural and synthetic alcohols (which may be branched or linear) and include alcohols and ethylene oxides, propylene oxides, butylene oxides or Alcohol alkoxylates prepared from mixtures thereof; Amine ethoxylates, alkanolamides and ethoxylated alkanolamides; Alkoxylated triglycerides such as ethoxylated soybean oil, castor oil and rapeseed oil; Alkylphenol alkoxylates such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate and dodecylphenol ethoxylate (phenol and ethylene oxide, propylene oxide, butylene oxide or theirs Prepared from mixing); Block polymers prepared from ethylene oxide or propylene oxide, and reverse block polymers wherein the end blocks are prepared from propylene oxide; Ethoxylated fatty acids; Ethoxylated fatty acid esters and oils; Ethoxylated methyl esters; Ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); Fatty acid esters, glycerol esters, lanolin derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; Other sorbitan derivatives such as sorbitan esters; Polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; Polyethylene glycol (peg); Polyethylene glycol fatty acid esters; Silicone surfactants; And sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.

Useful anionic surfactants include alkylaryl sulfonic acids and salts thereof; Carboxylated alcohol or alkylphenol ethoxylates; Diphenyl sulfonate derivatives; Lignin and lignin derivatives such as lignosulfonate; Maleic acid or succinic acid, or anhydrides thereof; Olefin sulfonates; Phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; Protein-based surfactants; Sarcosine derivatives; Styryl phenol ether sulfates; Sulfates and sulfonates of oils and fatty acids; Sulfates and sulfonates of ethoxylated alkylphenols; Sulfates of alcohols; Sulfates of ethoxylated alcohols; Sulfonates of amines and amides such as N, N-alkyltaurates; Sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzene; Sulfonates of condensed naphthalenes; Sulfonates of naphthalene and alkyl naphthalene; Sulfonates of petroleum refining; Sulfosuccinamate; And sulfosuccinates and derivatives thereof such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include amides and ethoxylated amides; Amines such as N-alkyl propanediamine, tripropylenetriamine and dipropylenetetraamine, and ethoxylated amines, ethoxylated diamines and propoxylated amines (amines and ethylene oxides, propylene oxides, butylene oxides or their Prepared from mixing); Amine salts such as amine acetate, and diamine salts; Quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and di-quaternary salts; And amine oxides such as alkyldimethylamine oxide and bis- (2-hydroxyethyl) -alkylamine oxide. Also useful for the compositions of the present invention are mixtures of nonionic and anionic surfactants, or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants, and their recommended usage, are described in McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co .; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964] and [A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987].

The compositions of the present invention may also contain formulation aids and additives known to those skilled in the art as formulation aids, some of which may be considered to also function as solid diluents, liquid diluents or surfactants. Such formulation aids and additives include pH (buffers), foaming during processing (defoamers such as polyorganosiloxanes), sedimentation (suspensioning agents) of active ingredients, viscosity (thixotropic thickeners), growth of microorganisms in containers (antimicrobial agents) ), Freezing (floating agent), color (dye / pigment dispersion), washing (deposition agent or sticker), evaporation (evaporation retardant), and other formulation properties of the product. Film-forming agents include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation aids and additives include those listed in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co. and PCT Publication No. WO 03/024222.

Compounds of Formula 1 and any other active ingredients are typically incorporated into the compositions of the present invention by dissolving the active ingredients in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the components. If the solvent of the liquid composition intended for use as an emulsifiable concentrate is not water miscible, an emulsifier is usually added to emulsify the active ingredient-containing solvent when diluted with water. Active ingredient slurries having a particle diameter of 2,000 μm or less can be wet milled using a media mill to obtain particles having an average diameter of less than 3 μm. Aqueous slurries can be prepared from a polished suspension concentrate (see, eg, US Pat. No. 3,060,084), or further processed by spray drying to form water dispersible granules. Dry formulations generally require a dry grinding process that produces an average particle diameter of 2 to 10 μm. Dusts and powders can be prepared by blending and generally by grinding (eg, using a hammer grinder or a fluid energy grinder). Granules and pellets can be prepared by spraying the active substance on the preformed granular carrier or by agglomeration techniques. Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57, and also WO 91 / See 13546. Pellets can be prepared as described in US Pat. No. 4,172,714. Water dispersible and water soluble granules can be prepared as taught in US Pat. No. 4,144,050, US Pat. No. 3,920,442, and German Pat. No. 3,246,493. Tablets may be prepared as taught in US Pat. No. 5,180,587, US Pat. No. 5,232,701 and US Pat. No. 5,208,030. Films can be prepared as taught in British Patent 2,095,558 and US Patent 3,299,566.

For further information regarding the field of formulation, see T. S. Woods, "The Formulator's Toolbox-Product Forms for Modern Agriculture" in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and TR Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also US Pat. No. 3,235,361, paragraph 6, line 16 to paragraph 7, line 19, and Examples 10-41; 5 paragraph 43 to 7 paragraph 62 in US Pat. Nos. 3,309,192, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-. 182; 3 paragraph 66 to 5 paragraph 17, and US Pat. Nos. 2,891,855, and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al, Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; And Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

In the examples below, all percentages are by weight and all formulations are prepared in a conventional manner. Compound numbers refer to compounds in Index Table A below. Without further elaboration, it is believed that one skilled in the art can, using the above description, utilize the present invention to its fullest extent. Accordingly, the following examples are merely illustrative and do not limit the disclosure in any way. Percentages are by weight unless otherwise indicated.

Example  A

High concentration Concentrate Compound 2 98.5% Silica airgel 0.5% Synthetic Amorphous Fine Silica 1.0%

Example  B

Wettability Powder Compound 11 65.0% Dodecylphenol Polyethylene Glycol Ether 2.0% Sodium ligninsulfonate 4.0% Sodium silicate aluminate 6.0% Montmorillonite (Plastic) 23.0%

Example  C

Granules Compound 12 10.0% Attapulgite granules (low volatility, 0.71 / 0.30 mm; U.S.S. No. 25-50 sieve) 90.0%

Example  D

Extruded Pellet Compound 19 25.0% Anhydrous sodium sulfate 10.0% Crude calcium ligninsulfonate 5.0% Sodium alkylnaphthalenesulfonate 1.0% Calcium / Magnesium Bentonite 59.0%

Example  E

Emulsifying Concentrate Compound 2 10.0% Polyoxyethylene Sorbitol Hexoleate 20.0% C ₆ -C ₁₀ Fatty Acid Methyl Ester 70.0%

Example  F

Microemulsion Compound 11 5.0% Polyvinylpyrrolidone-vinyl acetate copolymer 30.0% Alkylpolyglycoside 30.0% Glyceryl Monooleate 15.0% water 20.0%

Example  G

Seed treatment Compound 12 20.00% Polyvinylpyrrolidone-vinyl acetate copolymer 5.00% Montan wax 5.00% Calcium Lignin Sulfonate 1.00% Polyoxyethylene / Polyoxypropylene Block Copolymer 1.00% Stearyl Alcohol (POE 20) 2.00% Polyorganosilane 0.20% Colorant red dye 0.05% water 65.75%

Example  H

Fertilizer sticks Compound 19 2.5% Pyrrolidone-Styrene Copolymer 4.8% Tristyrylphenyl 16-ethoxylate 2.3% talc 0.8% Corn starch 5.0% Nitrophoska Permanent (registered trademark) 15-9-15 Delayed-release fertilizer (BASF) 36.0% kaoline 38.0% water 10.6%

The compounds of the present invention show activity against a wide range of invertebrate pests. Such pests include, for example, invertebrates that live in a variety of environments such as plant foliage, roots, soil, harvested crops or other foodstuffs, building structures or animal shells. Such pests include, for example, houseplants (including leaves, stems, flowers, and fruits), seeds, wood, textile fibers, or blood or tissues of animals, for example, whereby, for example, cultivated or stored crops Include invertebrates that cause damage or damage to scientific crops, forests, greenhouse crops, ornamental plants, seedling crops, stored food or textile products, or houses or other structures or their contents, or which are harmful to animal health or public health. Those skilled in the art will recognize that not all of the compounds are equally effective for all stages of growth of all pests.

Thus, the compounds and compositions of the present invention are agronomically useful for the protection of crops from herbivorous invertebrate pests and also non-agronomically useful for the protection of other horticultural crops and plants from herbivorous invertebrate pests. This utility is useful for crops and other plants (i.e. both agronomic and non-agronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide advantageous properties. Includes protection. Examples of these characteristics include resistance to herbicides, resistance to herbivorous pests (eg insects, mites, aphids, spiders, nematodes, snails, plant-pathogenic fungi, bacteria and viruses), improvement of plant growth, growth adverse conditions Such as increased resistance to high and low temperatures, low or high soil moisture and high salinity, increased flowering or fruiting, improved yields, faster ripening, higher quality and / or nutritional value of the harvest, or storage or processability of the harvest. Improvements are included. Transgenic plants can be modified to express a number of properties. Examples of plants having properties provided by genetic engineering or mutagenesis include the bactericidal Bacillus thuringiensis ) A variety of corn, cotton, soy and potato expressing toxicity, such as YIELD GARD®, KNOCKOUT®, STARLINK®, Bolgard ( BOLLGARD (R), NuCOTN (R) and NEWLEAF (R), and various herbicide-resistant corn, cotton, soybean and rapeseeds such as ROUNDUP READY N provides resistance to LIBERTY LINK®, IMI®, STS® and CLEARFIELD®, and glyphosate herbicides Crops that express acetyltransferase (GAT), or crops that contain the HRA gene that provides resistance to herbicides that inhibit acetolactate synthase (ALS). The compounds and compositions of the present invention may interact synergistically with a property introduced or genetically modified by genetic engineering, thereby enhancing the phenotype expression or effect of the property or the compounds and compositions of the present invention. May increase the effectiveness of invertebrate pest control. In particular, the compounds and compositions of the present invention may synergistically interact with phenotypic expression of proteins or other natural products that are toxic to invertebrate pests to provide pest control effects greater than the additive effect.

The compositions of the invention also contain fertilizers comprising plant nutrients, for example one or more plant nutrients selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc and molybdenum. Compositions may optionally be included. Of note is a composition comprising at least one fertilizer composition comprising at least one phytonutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnesium. The composition of the present invention further comprising one or more plant nutrients may be in liquid or solid form. Noteworthy are solid preparations in the form of granules, small sticks or tablets. Solid formulations comprising a fertilizer composition can be prepared by mixing a compound or composition of the invention with the fertilizer composition together with the preparation ingredients and then preparing the formulation by methods such as granulation or extrusion. Alternatively, solid preparations are prepared by spraying a solution or suspension of a compound or composition of the invention in a volatile solvent onto a prefabricated fertilizer composition in the form of a stereosterically stable mixture, such as granules, small sticks or tablets, and then evaporating the solvent. can do.

Non-agronomic uses refer to invertebrate pest control in areas other than the cropland of crop plants. Non-agronomic uses of the compounds and compositions of the present invention include the control of invertebrate pests in stored cereals, legumes and other foodstuffs, and textiles (eg, clothing and carpets). Non-agronomic uses of the compounds and compositions of the invention also include invertebrate pest control along tubular plants, forests, barns, roadsides and railroad tracks, and on grass (eg, lawns, golf courses, and pastures). Non-agronomic uses of the compounds and compositions of the present invention also include invertebrate pest control in homes and other buildings where humans and / or pets, farm animals, ranch animals, zoo animals or other animals may reside. . Nonagronomic uses of the compounds and compositions of the present invention also include controlling pests such as termites that can damage wood or other building materials used in buildings.

Non-agronomic uses of the compounds and compositions of the present invention also include protecting human and animal health by controlling invertebrate pests that are parasitic or infectious infectious diseases. Control of animal parasites control of external parasites parasitic on the body surface of the host animal (eg, shoulders, armpits, abdomen, thighs), and inside the host animal body (eg, stomach, small intestine, lungs). Control of internal parasites parasitic (vein, subcutaneous, lymphoid tissue). External parasitic or disease infectious pests include, for example, hair mites, mites, teeth, mosquitoes, flies, moths, and fleas. Internal parasites include filaments, duodenum and intestinal worms. The compounds and compositions of the present invention are suitable for systematically and / or non-systemically controlling invasion or infection by parasites in animals. The compounds and compositions of the present invention are particularly suitable for combating external parasitic or disease infectious pests. The compounds and compositions of the present invention include agricultural working animals such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, hens, turkeys, ducks, geese and bees; Pets and livestock such as dogs, cats, pet birds, and aquarium fish; And parasites that infect so-called experimental animals such as hamsters, guinea pigs, rats, and mice. The killing of these parasites reduces the mortality and performance (in terms of meat, milk, wool, leather, eggs, honey, etc.) and, therefore, animal livestock industry is more economical and simpler by applying the composition comprising the compound of the present invention. Done.

