CN112679467B - Heterocyclic substituted bicyclic ring Azole pesticides - Google Patents

Abstract

The present application relates to heterocycle substituted bicyclic azole pesticides, and discloses compounds of formula 1, N-oxides or salts thereof, wherein Q is Q-2, and A, R ¹、m、X¹、X²、X³、X⁴ and Y ² are as defined in the disclosure. Also disclosed are compositions comprising the compounds of formula 1, and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the application.

Description

Heterocyclic substituted bicyclazole pesticides

This application is a divisional application of Chinese patent application No. 201580079769.X, filed on September 15, 2016, with the invention name “Heterocyclic substituted bicyclic azole pesticidal agent”.

Technical Field

The present invention is directed to certain substituted bicyclazoles, N-oxides, salts and compositions thereof suitable for agricultural and non-agricultural use, and methods of using the same for controlling invertebrate pests such as arthropods in agronomic and non-agricultural settings.

Background Art

Controlling invertebrate pests is extremely important in achieving high crop efficiency. Invertebrate pests can cause a significant reduction in production to the damage of growing and stored crops, and thus cause an increase in cost for consumers. Controlling invertebrate pests in forestry, greenhouse crops, ornamental plants, nursery crops, stored food and fiber products, livestock, family, turf, wood products and public and animal health is also important. For these purposes, many products are commercially available, but there is a continuous need for more effective, lower cost, lower toxicity, safer to the environment or novel compounds with different sites of action.

Summary of the invention

The present invention is directed to compounds of formula 1 (including all geometric isomers and stereoisomers), N-oxides and salts thereof, and compositions comprising them, and their use for controlling invertebrate pests:

in

Q is

A is CH, CR ¹ or N;

each R ¹ is independently halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio or C ₁ -C ₄ haloalkylthio;

m is 0, 1, 2, or 3;

X ¹ , X ² , X ³ and X ⁴ are each independently CR ² , CR ³ or N, provided that (i) one of X ¹ , X ² , X ³ and X ⁴ is CR ² , and (ii) no more than one of X ¹ , X ² , X ³ and X ⁴ is N;

R ² is C(=Z)NR ⁶ R ⁷ , N(R ⁸ )C(=Z)R ⁹ , C(=NR ¹⁰ )R ¹¹ or Q ^a ;

each Z is independently O or S;

each R ³ is independently H, halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

Y ¹ is O, S or NR ⁴ ;

Y ² is N or CR ^5a ;

Y ³ is N or CR ^5b ;

R ⁴ is H or C ₁ -C ₄ alkyl;

R ^5a is H, halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

R ^5b is H, halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

R ⁶ is H, NR ¹⁵ R ¹⁶ , OR ¹⁷ , C(═NR ¹⁰ )R ¹¹ , C(O)OR ²¹ , C(O)NR ¹⁵ R ¹⁶ , C(O)R ²² , S(O) _n R ²³ or Q ^b ; or is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted by at least one R ^x ;

R ⁷ is H or Q ^b ; or C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted by at least one R ^x ; or

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

R ⁶ and R ⁷ taken together represent =S(O) _p R ¹⁸ R ¹⁹ or =S(=NR ²⁰ )R ¹⁸ R ¹⁹ ;

each R ^x is independently halogen, cyano, nitro, hydroxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, C _{1 -C 6 haloalkoxy, C 3 -C 6 cycloalkoxy ,} C(═NR ¹⁰ )R ¹¹ , C(O)OR ²¹ , C(O)NR ¹⁵ R ¹⁶ , OC(O)R ²² , NR ²⁵ R ²⁶ , NR ²⁴ C(O)R ²² , C(O)R ²² , S(O) _n R ²³ , Si(R ²⁸ ) ₃ , OSi(R ²⁸ ) ₃ , or Q ^b ;

R ⁸ is H, C(O)OR ²¹ , C(O)NR ¹⁵ R ¹⁶ , C(O)R ²² , S(O) _n R ²³ or Q ^b ; or is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted by at least one R ^x ;

R ⁹ is H, C(＝NR ¹⁰ )R ¹¹ , OR ²¹ or NR ¹⁵ R ¹⁶ ; or C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted by at least one R ^x ; or phenyl, phenoxy or a 5- or 6-membered heterocyclic aromatic ring, each of which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ -haloalkoxy; or a 3- to 6-membered heterocyclic non-aromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms, the heteroatoms being independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 1 carbon atom ring member is independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O) or S(O) ₂ , each ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each R ¹⁰ is independently OR ¹² , S(O) _n R ¹³ or NHR ¹⁴ ;

each R ¹¹ is independently H; or C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted by at least one R ^x ; or C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₃ -C ₆ cycloalkoxy, C(O)OR ²¹ , C(O)NR ¹⁵ R ¹⁶ , NR ²⁵ R ²⁶ , NR ²⁴ C(O)R ²² , C(O)R ²² or Q ^b ;

Each R ¹² is independently C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C(O)R ²² , S(O) _n R ¹³ or Q ^b ;

Each R ¹³ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

R ¹⁴ is C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C(O)R ²² or C(O)OR ²¹ ; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each R ¹⁵ is independently H, C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, C(O)R ²⁷ or S(O) ₂ R ²⁷ ; or is phenyl or a 5- or 6-membered heterocyclic aromatic ring, each of which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ¹⁶ is independently H, C ₁ -C ₆ alkyl or C ₁ -C ₄ haloalkyl; or

R ¹⁵ and R ¹⁶ together with the nitrogen atom to which they are attached form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms, said heteroatoms being independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

R ¹⁷ is C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl or C ₁ -C ₄ haloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C _{1 -C 4 haloalkyl, C 1 -C 4 alkoxy and} C ₁ -C ₄ haloalkoxy;

Each R ¹⁸ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ¹⁹ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy; or

R ¹⁸ and R ¹⁹ together with the sulfur atom to which they are attached form a ring;

R ²⁰ is H, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C(O)R ²² ; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²¹ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ halocycloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²² is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ halocycloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²³ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₆ cycloalkylalkyl or C ₃ -C ₆ halocycloalkylalkyl; or is phenyl, which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²⁴ is independently C ₁ -C ₄ alkyl;

Each R ²⁵ is independently H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²⁶ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy; or

R ²⁵ and R ²⁶ independently together with the nitrogen atom to which they are attached form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms, the heteroatoms being independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , the ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each R ²⁷ is independently C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy or NR ²⁹ R ³⁰ ; or is phenyl or a 5- or 6-membered heterocyclic aromatic ring, each of which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²⁸ is independently C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl or phenyl;

each R ²⁹ is independently H or Q ^b ; or is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each R ³⁰ is independently H or Q ^b ; or is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy; or

R ²⁹ and R ³⁰ together with the nitrogen atom to which they are attached form a 3- to 10-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , said ring being unsubstituted or substituted with up to 4 substituents independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

^Qa is a 5- to 10-membered aromatic ring or ring system, each ring or ring system containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 3 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , each ring or ring system is unsubstituted or substituted with at least one ^Rx ; or a 3- to 6-membered partially saturated ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , each ring is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each Q ^b is independently phenyl, a 5- or 6-membered heterocyclic aromatic ring or a 3- to 6-membered heterocyclic non-aromatic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , each ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each n is independently 0, 1 or 2; and

p is 1 or 2.

The present invention also provides a composition comprising a compound of formula 1, an N-oxide or salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent. In one embodiment, the present invention also provides a composition for controlling invertebrate pests, comprising a compound of formula 1, an N-oxide or salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent, and the composition optionally further comprises at least one additional biologically active compound or agent.

The present invention further provides a spray composition for controlling invertebrate pests, the spray composition comprising a compound of formula 1, its N-oxide or salt, or the above composition and a propellant. The present invention also provides a bait composition for controlling invertebrate pests, the bait composition comprising a compound of formula 1, its N-oxide or salt, or the composition described in the above embodiments, one or more food materials, optionally an attractant, and optionally a humectant.

The present invention also provides a capturing device for controlling invertebrate pests, the capturing device comprising the bait composition and a shell adapted to receive the bait composition, wherein the shell has at least one opening sized to allow the invertebrate pest to pass through the opening so that the invertebrate pest can approach the bait composition from a position outside the shell, and wherein the shell is further adapted to be placed in or near a location of potential or known activity of the invertebrate pest.

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

The present invention also provides a method for protecting seeds from invertebrate pests, the method comprising contacting the seeds with a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof (e.g., as a composition described herein). The present invention also relates to treated seeds. The present invention also provides a method for protecting animals from invertebrate parasitic pests, the method comprising applying a parasiticidal effective amount of a compound of formula 1, an N-oxide or a salt thereof (e.g., as a composition described herein) to the animal. The present invention also provides the use of a compound of formula 1, an N-oxide or a salt thereof (e.g., as a composition described herein) in protecting animals from invertebrate pests.

