JP2008510721A - New anthranilamides useful for the control of invertebrate pests - Google Patents

Abstract

［式中、
Ｑは式Ｑ−１、Ｑ−２およびＱ−３
よりなる群から選択され；
Ｒ^１はＸ−Ｚ−Ｏ−Ｒ^１１であり；
ＸはＯ、ＳまたはＮＲ^１２であり；
ＺはＣ_２〜Ｃ_４ハロアルキレンまたはＣ_２〜Ｃ_４ハロアルケニレンであり；そして
Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^１１、Ｒ^１２およびｎは本開示に定義された通りである］の化合物、そのＮ−オキシドおよび塩が開示される。式Ｉの化合物を含有する組成物、および無脊椎有害生物またはその環境を生物学的に有効な量の本発明の化合物または組成物と接触させることを含んでなる無脊椎有害生物の防除方法も開示される。Formula I, including all geometric and stereoisomers
[Chemical 1]

[Where:
Q is the formula Q-1, Q-2 and Q-3
Selected from the group consisting of;
R ¹ is X—Z—O—R ¹¹ ;
X is O, S or NR ¹² ;
Z is C ₂ -C ₄ haloalkylene or C ₂ -C ₄ haloalkenylene; and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹¹ , R ¹² and n are disclosed in this disclosure As defined], N-oxides and salts thereof. A composition comprising a compound of formula I and a method of controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or composition of the present invention. Disclosed.

Description

  The present invention relates to certain anthranilamides, their N-oxides, salts and compositions suitable for agricultural and non-agricultural uses, including their uses described below, and both agricultural and non-agricultural environments. Relates to their use for the control of invertebrate pests such as arthropods.

  Invertebrate pest control is extremely important to achieve high crop efficiency. Invertebrate pest damage to growing and stored crops can cause significant reductions in productivity, which can result in increased costs to consumers. Invertebrate pest control is also important in forestry, greenhouse crops, ornaments, seedlings, stored food and textile products, livestock, household goods, lawns, wood products, and public health and animal health. Many products for these purposes are commercially available, but there is a need for new compounds that are more effective, less expensive, less toxic, environmentally safe, or have different modes of action Sex persists.

  Patent Document 1 describes a formula i as an arthropod animal agent.

[In particular, R ¹ is CH ₃ , F, Cl or Br; R ² is F, Cl, Br, I or CF ₃ ; R ³ is CF ₃ , Cl, Br or OCH ₂ CF ₃ R ^4a is C ₁ -C ₄ alkyl; R ^4b is H or CH ₃ ; and R ⁵ is Cl or Br.] Discloses N-acyl anthranilic acid derivatives.

WO03 / 015519 pamphlet

  The present invention relates to compounds of formula I including all geometric and stereoisomers, their N-oxides, agricultural or non-agricultural salts, agricultural and non-agricultural compositions containing them and invertebrate harm It relates to their use for controlling organisms.

[Where:
Q is Q-1, Q-2 and Q-3

Selected from the group consisting of;
R ¹ is X—Z—O—R ¹¹ ;
X is O, S or NR ¹² ;
Z is _C 2 -C ₄ haloalkylene or _C 2 -C ₄ Haroarukeniren;
Each R ² is independently H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio , be a _C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C ₄ haloalkylsulfinyl or _C 1 -C ₄ haloalkylsulfonyl;
R ³ is H; or optionally substituted by halogen, respectively, cyano, nitro, _hydroxy, C 1 -C _{4 alkoxy,} C 1 -C _{4 alkylthio,} C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl, C} 2 ~ C _{4 alkoxycarbonyl,} C 1 -C _{4 alkylamino,} optionally substituted by one or more substituents selected from C 2 -C ₈ dialkylamino and _C 3 -C ₆ group consisting cycloalkylamino Good C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl;
R ⁴ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, OH, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylamino , _C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino, (C} 1 ~C _{4 alkyl) (C} 3 -C ₆ cycloalkyl) _amino, C 2 -C ₆ alkoxycarbonyl or _C 2 -C ₆ Alkylcarbonyl;
R ⁵ is H; G ¹ ; or optionally halogen, G ¹ , cyano, nitro, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C _{4, respectively. alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylcarbonyl,} C 3 _{~C 6} 1 or or more selected from the group consisting of trialkylsilyl and ^{G 2} Are C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl optionally substituted by a substituent of R ⁵ ; or R ⁵ is hydroxy, C ₁ -C _{4 alkoxy,} C 1 -C _{4 alkylamino,} C 2 -C _{8 dialkylamino,} C 3 -C ₆ cycloalkyl amino , C ₂ -C ₆ alkoxycarbonyl or C ₂ -C ₆ alkylcarbonyl; or R ⁴ and R ⁵ together with the nitrogen to which they are attached contain 2 to 6 carbon atoms And optionally forms a ring which may contain one additional atom of nitrogen, sulfur or oxygen, said ring optionally being C ₁ -C ₂ alkyl, halogen, cyano, nitro and C _1- Optionally substituted by 1 to 4 substituents selected from the group consisting of C ₂ alkoxy;
R ⁶ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ haloalkenyl, C ₂ -C _{6 haloalkynyl,} C 3 -C ₆ halocycloalkyl, halogen, cyano, _nitro, CO 2 H, CONH _{2, hydroxy,} C 1 -C _{4 alkoxy,} C 1 -C _{4 haloalkoxy,} C 1 -C _{4 alkylthio,} C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C _{4 haloalkylsulfinyl,} C 1 -C _{4 haloalkylsulfonyl,} C 1 -C ₄ alkylamino , _C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino,} C 2 -C _{6 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylaminocarbonyl,} it is a C 3 -C ₈ dialkylaminocarbonyl or _C 3 -C ₆ trialkylsilyl;
R ⁷ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ haloalkenyl, C ₂ -C _{6 haloalkynyl,} C 3 -C ₆ halocycloalkyl, halogen, cyano, _nitro, CO 2 H, CONH _{2, hydroxy,} C 1 -C _{4 alkoxy,} C 1 -C _{4 haloalkoxy,} C 1 -C _{4 alkylthio,} C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C _{4 haloalkylsulfinyl,} C 1 -C _{4 haloalkylsulfonyl,} C 1 -C ₄ alkylamino , _C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino,} C 2 -C _{6 alkylcarbonyl,} C 2 -C ₆ alkoxycarbonyl, C ₂ -C ₆ alkylaminocarbonyl, C ₃ -C ₈ dialkylaminocarbonyl or C ₃ -C ₆ trialkylsilyl; or R ⁷ is optionally C ₁ -C ₄ alkyl, C _{2, respectively.} -C _{4 alkenyl,} C 2 -C _{4 alkynyl,} C 3 -C _{6 cycloalkyl,} C 1 -C _{4 haloalkyl,} C 2 -C _{4 haloalkenyl,} C 2 -C _{4 haloalkynyl,} C 3 -C ₆ Haroshikuro alkyl, halogen, cyano, _nitro, C 1 -C _{4 alkoxy,} C 1 -C _{4 haloalkoxy,} C 1 -C _{4 alkylthio,} C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 alkylamino,} C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino,} C 4 -C ₇ Alkyl) _{cycloalkylamino,} C 2 -C _{4 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} one or selected from C 2 -C ₆ alkylaminocarbonyl and _C 3 -C ₈ group consisting dialkylaminocarbonyl Phenyl, benzyl or phenoxy optionally substituted by the above substituents;
Each G ¹ independently comprises one or two ring members, optionally selected from the group consisting of C (═O), S (O) and S (O) ₂ and optionally independent of R ^10. A 5- or 6-membered non-aromatic carbocyclic or heterocyclic ring optionally substituted by 1 to 4 substituents selected from
Each G ² is independently a phenyl ring, a phenoxy ring, or a 5-membered heteroaromatic ring in which each ring is optionally substituted by 1 to 3 substituents independently selected from R ⁹ Or a 6-membered heteroaromatic ring;
Each R ⁹ is independently C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ haloalkenyl. , C ₂ -C ₄ haloalkynyl, C ₃ -C ₆ halocycloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 alkylamino,} C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino, (C} 1 -C _{4 alkyl) (C} 3 -C ₆ cycloalkyl) _amino, C 2 -C _{4 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylaminocarbonyl,} C 3 -C ₈ dialkylamino carbonyl or _C 3 -C ₆ trialkylsilyl;
Each R ¹⁰ is independently C ₁ -C ₂ alkyl, halogen, cyano, nitro or C ₁ -C ₂ alkoxy;
R ¹¹ is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₈ alkoxyalkyl, C ₂ -C ₈ haloalkoxyalkyl, C ₂ -C ₈ alkoxyalkyl _haloalkyl, C 1 -C _{6 haloalkyl,} C 2 -C _{6 haloalkenyl,} C 2 -C _{6 haloalkynyl,} be a C 3 -C ₆ halocycloalkyl or _C 2 -C ₈ haloalkoxy haloalkyl;
R ¹² is H or C ₁ -C ₄ alkyl;
W is N or CR ² ;
V is N or CR ¹³ ;
Y is N or CR ¹⁴ ;
R ¹³ and R ¹⁴ are independently H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ haloalkyl, C _2- C ₆ haloalkenyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ halocycloalkyl, halogen, cyano, nitro, CO ₂ H, CONH ₂ , hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ halo _alkoxy, C 1 -C _{4 alkylthio,} located at C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C ₄ haloalkylsulfinyl or _C 1 -C ₄ haloalkylsulfonyl ;
L is a direct bond; or a 1- to 3-membered connecting chain selected from carbon, nitrogen, oxygen, sulfur, C (= E), S (O) and S (O) ₂ , but no more than 2 Are selected from C (═E), S (O) and S (O) ₂ , and the linking chain is optionally substituted by 1 to 3 substituents independently selected from R ¹⁵ May be;
Each R ¹⁵ is independently H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, halogen, cyano, COOH, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₂ -C ₆ alkoxy Carbonyl or C ₂ -C ₆ alkoxycarbonylalkyl; or a phenyl ring optionally substituted with 1 to 3 substituents each ring optionally selected independently from R ¹⁶ or a 5 or 6 membered A heteroaromatic ring;
Each R ¹⁶ is independently C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ haloalkenyl. , C ₂ -C ₄ haloalkynyl, C ₃ -C ₆ halocycloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C _{4 haloalkylsulfinyl,} C 1 -C _{4 haloalkylsulfonyl,} C 1 -C _{4 alkylamino,} C 2 -C ₈ dialkyl _amino, C 3 -C _{6 cycloalkylamino, (C} 1 _{~C 4 alkyl) (C} 3 -C ₆ cycloalkyl) _{amino, C} 2 ~ _{4 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylaminocarbonyl,} be a C 3 -C ₈ dialkylaminocarbonyl or _C 3 -C ₆ trialkylsilyl;
E is CH ₂ , O, S or NR ¹⁷ ;
R ¹⁷ is H; G ³ ; or optionally halogen, G ³ , cyano, nitro, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C _{4, respectively. alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylcarbonyl,} C 3 _{~C 6} 1 or or more selected from the group consisting of trialkylsilyl and ^{G 4} C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl or phenyl optionally substituted by a substituent of: R ¹⁷ is hydroxy, C ₁ -C _{4 alkoxy,} C 1 -C _{4 alkylamino,} C 2 -C _{8 dialkylamino,} C 3 -C ₆ Sik B alkyl _amino, C 2 -C ₆ alkoxycarbonyl or _C 2 -C ₆ alkylcarbonyl;
Each G ³ independently comprises one or two ring members optionally selected from the group consisting of C (═O), S (O) and S (O) ₂ and optionally independent of R ¹⁹ A 5- or 6-membered non-aromatic carbocyclic or heterocyclic ring optionally substituted by 1 to 4 substituents selected from
Each G ⁴ is independently a phenyl ring, a phenoxy ring, or a 5-membered heteroaromatic ring in which each ring is optionally substituted by 1 to 3 substituents independently selected from R ¹⁸ Or a 6-membered heteroaromatic ring;
Each R ¹⁸ is independently C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ haloalkenyl. , C ₂ -C ₄ haloalkynyl, C ₃ -C ₆ halocycloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkylamino, C ₂ -C ₈ dialkylamino, C ₃ -C ₆ cycloalkylamino, C ₄ -C ₇ (alkyl) cycloalkylamino, C ₂ -C _{4 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylaminocarbonyl,} C 3 -C ₈ dialkyl It is amino carbonyl, or _C 3 -C ₆ trialkylsilyl;
Each R ¹⁹ is independently C ₁ -C ₂ alkyl, halogen, cyano, nitro or C ₁ -C ₂ alkoxy; and n is 1, 2, 3 or 4.

  The present invention also includes a biologically effective amount of a compound of formula I, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, invertebrate harmful Also provided is a composition for controlling a living organism, optionally 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 controlling invertebrate pests comprising a biologically effective amount of a compound of Formula I or a composition as described above and a propellant. The present invention also provides an invertebrate harm comprising a biologically effective amount of a compound of formula I or a composition as described above, one or more food ingredients, optionally an attractant, and optionally a humectant. A feed composition for biocontrol is also provided.

The present invention further provides a trap device for invertebrate pest control comprising the feed composition and a housing adapted to receive the feed composition. Here, the housing is at least one sized to allow the invertebrate pest to pass through the opening so that the invertebrate pest can access the feed composition from a location outside the housing. And the housing is further adapted to be located at or near a potential or known active location of an invertebrate pest.

  The present invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of formula I (eg, as a composition as described above). To do. The invention also comprises a biologically effective amount of a compound according to Formula I, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, Such a method comprising contacting the invertebrate pest or its environment with a composition further comprising a biologically effective amount of at least one additional biologically active compound or agent. Also related.

  As used herein, the terms “comprising”, “comprising”, “including”, “including”, “having”, “having”, “containing” or “Contains” or any other variation thereof is intended to encompass non-exclusive inclusions. For example, a composition, mixture, process, method, article or device comprising a list of elements is not necessarily limited to only those elements, but is not expressly described or such compositions, mixtures, It may include other elements that are specific to the process, method, article or apparatus. Further, unless stated to the contrary, “or or or” refers to inclusive OR and not exclusive OR. For example, condition A or B is met by any one of the following: A is true (or present) and B is false (or absent). A is false (or absent) and B is true (or present). And both A and B are true (or present).

  Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be non-limiting with respect to the number of instances (ie, the number of occurrences) of the element or component. Thus, “a” or “an” should be read to include 1 or at least 1, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular. For example, a composition of the present invention comprises a biologically effective amount of a compound of formula I, which is read as the composition comprises one or at least one compound of formula I.