Examples of agronomic or non-agronomic invertebrate pests include eggs, larvae and adults of chestnut moths such as giant insect beetles, macropods, insects and heliotin (such as rice chestnut moth [Sesameia inferens)Sesamia inferens) Walker], corn stalk [Sesamia Nona grioides (Sesamia nonagrioides) Lefebvre], Southern Giant Beetle [Spodopteria eridania (Spdoptera eridania) Cramer], Cardinal giant beetle [Spodoptera fruitiferda]Spdoptera frugiperda) J.E. Smith], Pabamoth moth [Sofdorftera exigua (Spdoptera exigua) Huebner], Tobacco Seminar Room [Spodoptera Litoralis (Spdoptera littoralis) Boisduval], Yellow Striped Giant Beetle [Spodofterra ornitogalli (Spdoptera ornithogalli) Guenee], Roundup Seminar Room [Agrotis Ypsilon (Agrotis ipsilon) Hufnagel], Velvet Bean Caterpillar [Anticarsia Gemmamatlis (Anticarsia gemmatalis) Huebner], green fruit beetle [Litopane antennata (Lithophane antennata) Walker], Thief Moth [Varatra Brassicae (Barathra brassicae) Linnaeus], soybean beetle [Capital influenza (Pseudoplusia includens) Walker, Cabbage Beetle [Tricopflusiani (Trichoplusia ni) Huebner], Tobacco Moth [Heliotis Virescens (Heliothis virescens) Fabricius]}; Tree moths from the moth family, casebearers, fire moths, worms, cabbages and alluvial moths (such as the European Corn Bark [Austrian Nubilelis)Ostrinia nubilalis) Huebner], Navel Orange Bug [Amiellois Transitella (Amyelois transitella) Walker], corn root fire moth [Crambus Caliginoscelus (Crambus caliginosellus) Clemens], Turf Fire MothCrambinae)], For example, grass moths [Herfetogramma Riccassisalis (Herpetogramma licarsisalis) Walker, Sugar Cane Stem Bark [Chilo Inpuscatelus (Chilo infuscatellusSnellen], cherry tomato tree [Neoureshinodes eleganthalis (Neoleucinodes elegantalis) Guenee], Green Leaf Moth [Knapaloserus Medialis (Cnaphalocerus medinalis], Grape Horn Moth [Desmia Funeralis (Desmia funeralis) Huebner], melon worms [Diaphania nitidalis (Diaphania nitidalis) Stoll], Cabbage nucleus grub [Heruelala Hydralis (Helluala hydralis) Guenee], Yellow Stem Bark [Sirpopaga insertulas]Scirpophaga incertulas) Walker, early buds, [Sirpopaga inpuscatelus]Scirpophaga infuscatellusSnellen], White Stem Bark [Shirpopa Inotata (Scirpophaga innotata) Walker], the buds of the buds of the shootsScirpophaga nivella) Fabricius], Pseudomonas moth [Chilo Polycress (Chilo polychrysus) Meyrick], Cabbage larvae [Crosidolomia vinotalis (Crocidolomia binotalis) English]}; Leaf moths of moths, caterpillars, seed insects and fruit moths (eg codling moths [Sidiom pomonaella)Cydia pomonella) Linnaeus], Grape Moth [Endopizza Viteana (Endopiza viteana) Clemens], Peach Sprout Moth [Grapolita Molesta (Grapholita molesta) Busck], artificial citrus codling moth [Cryptoplevia leukotreta (Cryptophlebia leucotreta) Meyrick], Citrus Tree Root [Ecditolopa Aurantiana (Ecdytolopha aurantiana) Lima], red-striped leaf moth [Arrogotaenia belutina (Argyrotaenia velutinana) Walker], diagonal stripe leaf moth [Koristoneura Rosaceana (Choristoneura rosaceana) Harris], Light Brown Apple Moth [Epipia's Post Vita (Epiphyas postvittana) Walker], European Grape Moth [Eupoesila abigueella (Eupoecilia ambiguella) Huebner], apple sprout moth [Pandemis pyrusana (Pandemis pyrusana) Kearfott], omnivorous leaf horse moth [platinota stooltana]Platyota stultana) Walsingham], Striped Fruit Leaf Moth [Pandemis cerasana (Pandemis cerasana) Huebner], brown apple leaf moth [Pandemis heparana (Pandemis heparana) Denis &Schiffermueller]}; And many other economically important Lepidoptera {such as cabbage myth moths [Flutella xycilella]Plutella xylostella) Linnaeus], Pink Cotton Seeds [Pectinophora Gosipela]Pectinophora gossypiella) Saunders], cicadabang [Limantri Dispar (Lymantria dispar) Linnaeus], Peach Fruit Tree Root [Carphosina Niponensis (Carposina niponensis) Walsingham], Peach Branch Tree Root [Anarcia Lineatela (Anarsia lineatella) Zeller], Potato Moth Larva [Pitorimaea opulculella (Phthorimaea operculella) Zeller], speckled oyster moth [Litocholeth Blancardella (Lithocolletis blancardella) Fabricius], Asian Apple Oyster Moth [Litocholeth Lingoniella (Lithocolletis ringoniella) Matsumura], Perhaps Moth [Lerodeaupala]Lerodea eufala) Edwards], apple oyster moth [Leukofthera citella (Leucoptera scitella) Zeller]}; Eggs, larvae and adults of cockroaches, including cockroaches from the cockropods and the Pinnacleaceae, for example Oriental cockroaches [Blata Orientalis (Blatta orientalis) Linnaeus], Asian Cockroaches [Blatella Asahinai (Blatella asahinai) Mizukubo], German Cockroach [Blatella Germanica (Blattella germanica) Linnaeus], Brown Striped Cockroach [Supela Longgifalfa (Supella longipalpa) Fabricius], US Cockroach [Peripheretta Americana (Periplaneta americana) Linnaeus], Brown Cockroach [Periplanetta Brunnea (Periplaneta brunnea) Burmeister], Madeira Cockroach [Leuco-Paea]Leucophaea maderae) Fabricius], Smokey Brown Cockroach [Periplaneta Locosa]Periplaneta fuliginosa) Service], Australian Cockroach [Periplaneta australasia (Periplaneta australasiae) Fabricius], Lobster Cockroach [Naufoeta Cinerea (Nauphoeta cinerea) Olivier] and Slippery Cockroaches [Simplose Falls (Symploce pallens) Stephens]}; Eggs, fronds, fruits, roots, seeds, and vesicles of larvae and adult species of coleoptera, including weevil, weevil and weevil from weevil.Anthonomus grandis) Boheman], Rice Water WeevilLissorhoptrus oryzophilus) Kuschel], Grain weevil [Sitophilus Granarius (Sitophilus granarius) Linnaeus], rice weevil [Sitophilus orizae (Sitophilus oryzae) Linnaeus], annual year-old weevil weevil [Ristonotous maculolis (Listronotus maculicollis) Dietz], Sapphusium weevil [Sphenophorus parbulus (Sphenophorus parvulus) Gyllenhal], Hunting Weevil [Spernophorus Benatus Vestitus (Sphenophorus venatus vestitus], Denver weevil [Spernophorus Sicatritiatus (Sphenophorus cicatristriatus) Fahraeus]}; Leaf flea beetle beetle, cucumber leaf beetle, root beetle, leaf beetle, potato leaf beetle and oyster moth {for example, Colorado potato beetle [Leptino tarsa dessumineata]Leptinotarsa decemlineata)], Western Corn Root Beetle [Diabrotica Birgifera Birgifera (Diabrotica virgifera virgifera) LeConte]}; Scarabs and other beetles from the Chafer family {eg Japanese beetles [Popilia japonica (Popillia japonica) Newman], Backed Beetle [Anomaly Orientalis (Anomala orientalis) Waterhouse, Exomala OrientalisExomala orientalis(Waterhouse) Baraud], Northern Mask Beetle [Cyclocepala Borealis (Cyclocephala borealisArrow], Southern Masked Beetle [Cyclocephala Imakulata (Cyclocephala immaculata) Olivier or cyclocephala rudidaCyclocephala lurida) Bland], dung beetles and slugs [Apodius (Aphodius) Species], Black Grass Atahenius [Atahenius Sputteruls (Ataenius spretulus) Haldeman], Oak Leaf ScarabCotinis nitida) Linnaeus], Asian Garden Scarab [Maldera Castanea (Maladera castaneaArrow], May / June Scarab [Pilopaga (PhyllophagaSpecies] and European beetles [resortogloss mazalis]Rhizotrogus majalis) Razoumowsky]}; Occitan from the Occitanaceae; Worms from the coleopteran family; Woodworms from the tree family and wheat beetle from the family tree. In addition, agronomic and non-agronomic pests include eggs, adults, and larvae of the herbaceous species, including the herb from the herbaceous family, such as the European herb beetle [forpicula aurularia (Forficula auricularia) Linnaeus], the Black Herb Beetle [Celly soches Morio (Chelisoches morio) Fabricius]}; Prickly worm and larvae eggs, immature, adult and larvae, such as stink bugs from the Blinding hemipterae, cicada from the cicada, cicada larva from the cicadaEmpoasca) Species), bedbugs from the bedbug family [eg, Simex lectularius (Cimex lectulariusLinnaeus], Cicada from Cicada and Cicada, Horn Cicada from Cicada, Cicada from Cicada, Cicada from Cicada, Aphid from Aphid, Cicada from Root Beetle, Cicada from Cicada Beetles from the family of small insects, insects from the family of insects, insects from the family of insects, insects from the insect family of insects, insects from the hemipteran family, and chinch bugs (such as the hairy infestation [Blisus leucoterus hyrtus]Blissus leucopterus hirtus) Montandon and Southern Chin Bedbug [Blisus Insularis (Blissus insularis) Barber]}, and other seed bed bugs from the hemipteran family, foam bugs from the hemipteran family, pumpkin stink bugs from the hemipteran family, and red bed bugs from the hemipteran family, and starling stink bugs that harm cotton. In addition, eggs, larvae, larvae and adults of dust mites (such as mite mite), spider mite and red mite of leaf mite {for example, European red mite [Panonicus wool (Panonychus ulmi) Koch], two spotty spider mite [Tetranicus urticae (Tetranychus urticae) Koch], McDaniel's mite [Tetranicus McDanielle (Tetranychus mcdanieli) McGregor]}; Flat mite of wrinkles mite {For example citrus flat mite [Brevifalpus Levis (Brevipalpus lewisi) McGregor]}; Rust and snow mites of gall mites, and other leaf-ingested mites, and some mites that are important in human and animal health, ie dust mites of Bacillus mite, vesicle mites of follicular mites, round mites of the family Mites of the true mite family commonly known as true mites {e.g. deer mites [Ixodes scapularis (Ixodes scapularis) Say], Australian paralytic mite [Exodes holocycloss (Ixodes holocyclus) Neumann], the American mite [Dermassentor Variabilis (Dermacentor variabilis)], Isolated tick mite [Amblyomma Americanum (Amblyomma americanum) Linnaeus]}, and the mite of the mole family known as soft mites {for example, regressive fever mites [Ornito dorothy turicata (Ornithodoros turicata], Common poultry mite [Argas radidiatus (Argas radiatus)]}; Scabs and itching mites of ear mites, blister mites and scabies mites; Eggs, adults and immatures of locusts, including larvae, grasshoppers and crickets {e.g., mobile larvae [Melanoflu sanguinipes (Melanoplus sanguinipes) Fabricius, Melanoflue deferentialis (M. differentialis) Thomas], the US chief [Schistoserca Americana (Schistocerca americana) Drury], Desert Locust [Schistoserca Gregaria (Schistocerca gregaria) Forskal], Mobile Grasshopper [Rocusta Migrattoria (Locusta migratoria) Linnaeus], Shrub Grasshopper [Zonoserus (ZonocerusSpecies)], House Cricket [Acheta Domestikus (Acheta domesticus) Linnaeus], ground puppy {eg, tan puppy [Scapteriscus Vicinus (Scapteriscus vicinus) Scudder] and Southern Puppy [Scapteriscus BorelliiScapteriscus borellii) Giglio-Tos]}}; Peugeot flies (eg Liriomija)Liriomyza) Species, such as vegetable leaf oyster flies [Liriomiza Sativae (Liriomyza sativaeBlanchard]], etc., fruit flies (fruit flies), flower flies [eg Oscinella frit (Oscinella frit) Linnaeus], ground maggots, house flies [eg Musca Domestica (Musca domestica) Linnaeus], baby house flies [eg Pania canicularis (Fannia canicularis) Linnaeus, Pania Femoralis (F. femoralis) Stein], chimpanzees [e.g.Stomoxys calcitrans) Linnaeus], facial flies, horn flies, large black flies [eg chrysomia (Chrysomya) Species, Formia (Phormia), Adult and immature of the fly, as well as other muscoid fly pests, horse flies (eg, Tabanus)Tabanus) Species, horse flies [eg, gastrophilus (Gastrophilus) Species, Oestrus (Oestrus) Species, cowflies [eg Hipderma (Hypoderma) Species], deer flies [eg critsis (Chrysops) Species], ked [such as melopaggus obinuus (Melophagus ovinus) Linnaeus] and other shorthorn parrots, mosquitoes [eg, Aedes (Aedes) Bell, Anopheles (Anopheles) Bell, CoolexCulex) Species, mudflyes [eg, promulumium (Prosimulium) Species, SiriumSimulium) Species], biting back, sand flies, rhizomes, and other longhorn parrots; Onion shovel [Trip's Tabacchi (Throps tabaci) Lindeman], Flower Shovel [Franclinella]FrankliniellaSpecies, adult and immature of the coleoptera, including other leaf-eating shovels; Florida king ant [camponotus floridaus (Camponotus floridanus) Buckley], red king ant [Camponotus Perugineus (Camponotus ferrugineus) Fabricius], black king ant [camponotus pa. (Camponotus pennsylvanicus) De Geer], White-footed Ant [Techno Mirmex Albifes (Technomyrmex albipes) fr. Smith], big headed antPheidoleSpecies], ghost ant [tapinoma melanocefalum (Tapinoma melanocephalum) Fabricius], Love Ants [Monomorium Pharaohs (Monomorium pharaonis) Linnaeus], the small fire ant [Wasmannia auropunktata (Wasmannia auropunctata) Roger], Fire Ant [Solenopsis Geminata (Solenopsis geminata) Fabricius], imported red fire ant [Solenopsis invicta (Solenopsis invicta) Buren], the Argentine ant [Iri domirmex Humilis (Iridomyrmex humilis) Mayr], the crazy ant [paratrekina rongikornis (Paratrechina longicornis) Latreille], wrinkled ant [tetramorium kaespitum (Tetramorium caespitum) Linnaeus], cornfield ant [Lassius alienus (Lasius alienus) Foerster] and the smelly house ant [tapinoma cecil (Tapinoma sessile)], Including insects of felling insects, including ants of the family Ants. Other fellings include bees (including zucchini), bees, longevity wasps, wasps And leaf bee [Neodiprion (Neodiprion) Bell; SepusCephus) Bell]; Termitidae (for example Macrotermes)Macrotermes) Species, Odontotermes obesus (Odontotermes obesus) Rambur], Kalotermitidae [eg, Cryptotermes (Cryptotermes) Species and Rinotermitidae [eg, reticultermeth (Reticulitermes) Species, coptotermes (Coptotermes) Species, heterotermes tenuis (Heterotermes tenuis) Hagen] termite, Oriental subterranean termite [Reticulite meth Flavipes]Reticulitermes flavipes) Kollar], Western Underground Termite [Reticulite Mess Hesperus (Reticulitermes hesperus) Banks], Formosan Underground Termite [Coffitotermes Formosanus (Coptotermes formosanus) Shiraki], Western Indian Dried Wood Termite [Incitermes imigrins]Incisitermes immigrans) Snyder], powder post termite [Cryptotermes brevis (Cryptotermes brevis) Walker, Drywood Termite [Incitermes sniderry (Incisitermes snyderi) Light, Southeastern Underground Termite [Reticulite Mess Birginicus (Reticulitermes virginicus) Banks], Western Dried Termite [Incitermes Minor (Incisitermes minor) Hagen], tree termites, such as nasu titermes (Nasutitermes) Insect pests of termite, including species, and other termites of economic importance; Insect pests of the moth, such as worms [Lepisma sacarina (Lepisma saccharina) Linnaeus] and speckles [Thermovia domestica (Thermobia domestica) Packard]; Head lice [Pediculus fumanus capitis (Pediculus humanus capitis) De Geer], the body [pediculus Humanus (Pediculus humanus) Linnaeus], chicken body [Menacantus stramineus (Menacanthus stramineusNitszch], and the dog bites [Tricodextes canis (Trichodectes canis) De Geer], lint-free [Goniocottes Galinae (Goniocotes gallinae) De Geer], both bodies [bobi-cola orbis (Bovicola ovis) Schrank], short nose soi [Haematopinus aursterus (Haematopinus eurysternusNitzsch], Ginco Soi [Rinognathus Bvituli (Linognathus vituli) Linnaeus, and insect pests of the hairy neck, including vampire and radish parasites, which attack humans and animals; Oriental rat flea [Xenopsilla CeliaXenopsylla cheopis) Rothschild], cat fleasCtenocephalides felis) Bouche], Dog Flea [Ctenenocephalides Canis (Ctenocephalides canis) Curtis], Chicken Flea [Seratophyllus Galinae]Ceratophyllus gallinae) Schrank], Tick flea [Echidnogaga Galinaseah (Echidnophaga gallinacea) Westwood], the human flea [Fullex Iritans]Pulex irritans) Linnaeus, and insect pests of fleas, including other fleas that plague mammals and birds. Additional arthropod pests included include spiders from arachnids, such as brown recluse spiders (Loxoseles reclusa)Loxosceles reclusa) Gertsch & Mulaik] and the Black Widow Spider [Latrodectus Mactans (Latrodectus mactans) Fabricius, and centipedes from Grimamok, such as the money beetle [Scutigera coleoptrata (Scutigera coleoptrataLinnaeus]. In addition, the compounds of the present invention can be used for the production of nematode, roundworm, lumberjack, nematode, stern nematode and oilseed trees such as but not limited to economically important agronomic pests (i.e., root-knot nematodes)MeloidogyneNematode disease nematodes, root rot nematodesPratylenchusLesion nematodes, archery nematodes in the genusTrichodorusStump root nematodes, etc.) and animal and human health pests (i.e. all economically important reptiles, tapeworms, and roundworms, such as Strongillus vulgaris in horses)Strongylus vulgaris), Toxocara canis in dogs (Toxocara canis), Haemoncus Contortus (Haemonchus contortus), Dirophyllaria imitis in dogsDirofilaria immitis) Leidy, anofelocephala perfoliata in horses (Anoplocephala perfoliata), Pasciola hepatica in ruminantsFasciola hepatica) Are active against members of the nematode, tapeworm, fluke, and oral nematodes, including economically important members of Linnaeus et al.