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

DETAILED DESCRIPTION

As used herein, the terms "comprising," "including," "including," "having," "containing," "containing," "characterized by," or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any expressly specified limitation. For example, a composition, mixture, process, or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, or method.

The transitional phrase "consisting of" excludes any unrecited element, step, or ingredient. If in a claim, such a phrase would render the claim closed-ended so that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause in the body of a claim, rather than immediately following the preamble, it is limited only to the elements mentioned in that clause; other elements are not excluded from the claim as a whole.

The transitional phrase "consisting essentially of is used to qualify compositions or methods that include materials, steps, features, components, or elements in addition to those literally disclosed, provided that such additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of" is intermediate between "comprising" and "consisting of."

When the applicant has defined the present invention or a portion thereof using open-ended terms such as "comprising," it should be readily understood that (unless otherwise indicated) the specification should be interpreted as also describing the invention using the terms "consisting essentially of" or "consisting of."

In addition, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not to an exclusive "or". For example, condition A or B is satisfied by any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

Likewise, the indefinite article "a/an" before an element or component of the present invention is intended to be non-restrictive with respect to the number of instances (i.e., occurrences) of the element or component. Therefore, "a/an" should be understood to include one/a or at least one/a, and the singular word form of an element or component also includes the plural, unless the value clearly means the singular.

As mentioned in the present disclosure, the term "invertebrate pests" includes arthropods, gastropods, nematodes and worms that are economically important as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, ball woodlice and symphylans. The term "gastropod" includes snails, slugs and other stalked eyes. The term "nematodes" includes members of the phylum Nematoda, such as plant-eating nematodes and worm nematodes that parasitize animals. The term "worms" includes all parasites, such as roundworms (phylum Nematoda), heartworms (phylum Nematoda, cytopathogenes), flukes (phylum Platyhelminthes, class Trematoda), acanthocephala (phylum Acanthocephala) and tapeworms (phylum Platyhelminthes, class Cestoda).

In the context of the present disclosure, "invertebrate pest control" refers to the inhibition of invertebrate pest development (including mortality, feeding reduction, and/or mating disruption), and related expressions are defined in a similar manner.

The term "agronomy" refers to the production of field crops, e.g., for food and fiber, and includes the growing of maize or corn, soybeans and other legumes, rice, cereals (e.g., wheat, oats, barley, rye, and rice), leafy vegetables (e.g., lettuce, cabbage and other brassicas), fruiting vegetables (e.g., tomatoes, peppers, eggplant, crucifers, and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone, and citrus), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola, sunflower, and olives).

The term "nonagriculture" refers to applications other than field crops, such as horticultural crops (e.g., greenhouse, nursery, or ornamental plants not grown in the field), residential, agricultural, commercial, and industrial structures, turf (e.g., pastures, ranches, golf courses, lawns, athletic fields, etc.), wood products, stored products, agroforestry and vegetation management, public health (i.e., humans), and animal health (e.g., domesticated animals such as pets, livestock, and poultry, and non-domesticated animals such as wildlife).

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

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

The position of the variable ^R1 in the structure of Formula 1 is described by the numbering system shown below.

The wavy line in a structural fragment indicates the point at which the fragment is attached to the rest of the molecule. For example, when the variable Q in Formula 1 is defined as Q-1, the wavy line bisecting the bond in Q-1 means that Q-1 is attached to the rest of the structure of Formula 1 at that position, as shown below.

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

combination X ¹ X ² X ³ X ⁴ 1 CR ² CR ³ CR ³ CR ³ 2 CR ² N CR ³ CR ³ 3 CR ² CR ³ N CR ³ 4 CR ² CR ³ CR ³ N 5 CR ³ CR ² CR ³ CR ³ 6 N CR ² CR ³ CR ³ 7 CR ³ CR ² N CR ³ 8 CR ³ CR ² CR ³ N 9 CR ³ CR ³ CR ² CR ³ 10 N CR ³ CR ² CR ³ 11 CR ³ N CR ² CR ³ 12 CR ³ CR ³ CR ² N 13 CR ³ CR ³ CR ³ CR ² 14 N CR ³ CR ³ CR ² 15 CR ³ N CR ³ CR ² 16 CR ³ CR ³ N CR ²

In the above detailed description, the term "alkyl", used alone or in compound words such as "alkylthio" or "haloalkyl", includes straight or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl or different butyl, pentyl, or hexyl isomers. "Alkenyl" includes straight or branched olefins, such as vinyl, 1-propenyl, 2-propenyl and different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes, such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight or branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl and different butynyl, pentynyl and hexynyl isomers. "Alkynyl" may also include a portion consisting of multiple triple bonds, such as 2,5-hexadiynyl.

"Alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy and different butoxy, pentyloxy and hexyloxy isomers. "Alkylthio" includes branched or straight chain alkylthio moieties such as methylthio, ethylthio, and different propylthio, butylthio, pentylthio and hexylthio isomers.

"Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term "halogen", alone or in compound words such as "haloalkyl", or when used in a description such as "alkyl substituted by halogen", includes fluorine, chlorine, bromine or iodine. In addition, when used in compound words such as "haloalkyl", or when used in a description such as "alkyl substituted by halogen", the alkyl group may be partially or completely substituted by halogen atoms (which may be the same or different). Examples of "haloalkyl" or "alkyl substituted by halogen" include F ₃ C-, ClCH ₂ -, CF ₃ CH ₂ - and CF ₃ CCl ₂ -. The terms "halocycloalkyl", "haloalkoxy", "haloalkylthio", "haloalkenyl", "haloalkynyl" and the like are defined similarly to the term "haloalkyl". Examples of "haloalkoxy" include CF ₃ O-, CCl ₃ CH ₂ O-, HCF ₂ CH ₂ CH ₂ O- and CF ₃ CH ₂ O-. Examples of " _{haloalkylthio} " _{include CCl3S-} , _CF3S- , _CCl3CH2S- and _{ClCH2CH2CH2S- .}

As used herein, the chemical abbreviations S(O) and S(=O) refer to a sulfinyl moiety. As used herein, the chemical abbreviations SO ₂ , S(O) ₂ and S(=O) ₂ refer to a sulfonyl moiety. As used herein, the chemical abbreviations C(O) and C(=O) refer to a carbonyl moiety. As used herein, the chemical abbreviations CO ₂ , C(O)O and C(=O)O refer to an oxycarbonyl moiety. “CHO” refers to a formyl group.

The total number of carbon atoms in a substituent is indicated by a "Ci _{- Cj} " prefix, where i and j are numbers from 1 to 6. For example, _C1 - _C4 alkylsulfonyl represents methylsulfonyl to butylsulfonyl; _C2 alkoxyalkyl represents _CH3OCH2- ; _C3 alkoxyalkyl represents, for example, _{CH3CH ( OCH3 )} -, _CH3OCH2CH2- , or _CH3CH2OCH2- ; and _{C4 alkoxyalkyl} represents the various isomers of alkyl substituted _{with alkoxy groups} containing a total of _{four carbon} atoms, examples _{including CH3CH2CH2OCH2- and CH3CH2OCH2CH2- .}

When a compound is substituted with a substituent with a subscript indicating that the number of substituents may exceed 1, the substituents (when they exceed 1) are independently selected from the defined group of substituents, for example, (R ¹ ) _m , m is 0, 1, 2 or 3. In addition, when the subscript indicates a range, for example (R) _ij , then the number of substituents may be selected from integers between i and j (inclusive). When a group contains a substituent that may be hydrogen, for example R ³ or R ⁴ , then when the substituent is hydrogen, it is recognized that this is equivalent to the group being unsubstituted. When a variable group indicates that it may be optionally attached to a position, for example (R ¹ ) _m , where m may be 0, then hydrogen may be at the position even if not described in the variable group definition. When one or more positions on a group are said to be "not substituted" or "unsubstituted", then hydrogen atoms are attached to occupy any free valences.