In the above, the term “alkyl” used either alone or in combination words such as “alkylthio” or “haloalkyl” includes methyl, ethyl, n-propyl, i-propyl or various butyl, pentyl Or a linear or branched alkyl like a hexyl isomer is mentioned. “Alkenyl” includes straight- or branched-chain alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the various butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes linear or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the various butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include a moiety composed of a plurality of triple bonds such as 2,5-hexadiynyl. “Alkylene” refers to straight or branched chain alkanediyl. Examples of “alkylene” include CH ₂ , CH ₂ CH ₂ , CH (CH ₃ ), CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH ₃ ) and various butylene isomers. “Alkenylene” refers to a straight or branched alkenediyl containing one olefinic bond. Examples of “alkenylene” include CH═CH, CH ₂ CH═CH, CH═C (CH ₃ ) and various butenylene isomers. “Alkynylene” refers to a straight or branched alkynediyl containing one triple bond. Examples of “alkynylene” include C≡C, CH ₂ C≡C, C≡CCH ₂ and various butynylene isomers.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the various butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl” refers to an alkoxy substitution on an alkyl. Examples of “alkoxyalkyl” include CH ₃ OCH ₂ , CH ₃ OCH ₂ CH ₂ , CH ₃ CH ₂ OCH ₂ , CH ₃ CH ₂ CH ₂ CH ₂ OCH ₂ and CH ₃ CH ₂ OCH ₂ CH _2. . “Alkoxyalkoxy” refers to an alkoxy substitution on an alkoxy.

“Alkylthio” includes methylthio, ethylthio, and branched or straight chain alkylthio moieties such as various propylthio, butylthio, pentylthio and hexylthio isomers. “Alkylsulfinyl” includes both enantiomers of an 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 Various butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers are mentioned. 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 various butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. “Alkylamino”, “dialkylamino” and the like are defined as in the above examples. “Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term “cycloalkylamino” includes similar groups linked through a nitrogen atom, such as cyclopentylamino and cyclohexylamino. The term “alkylcycloalkylamino” refers to a branched or straight chain alkyl group and another cycloalkyl group attached to a nitrogen atom, such as methylcyclopentylamino and ethylcyclohexylamino.

The term “halogen”, either alone or in combination with words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine. Furthermore, when used in a combined word such as “haloalkyl”, said alkyl may be partially or fully substituted by halogen atoms which may be the same or different. Examples of “haloalkyl” include F ₃ C—, ClCH ₂ —, CF ₃ CH ₂ —, and CF ₃ CCl ₂ —. The terms “haloalkenyl”, “haloalkynyl”, “haloalkylene”, “haloalkenylene”, “halocycloalkyl”, “haloalkoxy”, “haloalkylthio” and the like are defined similarly to the term “haloalkyl”. Examples of “haloalkenyl” include (Cl) ₂ C═CHCH ₂ — and CF ₃ CH ₂ CH═CHCH ₂ —. Examples of “haloalkynyl” include HC≡CCHCl—, CF ₃ C≡C—, CCl ₃ C≡C— and FCH ₂ C≡CCH ₂ —. 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 —. It is done.

“Haloalkoxyalkyl” denotes a haloalkoxy substitution on an alkyl moiety. Examples of “haloalkoxyalkyl” include CF ₃ OCH ₂ —, CCl ₃ CH ₂ OCH ₂ CH ₂ —, HCF ₂ CH ₂ CH ₂ O (CH ₃ ) CH— and CF ₃ CH ₂ OCH ₂ CH ₂ — and Other straight chain or branched chain haloalkyl moieties attached to a straight chain or branched chain alkyl group. The terms “haloalkoxyhaloalkyl”, “alkoxyhaloalkyl” and the like are defined similarly to the term “haloalkoxyalkyl”.

“Alkylcarbonyl” refers to a straight or branched alkyl moiety attached 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 various butoxy or pentoxycarbonyl isomers. 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 various butylamino or pentylaminocarbonyl isomers. 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) - and the like.

“Trialkylsilyl” includes three branched and / or straight chain alkyl groups linked and linked through a silicon atom such as trimethylsilyl, triethylsilyl and t-butyl-dimethylsilyl. The total number of carbon atoms in the substituent is represented by the prefix “C _i -C _j ”, where i and j are numbers from 1 to j. For example, C ₁ -C ₄ alkylsulfonyl refers to methylsulfonyl to butylsulfonyl; C ₂ alkylaminoalkyl refers to CH ₃ NHCH ₂ —; C ₃ alkylaminoalkyl is, for example, CH ₃ (CH ₃ NH) CH— , CH ₃ NHCH ₂ CH ₂ — or CH ₃ CH ₂ NHCH ₂ —; and C ₄ alkylaminoalkyl refers to various isomerisms of alkyl groups substituted by alkylamino groups containing a total of 4 carbon atoms. Refers to the body and includes, for example, CH ₃ CH ₂ CH ₂ NHCH ₂ — and CH ₃ CH ₂ NHCH ₂ CH ₂ —. The terms “phenylcarbonyl”, “benzylcarbonyl” and the like are defined similarly to “alkylcarbonyl”. “Alkylcarbonylalkyl” refers to an alkylcarbonyl substitution on an alkyl moiety. Examples of “alkylcarbonylalkyl” include CH ₃ C (═O) CH ₂ CH ₂ — and (CH ₃ ) ₂ CHC (═O) CH ₂ (CH ₃ ) CH—. The terms “alkoxycarbonylalkyl”, “alkylaminocarbonylalkyl” and the like are defined similarly to “alkylcarbonylalkyl”.

The total number of carbon atoms in the substituent is represented by the prefix “C _i -C _j ”, where i and j are numbers from 2 to 8. For example, C ₁ -C ₄ alkylsulfonyl refers to methylsulfonyl to butylsulfonyl; C ₂ alkoxyalkyl refers to CH ₃ OCH ₂ ; C ₃ alkoxyalkyl refers to, for example, CH ₃ CH (OCH ₃ ), CH ₃ OCH ₂ CH ₂ or CH ₃ CH ₂ OCH ₂ refers to; and C ₄ alkoxyalkyl refers to various isomers of alkyl groups substituted by alkoxy groups containing a total of 4 carbon atoms, for example, CH ₃ CH ₂ CH ₂ OCH ₂ and CH ₃ CH ₂ OCH ₂ CH ₂ are mentioned.

When a compound is substituted with a substituent having a subscript that indicates that the number of substituents may be 1 or more, the substituent (if 1 or more) is a defined substituent, such as ( R ₂ ) _n , where n is 1, 2, 3 or 4 independently.

For example, with respect to R ² or R ⁶ , if a group contains a substituent that may be hydrogen, it is recognized that this substituent is taken as hydrogen, which is equivalent to said group that is unsubstituted.

  The compounds of the present invention can also exist as one or more stereoisomers. Various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will recognize that one stereoisomer may be more active and / or exhibit beneficial effects when enriched with respect to other stereoisomers or separated from other stereoisomers. will do. In addition, those skilled in the art know how to separate, concentrate and / or selectively produce said stereoisomers. The present invention therefore comprises compounds selected from formula I, their N-oxides and agriculturally suitable salts. The compounds of the invention may exist as mixtures of stereoisomers, as individual stereoisomers, or in optically active form.

  Those skilled in the art recognize that not all nitrogen-containing heterocycles can form N-oxides because nitrogen requires a lone pair of electrons available for oxidation to oxides, and those capable of forming N-oxides. Those skilled in the art will recognize the nitrogen-containing heterocycles. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of heterocyclic and tertiary amine N-oxides are well known to those skilled in the art and include peroxyacids such as peracetic acid and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, t-butylhydro Includes oxidation of heterocycles and tertiary amines with alkyl hydroperoxides such as peroxides, sodium perborate, and dioxiranes such as dimethyldioxirane. Methods for producing these N-oxides have been extensively described in the literature and have been reviewed. For example, T.W. L. TL Gilchrist, Comprehensive Organic Synthesis, Vol. 7, pages 748-750, S.C. V. Edited by S. V. Ley, Pergamon Press; M. Tissler and B.C. B. Stanovnik, Comprehensive Heterocyclic Chemistry, Vol. 3, pp. 18-20. J. et al. A. B. Tolton and A. B. Edited by A. McKillop, Pergamon Press; R. GR Grimmett and B.M. R. T.A. B. R. T. Keene, Advances in Heterocyclic Chemistry, Vol. 43, pp. 149-161. R. Edited by A.R. Katritzky, Academic Press; M. Tissler and B.C. B. Stanovnik, Advances in Heterocyclic Chemistry, Vol. 9, pp. 285-291. R. Catricky and A.R. J. et al. Edited by AJ Boulton, Academic Press; W. H. Cheeseman and E.G. S. G. W. S. Welstiuk, Advances in Heterocyclic Chemistry, Vol. 22, 390-392, A.E. R. Catricky and A.R. J. et al. See AJ Boulton, Academic Press.

  Examples of the salt of the compound of the present invention include 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- Acid addition salts with inorganic or organic acids such as toluenesulfonic acid or valeric acid. When the compound contains an acid group such as a carboxylic acid or a phenol, the salt of the compound of the present invention includes an organic base (for example, pyridine, ammonia or triethylamine) or an inorganic base (for example, sodium, potassium, lithium, calcium, And those formed by magnesium or barium hydrides, hydroxides or carbonates).

The term “aromatic ring system” refers to fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic (where aromatic represents what satisfies the Hückel rule for the ring system). The term “aromatic carbocycle” includes fully aromatic carbocycles and carbocycles in which at least one ring of the polycyclic ring system is aromatic (wherein aromatics represent those that satisfy the Hückel rule). The term “non-aromatic carbocycle” refers to fully saturated carbocycles as well as partially or fully unsaturated carbocycles in which the Hückel rule is not satisfied by any ring in the ring system. The term “aromatic heterocycle” includes fully aromatic heterocycles and heterocycles in which at least one ring of the polycyclic ring system is aromatic (where aromatic represents those that satisfy the Hückel rule). The term “non-aromatic heterocycle” refers to fully saturated and partially or fully unsaturated heterocycles in which the Hückel rule is not satisfied by any ring in the ring system. Heterocyclic ring systems can be attached by substituting hydrogen on the carbon or nitrogen through any available carbon or nitrogen. The term “optionally substituted” refers to a group that is unsubstituted or has at least one substituent other than hydrogen in relation to an aromatic ring group. In general, the number of optional substituents (if present) ranges from 1 to 4.

As described above, G ¹ (or G ³ ) optionally comprises one or two ring members selected from the group consisting of C (═O), S (O) and S (O) ₂ , and A 5- or 6-membered non-aromatic carbocyclic or heterocyclic ring optionally substituted by 1 to 4 substituents independently selected from R ¹⁰ (or R ¹⁹ ). Examples of 5- or 6-membered non-aromatic carbocycles or heterocycles optionally substituted by R ¹⁰ (or R ¹⁹ ) are those illustrated as G-1 to G-35 in Presentation 1. Is mentioned. It should be noted that when the point of attachment on these G groups is shown unfixed, the G group can be converted to the formula I by substitution of a hydrogen atom through any available carbon or nitrogen of the G group. It is possible to bind to the residues. Any substituent R ¹⁰ (or R ¹⁹ ) can be attached to any carbon or nitrogen by substitution of a hydrogen atom (since the substituent is an optional substituent, it is illustrated in Presentation 1 It has not been). Of note, when G comprises a ring selected from G-24 to G-31, G-34 and G-35, Q ² may be selected from O, S, NH or substituted N.

As noted above, G ₂ (or G ₄ ) is a phenyl ring optionally substituted with 1 to 3 substituents, each ring optionally selected independently from R ⁹ (or R ¹⁸ ), A phenoxy ring, a 5-membered heteroaromatic ring or a 6-membered heteroaromatic ring. An example of a phenyl ring optionally substituted by R ⁹ (or R ¹⁸ ) is the ring depicted as U-1 in Presentation 2, where R ^v is R ⁹ (or R ¹⁸ ); And r is an integer of 1-3. Examples of 5-membered heteroaromatic rings or 6-membered heteroaromatic rings optionally substituted by R ⁹ (or R ¹⁸ ) include rings U-2 to U-53 illustrated in Presentation 2 Wherein R ^v is R ⁹ (or R ¹⁸ ) and r is an integer from 1 to 3.

Although the structure U-I through U-53 is R ^v groups are shown, they are for an optional substituent, it need not be present should be noted. It should be noted that when R ^v is H when attached to an atom, this is identical to the fact that the atom is unsubstituted. Nitrogen atoms that require substitution to fill their valence are substituted by H or R ^v . It should be noted here that some U groups can only be substituted by less than 3 R ^v groups (eg, U-16 to U-21, U-32 to U-34 and U −40 can only be substituted by one R ^v ). It should be noted here that when the point of attachment between (R ^v ) _r and the U group is not fixed, (R ^v ) _r is any available carbon of the U group. It can be bonded to an atom. It should be noted here that if the point of attachment on the U group is shown unfixed, the U group can be represented by the substitution of a hydrogen atom through any available carbon of the U group. Be able to bind to the rest of I.

Embodiments of the present invention include the following:
Embodiment 1. FIG. R ¹¹ is C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₄ alkoxyalkyl, C ₂ -C ₄ haloalkoxyalkyl, C ₂ -C ₄ alkoxyalkyl _haloalkyl, C 1 -C _{4 haloalkyl,} C 2 -C _{4 haloalkenyl,} C 2 -C _{4 haloalkynyl,} C 3 -C ₆ halocycloalkyl or _C 2 -C a ₄ halo alkoxyhaloalkyl formula Compound of I.

Embodiment 2. FIG. The compound of Embodiment 1 wherein R ¹¹ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl.

Embodiment 3. FIG. A compound of Embodiment 2 wherein R ¹¹ is methyl, ethyl, CH ₂ CF ₃ , CF ₃ , CF ₂ CF ₃ , CF ₂ CF ₂ Br, CF ₂ CF ₂ CF ₃ or CF (CF ₃ ) ₂ .

Embodiment 4 FIG. Embodiment 4. A compound of Embodiment 3 wherein R ¹¹ is CF ₃ .

Embodiment 5. FIG. A compound of formula I wherein X is O.

Embodiment 6. FIG. A compound of formula I wherein Z is C ₂ haloalkylene.

Embodiment 7. FIG. A compound of Embodiment 6 R ¹ is ^{_{-X-CF 2 CHFO-R 11}} .

Embodiment 8. FIG. Embodiment 8. A compound of Embodiment 7 wherein R ¹ is —OCF ₂ CHFO—R ¹¹ .

Embodiment 9. FIG. Embodiment 9. A compound of Embodiment 8 wherein R ¹ is —OCF ₂ CHFOCF ₃ .

Embodiment 10 FIG. A compound of formula I wherein W is N, CH, CF, CCl, CBr or CI.