Insect pests of the compounds In particular, the moth neck of the present invention {e.g., Alabama are Gila years old child (Alabama argillacea ) Huebner (cotton leaf beetle), Archips argyrospila) Walker (ipmalyi fruit moth), chips are rosana (A. rosana) Linnaeus (European ipmalyi moths) and other chips are kind, fills can buy pre-leased (Chilo suppressalis ) Walker ( Cnaphloclocs ), Cnaphalocrosis medinalis ) Guenee (rice leaf moth), Crambus caliginoceleus Clemens (corn root fire moth), Crambus terterus teterrellus ) Zincken (Cyphoa moth), Sidian pomonella Linnaeus ( Caudling moth), Earias insulara ( Earias) insulana ) Boisduval (thorn cotton worm), Earias vitella ( Earias) vittella ) Fabricius (spotted cotton worm), Helicoverpa Armigera armigera ) Huebner (American cotton worm), Helicoverpa zea ) Boddie (king tobacco moth larvae), Heliotis nonresense Fabricius (cigarette moth), Herpetogram Riccasisalis Walker (grass moth), Lobesia lobesia botrana ) Denis & Schiffermueller ( Grapeum Moth), Pectinophora Gosipiella Saunders (Pink Cotton Seed), Phyllocnistis citrella ) Stainton (citrus oyster moth), Pieris brassicae Linnaeus (big white butterfly), Pieris la fay ( Pieris rapae ) Linnaeus (small white butterfly), flutella xyllostella Linnaeus (cabbage moth), Spodoptera xigua Huebner (pabamoth moth), Spodoptera litura fabricius (cigarette seminary moth, cluster larvae), spodoptera frugiperda JE Smith (recordable geoyeom worms), tricot Asian flu you Huebner (cabbage looper) and tuta apsol doubles (tuta absoluta ) shows high activity against Meyrick (tomato oyster moth)}.

Compounds of the invention are also known as Acyrthosiphon pisum ) Harris (pea aphids), Apis Krasivora ( Aphis craccivora) Koch (Acacia aphids), Apis waves bar (Aphis fabae) Scopoli (black bean aphid), Apis Notice feeder (Aphis gossypii ) Glover (cotton aphid, melon aphid), aphis pomi ( Aphis pomi ) De Geer ( aphy aphid), Apis spirola ( Aphis) spiraecola ) Patch (rose aphid), Aulacorthum Solani solani ) Kaltenbach (barbeard aphid), Chaetosiphon fragaefolii ) Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov / Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rose apple aphid), Eriosoma ranigerum Eriosoma lanigerum ) Hausmann (hair apple aphid), Hyalopterus pruni ) Geoffroy (Peach Powder Aphid), Lipaphis erysimi ) Kaltenbach (turnip aphid), Metopolophium dirhodum dirrhodum ) Walker (grain aphids), macrophage in Euphorbia ( Macrosiphum euphorbiae ) Thomas (Potato aphids), Missos Persicae ( Myzus persicae Sulzer (peach-potato aphid, peach hump aphid), Nasonovia ribisnigri Mosley (lettuce aphids), Pemphigus species (root aphids and hump aphids), Rhopalosiphum maidis ) Fitch (corn leaf aphid), lopalosi parody ( Rhopalosiphum padi ) Linnaeus (bird cherry-oat aphid), Schizapis Graminum graminum ) Rondani (Shinbion), Sitobion avenae ) Fabricius (British Grain Aphid), Therioaphis maculata ) Buckton (spot aphid aphid), Toxoptera auranti aurantii ) Boyer de Fonscolombe (black citrus aphid) and Toxoptera citricida ( Toxoptera citricida ) Kirkaldy (brown citrus aphid); Adelges species (cotton beetle); Phylloxera devastatrix ) Pergande (pecan vine root aphid); Bemisia Tabashi tabaci ) Gennadius (tobacco powder, sweet potato powder), Bemisia argentifoli ( Bemisia argentifolii) Bellows & Perring (eunip whitefly), di Death Valley right seat Li (Dialeurodes citri ) Ashmead and Trialeurodes vaporariorum ) Westwood (greenhouse flour ); Empoasca fabae) Harris (potato maemichung), Lao del Parks Austria Tel Ruth (Laodelphax striatellus) Fallen (aemyeolgu), Mark rolls Les Tess kwiah drill Linea tooth (Macrolestes quadrilineatus) Forbes (St. body maemichung), four Forte ticks sinti sepseu (Nephotettix cinticeps) Uhler (green maemichung), four ticks Forte Negro tooth pick (Nephotettix nigropictus) Stal (rice maemichung), Neela Regensburg Lou Pardo Bata (Nilaparvata lugens) Stal (BPH), Tampere that Linus My display (Peregrinus maidis ) Ashmead (corn), Sogatella furcifera ) Horvath ( whiteish extinct ), Sogatodes orizicola ) Muir (rice delphacid), Typhlocyba pomaria ) McAtee (white apple cicada ), Erythroneoura species (grape cicada); Magicidada septendecim Linnaeus (cycle cicada); Iseriya Purchasi purchasi ) Maskell (citrus beetle), Quadraspidiotus perniciosus Comstock (peg beetle); Planococcus citri citri ) Risso (citrus cherry beetle); Pseudococcus spp. (Other cherry beetle complexes); Cacopsylla pyricola ) Foerster (Pear aphid), Trioza diospyri ) has significant activity against members from cicada, including Ashmead (persimmon aphid).