Unless otherwise indicated, a "ring" or "ring system" as a component of Formula 1 (e.g., substituent Q ^a ) is carbocyclic or heterocyclic. The term "ring system" means two or more fused rings. The terms "bicyclic system" and "fused bicyclic system" mean a ring system consisting of two fused rings, which may be "single-sided fused", "bridged bicyclic" or "spirobicyclic". A "single-sided fused bicyclic system" means a ring system in which the two constituent rings have two adjacent atoms in common. A "bridged bicyclic system" is formed by bonding segments of one or more atoms to non-adjacent ring members of a ring. A "spirobicyclic system" is formed by bonding segments of two or more atoms to the same ring member of a ring. The term "fused heterobicyclic system" means a fused bicyclic system in which at least one ring atom is not carbon. The term "ring member" refers to an atom or other moiety (e.g., C(=O), C(=S), S(O) or S(O) ₂ ) that forms the skeleton of a ring or ring system.

The terms "carbocyclic ring", "carbocycle" or "carbocyclic ring system" denote a ring or ring system in which the atoms forming the ring backbone are selected exclusively from carbon. The terms "heterocyclic ring", "heterocycle" or "heterocyclic ring system" denote a ring or ring system in which at least one atom forming the ring backbone is not carbon (e.g., nitrogen, oxygen or sulfur). Typically, a heterocycle contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless otherwise indicated, a carbocyclic or heterocyclic ring may be a saturated or unsaturated ring. "Saturated" refers to a ring having a backbone consisting of atoms connected to each other by single bonds; unless otherwise indicated, the remaining valences are occupied by hydrogen atoms. Unless otherwise indicated, an "unsaturated ring" may be partially unsaturated or fully unsaturated. The expression "fully unsaturated ring" means a ring of atoms in which the bonds between the atoms in the ring are single bonds or double bonds according to valence bond theory, and furthermore the bonds between the atoms in the ring include as many double bonds as possible, but without cumulative double bonds (i.e. no C=C=C or C=C=N). The term "partially unsaturated ring" means a ring comprising at least one ring member bonded to an adjacent ring member by a double bond, and conceptually it is possible to accommodate a number of non-cumulative double bonds (i.e., in its fully unsaturated corresponding form) between adjacent ring members that is greater than the number of double bonds present (i.e., in its partially unsaturated form).

Unless otherwise indicated, heterocyclic rings and ring systems may be attached through any available carbon or nitrogen by replacing a hydrogen on said carbon or nitrogen.

"Aromatic" means that each ring atom is substantially in the same plane and has a p-orbital perpendicular to the plane of the ring, and wherein (4n+2) π electrons (where n is a positive integer) are associated with the ring to satisfy Huckel's rule. The term "aromatic ring system" means a carbocyclic or heterocyclic ring system, wherein at least one ring of the ring system is aromatic. When a fully unsaturated carbocyclic ring satisfies Huckel's rule, then the ring is also referred to as an "aromatic ring" or "aromatic carbocyclic ring". The term "aromatic carbocyclic ring system" means a carbocyclic ring system, wherein at least one ring of the ring system is aromatic. When a fully unsaturated heterocyclic ring satisfies Huckel's rule, then the ring is also referred to as a "heteroaromatic ring", "aromatic heterocyclic ring" or "heterocyclic aromatic ring". The term "aromatic heterocyclic ring system" means a heterocyclic ring system wherein at least one ring of the ring system is aromatic. The term "non-aromatic ring system" means a carbocyclic or heterocyclic ring system that may be fully saturated, as well as partially or fully unsaturated, provided that none of the rings in the ring system are aromatic. The term "non-aromatic carbocyclic ring system" denotes a carbocyclic ring in which none of the rings in the ring system is aromatic. The term "non-aromatic heterocyclic ring system" denotes a heterocyclic ring in which none of the rings in the ring system is aromatic.

The term "optionally substituted" in relation to heterocycles refers to a group that is unsubstituted or has at least one non-hydrogen substituent that does not eliminate the biological activity possessed by the unsubstituted analog. As used herein, unless otherwise indicated, the following definitions apply. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un)substituted". Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of one another.

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

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

Example 1

As indicated above, Q ^a can be (especially) 8-, 9- or 10-membered ortho-fused bicyclic ring system, optionally substituted by one or more substituents selected from the group of substituents as defined in the Summary of the Invention. Examples of 8-, 9- or 10-membered ortho-fused bicyclic ring systems optionally substituted by one or more substituents include rings U-81 to U-123 shown in Example 3, wherein R ^v is any substituent as defined for Q ^a in the Summary of the Invention, and r is generally an integer from 0 to 4.

Example 3

Although ^Rvgroup is shown in structure U-1 to U-123, it should be noted that because they are optional substituents, they do not have to exist.It should be noted that when ^Rv is H, when connected to atom, this is as if the atom is unsubstituted.Need to replace to fill the nitrogen-atom of its valence by H or ^RvReplace.It should be noted that when ( ^Rv ) _r and the point of attachment between U group are shown as floating, ( ^Rv ) _r can be connected to any available carbon atom or nitrogen-atom of U group.It should be noted that when the point of attachment on U group is shown as floating, U group can be connected to the remainder of formula 1 via replacement hydrogen atom by any available carbon or nitrogen of U group.It should be noted that some U groups can only be less than 4 ^Rvgroups replace (such as U-2 to U-5, U-7 to U-48 and U-52 to U-61).

A variety of synthetic methods are known in the art that allow the preparation of aromatic and nonaromatic heterocycles and ring systems; for extensive reviews, see the eight-volume set Comprehensive Heterocyclic Chemistry, eds. A. R. Katritzky and C. W. Rees, Pergamon Press, Oxford, 1984, and the twelve-volume set Comprehensive Heterocyclic Chemistry II, eds. A. R. Katritzky, C. W. Rees and E. F. V. Scriven, Pergamon Press, Oxford, 1996.

Compounds of the present invention may exist as one or more stereoisomers. Stereoisomers are isomers with the same composition but different arrangements of their atoms in space, and include enantiomers, diastereomers, cis-trans isomers (also referred to as geometric isomers) and atropisomers. Atropisomers are caused by restricted rotation around a single bond, where the rotation barrier is high enough to allow separation of isomeric species. It will be appreciated by those skilled in the art that a stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to one or more other stereoisomers, or when separated from one or more other stereoisomers. In addition, skilled technicians know how to separate, enrich and/or selectively prepare the stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen's Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

The present invention includes all stereoisomers, conformational isomers and mixtures thereof in all ratios and isotopic forms (such as deuterated compounds).

Those skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides, since nitrogen requires an available lone electron pair to oxidize to an oxide; those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines are capable of forming N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art, including oxidation of heterocycles and tertiary amines using peroxyacids such as peracetic acid and 3-chloroperoxybenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for preparing N-oxides have been extensively described and reviewed in the literature, see, for example: T. L. Gilchrist, Comprehensive Organic Synthesis, Vol. 7, pp. 748-750, S. V. Ley, ed., Pergamon Press; M. Tisler and B. Stanovnik, Comprehensive Heterocyclic Chemistry, Vol. 3, pp. 18-20, A. J. Boulton and A. McKillop, eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene, Advances in Heterocyclic Chemistry, Vol. 43, pp. 149-161, A. R. Katritzky, ed., Academic Press; M. Tisler and B. Stanovnik, Advances in Heterocyclic Chemistry, Vol. 43, pp. 149-161, A. R. Katritzky, ed., Academic Press; Chemistry, Vol. 9, pp. 285-291, A. R. Katritzky and A. J. Boulton, eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk, Advances in Heterocyclic Chemistry, Vol. 22, pp. 390-392, A. R. Katritzky and A. J. Boulton, eds., Academic Press.

Those skilled in the art recognize that, since the salts of compounds are in balance with their corresponding non-salt forms in the environment and under physiological conditions, salts share the biological utility of non-salt forms. Therefore, the salts of the compounds of various formulas 1 can be used to prevent and treat invertebrate pests. The salts of the compounds of formula 1 include acid addition salts with inorganic or organic acids, such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid or valeric acid. When the compound of formula 1 includes an acidic part such as a carboxylic acid or phenol, the salt also includes those formed with an organic or inorganic base, such as pyridine, triethylamine or ammonia, or an amide, hydride, hydroxide or carbonate of sodium, potassium, lithium, calcium, magnesium or barium. Therefore, the present invention includes compounds selected from formula 1, its N-oxide and suitable salts.