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

Embodiment 12 FIG. Each R ² is independently H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy; and n is A compound of formula I which is 1, 2 or 3.

Embodiment 13. FIG. Embodiment 13. A compound of Embodiment 12 wherein each R ² is independently H, Cl, F or Br; and n is 1 or 2.

Embodiment 14 FIG. A compound of Formula I wherein R ³ is H or C ₁ -C ₄ alkyl.

Embodiment 15. FIG. Embodiment 15. A compound of Embodiment 14 wherein R ³ is H.

Embodiment 16. FIG. A compound of Formula I wherein R ⁴ is H or C ₁ -C ₄ alkyl.

Embodiment 17. FIG. Embodiment 17. A compound of Embodiment 16 wherein R ⁴ is H.

Embodiment 18. FIG. R ⁵ is H; or each optionally substituted by one or more substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, OCH ₃ and S (O) _p CH ₃ A compound of formula I wherein C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl; and p is 0, 1 or 2.

Embodiment 19. FIG. Embodiment 18. A compound of Embodiment 18 wherein R ⁵ is H, methyl, ethyl, i-propyl or t-butyl.

Embodiment 20. FIG. R ⁶ is H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C _1- C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C ₄ haloalkylsulfinyl or _C 1 -C ₄ compounds of the formula I in which haloalkylsulfonyl.

Embodiment 21. FIG. Embodiment 20. A compound of Embodiment 20 wherein R ⁶ is CH ₃ , CF ₃ , OCHF ₂ , S (O) _q CF ₃ , S (O) _q CHF ₂ , cyano or halogen; and q is 0, 1 or 2.

Embodiment 22. FIG. Embodiment 22. A compound of Embodiment 21 wherein R ⁶ is F, Cl, Br, I, CH ₃ or CF ₃ .

Embodiment 23. FIG. Embodiment 22. A compound of Embodiment 22 wherein R ⁶ is Cl or CH ₃ .

Embodiment 24. FIG. R ⁷ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ haloalkenyl, C ₂ -C _{6 haloalkynyl,} C 3 -C ₆ halocycloalkyl, halogen, cyano, _nitro, C 1 -C _{4 alkoxy,} C 1 -C _{4 haloalkoxy,} C 1 -C _{4 alkylthio,} C 1 -C ₄ alkyl _sulfinyl, C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C _{4 haloalkylsulfinyl,} C 1 -C _{4 haloalkylsulfonyl,} C 1 -C _{4 alkylamino,} C 2 -C ₈ dialkylamino, C ₃ -C _{6 cycloalkylamino,} C 2 -C _{6 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C ₆ Alkylaminocarbonyl or _C 3 -C ₈ compounds of formula I wherein dialkylaminocarbonyl.

Embodiment 25. FIG. Embodiment 25. A compound of Embodiment 24 wherein R ⁷ is H, F, Cl, Br, I, cyano or CF ₃ .

Embodiment 26. FIG. Embodiment 26. A compound of Embodiment 25 wherein R ⁷ is Cl, Br or cyano.

Embodiment 27. FIG. Embodiment 26. A compound of Embodiment 26 wherein R ⁷ is Cl or cyano.

Embodiment 28. FIG. A compound of formula I wherein R ¹³ is H, CH ₃ , halogen or cyano.

Embodiment 29. FIG. Compounds of formula I V is ^{CR 13.}

Embodiment 30. FIG. Embodiment 29. A compound of Embodiment 29 wherein V is CH.

Embodiment 31. FIG. A compound of formula I wherein R ¹⁴ is H, CH ₃ , halogen or cyano.

Embodiment 32. FIG. The compounds of formula I Y is ^{CR 14.}

Embodiment 33. FIG. Embodiment 33. A compound of Embodiment 32 wherein Y is CH, CF, CCl or CBr.

Embodiment 34. FIG. Embodiment 34. A compound of Embodiment 33 wherein Y is CH.

Embodiment 35. FIG. A compound of formula I wherein L is a linking chain of 1 to 3 carbon atoms optionally substituted by 1 to 3 substituents independently selected from R ¹⁵ .

Embodiment 36. FIG. A compound of formula I wherein each R ¹⁵ is independently H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl.

Embodiment 37. FIG. A compound of formula I wherein L is C (= E) and E is oxygen.

Embodiment 38. FIG. A compound of Formula I wherein L is CH ₂ , CH ₂ CH ₂ or C═O.

Embodiment 39. FIG. L is A compound of Embodiment 38 is CH _2.

Embodiment 40. FIG. A compound of formula I wherein Q is Q-2 or Q-3.

Embodiment 41. FIG. A compound of formula I wherein Q is Q-1 or Q-3.

Embodiment 42. FIG. A compound of formula I wherein Q is Q-1 or Q-2.

Embodiment 43. FIG. A compound of formula I wherein Q is Q-1.

Embodiment 44. FIG. A compound of formula I wherein Q is Q-2.

Embodiment 45. FIG. A compound of formula I wherein Q is Q-3.

The combination of Embodiments 1-45 is demonstrated below:
Embodiment A. W is N, CH, CF, CCl, CBr or CI;
Each R ² is independently H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;
n is 1, 2 or 3;
R ³ is H or C ₁ -C ₄ alkyl;
R ⁴ is H or C ₁ -C ₄ alkyl;
R ⁵ is H; or each optionally substituted by one or more substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, OCH ₃ and S (O) _p CH ₃ which may _C 1 -C _{6 alkyl,} C 2 -C _{6 alkenyl,} C 2 -C ₆ alkynyl or _C 3 -C ₆ cycloalkyl;
p is 0, 1 or 2;
R ⁶ is CH ₃ , CF ₃ , OCHF ₂ , S (O) _p CF ₃ , S (O) _p CHF ₂ , cyano or halogen;
R ⁷ is H, F, Cl, Br, I, cyano or CF ₃ ;
V is CR ¹³ ; R ¹³ is H, CH ₃ , halogen or cyano;
A compound of formula I wherein Y is CR ¹⁴ ; and R ¹⁴ is H, CH ₃ , halogen or cyano.

Embodiment B. X is O;
A compound of Embodiment A wherein Z is C ₂ haloalkylene; and R ¹¹ is C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl.

Embodiment C. Q is Q-1;
W is N, CCl, CF or CH;
R ² is H, Cl, F or Br;
n is 1 or 2;
R ³ and R ⁴ are H;
R ⁵ is H, methyl, ethyl, i-propyl or t-butyl;
R ⁶ is F, Cl, Br, I, CH ₃ or CF ₃ ;
R ⁷ is Cl, Br or cyano;
A compound of Embodiment B wherein V is CH; and Y is CH, CF, CCl or CBr.

Embodiment D. R ¹ is —OCF ₂ CHF—O—R ¹¹ ; and R ¹¹ is methyl, ethyl, CH ₂ CF ₃ , CF ₃ , CF ₂ CF ₃ , CF ₂ CF ₂ Br, CF ₂ CF ₂ CF ₃ or CF _{(CF 3)} a compound of embodiment C is _2.

Embodiment E. R ¹ is —OCF ₂ CHFOCF ₃ ;
Y is CH;
R6 is Cl or CH _3; and the compound of embodiment D R7 is Cl or CN.

Embodiment F. Q is Q-2;
W is N, CCl, CF or CH;
R ² is H, Cl, F or Br;
n is 1 or 2;
R ³ and R ⁴ are H;
R ⁵ is H, methyl, ethyl, i-propyl or t-butyl;
R ⁶ is F, Cl, Br, I, CH ₃ or CF ₃ ;
R ⁷ is Cl, Br or cyano;
V is CH;
A compound of Embodiment B wherein Y is CH, CF, CCl or CBr; and L is CH ₂ , CH ₂ CH ₂ or C═O.

Embodiment G. R ¹ is —OCF ₂ CHF—O—R ¹¹ ; and R ¹¹ is methyl, ethyl, CH ₂ CF ₃ , CF ₃ , CF ₂ CF ₃ , CF ₂ CF ₂ Br, CF ₂ CF ₂ CF ₃ or CF A compound of Embodiment F that is (CF ₃ ) ₂ .

Embodiment H. R ¹ is —OCF ₂ CHFOCF ₃ ;
Y is CH;
Embodiment G. A compound of Embodiment G wherein R ⁶ is Cl or CH ₃ ; and R ⁷ is Cl or CN.

Embodiment I. Q is Q-3;
W is N, CCl, CF or CH;
R ² is H, Cl, F or Br;
n is 1 or 2;
R ³ and R ⁴ are H;
R ⁵ is H, methyl, ethyl, i-propyl or t-butyl;
R ⁶ is F, Cl, Br, I, CH ₃ or CF ₃ ;
R ⁷ is Cl, Br or cyano;
A compound of Embodiment B wherein V is CH; and Y is CH, CF, CCl or CBr.

Embodiment J. R ¹ is —OCF ₂ CHF—O—R ¹¹ ; and R ¹¹ is methyl, ethyl, CH ₂ CF ₃ , CF ₃ , CF ₂ CF ₃ , CF ₂ CF ₂ Br, CF ₂ CF ₂ CF ₃ or CF A compound of Embodiment I that is (CF ₃ ) ₂ .

Embodiment K. R ¹ is —OCF ₂ CHFOCF ₃ ;
Y is CH;
A compound of Embodiment J wherein R ⁶ is Cl or CH ₃ ; and R ⁷ is Cl or cyano.

Notable:
1- (3-Chloro-2-pyridinyl) -N- [4-cyano-2-methyl-6-[(methylamino) carbonyl] phenyl] -3- [1,1,2-trifluoro-2- ( Trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxamide;
1- (3-Chloro-2-pyridinyl) -N- [4-cyano-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -3- [1,1,2-tri Fluoro-2- (trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxamide;
N- [2- (aminocarbonyl) -4-cyano-6-methylphenyl] -1- (3-chloro-2-pyridinyl) -3- [1,1,2-trifluoro-2- (trifluoromethoxy) ) Ethoxy] -1H-pyrazole-5-carboxamide; and 1- (3-chloro-2-pyridinyl) -N- [4-cyano-2-[(ethylamino) carbonyl] -6-methylphenyl] -3- It is a compound selected from the group consisting of [1,1,2-trifluoro-2- (trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxamide.

  It also comprises a biologically effective amount of a compound of any of the preceding embodiments, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, optionally in biological Also noteworthy as an embodiment of the present invention is an invertebrate pest control composition further comprising a pharmaceutically effective amount of at least one additional biologically active compound or agent. Embodiments of the present invention further include a method of controlling an invertebrate pest comprising contacting an invertebrate pest or its environment with a biologically effective amount of a compound of any of the previous embodiments. (For example, as a composition described herein).

  Embodiments of the present invention also include compositions comprising any of the compounds of the previous embodiments in the form of a soil drench liquid formulation. Embodiments of the present invention control invertebrate pests comprising contacting soil with a liquid composition as a soil drench comprising a biologically effective amount of a compound of any of the previous embodiments. Further comprising a method.

  Embodiments of the present invention also include spray compositions for controlling invertebrate pests comprising a biologically effective amount of a compound of any of the previous embodiments and a propellant. An embodiment of the present invention is an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding embodiments, one or more food ingredients, optionally an attractant, and optionally a wetting agent. And a control bait composition. Embodiments of the present invention also include an invertebrate pest control device comprising the feed composition and a housing adapted to receive the feed composition. Here, the housing is at least one sized to allow the invertebrate pest to pass through the opening so that the invertebrate pest can access the feed composition from a location outside the housing. And the housing is further adapted to be located at or near a potential or known active location of an invertebrate pest.

Compounds of formula I can be made by one or more of the methods and variations described in Schemes 1-11 below. The definitions of Y, V, W, X, Z, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 in} the following compounds of formulas 1 to 15 are as defined above unless otherwise specified. As defined in the Summary of the Invention.

  As outlined in Scheme 1, reaction of a benzoxazinone of Formula 2 with an amine of Formula 3 can produce a compound of Formula I where Q is Q-1.

  This reaction can be carried out as such or in various suitable solvents including tetrahydrofuran, diethyl ether, dichloromethane or chloroform, at optimum temperatures ranging from room temperature to the reflux temperature of the solvent. The general reaction of benzoxazinones with amines to form anthranilamides is well documented in the chemical literature. For a review on benzoxazinone chemistry, see Jakobsen et al., Bioorganic and Medicinal Chemistry 2000, 8, 2095-2103, and references cited therein. G. M.M. See also GM Coppola, J. Heterocyclic Chemistry 1999, 36, 563-588.

  The benzoxazinone of formula 2 can be prepared by various methods. Three methods that are particularly useful are detailed in Schemes 2-4. In Scheme 2, the benzoxazinone of formula 2 is prepared directly by coupling of the carboxylic acid of formula 4 with the anthranilic acid of formula 5.

  This is the continuous addition of methanesulfonyl chloride to the pyrazole carboxylic acid of formula 4 followed by the addition of anthranilic acid of formula 5 followed by triethylamine and methanesulfonyl chloride in the presence of a tertiary amine such as triethylamine. With a second addition. This method generally gives good yields of benzoxazinone.

  Scheme 3 shows another preparation of a benzoxazinone of formula 2 with coupling of an acid chloride of formula 7 and an isatoic anhydride of formula 6 to provide the benzoxazinone of formula 2 directly. . A solvent such as pyridine or pyridine / acetonitrile is suitable for this reaction. Acid chlorides of formula 7 can be obtained from the corresponding acids of formula 4 by known methods such as chlorination with thionyl chloride or oxalyl chloride.

  As in Scheme 4, the benzoxazinone of formula 2 is prepared directly by coupling of the carboxylic acid of formula 4 with the anthranilic acid of formula 5. This includes the continuous addition of a pyridine base such as 3-picoline to a mixture of pyrazole carboxylic acid of formula 4 and anthranilic acid of formula 5 followed by the addition of methanesulfonyl chloride. This method gives good yields of benzoxazinone and is described in more detail in Example 1.

Anthranilic acid of formula 5 is available commercially or by various known methods. As shown in Scheme 5, an unreacted compound of formula 5a with N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or N-iodosuccinimide (NIS) in a solvent such as N, N-dimethylformamide, respectively. Direct halogenation of the substituted anthranilic acid can produce the anthranilic acid of formula 5b containing the R ⁷ substituent of chloro, bromo or iodo. Anthranilic acid of formula 5b represents an intermediate for a preferred set of compounds of formula I.