Compounds of the invention are also known as Acrosternum hilare ) Say (Full Color Norrin), Anasa Tritis tristis ) De Geer, Blissus Leucofterus Say, Chinex Rectularius Linnaeus, and Corythuca gossypii ) Fabricius (cotton shield beetle), Cyrtopeltis modesta ) Distant (tomato nori), Dysdercus suturellus ) Herrich-Schaeffer ( Euchistus) servus ) Say (brown stink bug), Euchistus variolius ( Euchistus) variolarius ) Palisot de Beauvois (1-spot stink bug), Graptosthetus species (composite seed beetle), Leptoglossus corculus) Say (large waist norinjae), Lee Goose Rhine up lease (Lygus lineolaris) Palisot de Beauvois (norinjae blind), your growing corruption dulra (Nezara viridula ) Linnaeus (southern stink bug), Oebalus pugnax ) Fabricius (rice stink bug), Oncopeltus fasciatus ) Dallas (large milkweed stink bug), Pseudatomoscelis seriatus ) is active against members from stink bugs, including Reuters. Other insect necks controlled by the compounds of the present invention include the herbaceous woodworm (for example, Frankliniella occidentalis Pergande (Western flower shovel ), Scirthothrips citri Moulton) (Citrus shovel ), Sericothrips variabilis Beach (soybean shovel ) and Thrips tabaci ) Lindeman (onion shovel)}; And coleopteran {eg, Leptinotarsa Leptinotarsa decemlineata ) Say (Colorado potato beetle), Epilachna or Epilachna varivestis) it includes Mulsant (Mexican bean beetle) and Rio Agde Tess (Agriotes), An ATO-house (Athous) in-house or monitor Li (Limonius)} in the caterpillar.

Some contemporary taxonomy note that cicada trees are placed as subtrees in stinkwood.

Of note is the use of the compounds of the present invention for the control of Chinese cabbage moths (Flutella xylostella). Of note is the use of the compounds of the invention for the control of cardinal macroworms (Spodoftera pruperferda). Of note is the use of the compounds of the invention for the control of cotton melon aphids (Apis gosipi).

In addition, the compounds of the present invention are insecticides, fungicides, nematicides, fungicides, acaricides, herbicides, growth regulators such as rooting promoters, infertility agents, signal chemicals, insect repellents, attractants, pheromones, intake promoters, other biologically active compounds Or can be mixed with one or more other biologically active compounds or agents, including insect pathogenic bacteria, viruses, or fungi, to form multicomponent pest insecticides that provide much broader agronomic and nonagronomic utility. Accordingly, the present invention also relates to a composition comprising a biologically effective amount of a compound of formula 1, or an N-oxide or salt thereof, and an effective amount of at least one additional biologically active compound or agent, which is at least one interface Active agents, solid diluents or liquid diluents. For the mixtures of the present invention, other biologically active compounds or agents may be formulated with the compounds of the present invention, including compounds of formula 1, to form premixes, or other biologically active compounds or agents may be compounds of formula 1 Formulated separately from the compounds of the present invention, including, the two agents may be combined together prior to application (eg, in a spray tank), or alternatively applied sequentially.

Other biologically active compounds or agents useful in the compositions of the present invention are macrocyclic lactones, neonicotinoids, octopamine receptor ligands, lianodine receptor ligands, ecdysone agonists, sodium channel modulators, chitin synthesis inhibitors, neraceotoxins Analogues, mitochondrial electron transfer inhibitors, cholinesterase inhibitors, cyclodiene pesticides, stripping inhibitors, GABA (γ-aminobutyric acid) -regulated chloride channel blockers, larval hormone mimetics, lipid biosynthesis inhibitors and biological agents (of Bacillus thuringiensis) Invertebrate pests with different modes of action or different chemical classes, including member nucleopolyheado virus (NPV), encapsulated delta-endotoxin of Bacillus thuringiensis, and natural or genetically modified viral pesticides) It may be selected from controlling agents.

Pyrethroids, carbamates, neonicotinoids, neurogenic sodium channel blockers, insecticidal macrocyclic lactones, γ-aminobutyric acid antagonists, insecticidal urea and larval hormone mimetics, members of Bacillus thuringiensis, Bacillus thuringiers Of note is a further biologically active compound or agent selected from the insectis delta-endotoxin, and insecticides in the group consisting of natural or genetically modified viral insecticides.

Examples of such biologically active compounds or agents that may be formulated with the compounds of the invention include insecticides such as abamectin, acetate, acetamiprid, acetoprole, amidoflumet (S-1955), avermectin, aza Diractin, azinephosph-methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartaf, chlorfenapyr, chlorfluazuron, chloranthraniliprole (DPX -E2Y45), Chlorpyriphos, Chlorpyriphos-methyl, Chromafenozide, Clotianidine, Cyflumetofen, Cyfluthrin, Beta-Sifluthrin, Sihalotrin, Gamma-Sihalotrin , Lambda-sihalothrin, cipermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diophenolran, emma Mectin, Endosulfan, Espenalerate, Ethiprolol, Phenothio Carb, phenoxycarb, phenpropatrine, penvalerate, fipronil, phlonicamid, flubendiamide, flucitrinate, tau-fluvalinate, flufenerim (UR-50701), Flufenoxuron, Phonophos, Halofenozide, Hexaflumuron, Hydramethylnon, Imidacloprid, Indoxacarb, Isopenfoss, Lufenuron, Malathion, Metaflumizone, Metaldehyde, Metamidofose, Methitathione, Metomil, Metoprene, Methoxycyclo, Metofluthrin, Monoclotophos, Methoxyphenozide, Nitenpyram, Nithiazine, Novalon, Nobiflumuron (XDE-007), Oxamyl , Parathion, parathion-methyl, permethrin, formate, posalon, phosphmet, phosphamidone, pyrimikarb, propenophosphate, profluthrin, protrifenbute, pymetrozine, pyraflulol , Pyrethrin, pyridalyl, pyrifluquinazone, pyriprolol, pyriproxyfen, rotenone, lia Dean, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetrameth, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlor Vinforce, tiacloprid, thiamethoxam, thiodicarb, thiosulfaf-sodium, tolfenpyrad, tralomethrin, triamate, trichlorphone and triflumuron; Fungicides such as acibenzolar, aldimorph, amissulbrom, azaconazole, azoxystrobin, benalacyl, benomil, ventiavalicarb, ventiavalicarb-isopropyl, vinomial, biphenyl, Vitertanol, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), boscalid / nicobifen, bromuconazole, burimate, butthiobate, carboxycin, carpropamide, captapol , Kaftan, carbendazim, chloroneb, chlorothalonil, clozolinate, clotrimazole, copper oxychloride, copper salts (e.g. copper sulfate and copper hydroxide), cyazopamide, cyflunamid, cymoxanyl, Ciproconazole, Cyprodinyl, Diclofluanide, Diclocimet, Diclomezine, Dicloran, Dietofencarb, Difenokazole, Dimethomorph, Dimoxistrobin, Dinicoazole, Di Nicoazole-M, dinocap, discostrovin, dithianon, Dodemorph, dodine, echonazol, etaconazole, edifeneforce, epoxyconazole, etaboksam, etirimole, ethriazole, pamoxadon, phenamidone, phenarimol, fenbuconazole, fencaramide, Fenfuram, phenhexamide, phenoxanyl, fenpiclonyl, phenpropidine, fenpropormoff, fentin acetate, fentin hydroxide, perbam, perfurazoate, perimzone, fluazinam, fludi Oxonyl, flumetober, fluoropicolide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamid, flutolanil, flutriafol, polpet, pocetyl-aluminum, fuberidazole, Furalacyl, furametapyr, hexaconazole, himexazole, guaztine, imazalyl, imibenconazole, iminottadine, iodicarb, ifconazole, ifprobenfos, ifprodione, ifprovalicab , Isoconazole, isoprothiolane, kasugamycin, cresoxime-methyl, mancozeb, mandif Pamide, maneb, mapanipirine, mefenoxam, mepronyl, metallaxyl, metconazole, metasulfocarb, metiram, metominostrobin / phenominostrobin, mepanipyrim, metrafenone, Myconazole, myclobutanyl, neo-asozin (ferric methane arsenate), noarimol, octylinone, opurais, orissastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxycin , Paclobutrazole, fenconazole, peniculon, penthiopyrad, perfurazoate, phosphonic acid, phthalide, picobenzamide, picoxistrobin, polyoxine, probenazole, prochloraz, procmidone , Propamocarb, propamocarb-hydrochloride, propiconazole, propineb, proquinazide, prothioconazole, pyraclostrobin, priazophosph, pyriphenox, pyrimethanyl, pyrronit Lean, pyroquilon, quinconazole, quinoxyphene, quintogen, silthiofam, sea Conazole, spiroxamine, streptomycin, sulfur, tebuconazole, techlazen, teclophthalam, technazen, tetraconazole, thibendazole, tifluzamide, thiophanate, thiophanate-methyl, tiram , Thiadinil, tolclofos-methyl, tolifluanide, triadimefon, triadimenol, triarimol, triazoside, tridemorph, trimorphamide tricyclazole, tripleoxystrobin, Tripolin, triticonazole, uniconazole, validamycin, vinclozoline, geneb, ziram and josamide; Nematicides such as aldicarb, imiciaforce, oxamyl and phenamifos; Fungicides such as streptomycin; Acaricides such as amitraz, quinomethionate, chlorobenzylate, cyhexatin, dicopol, dienochlor, ethoxazole, phenazakine, fenbutatin oxide, phenpropatrine, fenpyroximate, hexity Azox, propargite, pyridaben and tebufenpyrad; And entomopathogenic bacteria, such as Bacillus turing group N-Sys subspecies ahyijawayi (Aizawai), Bacillus turing group N-Sys subspecies Kur Starkey (Kurstaki) and Bacillus turing group encapsulated delta of N-Sys - for endotoxin (for example, selkap (Cellcap), MPV, MPVII), entomopathogenic fungi such as Pseudomonas aeruginosa, and baculovirus, nucleopolyheado virus (NPV) {such as Helicoverpa zea) nucleoside polyhedra virus (HzNPV), the analog Grappa eight o'clock Blow (Anagrapha falcifera) New polyhedra including viruses with CLEO (AfNPV)} insect pathogenic viruses and granules disease virus (GV) {such as Cydia Four Monella.All (Cydia pomonella ) granule disease virus (CpGV)}.

The compounds of the present invention and compositions thereof can be applied to plants genetically transformed to express proteins that are toxic to invertebrate pests (eg, Bacillus thuringiensis delta-endotoxin). Externally applied invertebrate pest control effects of the compounds of the present invention may synergize with expressed toxin proteins

General references to these agricultural preventive agents (ie, insecticides, fungicides, nematicides, acaricides, herbicides and biological agents) are described in The Pesticide Manual, 13th Edition, CDS Tomlin, Ed., British Crop Protection Council, Farnham, include Surrey, UK, 2003] and ^{[the BioPesticide Manual, 2 nd Edition} , LG Copping, Ed., British Crop Protection Council, Farnham, Surrey, UK, 2001].