Compounds selected from Formula 1, stereoisomers, tautomers, N- compounds and salts thereof are generally present in more than one form, and therefore Formula 1 includes all crystalline and non-crystalline compounds represented by Formula 1. Non-crystalline forms include solid embodiments such as waxes and gums, and liquid embodiments such as solutions and melts. Crystalline forms include embodiments representing substantially single crystal types and embodiments representing mixtures of polymorphs (i.e., different crystalline types). The term "polymorph" refers to a specific crystalline form of a compound that can be crystallized in different crystalline forms, which have different molecular arrangements and/or conformations in the crystal lattice. Although polymorphs may have the same chemical composition, they may also differ in composition due to the presence or absence of co-crystallized water or other molecules, which may be weakly or strongly bound to the crystal lattice. Polymorphs may differ in such chemical, physical, and biological properties, such as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspendability, dissolution rate, and bioavailability. Those skilled in the art will appreciate that polymorphs of compounds represented by Formula 1 may exhibit beneficial effects (e.g., suitability for preparing useful formulations, improved biological performance) relative to another polymorph or mixture of polymorphs of the same compound represented by Formula 1. The preparation and separation of specific polymorphs of compounds represented by Formula 1 may be achieved by methods known to those skilled in the art, including, for example, crystallization using selected solvents and temperatures. The compounds of the present invention may exist as one or more crystalline polymorphs. The present invention includes both individual polymorphs and mixtures of polymorphs, including mixtures enriched in one polymorph relative to the other. For a comprehensive discussion of polymorphism, see Polymorphism in the Pharmaceutical Industry, edited by R. Hilfiker, Wiley-VCH, Weinheim, 2006.

Embodiments of the invention as described in the Summary of the Invention include those described below. In the following Examples, references to "compounds of Formula 1" include the definitions of substituents specified in the Summary of the Invention unless otherwise defined in the Examples.

Embodiment 1. The compound as described in Formula 1, wherein Q is Q-1, Q-2 or Q-3.

Embodiment 2. The compound according to Formula 1, wherein Q is Q-1, Q-2 or Q-3, and Y ³ is CR ^5b .

Embodiment 3. The compound as described in Formula 1, wherein Q is Q-1 or Q-2.

Embodiment 4. The compound as described in Formula 1, wherein Q is Q-1.

Embodiment 5. The compound as described in Formula 1, wherein Q is Q-1, and Y ¹ is O or S.

Embodiment 6. The compound as described in Formula 1, wherein Q is Q-1, and Y ¹ is S.

Embodiment 7. The compound as described in Formula 1, wherein Q is Q-1, and Y ¹ is O.

Embodiment 8. The compound as described in Formula 1, wherein Q is Q-2.

Embodiment 9. The compound according to formula 1, wherein Q is Q-2, and Y ² is CR ^5a .

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

Embodiment 11. The compound as described in Embodiment 10, wherein A is CH, CF or N.

Embodiment 11a. The compound as described in Embodiment 10, wherein A is CF or N.

Embodiment 12. The compound as described in Embodiment 10, wherein A is CH or CF.

Embodiment 13. The compound as described in Embodiment 10, wherein A is CH.

Embodiment 14. The compound as described in Embodiment 10, wherein A is N.

Embodiment 15. A compound of Formula 1 or any one of Embodiments 1-9, wherein m is 1, and R ¹ is C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, or halogen.

Embodiment 16. The compound of Embodiment 15, wherein ^R1 is _CF3 , OMe, Me, or F.

Embodiment 17. The compound of embodiment 16, wherein ^R1 is _CF3 , OMe, Me, or F, and is in the 4-position.

Embodiment 18. The compound as described in Embodiment 17, wherein ^R1 is _CF3 and is in the 4-position.

Embodiment 19. A compound as described in Formula 1 or any one of Embodiments 1-9, wherein m is 0.

Embodiment 20. A compound of Formula 1 or any one of Embodiments 1-19, wherein ^X1 is ^CR2 , and ^X2 , ^X3 , and ^X4 are each independently ^CR3 ; or ^X2 is ^CR2 , and ^X1 , ^X3 , and ^X4 are each independently ^CR3 .

Embodiment 21. The compound of embodiment 20, wherein ^X1 is ^CR2 , and ^X2 , ^X3 and ^X4 are each independently ^CR3 .

Embodiment 22. The compound of embodiment 20, wherein ^X2 is ^CR2 , and ^Xi , ^X3 and ^X4 are each independently ^CR3 .

Embodiment 23. A compound as described in Formula 1 or any one of Embodiments 1-22, wherein each R ³ is independently H or halogen.

Embodiment 24. The compound as described in Embodiment 23, wherein each R ³ is independently H or F.

Embodiment 25. The compound of Embodiment 24, wherein each R ³ is H.

Embodiment 26. A compound according to Formula 1 or any one of Embodiments 1-25, wherein R ² is C(═Z)NR ⁶ R ⁷ , C(═NR ¹⁰ )R ¹¹ , or Q ^a .

Embodiment 27. A compound according to Formula 1 or any one of Embodiments 1-25, wherein R ² is C(═NR ¹⁰ )R ¹¹ .

Embodiment 28. A compound of Formula 1 or any one of Embodiments 1-25, wherein R ² is C(═NR ¹⁰ )R ¹¹ ; R ¹⁰ is C ₁ -C ₄ alkoxy; and R ¹¹ is C ₁ -C ₄ alkyl substituted with S(O) _n R ²³ .

Embodiment 29. A compound as in Formula 1 or any one of Embodiments 1-25, wherein R ² is C(=Z)NR ⁶ R ⁷ or Q ^a .

Embodiment 30. A compound according to Formula 1 or any one of Embodiments 1-25, wherein R ² is C(=Z)NR ⁶ R ⁷ .

Embodiment 31. A compound according to Formula 1 or any one of Embodiments 1-25, wherein R ² is C(=O)NR ⁶ R ⁷ .

Embodiment 32. A compound according to Formula 1 or any one of Embodiments 1-25, wherein R ² is C(=S)NR ⁶ R ⁷ .

Embodiment 33. A compound of Formula 1 or any one of Embodiments 1-25, wherein R ² is C(═O)NR ⁶ R ⁷ ; and R ⁶ is H, C(O)OR ²¹ , C(O)R ²² or C ₁ -C ₆ alkyl.

Embodiment 35. A compound of Formula 1 or any one of Embodiments 1-25, wherein R ² is C(═O)NR ⁶ R ⁷ ; and R ⁶ is H, C(O)OMe, C(O)Me, or methyl.

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

Embodiment 36a. A compound of Formula 1 or any one of Embodiments 1-25, wherein R ² is C(═O)NR ⁶ R ⁷ ; and R ⁶ is C(O)OMe.

Embodiment 36b. A compound as described in Formula 1 or any one of Embodiments 1-25, wherein R ² is C(═O)NR ⁶ R ⁷ ; and R ⁶ is C(O)Me.

Embodiment 36c. A compound of Formula 1 or any one of Embodiments 1-25, wherein R ² is C(═O)NR ⁶ R ⁷ ; and R ⁶ is methyl.

Embodiment 37. A compound according to Formula 1 or any one of Embodiments 1-25, wherein R ² is Q ^a .

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

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

Embodiment 40. The compound of Embodiment 39, wherein the heteroaromatic ring is a 5-membered heteroaromatic ring.

Embodiment 41. The compound as described in Embodiment 40, wherein the heteroaromatic ring is a 5-membered heteroaromatic ring with a nitrogen atom at the 2-position.

Embodiment 42. The compound as described in Embodiment 39, wherein the heteroaromatic ring is a 6-membered heteroaromatic ring.

Embodiment 43. The compound as described in Embodiment 42, wherein the heteroaromatic ring is a 6-membered heteroaromatic ring with a nitrogen atom at the 2-position.

Embodiment 44. The compound as described in Embodiment 43, wherein the heteroaromatic ring is a 6-membered heteroaromatic ring having a nitrogen atom at the 2-position and substituted with a C ₁ -C ₄ haloalkyl group.

Embodiment 45. The compound as described in Embodiment 44, wherein the heteroaromatic ring is a 6-membered heteroaromatic ring having a nitrogen atom at the 2-position and substituted with _CF3 .

The embodiments of the present invention, including the above embodiments 1-45 and any other embodiments described herein, can be combined in any manner, and the description of the variables in the embodiments relates not only to the compounds of Formula 1, but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. In addition, the embodiments of the present invention, including the above embodiments 1-45 and any other embodiments described herein and any combination thereof, relate to the compositions and methods of the present invention.

The combination of Examples 1-45 is shown below:

Embodiment A. A compound as described in Formula 1, wherein

^X1 or ^X2 is ^CR2 .

Embodiment B. The compound as described in Embodiment A, wherein

Q is Q-1 or Q-2.

Embodiment C. The compound as described in Embodiment B, wherein

Q is Q-1; and

^Y1 is O or S.

Embodiment D. The compound as described in Embodiment C, wherein

Q is Q-2; and

^Y2 is ^CR5a .

Embodiment E. A compound as described in any one of Embodiments A-D, wherein

A is CH or CF; and

m is 0.