As outlined in Scheme 6, the cyanoanthranilic acid of formula 5c can be prepared from the haloanthranilic acid of formula 5b. A haloanthranilic acid of formula 5b (R ⁷ is bromo or iodo) in a suitable solvent such as acetonitrile, N, N-dimethylformamide or N-methylpyrrolidinone, optionally at a temperature from room temperature to the reflux temperature of the solvent. ) And a metal cyanide (eg cuprous cyanide, zinc cyanide or potassium cyanide) and optionally a suitable palladium catalyst (eg tetrakis (triphenylphosphine) palladium (0) or dichlorobis (triphenylphosphine) palladium (II )), And optionally a metal halide (eg, cuprous iodide, zinc iodide or potassium iodide) to give compounds of formula 5c. If a palladium catalyst is used in the coupling reaction, a suitable solvent can be tetrahydrofuran or dioxane. Also, anthranilic acid of formula 5c may represent an intermediate of a preferred combination of compounds of formula I.

  Anthranilic acid of formula 5 wherein one or both of Y and Z are selected from N can be obtained by various known methods; see, for example, PCT Patent Publication No. WO 2002/070483.

  As outlined in Scheme 7, the preparation of the isatoic anhydride of formula 6 can be achieved from the isatin of formula 9 where Y and V are CH. F. D. Pop (FD Pop), Advanced in Heterocyclic Chemistry (Adv. Heterocycl. Chem.) 1975, 18, 1-58, and J. Org. F. M.M. From an aniline derivative of formula 8 according to literature procedures such as J.F.M.DaSilva et al., Journal of the Brazilian Chemical Society 2001, 12 (3), 273-324, Isatin of formula 9 is available. Oxidation of isatin 9 with hydrogen peroxide gives a good yield of the corresponding isatoic anhydride 6 (G. Reisssenweber and D. Mangold, Angewant Chemie (International Edition in English) 1980, 19, 222-223). Isatoic anhydride is also available from anthranilic acid 5 through a number of known procedures involving the reaction of 5 with phosgene or phosgene equivalents.

  Pyrazole acid 4a may represent a preferred combination of pyrazole acids for the synthesis of compounds of formula I. This preparation replaces 5-hydroxypyrazole of formula 10 in the presence of a base such as sodium hydroxide or potassium hydroxide in a polar solvent such as dimethyl sulfoxide, N, N-dimethylformamide or N-methylpyrrolidinone. With reaction with trifluoroethylene 11. Co-solvents such as toluene, tetrahydrofuran, dioxane and the like may also be used. The reaction is generally carried out in the range of 0 ° C. to room temperature. This method gives very good yields of the pyrazole ester of formula 12. The pyrazole ester of formula 12 is converted to the acid of formula 4a by conventional hydrolysis methods and is described in more detail in Example 1.

  The preparation of 5-hydroxypyrazole 10 is depicted in Scheme 9. For prior literature, see PCT Patent Publication No. 2004/046129 pamphlet. Reaction of aryl hydrazine 13 with diethyl maleate yields 5-hydroxypyrazoline 14. Oxidation of 14 with various oxidizing agents such as hydrogen peroxide, manganese dioxide, and most preferably potassium persulfate yields 5-hydroxypyrazole 10. This method is described in more detail in Example 1.

  As shown in Scheme 10, reaction of the Formula 14 intermediate with the acid chloride of Formula 7 can produce compounds of Formula I where Q is Q-2. This reaction can be carried out as such or in various suitable solvents including tetrahydrofuran, toluene, methylene chloride or chloroform at an optimum temperature ranging from room temperature to the reflux temperature of the solvent. Typical bases include amines such as triethylamine and pyridine, carbonates such as potassium carbonate and sodium carbonate, and hydrides such as potassium hydride and sodium hydride. See PCT Patent Publication No. WO 2003/062226 for examples of this type and for the preparation of intermediates of formula 15.

  The compound of formula I in which Q is Q-3 can be prepared directly by treating the compound of formula I in which Q is Q-1 with dehydrating reagents such as phosphoryl chloride, thionyl chloride and oxalyl chloride. it can. This reaction can be carried out as is or in solvents such as dichloromethane, dichloroethane, chloroform, benzene, toluene, xylene, tetrahydrofuran, dioxane and chlorobenzene at optimum temperatures ranging from 0 ° C. to the reflux temperature of the solvent. . See the PCT Patent Publication No. 2003/032731 for examples of this type of reaction.

  It will be appreciated that some of the reagents and reaction conditions described above for preparing compounds of formula I will not be compatible with the particular functional groups present in the intermediate. In these examples, incorporation of protected / deprotected sequences or functional interconversions in the synthesis system will help to obtain the desired product. The use and choice of protecting groups will be apparent to those skilled in the art of chemical synthesis (eg, Green, TW (Greene, TW); Watts, PGM (Wuts, PG)). M.) Protective Groups in Organic Synthesis, 2nd edition; see Wiley: New York, 1991). In some cases, after introduction of a given reagent as described in any individual scheme, additional conventional synthetic steps not described in detail are performed to complete the synthesis of the compound of formula I Those skilled in the art will recognize that this is necessary. One skilled in the art will also recognize that the combinations of steps illustrated in the above scheme need to be performed in an order other than that shown by the particular order proposed for preparing compounds of Formula I.

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

Without further details, it is believed that one skilled in the art using the foregoing can utilize the present invention to its fullest extent. Accordingly, the following examples are to be construed as merely illustrative and are not intended to limit the present disclosure to any form. The steps of the following examples illustrate the procedure for each step in the overall synthetic transformation, and the starting materials for each step need not necessarily be manufactured by a specific manufacturing practice whose procedures are described in other steps. . Percentages are by weight except for chromatographic solvent mixtures or unless otherwise specified. Unless otherwise noted, parts and percentages with respect to chromatographic solvent mixtures are by volume. ¹ H NMR spectra are reported at ppm low magnetic fields from tetramethylsilane, “s” means singlet, “d” means doublet, “t” means triplet, “ “q” means quartet, “m” means multiplet, “dd” means doublet doublet, “dt” means triplet doublet, and “Br s” means a broad singlet.

Example 1
1- (3-Chloro-2-pyridinyl) -N- [4-cyano-2-methyl-6-[(methylamino) carbonyl] phenyl] -3- [1,1,2-trifluoro-2- ( Trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxamide Step A: Preparation of ethyl 2- (3-chloro-2-pyridinyl) -5-oxo-3-pyrazolidinecarboxylate Mechanical Stirrer, Thermometer A 2 L 4-neck flask equipped with an addition funnel, reflux condenser and nitrogen inlet was charged with absolute ethanol (250 mL) and ethanol solution of sodium ethoxide (21%, 190 mL, 0.504 mol). The mixture was heated to reflux at about 83 ° C. It was then charged with 3-chloro-2-hydrazinopyridine (68.0 g, 0.474 mol). The mixture was reheated and refluxed for 5 minutes. The yellow slurry was then treated dropwise with diethyl maleate (88.0 mL, 0.544 mol) over 5 minutes. During the addition, the reflux rate increased significantly. By the end of all additions, the starting material dissolved. The resulting red orange solution was held at reflux for 10 minutes. After cooling to 65 ° C., the reaction mixture was treated with glacial acetic acid (50.0 mL, 0.873 mol). A precipitate formed. The mixture was diluted with water (650 mL) to dissolve the precipitate. The orange solution was allowed to cool with an ice bath. The product started to precipitate at 28 ° C. The slurry was held at about 2 ° C. for 2 hours. The product was isolated by filtration, washed with aqueous ethanol (40%, 3 × 50 mL) and then air dried on the filter for about 1 hour. The title product compound (70.3 g, 55% yield) was obtained as a highly crystalline, pale orange solid. ^No significant impurities were observed by ¹ H NMR.

¹ H NMR (Me ₂ SO-d ₆ ): δ 10.18 (s, 1H), 8.27 (d, 1H), 7.92 (d, 1H), 7.20 (dd, 1H), 4. 84 (d, 1H), 4.20 (q, 2H), 2.91 (dd, 1H), 2.35 (d, 1H), 1.22 (t, 3H)

Step B: Preparation of ethyl 2- (3-chloro-2-pyridinyl) -2,5-dihydro-5-oxo-1H-pyrazole-3-carboxylate 1- (3 stirred in dry acetonitrile (200 mL) To a suspension of -chloro-2-pyridinyl) -3-pyrazolidinone-5-carboxylate (27 g, 100 mmol) was added sulfuric acid (20 g, 200 mmol) in one portion. The reaction mixture was diluted to form a pale green, nearly clear solution before being concentrated again to form a pale yellow suspension. Potassium persulfate (33 g, 120 mmol) was added in one portion and then the reaction mixture was heated under mild reflux for 3.5 hours. After cooling using an ice bath, the white solid precipitate was removed by filtration and discarded. The acetonitrile mother liquor was concentrated and then diluted with water (400 mL) followed by extraction three times with diethyl ether (total 700 mL). Concentration of the diethyl ether phase to a reduced volume (75 mL) precipitated an off-white solid (3.75 g) which was collected by filtration. The ether mother liquor was further concentrated to give a second production of an off-white precipitate (4.2 g), which was collected by filtration. Further precipitation of an off-white solid (4.5 g) from the aqueous phase gave a total of 12.45 g of the title compound.

¹ H NMR (Me ₂ SO-d ₆ ): δ 10.6 (s, 1 H), 8.5 (d, 1 H), 8.19 (d, 1 H), 7.6 (t, 1 H), 6. 34 (s, 1H), 4.11 (q, 2H), 1.06 (t, 3H)

Step C: Preparation of ethyl 1- (3-chloro-2-pyridinyl) -3- [1,1,2-trifluoro-2- (trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxylate 1: To a solution of the pyrazole ester from Step B (1.0 g, 3.7 mmol) in 1 methanol / dimethyl sulfoxide (20 mL) was added potassium hydroxide (42 mg, 0.7 mmol). The mixture was stirred at room temperature for 5 minutes and then cooled to 0 ° C. Trifluoromethyl trifluorovinyl ether (ca. 1.0 mL) was then added dropwise and the reaction was warmed to room temperature and stirred overnight. The mixture was then diluted with water and extracted into diethyl ether (2 × 75 mL). The organic extract was dried over magnesium sulfate and concentrated. Chromatography of the crude product on silica gel using a 9: 1 to 7: 3 hexane / ethyl acetate gradient as diluent gave 1.44 g of the title compound as an oil.

¹ H NMR (CDCl ₃ ): δ 8.50 (d, 1H), 7.92 (d, 1H), 7.45 (dd, 1H), 6.81 (s, 1H), 5.9-6 1 (dt, 1H), 4.23 (q, 2H), 1.23 (t, 3H)

Step D: Preparation of 1- (3-Chloro-2-pyridinyl) -3- [1,1,2-trifluoro-2- (trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxylic acid Methanol (15 mL To a stirred solution of the pyrazole ester from Step C (1.26 g, 2.9 mmol) in) was added an aqueous solution of sodium hydroxide (131 mg, 3.2 mmol) in water (5 mL) and the mixture was Stir at room temperature for 30 minutes. 1N HCl solution was then added and the reaction mixture was extracted with ethyl acetate (2 × 100 mL). The ethyl acetate extract was dried over magnesium sulfate and concentrated to give the title compound.

¹ H NMR (CDCl ₃ ): δ 8.50 (d, 1H), 7.91 (d, 1H), 7.47 (dd, 1H), 6.87 (s, 1H), 5.9-6. 1 (dt, 1H)

Step E: Preparation of 2-amino-5-iodo-3-methylbenzoic acid 2-amino-3-methylbenzoic acid (Aldrich, 5 g, 33 mmol) in N, N-dimethylformamide (30 mL) To the solution was added N-iodosuccinimide (7.8 g, 34.7 mmol) and the reaction mixture was heated in a 75 ° C. oil bath overnight. After removing the oil bath, the reaction mixture was then slowly poured into ice water (100 mL) to precipitate a light gray solid. The solid was filtered and washed 4 times with water, then placed in a 70 ° C. vacuum oven and dried overnight. The desired intermediate was isolated as a light gray solid (8.8 g).

¹ H NMR (Me ₂ SO-d ₆ ): δ 7.86 (d, 1H), 7.44 (d, 1H), 2.08 (s, 3H)

Step F: Preparation of 2-amino-5-cyano-3-methylbenzoic acid Mixture of the product from Step E (17.0 g, 61.3 mmol) and copper cyanide (7.2 g, 78.7 mmol) Was heated in N, N-dimethylformamide (200 mL) from 140 ° C. to 145 ° C. for 20 hours. The reaction mixture was then cooled and most of the dimethylformamide was removed by concentration on a rotary evaporator under reduced pressure. Water (200 mL) was added to the oily solid followed by ethylenediamine (20 mL) and the mixture was stirred vigorously to dissolve most of the solid. Residual solids were removed by filtration, then concentrated hydrochloric acid was added to the filtrate to adjust the pH to 5. As the pH decreased, some solid precipitated. The resulting mixture was partitioned between ethyl acetate and water. The separated organic solution was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residual solid was triturated with a mixture of diethyl ether, hexane and ethyl acetate to give 7.61 g of the title compound as a tan solid.

¹ H NMR (Me ₂ SO-d ₆ ): δ 7.97 (s, 1H), 7.50 (s, 1H), 7.3-7.5 (br s, 1H), 2.12 (s, 3H)

Step G: 2- [1- (3-Chloro-2-pyridinyl) -3- [1,1,2-trifluoro-2- (trifluoromethoxy) ethoxy] -1H-pyrazol-5-yl] -8 Preparation of methyl-4-oxo-4H-3,1-benzoxazine-6-carbonitrile Carboxylic acid from Step D (0.7 g, 1.73 mmol) in acetonitrile (10 mL), Anthranil from Step F A mixture of acid (305 mg, 1.73 mmol) and 3-picoline (0.85 mL, 8.63 mmol) was stirred to form a homogeneous mixture, then the reaction mixture was cooled to −10 ° C. Methanesulfonyl chloride (0.34 mL, 4.3 mmol) in acetonitrile (5 mL) was added dropwise, then the reaction mixture was warmed to room temperature and stirred overnight. Water was then added to the reaction mixture followed by extraction with ethyl acetate. The ethyl acetate extract was dried over magnesium sulfate, concentrated and chromatographed on silica gel to give 0.9 g of the title compound.

¹ H NMR (CDCl ₃ ): δ 8.57 (d, 1H), 8.31 (s, 1H), 8.00 (d, 1H), 7.75 (s, 1H), 7.50 (dd, 1H), 7.10 (s, 1H), 5.95-6.15 (dt, 1H)

Step H: 1- (3-Chloro-2-pyridinyl) -N- [4-cyano-2-methyl-6-[(methylamino) carbonyl] phenyl] -3- [1,1,2-trifluoro- Preparation of 2- (trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxamide The product from Step G (125 mg, 0.23 mmol) was dissolved in acetonitrile (10 ml) and methylamine (2 in THF). 0.0M solution, 2.0 mL, 4.0 mmol) was added. The resulting solution was stirred at room temperature for 15 minutes. The reaction mixture was concentrated to dryness and the residue was suspended in hexane, which was filtered to give 109 mg of the title compound, a compound of the invention, as a white solid. m. p. 169-170 ° C.