One or more additional biologically active compounds or agents are abamectin, acetate, acetamiprid, acetoprole, aldicarb, amidoflumet, amitraz, avermectin, azadilactin, azinfos-methyl , Bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, cartaf, chinomethionate, chlorfenapyr, chlorfluazuron, chloranthraniliprole, chlorpyrifos, Chlorpyriphos-methyl, chlorobenzylate, chromafenozide, clothianidine, cyflumetophene, cyfluthrin, beta-cifluthrin, sihalothrin, gamma-sihalothrin, lambda-cy Halotrin, cyhexatin, cipermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dicopol, dieldrin, dienochlor, diflubenzuron, dimefluthrin, dimethoate, dino Tefuran, diophenolran, emamectin, endosulfan, espenvalerie , Etiprolol, ethoxazole, phenamifos, phenazanquine, fenbutatin oxide, phenothiocarb, phenoxycarb, phenpropatrine, fenpyroximate, fenvallate, fipronil, phlonica Mead, flubendiamide, flucitrinate, tau-fluvalinate, flufenerim, flufenoxuron, phonophos, halopefenidide, hexaflumuron, hexthiaxans, hydrmethylnon, imisia Force, imidacloprid, indoxacarb, isopenfose, lufenuron, malathion, metaflumizone, metaldehyde, metamidophos, methidathione, metomil, metoprene, methoxycyclo, methoxyphenozide , Metofluthrin, monoclotophos, nitenpyram, nithiazine, novaluron, nobiflumuron, oxamyl, parathion, parathion-methyl, permethrin, formate, posalon, phosphmet, phosphamidone, Pyrimycarb, propenophos, propflutrin, propargite, Protrifenbut, pymetrozine, pyraflulol, pyrethrin, pyridaben, pyridalyl, pyrifluquinazone, pyriprolol, pyriproxyfen, rotenone, lianodine, spinetoram, spinosad, spirof Rhodiclofen, spiromesifen, spirotetrameth, sulfpropos, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorbinfos, tiacloprid, thiamethoxam , Thiodicarb, thiosulfaf-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorphone, triflumuron, Bacillus thuringiensis subspecies aizai, bacillus thuringiensis subspecies Kurstaki, nucleopolyhead Rho virus, Bacillus thuringiensis encapsulated delta-endotoxin, baculovirus, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi The composition is notable names.

In particular, the at least one additional biologically active compound or agent is abamectin, acetate, acetamiprid, acetoprole, amidoflumet (S-1955), avermectin, azadilactin, azinfos-methyl, Bifenthrin, Bifenazate, Bistrifluron, Buprofezin, Carbofuran, Carthaf, Chlorfenapyr, Chlorfluazuron, Chlorpyriphos, Chlorpyriphos-methyl, Chromafenozide, Cloti Anidine, cyfluthrin, beta-cyfluthrin, sihalothrin, gamma-sihalothrin, lambda-sihalothrin, cipermethrin, cyromazine, deltamethrin, diapentthiuron, diazinon , Dieldrin, diflubenzuron, dimethoate, dinotefuran, diophenolran, emamectin, endosulfan, esfen valerate, ethiprolol, phenothiocarb, phenoxycarb, phenpropartrin, fenvalle Latex, fipronil, flonicamid, flubendiamide, flucitrinine , Tau-Fluvalinate, Flufenerim (UR-50701), Flufenoxuron, Halopenozide, Hexaflumuron, Hydramethylnon, Imidacloprid, Indoxacarb, Isopenfos, Lufenuron, Malathion, Metaflumizone, Metaldehyde, Metamidose, Metidathione, Methomil, Metoprene, Methoxycyclo, Methoxyphenozide, Metofluthrin, Monoclotophos, Nitenpyram, Nithiazine, Nothiazine Valuron, Nobiflumuron (XDE-007), Oxamyl, Parathion, Parathion-Methyl, Permethrin, Forate, Posalon, Phosmet, Phosphomidone, Pyrimicarb, Propenophos, Propflutrin , Protrifenbut, pymetrozine, pyrethrin, pyridalyl, pyriproxyfen, rotenone, lianodine, S1812 (Valent), spinosad, spirodiclofen, spiromesifen (BSN 2060) , Sulfofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorbin , Thiacloprid, thiamethoxam, thiodicarb, thiosulfaf-sodium, tolfenpyrad, tralomethrin, triamate, trichlorphone, triflumuron, aldicarb, phenamifos, amit Raz, chinomethionate, chlorobenzylate, cyhexatin, dicopol, dienochlor, ethoxazole, phenazaquine, fenbutatin oxide, fenpyroximate, hexthiaxans, propargite, pyridazene, Tebufenpyrad, Bacillus thuringiensis Aizawa, Bacillus thuringiensis Kurstaki, Bacillus thuringiensis delta-endotoxin, baculovirus, entomopathogenic bacteria, entomopathogenic viruses and entomopathogenic fungi Of note is the composition.

In addition, the one or more additional biologically active compounds or agents are abamectin, acetamiprid, amitraz, avermectin, azadirachtin, bifenthrin, buprofezin, cartaf, chlorantraniliprole , Chlorfenapyr, chlorpyriphos, clotianidine, cyfluthrin, beta-cifluthrin, sihalothrin, lambda-cyhalothrin, cipermethrin, cyromazine, deltamethrin, dieldrin , Dinotefuran, diophenolran, emamectin, endosulfan, esfenvalerate, etiprolol, phenothiocarb, phenoxycarb, fenvalerate, fipronil, phlonicamid, flubendiamide, flu Phenoxuron, Hexaflumuron, Hydramethylnon, Imidacloprid, Indoxacarb, Lufenuron, Metaflumizone, Methomil, Metoprene, Methoxyphenozide, Nitenpyram, Nithiazine, Novaluron, Oxa Wheat, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxy , Lyanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, tebufenozide, thiacloprid, thiamethoxam, thiodicarb, thiosulfaf-sodium, tralomethrin, triamate The composition of the present invention is selected from the group consisting of triflumuron, Bacillus thuringiensis subspecies Aizawa, Bacillus thuringiensis subspecies Kurstarki, nucleopolyheadovirus and encapsulated delta-endotoxin of Bacillus thuringiensis. Notable

In addition, the one or more additional biologically active compounds or agents may be cipermethrin, sihalothrin, cyfluthrin and beta-cifluthrin, esfenvalerate, penvalerate, tralomethrin, phenoticarb , Metomil, oxamyl, thiodicarb, acetamiprid, clothianidine, imidacloprid, thiamethoxam, tiacloprid, indoxacarb, spinosad, abamectin, avermectin, emamectin, endo Sulfan, ethiprole, fipronil, flufenoxuron, triflumuron, diophenolran, pyriproxyfen, pymetrozine, amitraz, Bacillus thuringiensis iizai, Bacillus thuringiensis Kurstaki, Bacillus thuringiensis Of note is a composition of the invention that is selected from the group consisting of delta-endotoxins and entomopathogenic fungi.

For embodiments in which one or more of these various mixing partners are used, the weight ratio of said various mixing partners (total) to the compound of formula 1 is typically from about 1: 3000 to about 3000: 1. Of note is a weight ratio of about 1: 300 to about 300: 1 (eg, a ratio of about 1:30 to about 30: 1). One skilled in the art can easily determine the biologically effective amount of active ingredient required for the desired biological activity range through simple experiments. It will be apparent that the range of invertebrate pests controlled by the inclusion of such additional components may extend beyond the range controlled by the compound of formula (1) alone.

In certain cases, the combination of a compound of the present invention with other biologically active (particularly invertebrate pest control) compounds or agents (ie, active ingredients) may produce an effect that is greater than an additive effect (ie, a synergistic effect). It is always desirable to reduce the amount of active ingredient released to the environment while ensuring effective pest control. If the synergy of invertebrate pest control active ingredients occurs at an application cost that achieves an agriculturally satisfactory level of invertebrate pest control, such a combination may be advantageous to reduce crop production costs and reduce environmental burden.

Of note is a combination of a compound of Formula 1 with one or more other invertebrate pest control active ingredients. Of particular note are combinations in which the other invertebrate pest control active ingredient has a different site of action than the compound of formula (1). In certain cases, combinations with one or more other invertebrate pest control active ingredients having similar control ranges but different sites of action will be particularly advantageous in resistance management. Thus, the compositions of the present invention may further comprise one or more additional invertebrate pest control active ingredients in a similar range of control but different sites of action. In addition, contacting a plant genetically modified to express an invertebrate pest compound (eg, a protein) or the locus of that plant with a biologically effective amount of a compound of the present invention may provide broader plant protection and control resistance. May be advantageous.

Table A below lists specific combinations of compounds of Formula 1 with other invertebrate pest control agents for illustration of the mixtures, compositions, and methods of the present invention. The first column of Table A lists the specific invertebrate pest control agents (eg, the first line is “abamectin”). The second column of Table A lists the mode of action or chemical class of invertebrate pest control agents (if known). The third column of Table A lists the embodiment (s) in the weight ratio relative to the ratio at which the invertebrate pest control agent can be applied to the compound of Formula 1 or to an N-oxide or salt thereof (eg, of Formula 1 Abamectin for the compound is "50: 1 to 1:50" by weight). Thus, for example, the first line of Table A specifically discloses that the combination of the compound of Formula 1 and abamectin may be applied in a weight ratio of 50: 1 to 1:50. The remaining lines in Table A are interpreted similarly. Table A lists specific combinations of the compounds of Formula 1 with other invertebrate pest control agents for illustration of the mixtures, compositions, and methods of the present invention, and includes additional embodiments in a weight ratio range for application rates.

One embodiment of invertebrate pest control agents (eg, insecticides and acaricides) for mixing with the compounds of the present invention are sodium channel modulators such as bifenthrin, cipermethrin, sihalothrin, lambda-sihalo Tririns, cyfluthrin, beta-cifluthrin, deltamethrin, dimefluthrin, espenvalerate, penvalerate, indoxacarb, metofluthrin, profluthrin, pyrethrin and tralomethrin; Cholinesterase inhibitors such as chlorpyrifos, metomil, oxamyl, thiodicarb and triamate; Neonicotinoids such as acetamiprid, clothianidine, dinotefuran, imidacloprid, nitenpyram, nithiazine, tiacloprid and thiamethoxam; Insecticidal macrocyclic lactones such as spinetoram, spinosad, abamectin, avermectin and emamectin; GABA (γ-aminobutyric acid) -modulating chloride channel blockers such as endosulfan, etiprolol and fipronil; Chitin synthesis inhibitors such as buprofezin, siromazin, flufenoxuron, hexaflumuron, lufenuron, novaluron, nobiflumuron and triflumuron; Larva hormone mimetics such as diophenolrans, phenoxycarb, metoprene and pyriproxyfen; Octopamine receptor ligands such as amitraz; Ecdysone agonists such as azadilactin, methoxyphenozide and tebufenozide; Lianodine receptor ligands such as lianodine, anthranyldiamide such as chlorantraniliprolol (see US Pat. No. 6,747,047, see PCT Publication WO 2003/015518 and WO 2004/067528) and flubendiamide (US Pat. 6,603,044); Nereisotoxin analogues such as cartaf; Mitochondrial electron transfer inhibitors such as chlorfenapyr, hydrmethylnon and pyridaben; Lipid biosynthesis inhibitors such as spirodiclofen and spiromesifen; Cyclodiene insecticides such as dieldrin; Cyflumetofen; Phenothiocarb; Floricamid; Metaflumizone; Pyraflulol; Pyridalyl; Pyriprolol; Pymetrozine; Spirotetramate; And thiosulfate-sodium. One embodiment of a biological agent for mixing with a compound of the present invention is a nucleopolyhead with viruses such as HzNPV and AfNPV; Encapsulated delta-endotoxins of Bacillus thuringiensis and Bacillus thuringiensis such as Cellcap, MPV and MPVII; And natural and genetically modified viral insecticides, including members of the Baculoviridae family and entomopathogenic fungi. It is noteworthy that the composition of the invention is one or more additional biologically active compounds or agents selected from invertebrate pest control agents listed in Table A above.

The weight ratio of the compound of formula 1, or a compound including an N-oxide or salt thereof, to an additional invertebrate pest control agent is typically 1000: 1 to 1: 1000, in one embodiment 500: 1 to 1: 500, In other embodiments 250: 1 to 1: 200, and in still other embodiments 100: 1 to 1:50.

Listed in Table B below are embodiments of certain compositions comprising a compound of Formula 1 (compound number refers to a compound in Index Table A) and additional invertebrate pest control agents.

Certain mixtures listed in Table B typically combine the compounds of Formula 1 with other invertebrate pest control agents in the proportions specified in Table A.

Invertebrate pests are intended to control biologically effective amounts of one or more compounds of the invention, usually in the form of a composition, to the environment to be protected, or directly to the environment of the pest, including agronomic and / or nonagronomic sites of infection. It is controlled agronomically and non-agronomically by applying to pests.