Embodiment F. A compound as described in Formula 1, wherein

A is CH or CF;

m is 0;

Q is Q-2;

Y ² is CR ^5a ;

^X1 is ^CR2 , and ^X2 , ^X3 and ^X4 are each CH; or ^X2 is ^CR2 , and ^X1 , ^X3 and ^X4 are CH; ^R2 is C(=Z) ^NR6R7 or ^{Qa .}

Embodiment G. A compound as described in Formula 1, wherein

A is CH or CF;

m is 0;

Q is Q-2;

Y ² is CR ^5a ;

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

^R2 is C(= ^{Z)NR6R7 or Qa} .

Embodiment H. A compound as described in Formula 1, wherein

A is CH or CF;

m is 0;

Q is Q-2;

Y ² is CR ^5a ;

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

^R2 is C(= ^{Z)NR6R7 or Qa} .

Embodiment 1. The compound as described in formula 1, wherein

A is CH;

m is 0;

Q is Q-2;

Y ² is CR ^5a ;

R ^5a is H;

^X1 is ^CR2 , and ^X2 , ^X3 and ^X4 are each CH; or ^X2 is ^CR2 , and ^X1 , ^X3 and ^X4 are CH; ^R2 is C(O) ^NR6R7 ; ^and

^R6 is H.

Embodiment J. A compound as described in Formula 1, wherein

A is CH;

m is 0;

Q is Q-2;

Y ² is CR ^5a ;

R ^5a is H;

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

^R2 is C(O) ^{NR6R7 ;} and

^R6 is H.

Embodiment K. A compound as described in Formula 1, wherein

A is CH;

m is 0;

Q is Q-2;

Y ² is CR ^5a ;

R ^5a is H;

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

^R2 is C(O) ^{NR6R7 ;} and

^R6 is H.

The combination of Examples 1-45 is shown below:

Embodiment A1. A compound of formula 1, wherein

Q is Q-2;

A is CH, CR ¹ or N;

each R ¹ is independently halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio or C ₁ -C ₄ haloalkylthio;

m is 0 or 1;

X ¹ , X ² , X ³ and X ⁴ are each independently CR ² , CR ³ or N, provided that (i) one of X ¹ , X ² , X ³ and X ⁴ is CR ² , and (ii) no more than one of X ¹ , X ² , X ³ and X ⁴ is N;

R ² is C(=Z)NR ⁶ R ⁷ , N(R ⁸ )C(=Z)R ⁹ , C(=NR ¹⁰ )R ¹¹ or Q ^a ;

each Z is independently O or S;

each R ³ is independently H, halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

Y ² is N or CR ^5a ;

R ^5a is H, halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

R ⁶ is H, NR ¹⁵ R ¹⁶ , OR ¹⁷ , C(=NR ¹⁰ )R ¹¹ , C(O)OR ²¹ , C(O)NR ¹⁵ R ¹⁶ , C(O)R ²² , S(O) _n R ²³ or Q ^b ; or

C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted with at least one R ^x ;

R ⁷ is H or Q ^b ; or C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted by at least one R ^x ; or

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

R ⁶ and R ⁷ taken together represent =S(O) _p R ¹⁸ R ¹⁹ or =S(=NR ²⁰ )R ¹⁸ R ¹⁹ ;

each R ^x is independently halogen, cyano, nitro, hydroxy, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, C _{1 -C 6 haloalkoxy, C 3 -C 6 cycloalkoxy ,} C(═NR ¹⁰ )R ¹¹ , C(O)OR ²¹ , C(O)NR ¹⁵ R ¹⁶ , OC(O)R ²² , NR ²⁵ R ²⁶ , NR ²⁴ C(O)R ²² , C(O)R ²² , S(O) _n R ²³ , Si(R ²⁸ ) ₃ , OSi(R ²⁸ ) ₃ , or Q ^b ;

R ⁸ is H, C(O)OR ²¹ , C(O)NR ¹⁵ R ¹⁶ , C(O)R ²² , S(O) _n R ²³ or Q ^b ; or is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted by at least one R ^x ;

R ⁹ is H, C(＝NR ¹⁰ )R ¹¹ , OR ²¹ or NR ¹⁵ R ¹⁶ ; or C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted by at least one R ^x ; or phenyl, phenoxy or a 5- or 6-membered heterocyclic aromatic ring, each of which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ -haloalkoxy; or a 3- to 6-membered heterocyclic non-aromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms, the heteroatoms being independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 1 carbon atom ring member is independently selected from C(=O) and C(=S), and the sulfur atom ring member is selected from S, S(O) or S(O) ₂ , each ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each R ¹⁰ is independently OR ¹² , S(O) _n R ¹³ or NHR ¹⁴ ;

each R ¹¹ is independently H; or C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted by at least one R ^x ; or C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₃ -C ₆ cycloalkoxy, C(O)OR ²¹ , C(O)NR ¹⁵ R ¹⁶ , NR ²⁵ R ²⁶ , NR ²⁴ C(O)R ²² , C(O)R ²² or Q ^b ;

Each R ¹² is independently C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C(O)R ²² , S(O) _n R ¹³ or Q ^b ;

Each R ¹³ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl;

R ¹⁴ is C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C(O)R ²² or C(O)OR ²¹ ; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each R ¹⁵ is independently H, C ₁ -C ₆ alkyl, C ₁ -C ₄ haloalkyl, C(O)R ²⁷ or S(O) ₂ R ²⁷ ; or is phenyl or a 5- or 6-membered heterocyclic aromatic ring, each of which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ¹⁶ is independently H, C ₁ -C ₆ alkyl or C ₁ -C ₄ haloalkyl; or

R ¹⁵ and R ¹⁶ together with the nitrogen atom to which they are attached form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms, said heteroatoms being independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

R ¹⁷ is C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl or C ₁ -C ₄ haloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C _{1 -C 4 haloalkyl, C 1 -C 4 alkoxy and} C ₁ -C ₄ haloalkoxy;

Each R ¹⁸ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ¹⁹ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy; or

R ¹⁸ and R ¹⁹ together with the sulfur atom to which they are attached form a ring;

R ²⁰ is H, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl or C(O)R ²² ; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²¹ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ halocycloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²² is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₆ halocycloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²³ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C ₃ -C ₆ cycloalkylalkyl or C ₃ -C ₆ halocycloalkylalkyl; or is phenyl, which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²⁴ is independently C ₁ -C ₄ alkyl;

Each R ²⁵ is independently H, C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²⁶ is independently C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl; or is phenyl, which is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy; or

R ²⁵ and R ²⁶ independently together with the nitrogen atom to which they are attached form a 3- to 7-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms, the heteroatoms being independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , the ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each R ²⁷ is independently C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy or NR ²⁹ R ³⁰ ; or is phenyl or a 5- or 6-membered heterocyclic aromatic ring, each of which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

Each R ²⁸ is independently C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl or phenyl;

each R ²⁹ is independently H or Q ^b ; or is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each R ³⁰ is independently H or Q ^b ; or is C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, each of which is unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy; or

R ²⁹ and R ³⁰ together with the nitrogen atom to which they are attached form a 3- to 10-membered ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , said ring being unsubstituted or substituted with up to 4 substituents independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

^Qa is a 5- to 10-membered aromatic ring or ring system, each ring or ring system containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 3 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , each ring or ring system is unsubstituted or substituted with at least one ^Rx ; or a 3- to 6-membered partially saturated ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(=O) and C(=S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , each ring is unsubstituted or substituted by at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each Q ^b is independently phenyl, a 5- or 6-membered heterocyclic aromatic ring or a 3- to 6-membered heterocyclic non-aromatic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), and the sulfur atom ring members are selected from S, S(O) or S(O) ₂ , each ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy and C ₁ -C ₄ haloalkoxy;

each n is independently 0, 1 or 2; and

p is 1 or 2.

Embodiment B1. The compound as described in Embodiment A1, wherein

^R2 is C(= ^{O)NR6R7 or Qa} .

Embodiment C1. The compound as described in Embodiment B1, wherein

^X1 is ^CR2 , and ^X2 , ^X3 and ^X4 are each independently ^CR3 ; or ^X2 is ^CR2 , and ^X1 , ^X3 and ^X4 are each independently ^CR3 ; and

^Qa is a 5- or 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 3 nitrogen atoms, each ring being unsubstituted or substituted with at least one ^Rx .

Embodiment D1. The compound as described in Embodiment C1, wherein

A is CH or CR ¹ ; and

Each R ¹ is independently halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio.

Embodiment E1. The compound as described in Embodiment D1, wherein

A is CH or CR ¹ ; and

Each R ¹ is independently cyano, F, CH ₃ , OCH ₃ or SCH ₃ .