¹ H NMR (CDCl ₃ ): δ 10.6 (br s, 1H), 8.45 (d, 1H), 7.85 (d, 1H), 7.56 (s, 2H), 7.41 (dd , 1H), 6.85 (s, 1H), 6.32 (br q, 1H), 5.95-6.15 (dt, 1H), 2.98 (d, 3H), 2.24 (s , 3H)

Example 2
1- (3-Chloro-2-pyridinyl) -N- [4-cyano-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -3- [1,1,2-tri Preparation of Fluoro-2- (trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxamide The product from Example 1, Step G (100 mg, 0.18 mmol) was dissolved in acetonitrile (10 ml) and isopropyl Amine (0.6 mL, 7.1 mmol) was added. The resulting solution was stirred at room temperature for 20 minutes. The reaction mixture was concentrated to dryness, suspended in hexane and filtered to give 93 mg of the title compound, a compound of the invention, as a white solid. m. p. 184-185 ° C.

¹ H NMR (CDCl ₃ ): δ 8.45 (d, 1H), 7.85 (d, 1H), 7.54 (s, 2H), 7.40 (dd, 1H), 6.90 (s, 1H), 5.95-6.15 (dt, 1H), 6.05 (brd, 1H), 4.20 (m, 1H), 2.23 (s, 3H), 1.23 (d, 6H)

  The compounds in Tables 1-11 below can be made by procedures described herein, along with methods known in the art. In the table, the following abbreviations are used: t means tertiary, i means iso, Me means methyl, Et means ethyl, i-Pr means isopropyl, Bu Means butyl, CN means cyano, 2-Cl-4-F means 2-chloro-4-fluoro.

Formulation / Efficacy The compounds of the present invention can generally be used as a formulation or composition with a carrier suitable for agricultural and non-agricultural applications comprising at least one liquid diluent, solid diluent or surfactant. is there. The formulation or composition component is selected to be consistent with the physical properties of the active ingredient, the mode of application, and environmental factors such as soil type, humidity and temperature. Useful formulations may optionally be concentrated into gels, such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and / or suspoemulsions), etc. Contains a lot of liquid. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films (including seed treatments), etc. that may be water dispersible (“hydrated”) or water soluble. The active ingredient can be (micro) encapsulated and further formed into a suspension or solid formulation, or the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay the release of the active ingredient. The sprayable formulation can be applied to a suitable medium and can be used at a spray volume of about 1 to several hundred liters per hectare. High strength compositions can be used initially as intermediates for further formulations.

  Formulations typically contain effective amounts of active ingredients, diluents and surfactants within the appropriate range of addition to the following 100% by weight.

  Exemplary solid diluents include those of Watkins et al., Handbook of Insectide Dusted Diluents and Carriers, 2nd edition, Dorland Books, Caldwell. ), New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide 2nd Edition, Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allred Publishing Corporation (W) and New Jersey (W) and New Jersey (W) and Ridgewood (R) , Encyclopedia of Surface Active Agents, Chemical Publishing Company, Inc., New York, 196, Encyclopedia of Surface Active Agents, Chemical Publishing Company, Inc., New York, 196 It describes the use of surfactants and recommended. All formulations may contain small amounts of additives to reduce foaming, caking, corrosion, microbial growth, etc., or thickeners to increase viscosity.

Examples of the surfactant include polyethoxylated alcohol, polyethoxylated alkylphenol, polyethoxylated sorbitan fatty acid ester, dialkylsulfosuccinate, alkylsulfate, alkylbenzenesulfonate, organosilicone, N, N-dialkyltaurate, lignin. The number of glucose units called sulfonate, naphthalenesulfonate formaldehyde condensate, polycarboxylate, glycerol ester, polyoxyethylene / polyoxypropylene block copolymer, and degree of polymerization (DP) can range from 1 to 3 and alkyl polyglycosides alkyl units can range from _C 6 _{-C 14} (Pure and Applied chemistry (Pure and Applied Chemist y) 72,1255-1264 see) and the like. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Examples of the liquid diluent include water, N, N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, glycerin, triacetin, olive oil, castor oil, flaxseed oil, tung oil , Sesame oil, corn oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil and coconut oil, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetate esters, and Included are alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

  Useful formulations of the present invention may contain materials known as formulation aids including antifoams, film forming elements and dyes and are well known to those skilled in the art.

  Antifoaming agents include water dispersible liquids comprising a polyorganosiloxane such as Rhodorsil® 416. Film forming elements include polyvinyl acetate, polyvinyl acetate copolymer, polyvinyl pyrrolidone-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl alcohol copolymer and wax. Examples of the dye include water-dispersible liquid pigment compositions such as Pro-lzed (registered trademark) Carlant Red. Those skilled in the art will recognize that this is not a complete list of formulation adjuvants. Suitable examples of formulation adjuvants include those described herein, as well as McCutcheon's 2001 published by MC Publishing Company, Volume 2: Functional Materials ( Functional materials) and those described in International Publication No. 03/024222 pamphlet.

  By simply mixing the components, a solution containing the emulsifiable concentrate can be produced. Dusts and powders can be produced by blending and usually grinding in a hammer mill or fluid energy mill. The suspension is usually produced by wet grinding. See, for example, US Pat. No. 3,060,084. Granules and pellets can be produced by spraying the active material onto preformed granule carriers or by agglomeration techniques. Browning, “Agglomeration”, Chemical Engineering, December 4, 1967, pp. 147-48, Perry's Chemical Engineer's Handbook, See 4th edition, McGraw-Hill, New York, 1963, pp. 8-57 and below and WO 91/13546. Pellets can be produced 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 DE 3,246,493. Tablets can be manufactured 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 made as taught in GB 2,095,558 and US Pat. No. 3,299,566.

  For further information regarding the field of formulation, see US Pat. No. 3,235,361, column 6, lines 16-7, line 19 and Examples 10-41; US Pat. No. 3,309, No. 192, column 5, lines 43-7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166 167 and 169-182; U.S. Pat. No. 2,891,855, column 3, lines 66-5, line 17 and Examples 1-4; Klingman, Weed Control As A Science (Weed Control as a Science), John Willy and Sons, Inc. (John Wiley and Sons, Inc), New York, 1961, pp. 81-96; and Hance et al., Weed Control Handbook, 8th edition, Blackwell Scientific Publications, Oxford 1989; Developments in formation technology, PJB Publications, Richmond, UK, 2000. See, Developments in formation technology, PJB Publications, UK, Richmond, UK.

  In the following examples, all percentages are by weight and all formulations are made by conventional methods. “Active ingredient” refers to a compound of formula I. Without further details, it is believed that one skilled in the art using the foregoing can utilize the present invention to its fullest extent. Accordingly, the following examples are to be construed as merely illustrative and are not intended to limit the present disclosure to any form. Percentages are by weight unless otherwise noted.

  The compounds of the invention are characterized by having a favorable metabolic and / or soil residue pattern and exhibit activity in controlling a range of agricultural and non-agricultural invertebrate pests. In addition, the compound of the present invention is characterized by having foliar treatment and soil treatment organization that are convenient in plants, and the foliage is not in direct contact with the invertebrate pest control composition comprising the compound of the present invention. And, in the context of the present disclosure, “control of invertebrate pests” refers to the development or harmfulness of invertebrate pests that greatly reduce feeding. Meaning the inhibition of other damage or damage caused by the organism (including killing), and related expressions are similarly defined.) As used in this disclosure, the term “invertebrate pest” Including arthropods, gastropods and nematodes which are important from an economic point of view as pests. The term “arthropod” includes insects, ticks, spiders, scorpions, centipedes, millipedes, dandelions and komcades. The term “gastropod” includes snails, slugs and other striated eyes. The term "nematode" includes all worms, including roundworms, dogworms, and plant parasitic nematodes (C. elegans), flukes (C. elegans), phylums and tapeworms (Coleoptera) including. One skilled in the art will appreciate that not all compounds are equally effective against all pests. The compounds of the present invention are active against economically important agricultural and non-agricultural pests. The term “agricultural” refers to the production of crops such as food and fiber, including corn, soybeans and other legumes, rice, cereals (eg, wheat, oats, barley, rye, rice, corn), Leafy vegetable crops (eg lettuce, cabbage and other Brassica crops) results vegetable crops (eg tomatoes, peppers, eggplants, cross flowers and cucurbits), potatoes, sweet potatoes, grapes, cotton, fruit trees (eg pears) Fruit, stones and citrus fruits), fruit trees (berries, cherries) and other specialty crops (eg canola, sunflower, olive). The term “non-agricultural” refers to other horticultural crops (eg, ornamental plants not grown in greenhouses, nurseries or wilderness), residential and commercial buildings in urban and industrial environments, lawns (commercial, golf, residential , Recreational, etc.), wood products, storage products, agriculture-forestry and plant management, public health (human health) and animal health (pets, livestock, poultry) applications. For reasons of invertebrate pest control scope and economic importance, protection of crops from damage or injury caused by invertebrate pests by invertebrate pest control is an embodiment of the present invention.

Agricultural and non-agricultural pests include army worms, rhizomes, loopers, tobacco moths (Spodoptera fugiperda J.E. Smith), Spodoptera exigua H. (Agrotis ipsilon (Hufnagel)), nettle gulp (Trichoplusia ni huebner), moth (Heliothis virescens, worms, worms, etc.) Pests, corn worms, stink bugs, pests that damage leaves and leave leaf veins (Ostrinia n bilalis Hübner), navel orange worm (Amyelois transitella walker (Walker)); Pests that feed on, pests that feed on seeds, pests that feed on fruits (Cydia pomonella linnaeus), Grapeberry moss (Clenmens), Nashihime Sukui Target Many other lepidoptera (Plutella xylostella linnae), cottonseed beetle (Pectinophora gossypia), juveniles (Lymantria linpa), etc. Family and cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai mizukubo), abalone cockroach (p), a cockroach (p), a cockroach (p) ius)), American cockroach (Periplaneta americana Linnaeus), Japanese cockroach (Permelanea brunea) (Burmeister), Japanese cockroach (Leucophaea maderae) Nymphs and adults; weevil, weevil, weevil weevil (Anthonymus grandis Boheman) , Weevil (Sytophilus oryzae) Linnaeus); flea beetles, cucurbits, root-feeding nematodes, leaf beetles, potato beetles and leaf beetles (Leptinotarsa decelineta citrus) LeConte), etc .; Scarabaeidae scarab beetles and other beetles (Popilia japonica Newman (Newman) rastrozo), European chafer Obushimushi family beetle; Elateridae click beetle; beetle family beetles include foliar larvae and adults of the order Coleoptera including the red flour beetle in Tenebrionidae. Agricultural and non-agricultural pests include the earliest beetle (Fornicula auricularia, Linnaeus), black earwig (Chelisoches), and the like. Lepidoptera and other larvae; Kasmikamushi of Kasmamemushi, Cicadas of Micaceae, Yokobayami of the family of leafhoppers (Empoasca spp., Etc.), Fulgoroidae and Pleurotus Plant hoppers, hornworms, pheasants, whiteflies, aphids, aphids, aphids Nymphalidae, Pterocalidae, Buprestidae, Sphaerophyceae, and Mysticidae, Aphididae, Aphididae, Aphididae, Cinch bug, and a clinch bug, Blissus sp. Also included are adults and nymphs of the order Hemiptera, Hemiptera, Hemiptera, Hemipodidae, Hemikamushi, Hoshikamushi, Hoshikamushi, Hemikamushi, Hoshikamushi, Hemikamushi. In addition, spider mites and mites (Rick spider mites (Pananychus ulmi Koch (Koch)), Nami spider mites (Tetranychus urticae Koch (Koch)), McDani mites (McGregor spider mites) Spider mites, such as spider mites (Brevipalpus lewisi McGregor), Scarlet mites and Fusi mites of the family Acaridae and other foliar mites, and mites that are important to human and animal health, i.e. Acarid mites of the family, mites of the family Acaridaceae, ticks of the ticks (Ixodes scapular) s Say), Australian ticks (Ixodes holoculus) Newman (Neumann), Kakuma tick (Dermacentor variabilis sei (Say)), Lone star tick (Amblyomma americinum) Adults and larvae of scabies and scabies mites of the family, Hymenididae; grasshoppers, locusts and crickets (Melanoplus sanguinipes Fabricis, M. differentialisuris (Thomas), American locust )) (Chistocerca gregaria Forscal (Forscal)), Tossama grasshopper (Locusta migratoria linp (Linnaeus)), bush locust (Zocerus spp.) ) Etc.) and other adults and larvae of the order Coleoptera, chironomids, fruit flies (Flyfidae), Frost flies (Linnaeus), maggots, Musca domestica (Linae), and others (Fannaia canularis Linne ( innaeus), F. femorialis stain (Stein, etc.), flies (Stomoxys calcitrans Linnaeus), house fly (face fly), flies, Chrysomya spp., Pharmia sp. Tabanus spp., Etc., foal fly (Gastrophilus spp., Oestrus spp., Etc.), cow fly (Hypoderma spp., Etc.), hornfly (Chrysops spp.), Hornfly (Melophagus usLin, etc.) , Mosquitoes (Aedes spp., Anopheles spp., Culex spp., Etc.), Adults and larvae of Diptera including Thymus (Prosimulium spp., Simulium spp., Etc.), Cronucaca, Snail flies, scarids and other long-horned subsects; (Thrower trips) (Franklinella spp.) And other phagocytic thrips, adults and juveniles of the order Cantoptera; De Geer), Monomorium phalaonis Linnaeus (Linnaeuus) )), Antarctic ants (Wasmannia auropuncata Roger), Red ants (Solenopsis geminata) (Fabricius), Fire ants (Solenopsis invicita Burren), Argentine ants (Iridomir) )), White whale ants (Tetramorium caespitum linnaeus), Japanese tiger squirrels (Lasius alienus Forster), stag beetle (Tapinoma sessile sei (Say)), Hornets, yellow jackets, large wasps, sawflies (Neodiprion spp.). Cephus spp. ) And other insect pests; Reticulitermes flavipes (Kollar), Termites (Reticulites hesperus banks (Bunks)), White termites (Coptermes imoster) Termite insect pests such as termites that are important from the viewpoint of Cinder (Snyder) and other economic points of view; Lepisma saccharina Linnaeus, Thermida domestica Packard, etc. Insect pests; body lice (P diculus humanus capitis de Geer), head lice (Pediculus humanus humanus linneus), chicken lice (Mecananthus stramineus dhi (Nitszch)) Goniocotes gallinae De Geer), sheep lice (Bovicola ovis Schrank),
Short-nosed cattle louse (Haematopinus eurystenus nits (Nitszch)), Bovine louse (Lynatus) Insect pests; Xenopsilla cheopis Rocheschild, cat flea (Ctenocephalides felis bouche), Cenocephalides canis walnut (Ctenocephalides canis curtis) Schrank), Echindophaga gallinacea Westwood, Pulp irritans Linnaeus, and other fleas that afflict humans and birds include flea insect pests. Still other arthropod pests that are included are the spiders of the order Spiders, such as the spider spiders (Loxoceles recrusa gretsch and Mulaik) and the black widow spider (Latrodictus mactans Fabricius) And centipedes such as Linnaeus)). The compounds of the present invention are important agricultural pests from an economic point of view (ie root-knot nematodes, root-nematode rooted nematodes, crimson nematodes, etc.) as well as animals and humans. Health harmful pests (ie, all flukes, tapeworms and roundworms important from an economic point of view; equine common roundworms (Strongylus vulgaris), canine dog roundworms (Toxocara canis), sheep tortoises (Haemonchus) contortus, dog canineous filamentous worms (Dirofilaria immitis lady (Leidy)), equine foliate worms (Anolocephala perfoliata), ruminant hepatic worms (Fansiola hepatica Linneus) ) Etc.), but not limited to this, such as worms, roundworms, helminths, rhabdididae, cirrus nematode, enoprus It is also active against worms, tapeworms, flukes and larvae of the phylum.