Accordingly, the present invention further provides a invertebrate pest or environment thereof in a biologically effective amount of at least one compound of the invention, or a composition comprising at least one compound, or at least one compound and at least one biologically effective amount. Methods of controlling invertebrate pests in agronomic and / or nonagronomic applications comprising contacting a composition comprising a further biologically active compound or agent. Examples of suitable compositions comprising a compound of the invention and a biologically effective amount of at least one additional biologically active compound or agent include granule compositions, wherein the additional active compound is present on or is present on the same granule as the compound of the invention. It is present on granules separate from the granules of the compounds of the invention.

In order to achieve protection of crops from invertebrate pests by contact with the compounds or compositions of the present invention, the compounds or compositions are usually used in the seeds of crops before sowing, on the leaves of crop plants (e.g., leaves, stems, flowers, berries). On, or before or after sowing of the crop is applied to the soil or other growth medium.

One embodiment of the contacting method is by spraying. Alternatively, granular compositions comprising the compounds of the present invention may be applied to plant houseplants or soil. The compounds of the present invention can also be effectively delivered through plant uptake by contacting the plant with a composition comprising a compound of the present invention, which is applied as soil irrigation of a liquid formulation, as a granule formulation for soil, seedling box treatment or graft dipping. . Note that the composition of the present invention is in the form of a soil irrigation liquid formulation. Also of note are methods of controlling invertebrate pests comprising contacting the invertebrate pest or environment thereof with a biologically effective amount of a compound of the invention or a composition comprising a biologically effective amount of a compound of the invention. In addition, attention is given to methods of controlling invertebrate pests in which the environment is soil and the composition is applied to the soil as a soil irrigation preparation. In addition, it is noted that the compounds of the present invention are also effective by topical application to the site of infection. Other contact methods include direct and residual spraying, air spraying, gels, seed coating, microencapsulation, systemic absorption, bait, ear tag, bolus, sprayer, fumigant, aerosol, dust and many others. Application of the compounds or compositions of the invention. One embodiment of the contacting method is a dimensionally stable fertilizer granule, stick or tablet comprising the mixture or composition of the present invention. The compounds of the present invention may also be impregnated into materials for making invertebrate control devices (eg insect netting).

The compounds of the present invention are also useful for seed treatment to protect seeds from invertebrate pests. In the context of the present disclosure and claims, seed treatment means contacting a seed with a biologically effective amount of a compound of the invention, typically formulated with a composition of the invention. This seed treatment protects the seed from invertebrate pest soils and may also protect the roots and other plant parts that are in contact with the soil of the seedlings that are generally developed from the germinating seed. Seed treatment may also provide protection of houseplants by translocation of the compound or second active ingredient of the invention into the developing plant. Seed treatment may also be applied to all types of seeds, including those for which plants genetically modified to express specialized properties will germinate. Representative examples include expressing proteins that are toxic to invertebrate pests, such as Bacillus thuringiensis toxin, or expressing herbicide tolerance, such as glyphosate acetyltransferase, which provides resistance to glyphosate.

One method of seed treatment is to spray or spray the seed with a compound of the invention (ie as a formulated composition) prior to sowing of the seed. Compositions formulated for seed treatment typically comprise a film former or adhesive. Thus, seed coating compositions of the invention typically comprise a biologically effective amount of a compound of formula 1, or an N-oxide or salt thereof, and a film former or adhesive. Seeds may be coated by spraying a flowable suspension concentrate directly onto the tumbling bed of the seed and then drying the seed. Alternatively, other types of formulations can be sprayed onto the seeds, such as wet powders, solutions, suspending agents, emulsifying concentrates and emulsions in water. This method is particularly useful for applying membrane coatings on seeds. Various coating devices and methods are known to those skilled in the art. Suitable methods are described in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994 BCPC Mongraph No. 57 and those listed in the references listed herein.

Treated seeds typically comprise a compound of the present invention in an amount of about 0.1 g to 1 kg (ie, about 0.0001 to 1% by weight of the seed before treatment) per 100 kg of seed. Flowable suspensions formulated for seed treatment typically comprise about 0.5 to about 70% of the active ingredient, about 0.5 to about 30% of the membrane-forming adhesive, about 0.5 to about 20% of the dispersing agent, 0 to about 5% of the thickener, pigments And / or 0 to about 5% dye, 0 to about 2% antifoam, 0 to about 1% preservative and 0 to about 75% volatile liquid diluent.

The compounds of the present invention may be incorporated into bait compositions that are consumed by invertebrate pests or used in devices such as traps, baits, and the like. Such bait compositions may comprise (a) an active ingredient, ie, a biologically effective amount of a compound of Formula 1, or an N-oxide or salt thereof; (b) one or more foods; Optionally in the form of a granule comprising (c) an attractant, and optionally (d) one or more wetting agents. About 0.001 to 5% active ingredient, about 40 to 99% food and / or very effective at controlling soil invertebrate pests at very low application rates, especially at doses of lethal active ingredients by ingestion than by direct contact Or attractant; And granules or bait compositions optionally comprising about 0.05 to 10% wetting agent. Some foods can act as both food sources and attractants. Food includes carbohydrates, proteins and lipids. Examples of foods include edible powders, sugars, starches, animal fats, vegetable oils, yeast extracts and milk solids. Examples of attractants are odorants and flavoring agents, such as fruit or plant extracts, perfumes, or other agents known to attract targets of other animal or plant components, pheromones, or invertebrate pests. Examples of humectants, ie moisture retainers, are glycols and other polyols, glycerin and sorbitol. Of note are the bait compositions (and methods of using such bait compositions) used to control one or more invertebrate pests selected from the group consisting of ants, termites and cockroaches. The device for controlling invertebrate pests includes a bait composition of the invention and a housing suitable for containing the bait composition, wherein the housing is one or more sized to allow the invertebrate pest to pass through to access the bait composition from a location outside the housing. It has an opening and is further suitable for placement at or near the site of potential or known activity of invertebrate pests.

Although the compounds of the present invention can be applied without other auxiliaries, most applications will include formulations comprising one or more active ingredients with suitable carriers, diluents and surfactants, possibly in combination with food according to the intended use. . One application method involves spraying an aqueous dispersion or refined oil solution of a compound of the present invention. Spray oils, spray oil concentrates, sparger stickers, adjuvants, other solvents, and combinations with synergists such as piperonyl butoxide often improve compound efficiency. For nonagronomic uses, such spraying can be applied from a spray container, such as a can, bottle or other container, by pumping or by releasing it from a pressurized container, for example a pressurized aerosol spray can. Such spray compositions may take various forms, for example, in the form of sprays, mists, bubbles, fumes or mists. Thus, such spray compositions may optionally further comprise propellants, blowing agents, and the like. Of note is a spray composition comprising a biologically effective amount of a compound or composition of the invention and a carrier. One embodiment of such a spray composition comprises a biologically effective amount of a compound or composition of the invention and a propellant. Representative propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures thereof. . Used individually or in combination to control one or more invertebrate pests selected from the group consisting of mosquitoes, ink flies, chimpanzees, stag flies, horse flies, wasps, bumblebees, bumblebees, ticks, spiders, ants, hornbills, etc. Of note are spray compositions (and methods of using such spray compositions dispensed from spray containers).

Non-agronomic uses are usually administered from invertebrate parasites, more particularly from invertebrate parasites, by administering to the animal to be protected a pesticidal effective amount (ie, a biologically effective amount) of the compound in the form of a formulation formulated for veterinary use. Warm-blooded vertebrates (eg, mammals or birds), most particularly those that protect mammals. Thus, it is noteworthy that methods of protecting animals, including administering to the animal a pesticidal effective amount of a compound of the present invention. The terms "pesticide" and "pesticide" as mentioned in the present disclosure and claims mean an observable effect on invertebrate parasites that provide protection of the animal from pests. Insecticidal effects usually mean reducing the incidence or activity of invertebrate parasite targets. Such effects on pests include necrosis, death, retardation of growth, reduction of mobility or reduction of retention ability on or within the host animal, reduction of nutrition and inhibition of reproduction. This effect on invertebrate parasites provides control (including prevention, degradation or elimination) of parasitic infections in animals. Examples of invertebrate parasites that are controlled by administering a pesticidal effective amount of a compound of the present invention to an animal to be protected include external parasites (arthropods, mites, etc.) and internal parasites (enteritis, for example nematodes, arachnids, tapeworms, shoeworms, etc.). ) Is included. In particular, the compounds of the present invention are flies, such as Haematobia ( Lyperosia ) iritans (horn flies), Stomoxis calcitrance ( chimpanzees ), Simulium spp . ( Muflies ), glossies Glossina species ( Czech fly), Hydrotaea iritans irritans) (head flies) museuka brother tumnal lease (Musca autumnalis ) (Face Paris), Musca Domestica ( Housefly ), Morelia Simplex simplex ) (sweet fly), tabanus ( horsefly ), Hypoderma bovis ), Hypoderma lineatum ), Lucilia Sericata sericata ), Lucilia Cupri cuprina ) (copper fly ), Calliphora species ( gold fly ), Protophormia species Oestrus ovis ) (horsefly inside the nose), Culicoides species (on the back), Hippobosca equine ), Gastrophilus instestinalis , Gastrophilus haemoroidalis haemorrhoidalis ) and Gastrophilus naslis ); For example, Bovicola Bovis bovis ) ( Damalinia bovis )), Bovicola equi , Haematopinus asini ), Felicola subsustratus subrostratus ), Heterodoxus spiniger ), Lignonathus setosus ) and Trichodectes canis ; Ked, such as melofagus gouin; Little ticks, such as the Psoroptes species, Sarcoptes scabei , Chorioptes bovis , Demodex Equi equi , Cheyletiella spp., Notoedres cati ), Trombicula spp. and Otodectes cyanotis ) (ear mites); Mites such as Ixodes species, Boophilus species, Rhipicephalus species, Amblyomma species, Dermacentor species, Hyalomma species and Haemapisalis ( Haemaphysalis ) species; And fleas, such as the Xenocephalides Felice (cat flea) and the Xenocephaides canis (dog flea).

Non-agronomic applications in the field of veterinary medicine include compounds or compositions of the present invention, e.g. in the form of tablets, capsules, drinks, irrigation preparations, granules, pastes, bolus, feed-through procedures or suppositories. By administration; Or parenteral administration, such as by injection (including intramuscular, subcutaneous, intravenous, intraperitoneal), or by transplantation; By intranasal administration; Topical administration, for example impregnation or dipping, spraying, washing, application in the form of a powder coating or to a small portion of the animal, and articles such as neck collars, ear tags, tail bands, limb bands or bridles By conventional means.

Typically, pesticidal compositions according to the invention are formulated for the compounds of formula 1 or their N-oxides or salts and intended routes of administration (eg oral, topical or parenteral administration (such as injection)) and standard guidelines. Mixtures with one or more pharmaceutically or veterinary acceptable carriers, including excipients and adjuvants selected according to the invention. Suitable carriers are also selected based on their compatibility with one or more active ingredients in the composition, including considerations such as stability to pH and moisture content. Thus, it is noteworthy that compositions for protecting animals from invertebrate parasites, which contain a pesticidal effective amount of a compound of the invention and at least one carrier.

For parenteral administration, including intravenous, intramuscular and subcutaneous injection, the compounds of the present invention may be formulated as suspensions, solutions or emulsions in oily or aqueous vehicles, and may be formulated with suspending, stabilizing and / or dispersing agents. It may contain the same additives. Injectable pharmaceutical compositions preferably include an aqueous solution of the active ingredient (eg, a salt of the active compound) in water-soluble form in a physiologically compatible buffer containing other excipients or adjuvants as known in the pharmaceutical art. .