Embodiment F1. A compound as described in Embodiment E1, wherein

m is 0; and

A is CH or CF.

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

N-(1-methylethyl)-2-(3-pyridyl)-2H-indazole-4-carboxamide (Compound 8);

N-cyclopropyl-2-(3-pyridyl)-2H-indazole-4-carboxamide (Compound 14);

N-cyclohexyl-2-(3-pyridyl)-2H-indazole-4-carboxamide (Compound 16);

2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide (Compound 19);

2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carboxamide (Compound 41);

2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylic acid methyl ester (Compound 42);

N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridyl)-2H-indazole-5-carboxamide (Compound 51);

N-(2,2-difluoropropyl)-2-(3-pyridyl)-2H-indazole-5-carboxamide (Compound 54);

2-(3-pyridinyl)-N-(2-pyrimidinylmethyl)-2H-indazole-5-carboxamide (Compound 55); and

N-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide (Compound 76).

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

Compound 19;

Compound 42;

Compound 55;

Compound 345;

Compound 348;

Compound 636;

Compound 644;

Compound 645;

Compound 647;

Compound 648;

Compound 658;

Compound 683;

Compound 684;

Compound 685;

Compound 686;

Compound 736;

Compound 804;

Compound 818;

Compound 819;

Compound 826;

Compound 836;

Compound 839;

Compound 843;

Compound 844;

Compound 855; and

Compound 865.

Notably, the compounds of the invention are characterized by favorable metabolism and/or soil residue patterns and exhibit activity against a broad spectrum of agronomic and non-agronomic invertebrate pests.

It is particularly noteworthy that, due to the invertebrate pest control spectrum and economic importance, protecting crops from damage or injury caused by invertebrate pests by controlling invertebrate pests is an embodiment of the present invention. The compounds of the present invention also protect leaves or other plant parts that are not in direct contact with the compound of Formula 1 or a composition comprising the compound due to their favorable translocation characteristics or systemic properties in plants.

Also noteworthy as an embodiment of the present invention is a composition comprising a compound as described in any of the preceding embodiments, as well as any other embodiments described herein and any combination thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent, optionally further comprising at least one additional biologically active compound or agent.

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

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

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

Embodiments of the invention also include methods for protecting seeds from invertebrate pests comprising contacting the seeds with a biologically effective amount of a compound as described in any of the preceding embodiments.

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

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

The present invention also relates to methods wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1, an N-oxide or salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent, with the proviso that these methods are not methods of medical treatment of the human or animal body by therapy.

Compounds of formula 1 can be prepared by one or more of the following methods and variations as described in Schemes 1-13. Unless otherwise indicated, the definitions of substituents in the compounds of formulas 1-23 below are as defined above in the Summary of the Invention. Compounds of formulas 1a-1g are different subsets of compounds of formula 1, and all substituents of formulas 1a-1g are as defined above for formula 1. The following abbreviations are used: THF is tetrahydrofuran, DMF is N,N-dimethylformamide, NMP is N-methylpyrrolidone, Ac is acetate, MS is mesylate, Tf is trifluoromethanesulfonate, and Nf is perfluorobutanesulfonate.

Compounds of Formula 1a (Formula 1 wherein Q is Q-1, Q-3 or Q-4) can be prepared as shown in Scheme 1 by coupling a heterocyclic compound of Formula 2 (wherein LG is a suitable leaving group such as Cl, Br, I, Tf or Nf) with a heterocyclic compound of Formula 3 (wherein M is a suitable metal or metalloid such as Mg, Zn or B species) in the presence of a catalyst and a suitable ligand. The catalyst may be composed of a transition metal such as Pd (e.g., Pd(OAc) ₂ or Pd ₂ (dba) ₃ and a mono- or bidentate ligand such as PPh ₃ , PCy ₃ , Pt-Bu ₃ , 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl, 4,5-bisdiphenylphosphino-9,9-dimethylxanthene, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl and 1,1'-bis(diphenylphosphino)ferrocene. Typical bases used include carbonates such as sodium carbonate or cesium carbonate, phosphates such as potassium triphosphate, amines such as ethyldiisopropylamine, or alkoxides such as sodium tert-butoxide. Typical solvents include THF, dioxane, toluene, ethanol, DMF, water or mixtures thereof. Typical reaction temperatures range from ambient temperature to the boiling point of the solvent.

Solution 1

Compounds of Formula 1a (Formula 1 wherein Q is Q-1, Q-3 or Q-4) can also be prepared by coupling compounds of Formula 4 with compounds of Formula 5 (wherein LG is a suitable leaving group such as Cl, Br, I, Tf or Nf) in the presence of a catalyst and a suitable ligand as shown in Scheme 2. Various catalysts can be used in the method of Scheme 2, and these catalysts can be generated from transition metal species such as copper or Pd (e.g., complexes such as Pd(OAc) ₂ or Pd ₂ (dba) ₃ ) and ligands. Typical ligands can be monodentate or bidentate, and include PPh ₃ , PCy ₃ , Pt-Bu ₃ , 2-dicyclohexylphospho-2,4,6-triisopropylbiphenyl, 4,5-bisdiphenylphosphino-9,9-dimethylxanthene, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl and 1,1'-bis(diphenylphosphino)ferrocene. Typical bases used include carbonates such as sodium carbonate or cesium carbonate, phosphates such as potassium triphosphate, amines such as ethyl diisopropylamine, or alkoxides such as sodium tert-butoxide. Additives such as molecular sieves, _Bu4N ^{+ Br-} or copper salts or silver salts (e.g., AgOAc) can be beneficial. Typical reaction solvents include THF, dioxane, toluene, ethanol, DMF, water or mixtures thereof. Typical reaction temperatures are in the range from ambient temperature to the boiling point of the solvent. For example, see Chemical Communications 2011, 47(17), pp. 5043-5045; Journal of the American Chemical Society 2010, 132(11), pp. 3674-3675; Heterocycles 2011, 83(6), pp. 1371-1376; U.S. Patent Application Publication 20090076266; Bulletin of the Chemical Society of Japan 1998, 71(2), pp. 467-473; Tetrahedron Letters 2008, 49(10), pp. 1598-1600; and Tetrahedron Letters 2010, 51(42), pp. 5624-5627.

Solution 2

Compounds of formula 2 wherein LG is a halogen can be prepared from the corresponding amine by treatment with an ON ⁺ source such as isoamyl nitrite or tert-butyl nitrite or nitrous acid in the presence of a halogen source such as _CuBr2 or _BnNEt3 ^{+ Br-} . Preferred reaction conditions include aqueous or organic solvents such as THF or acetonitrile, and reaction temperatures ranging from 0°C to the boiling point of the solvent.

Compounds of formula 2 wherein LG is Cl or Br can also be prepared from the corresponding hydroxy compounds by treatment with a halogenating agent such as POCl ₃ , PCl ₅ , PBr ₃ or SOCl _2. Compounds of formula 2 wherein LG is OMS or OTf can also be prepared from the corresponding hydroxy compounds by treatment with MsCl or Tf ₂ O.

Compounds of formula 4 can be prepared from the corresponding amine compounds by treatment with an ON ⁺ source such as isoamyl nitrite or tert-butyl nitrite. Preferred reaction conditions include ethereal solvents such as THF at temperatures ranging from ambient temperature to the boiling point of the solvent.

Compounds of formula 6 can be prepared by electrophilic halogenation of the corresponding compounds of formula 7 by treatment with a halogenating agent such as N-bromosuccinimide in a suitable solvent such as DMF, NMP or acetic acid at temperatures ranging from ambient temperature up to the boiling point of the solvent (Scheme 3).

Solution 3

2-Aminobenzothiazoles of formula 8 can be prepared from ortho-unsubstituted anilines of formula 9 and thiocyanate anions (wherein M is K ⁺ , Na ⁺ or _Bu4N ⁺ ) as shown in Scheme 4. The reaction can be carried out in a single step in, for example, acetic acid, or via an intermediate thiourea followed by oxidation. Suitable oxidizing agents include bromine.

Solution 4

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

Solution 5

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

The compound of formula 1c can be prepared from the compound of formula 11 by the method shown in Scheme 6 in the presence of a copper (II) catalyst such as Cu (OAc) ₂ or CuBr ₂ via oxidation of the compound of formula 11 with molecular oxygen or a peroxide such as tert-butyl hydroperoxide. Typical reaction conditions include an alcohol solvent such as tert-amyl alcohol, DMF, NMP or ammonia, and a reaction temperature of from 60 ° C to the boiling point of the solvent.