  The compounds of the present invention include Lepidoptera (Alabama argillacea Huebner), fruit tree caterpillars (Archips argyrospila Walker), A. rosana Linnaeus (Archips s. Cnaphalocrosis medinalis Guenee, Clambus caligninosellus Clemens, Shibatsuga (Crambus teterellarus Zinken), Boisduval), Kusaobiringa (Earias vittella Fabricius), cotton bollworm (Helicoverpa armigera Huebner), larvae (Helicoverpa zea Boddie of tobacco budworm), larvae (Heliothis virescens Fabricius of tobacco budworm), black Obi Chrono moth (Herpetogramma licarsisalis Walker), Hosobahimehamaki (Lobesia botrana Denis & Schiffermueller), cotton red moth (Pectinophora gossypiella Saunders), citrus leaflet (Phyllocnitis citriella Stainton) Giant cabbage butterfly (Pieris brassicae Linnaeus), cabbage butterfly (Pieris rapae Linnaeus), diamondback moth (Plutella xylostella Linnaeus), beet armyworm (Spodoptera exigua Huebner), common cutworm (Spodoptera litura Fabricius), a kind of fall armyworm (Spodoptera frugiperda J.E.Smith), nettle It exhibits particularly high activity against pests of the species such as Trichoplusia ni Huebner and one of the species Kibaga (Tuta absoluta Meyrick).

  In addition, the compounds of the present invention include pea aphid (Aphysis phioni pisum Harris), bean aphid (Aphis craccivora Koch), bean aphid (Aphis fossi sipoli), Snowy aphids (Aphis spiraecola Patch), potato aphids (Aulacorthum solani Kaltenbach), strawberry aphids (Chaetosifon fragae phurai Dura) (Russia) v / Mordvilko), rose apple aphid (Dysaphis plantaginea Paaserini), woolly apple aphid (Eriosoma lanigerum Hausmann), Momoko butterbur aphid (Hyalopterus pruni Geoffroy), fake radish aphid (Lipaphis erysimi Kaltenbach), aphids to get in cereals (Metopolophium dirrhodum Walker), Tulip beetle aphid (Macrosipum euphorbiae Thomas), peach aphid (Myzus persicae Sulzer), lettuce aphid Nasonobia rivisnigri Mosley), Cobb Abra Shi (Pemphigus spp.), Corn aphid (Rhopalosiphum maidis Fitch), wheat constricted aphid (Rhopalosiphum padi Linnaeus), oat green aphid (Schizaphis graminum Rondani), wheat aphid (Sitobion avenae Fabricius), spotted alfalfa aphid (Therioaphis maculata Buckton) , Toxoptera aurantii Boyer de Fonscolombe and Toxoptera citricida Kirkaldy, Adelges spp. ), Pecan phylloxera (Phylloxera devastatrix Pergande), tobacco whitefly (Bemisia tabaci Gennadius), silverleaf whitefly (Bemisia argentifolii Bellows & Perring), mandarin orange whitefly (Dialeurodes citri Ashmead) and greenhouse whitefly (Trialeurodes vaporariorum Westwood), potato leafhopper (Empoasca fabae Harris, Lamindelfax striatellus Fallen, Macrostes quadrilinetus Forbes, Blackfin tuna Fences (Nephotettix cinticeps Uhler), cross di leafhopper (Nephotettix nigropictus Stal), brown planthopper (Nilaparvata lugens Stal), corn planthopper (Peregrinus maidis Ashmead), Sejirounka (Sogatella furcifera Horvath), Ineunka (Sogatodes orizicola Muir), white apple leafhopper (Typhlocyba pomaria McAtee), Erythroneura spp., 17-year seminar (Magcidada stendecim Linnaeus), Iceria scale insect (Icerya) urchasi Maskell), San Jose scale insects (Quadraspidiotus perniciosus Comstock), mandarin orange mealybug (Planococcus citri Risso), other mealybugs (Pseudococcus spp.), European pear pheasant Rami (Cacopsylla pyricola Foerster), the wings, including Kakikijirami (Trioza diospyri Ashmead) Has commercially useful activity against worms of the eye.

  Further, the compounds of the present invention include Acrosterum hilare Say, a kind of helicate beetle (Anasa tristis de Geer), a kind of common leaf turtle (Bissus leucopterus leucopterus Say), a cotton race bug Distant, red stink bug (Dysdercus sturellus Herrich-Schaeffer), a kind of brown stink bug (Euchistus servus Say), eutistus variolavida dasio Memushi (Graptosthetus spp.), Pine flea helicopter stink bug (Leptoglossus corculus Say), green blind turtle (Lygus lineolaris Palisot de Beauvois), southern green stink bug (Nezara viridula Linnaeus), Inekamemushi (Oebalus pugnax Fabricius), a kind of chinch bugs (Oncopeltus fasciatus It also has activity against hemipod worms including Dallas and cottonseed potato beetle (Pseudatomocelis seratus Reuter) Other insects controlled by the compounds of the present invention include the common moths (Franklinella occident) lis Pergande), oranges thrips (Scirthothrips citri Moulton), soybean thrips (Sericothrips variabilis Beach) and Welsh onion thrips (Thrips tabaci Lindeman like; Coleoptera (Colorado potato beetle (Leptinotarsa decemlineata Say), bean beetle (Epilachna varivestis Mulsant) and Aguriotesu (Agriotes ), Genus Atous, or Limonius larvae.

  Of note is the use of the compounds of the invention for the control of silver leaf whiteflies (Bemisia argentifolii). Of note is the use of the compounds of the present invention for controlling Franklinella occidentalis. Of note is the use of the compounds of the present invention for the control of Empoasca fabae. Of note is the use of the compounds of the invention for the control of corn planthopper (Peregrinus maidis). Of note is the use of the compounds of the present invention for controlling Aphis gossypi. Of note is the use of the compounds of the present invention for the control of peach persicae.

  One or more compounds of the present invention can also be mixed with one or more “other” biologically active compounds or agents. “Other” biologically active compounds or agents do not include compounds of formula I. Such "other" biologically active compounds or agents include insecticides, fungicides, fungicides, nematicides, bactericides, acaricides, root regulators, growth regulators, infertility Agents, signaling chemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, viruses or fungi And multi-component pest control agents that provide non-agricultural benefits. Accordingly, the present invention comprises a biologically effective amount of a compound of formula I and an effective amount of at least one additional biologically active compound or agent, and at least one surfactant. It also relates to a composition that may further comprise a solid or liquid diluent. Examples of such biologically active compounds or agents that can be combined with the compounds of the present invention are abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinephos-methyl, bifenthrin, bifenazate, buprofezin , Carbofuran, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chrome aphenozide, clothianidin, cyfluthrin, β-cyfluthrin, cyhalothrin, λ-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinone, diflubens , Dimethoate, geophenolan, emamectin, endosulfan, esfenvalerate, etiprole, fenoticarb, phenoxy Cicarb, fenpropatoline, fenvalerate, fipronil, flonicamid, flucitrinate, τ-fulvalinate, flufenelim (UR-50701), flufenoxuron, honofos, halofenozide, hexaflumuron, imidacloprid, indoxacarb, isofenphos, lufenuron , Malathion, metaldehyde, methamidophos, metidathion, methomyl, methoprene, methoxychlor, monocrotofos, methoxyphenozide, nithiazine, novallon, nobiflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, folate, hosalon, phosmethidone, Pirimicarb, profenofos, pymetrozine, pyridalyl, pyriproxyfen, rotenone, spinosa Insecticides such as spiromesifen (BSN 2060), sulprophos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorbinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, trichlorfone and triflumuurone; , Benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromconazole, carpropamide, captahol, captan, carbendazim, chloronebu, chlorothalonil, copper chloride, copper salt, cyflufenamide, simoxanil, cyproconazole Cyprodinil, (S) -3,5-dichloro-N- (3-chloro-1-ethyl-1-methyl-2-oxopropyl) -4-methylbenzami (RH7281), diclocimet (S-2900), dichromedin, dichlorane, diphenoconazole, (S) -3,5-dihydro-5-methyl-2- (methylthio) -5-phenyl-3- (phenylamino) -4H -Imidazol-4-one (RP407213), dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dodin, edifenphos, epoxiconazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramide (SZX0722), fenpiclonil, Fenpropidin, Fenpropimorph, Fentine Acetate, Fentine Hydroxide, Fluazinam, Fludioxonil, Flumetobar (RPA403397), Flumorph / Flumorulin (SYP-L19) ), Fluoxastrobin (HEC5725), fluquinconazole, flucinazole, flutolanil, flutriahol, holpet, fosetyl-aluminum, furaxyl, furametapyr (S-82658), hexaconazole, ipconazole, iprobenphos, iprodione, isoprothiolane, kasugamycin , Cresoxime-methyl, Mancozeb, Manebu, Mefenoxam, Mepronil, Metalaxyl, Metoconazole, Metominostrobin / phenominostrobin (SSF-126), Metraphenone (AC375839), Microbutanyl, Neo-Asodine (Merthoarsonate Ferric), Nicobifen (BAS510), Orizastrobin, Oxadixyl, Penconazole, Pencyclone, Probenazole, Proc Raz, propamocarb, propiconazole, proquinazide (DPX-KQ926), prothioconazole (JAU6476), pyrifenox, pyraclostrobin, pyrimethanil, pyroxylone, quinoxyphene, spiroxamine, sulfur, tebuconazole, tetraconazole, thiabendazole, tifluzamide, Bactericides and fungicides such as thiophanate-methyl, thiram, thiazinyl, triadimephone, triadimenol, tricyclazole, trifloxystrobin, triticonazole, validamycin and vinclozoline; nematicides such as aldicarb, oxamyl and fenamifos; Bactericides such as streptomycin; amitraz, quinomethionate, chlorobenzilate, cyhexatin, dicophore, dienochlor Bacillus thuringens, including the genus Aizawai and Kurstaki; and mitoxazole, phenazaquin, fenbutatin oxide, fenpropatoline, fenpyroximate, hexothiazox, propargite, pyridaben and tebufenpyrad; thuringiensis), biological agents such as Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi. Applying the compounds of the present invention and compositions thereof to plants genetically transformed to express protein toxicity (eg, Bacillus thuringiensis toxin) against invertebrate pests Can do. The effect of the exogenously applied invertebrate pest control compound of the present invention may be synergistic with the expressed toxin protein.

  For a general reference to these agricultural protective agents, see The Pesticide Manual, 13th edition, C.I. D. S. C. D. S. Tomlin, British Crop Protection Council, Farnham, Surrey, UK, 2003.

  One embodiment of insecticides and acaricides for mixing with the compounds of the present invention includes: pyrethroids such as acetamiprid, cypermethrin, cyhalothrin, cyfluthrin, β-cyfluthrin, esfenvalerate, fenvalerate and tralomethrin; Carbamates such as methomyl, oxamyl and thiodicarb; neonicotinoids such as clothianidin, imidacloprid and thiacloprid; neuronal sodium channel blockers such as indoxacarb; insecticidal macrocyclic lactones such as spinosad, abamectin, avermectin and emamectin Gamma-amino tangle acid (GABA) antagonists such as endosulfan, etiprole and fipronil; of flufenoxuron and triflumuron Insecticidal ureas such as; larval hormone mimetics such as geophenolane and pyriproxyfen; pymetrozine; and amitraz. One embodiment of a biological agent to be mixed with a compound of the present invention includes natural and genetic modifications including Bacillus thuringiensis and Bacillus thuringiensis delta endotoxins, and members of the Baculoviridae family Examples include viral insecticides, and carnivorous fungi and molds.

  Another embodiment of the mixture includes a mixture of a compound of the invention and cyhalothrin, a mixture of a compound of the invention and β-cyfluthrin, a mixture of a compound of the invention and esfenvalerate, a compound of the invention and methomyl A mixture of a compound of the present invention and imidacloprid, a mixture of a compound of the present invention and thiacloprid, a mixture of a compound of the present invention and indoxacarb, a mixture of a compound of the present invention and abamectin, a compound of the present invention A mixture of a compound of the present invention and etiprol, a mixture of a compound of the present invention and fipronil, a mixture of a compound of the present invention and flufenoxuron, a mixture of a compound of the present invention and pyriproxyfen, Mixtures of compounds of the present invention and pymetrozine, mixtures of compounds of the present invention and amitraz Mixtures of a compound with Bacillus thuringiensis (Bacillus thuringiensis) of the present invention, and compounds with a mixture of Bacillus thuringiensis (Bacillus thuringiensis) delta endotoxin present invention are mentioned.

  In certain instances, combinations with other invertebrate pest control compounds or agents having a similar range of control but different modes of action are particularly advantageous for resistance treatment. Accordingly, the compositions of the present invention may further comprise a biologically effective amount of at least one additional invertebrate pest control compound or agent having a similar range of control but different modes of action. Contacting a plant or plant location that has been genetically modified to express a plant protection compound (eg, a protein) with a biologically effective amount of a compound of the present invention also provides a broader range of plant protection. Can be advantageous for resistance treatment.