Oral administration, including solutions (in the most readily available forms for absorption), emulsions, suspensions, pastes, gels, capsules, tablets, bolus powders, granules, ruminant-maintenance and food / water / rock salt blocks In the case of the compounds of the present invention are suitable for oral dosage compositions binders / fillers known in the art such as sugars (eg, lactose, sucrose, mannitol, sorbitol), starches (eg maize starch, wheat Starch, rice starch, potato starch), cellulose and derivatives thereof (eg methylcellulose, carboxymethylcellulose, ethylhydroxycellulose), protein derivatives (eg zein, gelatin) and synthetic polymers (eg Polyvinyl alcohol, polyvinylpyrrolidone). If desired, lubricants (eg magnesium stearate), disintegrants (eg crosslinked polyvinylpyrrolidinone, agar, alginic acid) and dyes or pigments may be added. Pastes and gels also often contain adhesives (eg, acacia, alginic acid, bentonite, cellulose, xanthan gum, colloidal magnesium aluminum silicate) to help keep the composition in contact with the oral cavity and not easily drain.

When the pesticidal composition is in the form of a feeding concentrate, the carrier is typically selected from high performance feeding, feeding grains or protein concentrates. Such feeding concentrate-containing compositions may comprise, in addition to the pesticidal active ingredient, additives useful for promoting animal health or growth, improving the quality of meat from slaughtered animals, or otherwise for animal husbandry. Such additives may include, for example, vitamins, antibiotics, chemotherapeutic agents, bacteriostatic agents, bacteriostatic agents, coccidial preventive agents and hormones.

Compounds of the invention have been found to have desirable pharmacokinetic and pharmacodynamic properties that provide systemic utilization from oral administration and ingestion. Thus, after ingestion by the animal to be protected, a pesticidal effective concentration of the compound of the invention protects blood-sucking pests such as fleas, ticks and animals treated therefrom. Thus, a composition for the protection of animals from invertebrate parasites, comprising an oral dosage form (ie, in addition to a pesticidal effective amount of a compound of the invention, a binder and filler suitable for oral administration, and one or more carriers selected from feeding concentrate carriers) It is noteworthy.

Topical dosage formulations are typically in the form of powders, creams, suspensions, sprays, emulsions, foams, pastes, aerosols, ointments, plasters or gels. More typically, topical formulations are aqueous solutions which may be in the form of concentrates which are diluted prior to use. Insecticidal compositions suitable for topical administration typically comprise a compound of the invention and one or more topically suitable carriers. For insecticidal compositions applied topically to the outside of the animal as a line or spot (ie, "spot-on treatment"), the active ingredient migrates over the epidermis of the animal to cover most or all of its outer surface area. As a result, the treated animals are particularly protected from invertebrate pests, such as mites, fleas and their eating epidermis. Thus, topically localized dosage formulations often include one or more organic solvents to promote the movement of the active ingredient on the skin and / or penetration of the animal into the epidermis. Solvents commonly used as carriers in such formulations include propylene glycol, paraffins, aromatics, esters such as isopropyl myristate, glycol ethers, and alcohols such as ethanol and n-propanol.

The application rate required for effective control (ie, "biologically effective amount") depends on the species of invertebrate to be controlled, the pest's life cycle, life stage, size, place of residence, time of year, host crop or animal, dietary behavior, It will depend on factors such as mating behavior, ambient humidity and temperature. Under normal circumstances, the application rate of about 0.01 to 2 kg of active ingredient per hectare is sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg / ha may be sufficient or as much as 8 kg / ha. May be required. For non-agronomic uses, effective use rates will range from about 1.0 to 50 mg / m ² , but amounts as low as 0.1 mg / m ² may be sufficient or amounts as high as 150 mg / m ² may be required. . One skilled in the art can readily determine the biologically effective amount required for the desired level of invertebrate pest control.

Typically, for veterinary use, the compound of formula 1 or an N-oxide or salt thereof is administered in a pesticidal effective amount to an animal to be protected from invertebrate parasites. A pesticidal effective amount is the amount of active ingredient required to achieve an observable effect of reducing the incidence or activity of an invertebrate parasite target. Those skilled in the art will vary in accordance with the pesticidal effective amount of the various compounds and compositions of the present invention, the desired pesticidal effect and duration, the species of the targeted invertebrate pest, the animal to be protected, the mode of application, and the like. It will be appreciated that this can be determined by a simple experiment.

For oral administration to warm blooded animals, the daily dose of a compound of the invention is typically from about 0.01 mg to about 100 mg, more typically from about 0.5 mg to about 100 mg per kg body weight of the animal. For topical (eg skin) administration, saliva and sprays typically contain from about 0.5 ppm to about 5000 ppm, more typically from about 1 ppm to about 3000 ppm of the compound of the present invention.

The following abbreviations have been used in indexes Tables A to B: Me is methyl and CF ₃ means trifluoromethyl. The abbreviation “Ex.” Stands for “Example” and follows the number indicated in the Examples in which the compounds were prepared. In Index Table A, (R ² ) _m shown represents the combination of (R ² ) _n when Z of the compound of formula 1 is CR ² .

<Index table A>

<Index table B>

Biological of the Invention Example

The following tests demonstrate the control efficiency of the compounds of the present invention against specific pests. "Control efficiency" refers to the inhibition (including mortality) of invertebrate pest outbreaks resulting in significantly reduced feeding. However, the pest control protection provided by the compounds is not limited to these species. See Indexes Tables A to B for descriptions of compounds.

Exam A

To assess the control of Chinese cabbage moth (Flutella xylostella), the test unit consisted of a small open container with 12-14 days old radish plants inside. It was pre-infected with 10 to 15 newborn larvae on insect feed pieces using a core sampler to collect plugs from a rigid insect feed sheet with a large number of larvae grown thereon, containing larvae and feed. One plug was transferred to the test unit. The larvae transferred to the test plants as feed plugs were dried.

Test compounds were prepared at 300 ppm X-77 ™ Spreader Lo-Foam Formula, containing 10% acetone, 90% water, and alkylarylpolyoxyethylene, free fatty acids, glycols, and isopropanol. It was formulated using a solution containing an ionic surfactant (Loveland Industries, Inc., Grillley, Colorado). Formulated compounds were placed on a 1/8 JJ custom body (Spraying Systems Co., Whitton, Ill.), Located 1.27 cm (0.5 inch) above the top of each test unit. It was applied in 1 mL of liquid through a SUJ2 spray nozzle equipped with a. In this test all experimental compounds were sprayed at 250 ppm and repeated three times. After spraying the formulated test compounds, each test unit was dried for 1 hour and then the black screening cap was placed on top. Test units were maintained for 6 days at 25 ° C. and 70% relative humidity in the growth chamber. The control efficiency levels of the test compounds were then assessed visually based on the houseplant feeding damage and larval mortality of each test unit.

Of the compounds of formula 1 tested, compounds 2, 11, 12 and 19 exhibited very good or excellent levels of plant protection (up to 30% feeding damage or at least 70% mortality).

Exam B

To evaluate the control of additional macroworms (Spodoftera pruperiferda), the test unit consisted of a small open container with corn (maize) plants 4-5 days old inside. It was pre-infected (using a core sampler) with 10 to 15 one day old larvae on insect feed pieces. As described in Test A, test compounds were formulated, sprayed at 250 ppm and repeated three times. After spraying, the test unit was maintained in the growth chamber and then evaluated visually as described in Test A.

Of the compounds of Formula 1 tested, Compound 2 exhibited very good or excellent levels of plant protection (up to 20% feeding damage or at least 80% mortality).

Exam C

To assess the control of cotton melon aphid (Apis gosipi) via contact and / or systematic means, the test unit consisted of a small open container with cotton plants 6 to 7 days old inside. This was pre-infected by placing 30 to 40 aphids on a piece of leaf incision (cut-leaf method) from the culture plant on the leaves of the test plant. When the leaf fragments dried, the larvae moved to the test plant. After pre-infection, the soil of the test unit was covered with a layer of sand.

As described in Test A, test compounds were formulated and sprayed at 250 ppm. The application was repeated three times. After spraying the formulated test compounds, each test unit was dried for 1 hour and then the black screening cap was placed on top. Test units were maintained for 6 days at 19-21 ° C. and 50-70% relative humidity in growth chambers. Each test unit was then visually evaluated for insect mortality.

Of the compounds of Formula 1 tested, Compound 2 exhibited at least 80% mortality.

Claims (26)