Solution 6

2-aminoazo compounds of Formula 11 can be prepared by reaction of aniline of Formula 9 with diazonium salt of Formula 12 by methods known in the art (see, e.g., March, J., Advanced Organic Chemistry, Wiley, 1992, pp. 525-526). Compounds of Formula 11 can also be prepared by reaction of aryl nitroso compounds of Formula 13 with diamines of Formula 14 in a solvent such as acetic acid. These two methods are shown in Scheme 7.

Solution 7

Compounds of formula 1d can be prepared by condensation of compounds of formula 14 (wherein Lg is a suitable leaving group such as Cl or Br) with aminopyridine or aminodiazine of formula 16, as shown in Scheme 8. Typical reaction conditions include alcoholic solvents such as ethanol or toluene, and reaction temperatures ranging from ambient temperature to the boiling point of the solvent. The pyridine nitrogen can be optionally protected as a _BH3 adduct, an N-oxide, or a 2- or 6-halopyridine derivative.

Solution 8

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

Solution 9

Compounds of formula 1e can also be prepared by rearrangement of compounds of formula 17 by treatment with a base as shown in Scheme 10 (see, for example, J. Het Chem [Journal of Heterocyclic Chemistry] 1970, 7, p. 1019). Compounds of formula 17 can be prepared by the methods described in WO2008006540 and J. Org. Chem. [Journal of Organic Chemistry], 1966, p. 251.

Solution 10

Intermediates of formula 18 can be prepared by the method shown in Scheme 11 by treating 2-aminopyridines of formula 15 with an isocyanate followed by hydroxylamine and an appropriate base such as triethylamine.

Solution 11

Compounds of Formula 1 wherein Q is Q-4 can also be prepared by the method described in Synthesis Example 6.

Compounds of formula 1f can be prepared by oxidative cyclization of an aryl aldehyde of formula 20 with an aniline of formula 19 having an ortho-halogen (preferably _iodine ) in the presence of sulfur both as a sulfur source and as an oxidant as shown in Scheme 12. The reaction is carried out in the presence of a base such as _K2CO3 in a suitable solvent such as water or DMF and is catalyzed by the addition of a copper salt (e.g., CuI or _CuCl2 ) and preferably a suitable ligand such as 1,10-phenanthroline. Typical reaction temperatures range from 70°C to the boiling point of the solvent.

Solution 12

Compounds of formula 1f can also be prepared by cyclization of 2-halosulfamides of formula 21 with bases such as KOtBu, NaH, DBU or Cs ₂ CO ₃ in a suitable solvent such as toluene or DMF, optionally with the addition of a copper salt such as CuI, and preferably a suitable ligand such as 1,10-phenanthroline as shown in the second reaction of Scheme 12. The reaction can also be catalyzed by Pd species (e.g. prepared from Pd ₂ (dba) ₃ and (t-Bu) ₂ Po-biphenyl), a base such as Cs ₂ CO ₃ in a suitable solvent such as 1,2-dimethoxyethane or dioxane. Typical reaction temperatures range from 80°C to the boiling point of the solvent. For copper and Pd catalyzed reactions, the halogen substituents on the compounds of formula 21 are preferably Br or I. See, for example, Journal of Organic Chemistry 2006, 71(5), pp. 1802-1808; Tetrahedron Letters 2003, 44(32), pp. 6073-6077; Synthetic Communications 1991, 21(5), pp. 625-33; and European Patent Application No. 450420.

Compounds of Formula 1f can also be prepared by oxidative cyclization of thioamides of Formula 22, as shown in the third reaction of Scheme 12. Oxidants commonly used in this method include bromine or iodine, DDQ, and K ₃ Fe(CN) ₆ . See, for example, Tetrahedron 2007, 63(41), pp. 10276-10281; Synthesis 2007, (6), 819-823; and U.S. Patent Application Publication No. 20120215154.

The three methods described in Scheme 12 can be used to prepare compounds wherein X ¹ -X ⁴ are carbon atoms, or wherein one of X ¹ -X ⁴ is nitrogen (see, for example, J. Heterocyclic Chem. 2009, 46, p. 1125 and references cited therein).

The intermediates used in the preparation of the compounds of formula 1 and the compounds of formula 1 wherein Z is S can be prepared by sulfiding the corresponding compounds wherein Z is _O with, for example, Lawrence's reagent (CAS No. 19172-47-5), Belleau's reagent (CAS No. 88816-02-8) or _P2S5 . The sulfidation reaction is generally carried out in a solvent such as toluene, xylene or dioxane and at an elevated temperature from 80°C to the boiling point of the solvent.

Compounds of formula 1 wherein R ² is C(O)NR ⁶ R ⁷ can be prepared by carbonylating corresponding compounds wherein R ² is halogen (preferably Br or I) or wherein R ² is sulfonate (e.g., trifluoromethanesulfonate or perfluorobutanesulfonate). The reaction is carried out at a pressure between atmospheric pressure and 25 bar, optionally under microwave heating, and generally at elevated temperatures in the range of 80° C. to 160° C. in the presence of a carbon monoxide source such as carbon monoxide gas or Mo(CO) _6. Typical reaction solvents include DMF, NMP, toluene or ether solvents such as THF or dioxane.

Compounds of Formula 1 wherein ^{R is Qa can} be prepared as shown in Scheme 13. The method of Scheme 13 is similar to that described in Scheme 1. M is a suitable metal or metalloid such as Mg, Zn or B species, and ^R corresponds to LG in Scheme 1 and is a suitable leaving group such as Cl, Br, I, Tf or Nf.

Solution 13

Compounds of formula 1 wherein R ² is Q ^a and Q ^a is bonded to Q via a nitrogen atom in Q ^a can be prepared by a method similar to Scheme 13. In this method, M in the compound of formula 23 is hydrogen. Coupling reagents include copper (I) salts such as CuI, and suitable ligands such as trans-bis (N, N-dimethyl-1,2-cyclohexane diamine. Typical reaction conditions include solvents such as toluene or dioxane, and elevated reaction temperatures in the range of from 80°C to the boiling point of the solvent.

It should be recognized that some of the reagents and reaction conditions described above for the preparation of compounds of Formula 1 may not be compatible with certain functional groups present in the intermediates. In these cases, incorporating protection/deprotection sequences or functional group interconversions into the synthesis will help to obtain the desired product. The use and selection of protecting groups will be apparent to those skilled in the art of chemical synthesis (see, e.g., Greene, T.W.; Wuts, P.G.M. Protective Groups in Organic Synthesis, 2nd edition; Wiley: New York, 1991). Those skilled in the art will recognize that in some cases, after the introduction of the reagents depicted in the various schemes, additional conventional synthetic steps that are not described in detail may be required to complete the synthesis of the compounds of Formula 1. Those skilled in the art will also recognize that the combination of steps shown in the above schemes may need to be performed in an order different from the specific sequence presented for the preparation of the compounds of Formula 1.

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

Without further elaboration, it is believed that one skilled in the art can utilize the present invention to its maximum extent using the foregoing description. Therefore, the following synthetic examples should be interpreted as merely illustrative and not limiting the present disclosure in any way. The steps in the following synthetic examples illustrate the procedures for each step in the overall synthetic transformation, and the starting materials for each step do not necessarily have to be prepared by specific preparative experiments whose procedures are described in other examples or steps. Percentages are by weight, except for chromatographic solvent mixtures or unless otherwise specified. Unless otherwise specified, the parts and percentages of chromatographic solvent mixtures are by volume. ¹ H NMR spectra are reported in ppm downfield from tetramethylsilane. "s" means single peak, "d" means doublet, "t" means triplet, "q" means quartet, "m" means multiplet, "dd" means double doublet, "dt" means double triplet, "br s" means broad singlet. DMF means N,N-dimethylformamide. Compound number refers to Index Table AN.

Synthesis Example 1

Preparation of N-[2-(methylthio)ethyl]-2-(3-pyridyl)-7-benzothiazolecarboxamide (Compound 84)

Step A: Preparation of ethyl 3-[(aminothiomethyl)amino]benzoate

3-aminobenzoic acid ethyl ester (35.25g, 213.6mmol) is dissolved in chlorobenzene (250mL) and cooled to -10 ℃.Concentrated sulfuric acid (5.93mL) is added, followed by KSCN (21.76g) and 18-crown ether-6 (600mg), and the reaction mixture is heated at 100 ℃ for 14 hours.Hexane is added to the cooling mixture, and the solid of the precipitation is separated by filtration.Solid is slurried in a mixture of water and hexane, and the slurry is stirred for 1 hour.Solid is separated by filtration and vacuum dried overnight to obtain the title compound (40.7g) as a gray solid. ¹ H NMR (DMSO-d ₆ ) δ: 10.10+9.87 (two s, 1H), 8.08+8.05 (two s, 1H), 7.66-7.80 (m, 2H), 7.43-7.51 (m, 1H), 8.0-7.0 (br s, 2H), 4.28-4.35 (m, 2H), 1.29-1.35 (m, 3H).