  Biological compositions comprising the compounds of the invention directly in pest environments, including agricultural and / or non-agricultural ectoparasites, in areas to be protected, or directly on pests to be controlled By applying in an effective amount, invertebrate pests are controlled in agricultural and / or non-agricultural applications. Agricultural applications typically involve the seeds of a crop before planting, the leaves, stems, flowers and / or fruits of the crop plant, or the soil or other growth medium before or after planting the plant. Or protection of crops from invertebrate pests by application of a mixture. Non-agricultural application refers to the control of invertebrate pests in fields other than crops. Non-agricultural applications include the control of invertebrate pests in stored grains, beans and other food products, and textiles such as clothing and carpets. Non-agricultural applications include the control of invertebrate pests in decorative plants, forests, gardens, along roads and railways, and in turf fields such as lawns, golf courses and pastures. Non-agricultural applications also include invertebrate pest control in homes and other buildings occupied by humans and / or companion animals, farm animals, ranch animals, zoo animals or other animals. Non-agricultural applications also include the control of pests such as termites that can damage wood or other structural materials used in buildings. Non-agricultural applications also include the protection of human and animal health by controlling invertebrate pests that are parasitic or transmit contagious diseases. Examples of such pests include tsutsugamushi, mites, lice and fleas.

  Accordingly, the present invention provides an invertebrate pest or environment thereof, a biologically effective amount of one or more compounds of the invention, or a composition comprising at least one such compound, or at least one. Agrochemical and / or non-agricultural, comprising contacting with a composition comprising such a compound and a biologically effective amount of at least one additional biologically active compound or agent Further comprising a method of controlling invertebrate pests in application. Examples of suitable compositions comprising a compound of the present invention and a biologically effective amount of at least one additional active compound or drug include additional biologically active compounds and compounds of the present invention. Mention may be made of granule compositions which are present on the same granules or on granules which are separated from the granules in which the compounds according to the invention are present.

  One embodiment of the contact method is by spraying. Alternatively, a granule composition comprising the compound of the present invention can be applied to the plant foliage or soil. The compounds of the present invention provide for plant uptake by contact of a plant with a composition comprising a compound of the present invention applied as a liquid formulation of a soil liquid medicine, a granule formulation into soil, a nursery box treatment or transplantation penetration. It can also be transported effectively. Of note is the composition of the present invention in the form of a soil drench liquid formulation. Also of note is a method of controlling an invertebrate pest comprising contacting the invertebrate pest soil environment with a biologically effective amount of a compound of the present invention. Of further note are the compounds of the present invention that are also effective by topical application to ectoparasite locations. Other contact methods include direct and residual spray, air spray, gel, seed coat, microencapsulation, osmotic uptake, feed, ear tag, bolus, mist generator, fumigant, aerosol, dust, etc. Application of the compound or composition may be mentioned. To make an invertebrate control device (eg, insect net), the material of the invention may be impregnated.

  The compounds of the invention can be incorporated into feed compositions that are consumed by invertebrate pests or used in devices such as traps, feed stations, and the like. Such a feed composition comprises (a) an active ingredient, i.e. a biologically effective amount of a compound of formula I, its N-oxide or salt, (b) one or more food ingredients, optionally ( c) in the form of granules comprising an attractant and optionally (d) one or more humectants. Of note, comprises between about 0.001-5% active ingredient, about 40-99% food material and / or attractant, and optionally about 0.05-10% humectant. Granules or feed compositions, which can be effective in controlling soil invertebrate pests at very low application rates, especially at application levels of active ingredient that are lethal by ingestion rather than direct contact. Some food materials can function as both food sources and attractants. Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starch, animal fat, vegetable oil, yeast extract and milk solids. Examples of attractants include odorants and flavors such as fruit or plant extracts, flavorings, or other animal or plant components, pheromones, or other agents known to attract the target invertebrate pests It is an agent. Examples of humectants, ie agents that retain moisture, are glycols and other polyols, glycerin and sorbitol. Of note is a feed composition used to control at least one invertebrate pest selected from the group consisting of ant, termite and cockroach (and such feed composition). Is a method of using An invertebrate pest control device may comprise a feed composition of the present invention and a housing adapted to receive the feed composition. Here, the housing is at least one opening sized to allow the invertebrate pest to pass through the opening so that the invertebrate pest can access the feed composition from a location outside the housing. And the housing is further adapted to be located at or near a potential or known active location of an invertebrate pest.

  The compounds of the present invention can be applied without the use of additional adjuvants, but the most frequent application is with appropriate carriers, diluents and surfactants, as well as food depending on the expected end use if possible. A formulation comprising one or more active ingredients in combination. One preferred method of application involves spraying an aqueous dispersion or purified oil solution of the compound of the invention. Combinations with spray oils, spray oil concentrates, spreaders, adjuvants, other solvents and synergists such as piperonyl butoxide often also increase compound efficacy. For non-agricultural use, applying such sprays from spray containers such as cans, bottles or other containers, by means of pumps or by releasing it from high pressure containers, such as pressurized aerosol spray cans. it can. Such spray compositions can take a variety of forms, such as sprays, mists, foams, femes or fog. Accordingly, such spray compositions can optionally further include a spray, a foaming agent, and the like. Of note is a spray composition comprising a biologically effective amount of a compound or composition of the present invention and a carrier. One embodiment of such a spray composition comprises a biologically effective amount of a compound or composition of the present invention and a propellant. Exemplary propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbon, chlorofluorocarbon, dimethyl ether, and mixtures thereof. It should be noted that mosquito, black fly, stable fly, deer fly, horse fly, large wasp, wasp ( Used to control at least one invertebrate pest selected from the group consisting of yellow jack, hornet, tick, spider, ant, gnat, etc. Spray compositions (and methods utilizing such spray compositions dispensed from spray containers).

  The application rate required for effective control (ie, “biologically effective amount”) depends on the invertebrate species to be controlled, the life cycle of the pest, the life stage, size, location, age Depending on factors such as host crop or animal, feeding behavior, mating behavior, ambient humidity, temperature, etc. Under normal circumstances, an application rate of about 0.01 to 2 kg of active ingredient per hectare is sufficient to control pests in agricultural ecosystems, but as little as 0.0001 kg / ha is sufficient Or as high as 8 kg / ha may be required. For non-agricultural applications, effective usage rates range from about 1.0 to 50 mg / square meter, but as little as 0.1 mg / square meter is sufficient, or as much as 150 mg / square meter is required. May be. One skilled in the art can readily determine the biologically effective amount required for the desired level of invertebrate pest control.

  The following tests demonstrate the control efficacy of the compounds of the invention against specific pests. By “control efficacy” is meant suppression of invertebrate pest development (including death) that causes significantly reduced feeding. However, the pest control protection obtained by the compounds is not limited to these types. See Index Table A for compound descriptions. The following abbreviations are used in the index table: i means iso, Me means methyl, Pr means propyl, i-Pr means isopropyl, and CN means cyano. The abbreviation “Ex.” Stands for “Example” followed by a number indicating the example in which the compound is prepared.

Biological Example of the Invention Test A
In order to evaluate the control of Spodoptera frugiperda, the test unit consisted of a small open container containing a 4-5 day old corn plant. This was pre-infested (by the use of a core sampler) with 10-15 individual larvae in a piece of insect diet.

  10% acetone, 90% water, and 300 ppm X-77 ™ Spreader Low-Form Formula nonionic surfactant (containing alkylaryl polyoxyethylene, free fatty acid, glycol and isopropanol) Test compounds were formulated using a solution containing (Loveland Industries, Inc. Greeley, Colorado, USA), Greeley, Colorado, USA. SUJ2 nebulizer nozzle with 1/8 JJ custom body located 1.27 cm (0.5 inch) above each test unit (Spraying Systems Co. Wheaton, Illinois, Wheaton, Illinois, USA) , USA)) and the formulated compound was applied in 1 mL liquid. In these tests all experimental compounds were sprayed at 10 ppm and repeated three times. After spraying the formulated test compound, each test unit was allowed to dry for 1 hour and then a black screen cap was placed on top. The test unit was held for 6 days in the growth chamber at 25 ° C. and 70% relative humidity. Each test unit was then visually assessed for insect mortality.

  Of the compounds tested, the following resulted in mortality of at least 80%: 2, 5, 6, 7, 9, 11, 12, 13, and 14.

Test B
In order to evaluate the control of the potato leafhopper (Empoasca Fabae Harris) by contact and / or osmotic transfer means, a test unit was constructed with a small open container containing 3-4 day old corn plants. Prior to application, white sand was added to the top of the soil and sprayed with water to form a sand surface.

  Test compounds were formulated as described in Test A, sprayed at 50 ppm, and application was repeated three times. After spraying, the test units were allowed to dry for 1 hour before they were post-infested by 5 potato leafhoppers (18-21 day-old adults). A black screen cap was placed on top of the cylinder. The test unit was held for 6 days in a growth chamber at 20 ° C. and 70% relative humidity. Each test unit was then visually assessed for insect mortality.

  Of the compounds tested, the following resulted in mortality of at least 80%: 3 and 7.

Claims (26)