A compound of Formula 1, or an N-oxide or salt thereof: <Formula 1>

In the formula, Z is N or CR ² ; A ¹ is CR ⁴ or N; A ² is CR ⁵ or N; A ³ is CR ⁶ or N; A ⁴ is CR ⁷ or N; Q is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy , C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano, nitro, C (O) NR ⁸ R ⁹ , C (O) OR ¹⁰ , phenyl and pyridinyl ( Each phenyl and pyridinyl is optionally substituted with one or more substituents independently selected from R ¹¹ ) or a 5- or 6-membered saturated or unsaturated heterocycle optionally substituted with one or more substituents independently selected from; or Q is C (O) NR ¹² R ¹³ , C (S) NR ¹² R ¹³ , S (O) ₂ NR ¹⁴ R ¹⁵ or R ¹⁶ ; R ¹ is cyano or C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ optionally substituted with one or more substituents independently selected from R ¹⁷ Cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl; Each R ² is independently H, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, C ₂ -C ₄ alkoxycarbonyl, C ₂ -C ₄ alkylaminocarbonyl, C ₃ -C ₉ dialkylaminocarbonyl, cyano or nitro; R ³ is H, cyano or —CHO or C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, optionally substituted with one or more substituents independently selected from R ¹⁸ , C ₃ -C ₆ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl, C ₄ -C ₇ cycloalkylalkyl, phenyl, C ₂ -C ₆ alkylcarbonyl, C ₂ -C ₆ alkoxycarbonyl, C ₂ -C ₆ alkylaminocarbonyl or C ₃ -C ₉ dialkylaminocarbonyl; R ⁴ , R ⁵ , R ⁶ and R ⁷ are H, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano, and independently of the other, is selected from nitro; or R ⁶ and R ⁷ are taken together, with 1 or 2 carbon atoms, 0 or 2 nitrogen atoms, 0 or 1 oxygen atom and 0 or 1 sulfur as ring members in addition to A ³ and A ⁴ bridgehead atoms To form a fused aromatic ring containing three atoms selected from atoms, or four atoms selected from 2 to 4 carbon atoms and 0 to 2 nitrogen atoms; Each R ⁸ , R ¹² and R ¹⁴ is independently H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl, C ₄ -C ₇ cycloalkylalkyl, C ₂ -C ₇ alkylcarbonyl, C ₂ -C ₆ alkoxyalkyl or C ₂ -C ₇ alkoxycarbonyl; Each R ⁹ , R ¹⁰ , R ¹³ and R ¹⁵ is independently H or C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C optionally substituted with one or more substituents independently selected from R ¹⁹ ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl; Each of R ¹¹ , R ²³ and R ²⁴ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylaminosulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, C ₂ -C ₄ alkoxycarbonyl, cyano or nitro; R ¹⁶ is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ halo Alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C _1- C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano or nitro; Each R ¹⁷ and R ¹⁸ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulphur Phonyl, cyano or nitro; Each R ¹⁹ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₂ -C ₆ alkylcarbonyl, C ₂ -C ₆ alkoxycarbonyl, C ₃ -C ₆ trialkylsilyl, cyano, nitro or Q ¹ ; Each Q ¹ is independently halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C _1- C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsul Ponyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano, nitro, C (O) NR ²⁰ R ²¹ , C (O) OR ²² , Phenyl or 5- or 6-membered saturated or unsaturated hetero optionally substituted with one or more substituents independently selected from phenyl and pyridinyl (each phenyl and pyridinyl is optionally substituted with one or more substituents independently selected from R ²³ ) Cycle; Each R ²⁰ is independently H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl, C ₄ -C ₇ cycloalkylalkyl, C ₂ -C ₆ alkoxyalkyl, C ₂ -C ₇ alkylcarbonyl or C ₂ -C ₇ alkoxycarbonyl; Each R ²¹ and R ²² is independently H or C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ Cycloalkyl, C ₄ -C ₇ alkylcycloalkyl, C ₄ -C ₇ cycloalkylalkyl, phenyl or pyridinyl, each phenyl and pyridinyl optionally substituted with one or more substituents independently selected from R ²⁴ ; n is 1, 2, 3 or 4; Provided that Z is CR ² , A ¹ is CR ⁴ , A ² is CR ⁵ , A ³ is CR ⁶ , A ⁴ is CR ⁷ , Q is Br or cyano, R ¹ is methyl, R ³ is not phenyl when each R ² is H and R ⁴ , R ⁵ , R ⁶ and R ⁷ are H. The method of claim 1, Q is halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy , C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ alkylsulfinyl, C ₁ -C ₆ haloalkylsulfinyl, C ₁ -C ₆ alkylsulfonyl, C ₁ -C ₆ haloalkylsulfonyl, C ₁ -C ₆ alkylamino, C ₂ -C ₈ dialkylamino, cyano, nitro, C (O) NR ⁸ R ⁹ , C (O) OR ¹⁰ , phenyl and pyridinyl (each Phenyl and pyridinyl of is optionally substituted with one or more substituents independently selected from R ¹¹ ), pyridinyl, pyrimidinyl, triazinyl, pyrazolyl, triazolyl, imida 5- or 6-membered unsaturated heterocycles selected from zolyl, oxazolyl, isoxazolyl, thiazolyl and isothiazolyl; Or Q is C (O) NR ¹² R ¹³ , S (O) ₂ NR ¹⁴ R ¹⁵ or R ¹⁶ ; Z is CR ² ; At most one of A ¹ , A ² , A ³ and A ⁴ is N; R ¹ is C ₁ -C ₃ alkyl optionally substituted with one or more substituents independently selected from R ¹⁷ ; Each R ² is independently hydrogen, halogen or C ₁ -C ₂ haloalkyl; R ³ is H or cyano or C ₁ -C ₄ alkyl optionally substituted with one or more halogens; R ⁴ and R ⁵ are independently selected from H, halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano and nitro; R ⁶ and R ⁷ are independently selected from H, halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano and nitro; Or R ⁶ and R ⁷ are taken together to form a fused aromatic ring containing 3 or 4 carbon atoms and 4 atoms selected from 0 or 1 nitrogen atom as ring member in addition to A ³ and A ⁴ leg atoms; ; Each R ⁸ is independently H, C ₁ -C ₆ alkyl, C ₂ -C ₇ alkylcarbonyl or C ₂ -C ₇ alkoxycarbonyl; Each R ⁹ and R ¹⁰ is independently H, or optionally substituted with one or more substituents selected from R ¹⁹ , C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₄ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl; Each of R ¹² and R ¹⁴ is independently H, C ₁ -C ₆ alkyl, C ₂ -C ₇ alkylcarbonyl or C ₂ -C ₇ alkoxycarbonyl; Each R ¹³ and R ¹⁵ is independently H, or optionally substituted with one or more substituents selected from R ¹⁹ , C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₄ cycloalkyl, C ₄ -C ₇ alkylcycloalkyl or C ₄ -C ₇ cycloalkylalkyl; R ¹⁶ is halogen, C ₁ -C ₃ haloalkyl, C ₂ -C ₄ dialkylamino, cyano or nitro; Each R ¹⁹ is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, C ₂ -C ₄ alkylcarbonyl, C _2- Independently selected from C ₄ alkoxycarbonyl, cyano, nitro and Q ¹ ; Each Q ¹ is independent from phenyl, pyridinyl and thiazolyl, optionally substituted with one or more substituents independently selected from halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano, phenyl and pyridinyl Is selected; n is 1 or 2; The compound of claim 2, wherein R ¹ is C ₁ -C ₃ alkyl optionally substituted with one or more halogens. The method of claim 3, Q is attached to the remainder of Formula 1 via nitrogen and is halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, cyano, nitro Or a 5-membered unsaturated heterocycle selected from pyrazolyl, triazolyl and imidazolyl, optionally substituted with one or more substituents independently selected from C (O) NR ⁸ R ⁹ and C (O) OR ¹⁰ ; Or Q is C (O) NR ¹² R ¹³ ; R ¹ is CF ₃ ; R ⁶ and R ⁷ are independently selected from halogen, C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl, cyano and nitro; Or R ⁶ and R ⁷ are taken together to form a fused aromatic ring containing four carbon atoms as ring member in addition to A ³ and A ⁴ leg atoms; Each R ⁸ is H; Each R ⁹ and R ¹⁰ is independently halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfonyl, cyano and one or less C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from Q ¹ of; Each of R ¹² and R ¹⁴ is independently H; Each R ¹³ and R ¹⁵ is independently H or C ₁ -C ₄ alkyl optionally substituted with one or more substituents selected from R ¹⁹ ; R ¹⁹ is independently selected from halogen and Q ¹ . The compound of claim 4, wherein R ³ is methyl, ethyl or CH ₂ CF ₃ . The method of claim 1, 4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -2-methyl-N- (2-pyridinylmethyl) benzamide, 4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] -N- (2,2 , 2-trifluoroethyl) benzamide, 4- [5- (3,5-Dichlorophenyl) -4,5-dihydro-1- (2,2,2-trifluoroethyl) -5- (trifluoromethyl) -1H-pyrazole- 3-yl] -N- (2-pyridinylmethyl) benzamide and 1- [4- [5- (3,5-dichlorophenyl) -4,5-dihydro-1-methyl-5- (trifluoromethyl) -1H-pyrazol-3-yl] phenyl] -1H -1,2,4-triazole Compound selected from the group consisting of. A composition comprising the compound of claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and optionally further comprising at least one additional biologically active compound or agent. A biologically effective amount of the compound of claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent , Invertebrate pest control composition. The method of claim 8, wherein the one or more additional biologically active compounds or agents are macrocyclic lactones, neonicotinoids, octopamine receptor ligands, lianodine receptor ligands, ecdysone agonists, sodium channel modulators, chitin synthesis inhibitors. , Nereisotoxin analogues, mitochondrial electron transfer inhibitors, cholinesterase inhibitors, cyclodiene insecticides, stripping inhibitors, γ-aminobutyric acid-regulated chloride channel blockers, larval hormone mimetics, lipid biosynthesis inhibitors and biological agents (Bacillus thuringer Nucleopolyhead, a member of Bacillus thuringiensis , including insecticides in the group consisting of viruses, encapsulated delta-endotoxin of Bacillus thuringiensis, and natural or genetically modified viral insecticides) Composition. The method of claim 8, wherein the one or more additional biologically active compounds or agents are abamectin, acetate, acetamiprid, acetoprole, aldicarb, amidoflumet, amitraz, avermectin, azadirach Tin, Azinfos-methyl, Bifenthrin, Bifenazate, Bistrifluron, Buprofezin, Carbofuran, Carthaf, Kinomethione, Chlorfenapyr, Chlorfluazuron, Chlorlantriilif Roll, Chlorpyriphos, Chlorpyriphos-methyl, Chlorobenzylate, Chromafenozide, Clotianidine, Cyflumetofen, Cyfluthrin, Beta-Sipflutrin, Sihalothrin, Gamma-Sihal Rotrine, lambda-sihalothrin, cyhexatin, cipermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dicopol, dieldrin, dienochlor, diflubenzuron, dimefluthrin , Dimethoate, dinotefuran, diophenolran, emamectin, endosul , Esfenvalerate, ethyprolol, ethoxazole, phenamifos, phenazaquine, fenbutatin oxide, phenothiocarb, phenoxycarb, phenpropatrine, fenpyroximate, penvalerate, blood Pronyl, phlonomamide, flubendiamide, flucitrinate, tau-fluvalinate, flufenerim, flufenoxuron, phonophos, halopenozide, hexaflumuron, hexiaxans, hydra Methylnon, imicia force, imidacloprid, indoxacarb, isofenfoss, lufenuron, malathion, metaflumizone, metaldehyde, metamidofos, methidathion, metomile, methoprene, methoxycyclo, Methoxyphenozide, Metofluthrin, Monoclotophos, Nitenpyram, Nithiazine, Novaluron, Nobiflumuron, Oxamyl, Parathion, Parathion-methyl, Permethrin, Forate, Posalon, Posmet , Phosphamidone, pyrimycarb, propenophos, propflute , Propargite, protrifenbut, pymetrozine, pyraflulol, pyrethrin, pyridaben, pyridalyl, pyrifluquinazone, pyriprolol, pyriproxyfen, rotenone, lianodine, spinetoram , Spinosad, spirodiclofen, spiromesifen, spirotetramet, sulfpropos, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufoss, tetrachlorbinfos, tiaclo Fried, thiamethoxam, thio dicarboxylic dissolve, thiosulfate Tharp-sodium, tolyl penpi lard, Neutral Romero trim, triaza formate, tri-chlor phones, triple base muron, Bacillus turing group N-Sys subspecies ahyijawayi (Aizawai), Bacillus turing group N-Sys by endotoxin, baculovirus, entomopathogenic bacteria, entomopathogenic virus and entomopathogenic fungi - Mercure subspecies Starkey (kurstaki), nucleoside polyhedra with the virus, Bacillus turing machine encapsulated delta N-Sys The composition is selected from the group eojin. The method of claim 10, wherein the one or more additional biologically active compounds or agents are abamectin, acetamiprid, amitraz, avermectin, azadirachtin, bifenthrin, buprofezin, cartaf, chloran Traniliprole, Chlorfenapyr, Chlorpyriphos, Clothianidine, Cyfluthrin, Beta-Scifluthrin, Sihalothrin, Lambda-Sihalotrin, Cipermethrin, Cyromazine, Delta Met Lean, dieldrin, dinotefuran, diophenolran, emamectin, endosulfan, esfenvalerate, ethiprole, phenothiocarb, phenoxycarb, penvalerate, fipronil, phlonicamid, flubene Diamide, flufenoxuron, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, metomil, metoprene, methoxyphenozide, nitenpyram, nithiazine, nothazine Baluron, oxamil, pymetrozine, pyrethrin, pyridaben, pyridalyl, Riloxifene, Lianodine, Spinetoram, Spinosad, Spirodiclofen, Spiromethsifen, Tebufenozide, Tiacloprid, Tiamethoxam, Thiodicarb, Thiosulfaf-Sodium, Tralomethrin, The composition is selected from the group consisting of triamate, triflumuron, Bacillus thuringiensis subspecies Aizawa, Bacillus thuringiensis subspecies Kurstaki, nucleopolyheadovirus and encapsulated delta-endotoxin of Bacillus thuringiensis. . The composition of claim 8 in the form of a soil drench liquid formulation. (a) a biologically effective amount of the compound of claim 1 or the composition of claim 8; And (b) propellants Including, spray composition for invertebrate pest control. (a) a biologically effective amount of the compound of claim 1 or the composition of claim 8; (b) one or more foods; (c) optionally attractant; And (d) optionally a humectant A bait composition for invertebrate pest control comprising a. (a) the bait composition of claim 14; And (b) has one or more openings of a size that allows the invertebrate pest to pass through to access the bait composition from a location outside the housing, and additionally for placement at or near the site of potential or known activity of the invertebrate pest; Suitable housing for accommodating the bait composition Including, invertebrate pest control trap device. A method of controlling an invertebrate pest, comprising contacting the invertebrate pest or its environment with a biologically effective amount of the compound of claim 1. A method of controlling an invertebrate pest, comprising contacting the invertebrate pest or its environment with the composition of claim 8. The method of claim 17, wherein the environment is soil and the composition is applied to the soil as a soil irrigation agent. A method for controlling a cockroach, ant or termite, comprising contacting the cockroach, ant or termite with the bait composition in the trap device of claim 15. Mosquitoes, moths, mosquitoes, flies, stag flies, horse flies, wasps, bumblebees, bumblebees, ticks, spiders, ants, or nymphs, including contacting the spray composition of claim 13 dispensed from the spray container, How to control chimpanzees, stag flies, horse flies, wasps, bumblebees, bumblebees, ticks, spiders, ants or antlers. A method of protecting a seed from invertebrate pests comprising contacting the seed with a biologically effective amount of the compound of claim 1. The method of claim 21, wherein the seed is coated with the compound of claim 1 formulated with a composition comprising a film former or an adhesive. A treated seed comprising the compound of claim 1 in an amount of about 0.0001 to 1% by weight of the seed before treatment. A composition for protecting an animal from invertebrate parasites comprising a pesticidal effective amount of the compound of claim 1 and at least one carrier. The composition of claim 24 in form for oral administration. A method of protecting an animal from invertebrate parasites, comprising administering to the animal a pesticidal effective amount of the compound of claim 1.