Formula I

[Where:
Q is Q-1, Q-2 and Q-3

Selected from the group consisting of;
R ¹ is X—Z—O—R ¹¹ ;
X is O, S or NR ¹² ;
Z is _C 2 -C ₄ haloalkylene or _C 2 -C ₄ Haroarukeniren;
Each R ² is independently H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio , be a _C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C ₄ haloalkylsulfinyl or _C 1 -C ₄ haloalkylsulfonyl;
R ³ is H; or optionally substituted by halogen, respectively, cyano, nitro, _hydroxy, C 1 -C _{4 alkoxy,} C 1 -C _{4 alkylthio,} C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl, C} 2 ~ C _{4 alkoxycarbonyl,} C 1 -C _{4 alkylamino,} optionally substituted by one or more substituents selected from C 2 -C ₈ dialkylamino and _C 3 -C ₆ group consisting cycloalkylamino Good C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl;
R ⁴ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, OH, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylamino , _C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino, (C} 1 ~C _{4 alkyl) (C} 3 -C ₆ cycloalkyl) _amino, C 2 -C ₆ alkoxycarbonyl or _C 2 -C ₆ Alkylcarbonyl;
R ⁵ is H; G ¹ ; or optionally halogen, G ¹ , cyano, nitro, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C _{4, respectively. alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylcarbonyl,} C 3 _{~C 6} 1 or or more selected from the group consisting of trialkylsilyl and ^{G 2} Are C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or C ₃ -C ₆ cycloalkyl optionally substituted by a substituent of R ⁵ ; or R ⁵ is hydroxy, C ₁ -C _{4 alkoxy,} C 1 -C _{4 alkylamino,} C 2 -C _{8 dialkylamino,} C 3 -C ₆ cycloalkyl amino , C ₂ -C ₆ alkoxycarbonyl or C ₂ -C ₆ alkylcarbonyl; or R ⁴ and R ⁵ together with the nitrogen to which they are attached contain 2 to 6 carbon atoms And optionally forms a ring which may contain one additional atom of nitrogen, sulfur or oxygen, said ring optionally being C ₁ -C ₂ alkyl, halogen, cyano, nitro and C _1- Optionally substituted by 1 to 4 substituents selected from the group consisting of C ₂ alkoxy;
R ⁶ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ haloalkenyl, C ₂ -C _{6 haloalkynyl,} C 3 -C ₆ halocycloalkyl, halogen, cyano, _nitro, CO 2 H, CONH _{2, hydroxy,} C 1 -C _{4 alkoxy,} C 1 -C _{4 haloalkoxy,} C 1 -C _{4 alkylthio,} C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C _{4 haloalkylsulfinyl,} C 1 -C _{4 haloalkylsulfonyl,} C 1 -C ₄ alkylamino , _C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino,} C 2 -C _{6 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylaminocarbonyl,} it is a C 3 -C ₈ dialkylaminocarbonyl or _C 3 -C ₆ trialkylsilyl;
R ⁷ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ haloalkyl, C ₂ -C ₆ haloalkenyl, C ₂ -C _{6 haloalkynyl,} C 3 -C ₆ halocycloalkyl, halogen, cyano, _nitro, CO 2 H, CONH _{2, hydroxy,} C 1 -C _{4 alkoxy,} C 1 -C _{4 haloalkoxy,} C 1 -C _{4 alkylthio,} C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C _{4 haloalkylsulfinyl,} C 1 -C _{4 haloalkylsulfonyl,} C 1 -C ₄ alkylamino , _C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino,} C 2 -C _{6 alkylcarbonyl,} C 2 -C ₆ alkoxycarbonyl, C ₂ -C ₆ alkylaminocarbonyl, C ₃ -C ₈ dialkylaminocarbonyl or C ₃ -C ₆ trialkylsilyl; or R ⁷ is optionally C ₁ -C ₄ alkyl, C _{2, respectively.} -C _{4 alkenyl,} C 2 -C _{4 alkynyl,} C 3 -C _{6 cycloalkyl,} C 1 -C _{4 haloalkyl,} C 2 -C _{4 haloalkenyl,} C 2 -C _{4 haloalkynyl,} C 3 -C ₆ Haroshikuro alkyl, halogen, cyano, _nitro, C 1 -C _{4 alkoxy,} C 1 -C _{4 haloalkoxy,} C 1 -C _{4 alkylthio,} C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 alkylamino,} C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino,} C 4 -C ₇ Alkyl) _{cycloalkylamino,} C 2 -C _{4 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} one or selected from C 2 -C ₆ alkylaminocarbonyl and _C 3 -C ₈ group consisting dialkylaminocarbonyl Phenyl, benzyl or phenoxy optionally substituted by the above substituents;
Each G ¹ independently comprises one or two ring members, optionally selected from the group consisting of C (═O), S (O) and S (O) ₂ and optionally independent of R ^10. A 5- or 6-membered non-aromatic carbocyclic or heterocyclic ring optionally substituted by 1 to 4 substituents selected from
Each G ² is independently a phenyl ring, a phenoxy ring, or a 5-membered heteroaromatic ring in which each ring is optionally substituted by 1 to 3 substituents independently selected from R ⁹ Or a 6-membered heteroaromatic ring;
Each R ⁹ is independently C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ haloalkenyl. , C ₂ -C ₄ haloalkynyl, C ₃ -C ₆ halocycloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 alkylamino,} C 2 -C _{8 dialkylamino,} C 3 -C _{6 cycloalkylamino, (C} 1 -C _{4 alkyl) (C} 3 -C ₆ cycloalkyl) _amino, C 2 -C _{4 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylaminocarbonyl,} C 3 -C ₈ dialkylamino carbonyl or _C 3 -C ₆ trialkylsilyl;
Each R ¹⁰ is independently C ₁ -C ₂ alkyl, halogen, cyano, nitro or C ₁ -C ₂ alkoxy;
R ¹¹ is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₈ alkoxyalkyl, C ₂ -C ₈ haloalkoxyalkyl, C ₂ -C ₈ alkoxyalkyl _haloalkyl, C 1 -C _{6 haloalkyl,} C 2 -C _{6 haloalkenyl,} C 2 -C _{6 haloalkynyl,} be a C 3 -C ₆ halocycloalkyl or _C 2 -C ₈ haloalkoxy haloalkyl;
R ¹² is H or C ₁ -C ₄ alkyl;
W is N or CR ² ;
V is N or CR ¹³ ;
Y is N or CR ¹⁴ ;
R ¹³ and R ¹⁴ are independently H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ haloalkyl, C _2- C ₆ haloalkenyl, C ₂ -C ₆ haloalkynyl, C ₃ -C ₆ halocycloalkyl, halogen, cyano, nitro, CO ₂ H, CONH ₂ , hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ halo _alkoxy, C 1 -C _{4 alkylthio,} located at C 1 -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C ₄ haloalkylsulfinyl or _C 1 -C ₄ haloalkylsulfonyl ;
L is a direct bond; or a 1- to 3-membered connecting chain selected from carbon, nitrogen, oxygen, sulfur, C (= E), S (O) and S (O) ₂ , but no more than 2 Are selected from C (═E), S (O) and S (O) ₂ , and the linking chain is optionally substituted by 1 to 3 substituents independently selected from R ¹⁵ May be;
Each R ¹⁵ is independently H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, halogen, cyano, COOH, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₂ -C ₆ alkoxy Carbonyl or C ₂ -C ₆ alkoxycarbonylalkyl; or a phenyl ring optionally substituted with 1 to 3 substituents each ring optionally selected independently from R ¹⁶ or a 5 or 6 membered A heteroaromatic ring;
Each R ¹⁶ is independently C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ haloalkenyl. , C ₂ -C ₄ haloalkynyl, C ₃ -C ₆ halocycloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C _{4 alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 1 -C _{4 haloalkylthio,} C 1 -C _{4 haloalkylsulfinyl,} C 1 -C _{4 haloalkylsulfonyl,} C 1 -C _{4 alkylamino,} C 2 -C ₈ dialkyl _amino, C 3 -C _{6 cycloalkylamino, (C} 1 _{~C 4 alkyl) (C} 3 -C ₆ cycloalkyl) _{amino, C} 2 ~ _{4 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylaminocarbonyl,} be a C 3 -C ₈ dialkylaminocarbonyl or _C 3 -C ₆ trialkylsilyl;
E is CH ₂ , O, S or NR ¹⁷ ;
R ¹⁷ is H; G ³ ; or optionally halogen, G ² , cyano, nitro, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C _{4, respectively. alkylsulfinyl,} C 1 -C _{4 alkylsulfonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylcarbonyl,} C 3 _{~C 6} 1 or or more selected from the group consisting of trialkylsilyl and ^{G 4} of which may be substituted with a substituent _C 1 -C _{6 alkyl,} C 2 -C _{6 alkenyl,} C 2 -C _{6 alkynyl,} or a C 3 -C ₆ cycloalkyl phenyl; or ^{R 17} is hydroxy, C ₁ -C _{4 alkoxy,} C 1 -C _{4 alkylamino,} C 2 -C _{8 dialkylamino,} C 3 -C ₆ cycloalk _Kiruamino, it is C 2 -C ₆ alkoxycarbonyl or _C 2 -C ₆ alkylcarbonyl;
Each G ³ independently comprises one or two ring members optionally selected from the group consisting of C (═O), S (O) and S (O) ₂ and optionally independent of R ¹⁹ A 5- or 6-membered non-aromatic carbocyclic or heterocyclic ring optionally substituted by 1 to 4 substituents selected from
Each G ⁴ is independently a phenyl ring, a phenoxy ring, or a 5-membered heteroaromatic ring in which each ring is optionally substituted by 1 to 3 substituents independently selected from R ¹⁸ Or a 6-membered heteroaromatic ring;
Each R ¹⁸ is independently C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₂ -C ₄ haloalkenyl. , C ₂ -C ₄ haloalkynyl, C ₃ -C ₆ halocycloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkylamino, C ₂ -C ₈ dialkylamino, C ₃ -C ₆ cycloalkylamino, C ₄ -C ₇ (alkyl) cycloalkylamino, C ₂ -C _{4 alkylcarbonyl,} C 2 -C _{6 alkoxycarbonyl,} C 2 -C _{6 alkylaminocarbonyl,} C 3 -C ₈ dialkyl It is amino carbonyl, or _C 3 -C ₆ trialkylsilyl;
Each R ¹⁹ is independently C ₁ -C ₂ alkyl, halogen, cyano, nitro or C ₁ -C ₂ alkoxy; and n is 1, 2, 3 or 4]
Or an N-oxide or salt thereof. W is N, CH, CF, CCl, CBr or CI;
Each R ² is independently H, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, halogen, cyano, nitro, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;
n is 1, 2 or 3;
R ³ is H or C ₁ -C ₄ alkyl;
R ⁴ is H or C ₁ -C ₄ alkyl;
R ⁵ is H; or each optionally substituted by one or more substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, OCH ₃ and S (O) _p CH ₃ which may _C 1 -C _{6 alkyl,} C 2 -C _{6 alkenyl,} C 2 -C ₆ alkynyl or _C 3 -C ₆ cycloalkyl;
p is 0, 1 or 2;
R ⁶ is CH ₃ , CF ₃ , OCHF ₂ , S (O) _p CF ₃ , S (O) _p CHF ₂ , cyano or halogen;
R ⁷ is H, F, Cl, Br, I, cyano or CF ₃ ;
V is CR ¹³ ; R ¹³ is H, CH ₃ , halogen or cyano;
A compound according to claim 1 wherein Y is CR ¹⁴ ; and R ¹⁴ is H, CH ₃ , halogen or cyano. X is O;
Z is _{C 2} haloalkylene; and A compound according to claim 2 ^{R 11} is _C 1 -C ₄ alkyl or _C 1 -C ₄ haloalkyl. Q is Q-1;
W is N, CCl, CF or CH;
R ² is H, Cl, F or Br;
n is 1 or 2;
R ³ and R ⁴ are H;
R ⁵ is H, methyl, ethyl, i-propyl or t-butyl;
R ⁶ is F, Cl, Br, I, CH ₃ or CF ₃ ;
R ⁷ is Cl, Br or cyano;
4. A compound according to claim 3 wherein V is CH; and Y is CH, CF, CCl or CBr. R ¹ is —OCF ₂ CHF—O—R ¹¹ ; and R ¹¹ is methyl, ethyl, CH ₂ CF ₃ , CF ₃ , CF ₂ CF ₃ , CF ₂ CF ₂ Br, CF ₂ CF ₂ CF ₃ or CF The compound according to claim 4, which is (CF ₃ ) ₂ . R ¹ is —OCF ₂ CHFOCF ₃ ;
Y is CH;
R ⁶ is Cl or CH _3; and the compound of claim 5 ^{R 7} is Cl or cyano. Q is Q-2;
W is N, CCl, CF or CH;
R ² is H, Cl, F or Br;
n is 1 or 2;
R ³ and R ⁴ are H;
R ⁵ is H, methyl, ethyl, i-propyl or t-butyl;
R ⁶ is F, Br, I, CH ₃ or CF ₃ ;
R ⁷ is Cl, Br or cyano;
V is CH;
Y is CH, CF, CCl or be a CBr; and the compound of claim 3 L is _CH 2, _CH 2 CH ₂ or C = O. R ¹ is —OCF ₂ CHF—O—R ¹¹ ; and R ¹¹ is methyl, ethyl, CH ₂ CF ₃ , CF ₃ , CF ₂ CF ₃ , CF ₂ CF ₂ Br, CF ₂ CF ₂ CF ₃ or CF The compound according to claim 7, which is (CF ₃ ) ₂ . R ¹ is —OCF ₂ CHFOCF ₃ ;
Y is CH;
R ⁶ is Cl or CH _3; and the compound of claim 8 ^{R 7} is Cl or cyano. Q is Q-3;
W is N, CCl, CF or CH;
R ² is H, Cl, F or Br;
n is 1 or 2;
R ³ and R ⁴ are H;
R ⁵ is H, methyl, ethyl, i-propyl or t-butyl;
R ⁶ is H, Cl, Br, I, CH ₃ or CF ₃ ;
R ⁷ is Cl, Br or cyano;
4. A compound according to claim 3 wherein V is CH; and Y is CH, CF, CCl or CBr. R ¹ is —OCF ₂ CHF—O—R ¹¹ ; and R ¹¹ is methyl, ethyl, CH ₂ CF ₃ , CF ₃ , CF ₂ CF ₃ , CF ₂ CF ₂ Br, CF ₂ CF ₂ CF ₃ or CF The compound according to claim 10, which is (CF ₃ ) ₂ . R ¹ is —OCF ₂ CHFOCF ₃ ;
Y is CH;
R ⁶ is Cl or CH _3; and the compound of claim 11 ^{R 7} is Cl or cyano. 1- (3-Chloro-2-pyridinyl) -N- [4-cyano-2-methyl-6-[(methylamino) carbonyl] phenyl] -3- [1,1,2-trifluoro-2- ( Trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxamide;
1- (3-Chloro-2-pyridinyl) -N- [4-cyano-2-methyl-6-[[(1-methylethyl) amino] carbonyl] phenyl] -3- [1,1,2-tri Fluoro-2- (trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxamide;
N- [2- (aminocarbonyl) -4-cyano-6-methylphenyl] -1- (3-chloro-2-pyridinyl) -3- [1,1,2-trifluoro-2- (trifluoromethoxy) ) Ethoxy] -1H-pyrazole-5-carboxamide; and 1- (3-chloro-2-pyridinyl) -N- [4-cyano-2-[(ethylamino) carbonyl] -6-methylphenyl] -3- The compound of claim 1 selected from the group consisting of [1,1,2-trifluoro-2- (trifluoromethoxy) ethoxy] -1H-pyrazole-5-carboxamide.   A biologically effective amount of the compound of claim 1 and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, optionally a biological A composition for controlling invertebrate pests, which may further comprise a pharmaceutically effective amount of at least one additional biologically active compound or agent.   At least one additional biologically active compound or agent is pyrethroid, carbamate, neonicotinoid, neuronal sodium channel blocker, insecticidal macrocyclic lactone, γ-aminobutyric acid (GABA) antagonist, insecticidal urea And a juvenile hormone mimic, a member of Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, and a pesticide selected from the group consisting of naturally occurring or genetically modified virus insecticides The composition according to claim 14.   At least one additional biologically active compound or agent is abamectin, acephate, acetamiprid, acetoprole, amidoflumet (S-1955), avermectin, azadirachtin, azinephos-methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, Carbofuran, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chrome aphenozide, clothianidin, cyfluthrin, β-cyfluthrin, cyhalothrin, λ-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, diflubenone Dimethoate, dinotefuran, geophenolane, emamectin, endosulfan, esfenvalerate, ethiprole, Phenoticarb, phenoxycarb, fenpropatoline, fenvalerate, fipronil, flonicamid, flucitrinate, τ-fulvalinate, flufenerim (UR-50701), flufenoxuron, γ-cyhalothrin, halofenozide, hexaflumuron, imidacloprid, indoxa Carb, isofenphos, rufenuron, malathion, metaldehydride, methamidophos, methidathion, methomyl, metoprene, methoxychlor, methoxyphenozide, methofluthrin, monocrotophos, methoxyphenozide, nobarulone, nobiflumuron (XDE-007), oxamyl, parathion, parathion, methyl Hosalon, Phosmet, Phosfamidon, Pirimicarb, Profenofos, Proflutri , Protrifen bute, pymetrozine, pyridalyl, pyriproxyfen, rotenone, S1812 (valent), spinosad, spiromesifen (BSN2060), sulprophos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorbinphos, thiacloprid, thiamethoxam, Thiodicarb, thiosultap-sodium, tolfenpyrad, tolomethrin, trichlorfone, triflumulone, aldicarb, phenamiphos, amitraz, chinomethionate, chlorobenzilate, cyhexatin, dicohol, dienochlor, ethoxazole, phenazaquin, fenbutatin oxide, fenpyroxipyr , Bacillus Thuring Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis delta endotoxin, insect pathogen, baculovirus, baculovirus 15. A composition according to claim 14 selected from the group consisting of molds.   At least one additional biologically active compound or agent is cypermethrin, cyhalothrin, cyfluthrin and β-cyfluthrin, esfenvalerate, fenvalerate, tralomethrin, phenothicarb, methomyl, oxamyl, thiodicarb, acetamiprid, clothianidin, imidacloprid, Thiamethoxam, thiacloprid, indoxacarb, spinosad, abamectin, avermectin, emamectin, endosulfan, etiprole, fipronil, flufenoxuron, triflumuron, diophenolan, pyriproxyfen, pymetrozine, amitraz, bacillus thuringiensis isawas Bacillus thuringiensis Kurusutaki (Bacillus thuringiensis kurstaki), Bacillus thuringiensis (Bacillus thuringiensis) composition according to claim 16 which is selected from the group consisting of delta endotoxin as well as Shokuchu resistant fungi.   15. A composition according to claim 14 in the form of a soil drench liquid formulation. A spray composition for controlling invertebrate pests comprising (a) a biologically effective amount of the compound of claim 1 or the composition of claim 14 and (b) a propellant. (A) a biologically effective amount of the compound of claim 1 or the composition of claim 14;
(B) one or more food ingredients,
A feed composition for controlling invertebrate pests comprising (c) an attractant optionally and (c) optionally a humectant. (A) the feed composition of claim 20, and (b) a housing configured to receive the feed composition, wherein an invertebrate pest approaches the feed composition from a location outside the housing. The housing has at least one aperture sized to allow the invertebrate pest to pass through the aperture, and the housing is a potential or known active location of the invertebrate pest or its An invertebrate pest control trap apparatus comprising a housing further configured to be disposed in the vicinity.   A method of controlling an invertebrate pest comprising contacting an invertebrate pest or its environment with a biologically effective amount of the compound of claim 1.   A method for controlling an invertebrate pest comprising contacting an invertebrate pest or its environment with the composition of claim 14.   24. The method of claim 23, wherein the environment is soil and the composition is applied to the soil as a soil drench formulation.   A method for controlling cockroaches, ants or termites comprising contacting cockroaches, ants or termites with the feed composition in the trap device of claim 21.   21. The mosquito, buoy, horn fly, hornfly, ab, large wasp, yellow jack, hornet, tick, spider, ant or gnat are dispensed from the spray container. Control of mosquitoes, flyfish, horn flies, crabs, abs, large wasps, yellow jacks, hornets, ticks, spiders, ants or gnats, comprising contacting with a spray composition Method.