Step B: Preparation of ethyl 2-amino-7-benzothiazolecarboxylate

The product of step A was taken up in chloroform (300 mL) and acetic acid (200 mL) and bromine (21 mL) in chloroform (100 mL) were added dropwise over 1.5 hours. The reaction mixture was then heated at 70°C for 4 hours, cooled, filtered, and the separated solid was washed with 50 mL 1:1 acetone/chloroform. The solid was added to a solution of Na ₂ CO ₃ (25 g) in water (400 mL) and stirred for 20 minutes. The suspension was filtered, and the separated solid was washed with water and dried in vacuo overnight to give the title compound (6.73 g) as a white solid. The organic filtrate was concentrated and reslurried in 100 ml 1:1 chloroform/acetone and treated as described above to give an additional 8.1 g of a white solid (90% purity, the remaining 10% being regioisomeric benzothiazole). ¹ H NMR (DMSO-d ₆ ) δ: 7.66 (dd, J = 7.7, 0.9 Hz, 1H), 7.60 (s, 1H), 7.57 (dd, 1H), 7.35 (t, J = 7.8 Hz, 1H), 4.37 (q, J = 7.1 Hz, 2H), 1.36 (t, J = 7.1 Hz, 3H).

Step C: Preparation of ethyl 2-chloro-7-benzothiazolecarboxylate

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

Step D: Preparation of 2-(3-pyridyl)-7-benzothiazolecarboxylic acid

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

The above-mentioned product obtained is dissolved in ethanol (100mL) and processed with 1N NaOH solution (24.8mL).Reaction mixture was heated under reflux for 1.5 hours, then cooled, neutralized with concentrated HCl (2.0mL), and concentrated.Resistates is dried in vacuo to obtain the mixture of title compound and NaCl, which is used for the next step without further purification.

Step E: Preparation of N-[2-(methylthio)ethyl]-2-(3-pyridinyl)-7-benzothiazolecarboxamide

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

The crude acid chloride (containing 120 mol% NaCl, 114 mg, 0.3 mmol) was treated with dichloromethane (5 mL), MeSCH ₂ CH ₂ NH ₂ (33 μL) and triethylamine (125 μL), and the reaction mixture was then stirred at ambient temperature for 14 hours. The reaction mixture was diluted with saturated aqueous NaHCO ₃ solution, extracted twice with dichloromethane, and dried over MgSO _4. The combined organic layers were concentrated, and the residue was purified by column chromatography (silica gel eluted with 30% ethyl acetate to 100% ethyl acetate in hexanes) to give 65 mg of the title compound, a compound of the present invention. ¹ H NMR (CDCl ₃ ) δ: 9.39 (d, J = 1.7Hz, 1H), 8.74 (d, J = 3.3Hz, 1H), 8.40-8.47 (dt, 1H), 8.26 (dd, J = 8.0, 0.9Hz, 1H), 7.71 (dd, J = 7.6, 0.9Hz, 1H), 7.58-7.64 (t ,1H),7.47(dd,J＝7.2,5.0Hz,1H),6.94(br t,1H),3.75-3.82(q,2H),2.80-2.88(t,2H),2.18(s,3H).

Synthesis Example 2

Preparation of 2-(5-fluoro-3-pyridyl)-N-(2,2,2-trifluoroethyl)-6-benzothiazolecarboxamide (Compound 127)

Step A: Preparation of 2-(5-fluoro-3-pyridyl)-6-benzothiazolecarboxylic acid

Methyl 4-amino-3-iodobenzoate (1.93 g, 6.96 mmol) was combined with K ₂ CO ₃ (1.92 g), S ₈ (668 mg), CuCl ₂ -2H ₂ O (119 mg), 1,10-phenanthroline (125 mg) and 5-fluoro-3-pyridinecarboxaldehyde (957 mg) in H ₂ O (30 mL), and the reaction mixture was heated at reflux for 16 hours. The cooled reaction mixture was filtered, and the filtrate was treated with NH ₄ Cl (1.49 g). The reaction mixture was stirred at ambient temperature for 10 minutes, filtered, and the solid was dried in vacuo to produce a gray solid. The solid was suspended in dioxane, the suspension was heated to reflux, cooled and filtered to isolate the solid. The solid was rinsed with ether to give the title compound (0.66 g). ¹ H NMR (DMSO-d ₆ ) δ: 9.15 (s, 1H), 8.80 (d, J=2.7Hz, 1H), 8.65 (s, 1H), 8.39 (dt, J=9.5, 2.2Hz, 1H), 8.10 (d, 1H), 8.05 (d, 1H), 8.0-6.5 (br s).

Step B: Preparation of 2-(5-fluoro-3-pyridyl)-N-(2,2,2-trifluoroethyl)-6-benzothiazolecarboxamide

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

The crude acid chloride (103 mg, 0.31 mmol) was treated with dichloromethane (5 mL), triethylamine (131 μL) and CF ₃ CH ₂ NH ₂ (29 μL), and the reaction mixture was stirred at ambient temperature for 3 days. The reaction mixture was diluted with saturated aqueous NaHCO ₃ solution, extracted twice with dichloromethane, and dried over MgSO _4. The combined organic layers were concentrated, and the residue was purified by column chromatography (silica gel eluted with 20% to 40% ethyl acetate in hexanes) to give the title compound, a compound of the invention (52 mg) as a white solid. ¹ H NMR (CDCl ₃ ) δ: 9.32 (br s, 1H), 8.77 (d, J = 4.3Hz, 1H), 8.48 (d, J = 1.4Hz, 1H), 8.40 (dt, J = 7.9, 2.0Hz, 1H), 8.16 (d, J = 8.5Hz, 1H), 7.90 (dd, J = 8.5, 1.7Hz, 1H), 7.48 (dd, J＝7.8, 4.7Hz, 1H), 6.48 (br t, 1H), 4.20 (qd, J＝9.0Hz, 1H).

Synthesis Example 3

Preparation of N-(1-methylethyl)-2-(3-pyridyl)-2H-indazole-4-carboxamide (Compound 8)

Step A: Preparation of N-[(2-bromo-6-fluorophenyl)methylene]-3-pyridinamine

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

Step B: Preparation of 4-bromo-2-(3-pyridyl)-2H-indazole

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

Step C: Preparation of N-(1-methylethyl)-2-(3-pyridyl)-2H-indazole-4-carboxamide

The product of step B (200 mg, 0.727 mmol), isopropylamine (183 μL, 2.18 mmol), trans-bis(acetoxy)bis[o-(di-o-tolylphosphino]benzyl]dipalladium(II) (17 mg, 0.018 mmol), tri-tert-butylphosphonium tetrafluoroborate (10.5 mg, 0.036 mmol), molybdenum hexacarbonyl (192 mg, 0.727 mmol), 1,8-diazabicycloundec-7-ene (473 μL, 2.18 mmol) and DMF (5 mL) were placed in a microwave vial and irradiated at 160° C. for 40 min. The reaction mixture was then cooled to room temperature and heated by The product was filtered through a pad of Cetirizine. The filtrate was diluted with saturated _NaHCO3 solution and extracted with dichloromethane. The organic layer was dried ( _MgSO4 ), filtered, concentrated, and the residue was purified by column chromatography (silica gel eluted with 0-10% acetone in chloroform). Trituration of the resulting solid with diethyl ether afforded the title compound, a compound of the invention, as a white solid (45 mg). ¹ H NMR (CDCl ₃ ) δ: 9.26 (d, J = 2.2Hz, 1H), 9.09 (d, J = 0.9Hz, 1H), 8.67 (dd, J = 4.7, 1.4Hz, 1H), 8.29 (ddd, J = 8.3, 2.6, 1.4Hz, 1H), 7.92 (dt, J = 8.5, 0.9Hz, 1H), 7.48(m,1H),7.31-7.41(m,2H),6.15(s,1H),4.31-4.41(m,1H),1.33(d,J＝6.6Hz,6H).

Synthesis Example 4

Preparation of 2-(3-pyridyl)-N-[1-(2,2,2-trifluoroethyl)]imidazo[1,2-a]pyridine-6-carboxamide (Compound 457)

Step A: Preparation of methyl 2-(3-pyridyl)imidazo[1,2- a ]pyridine-6-carboxylate

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

Step B: Preparation of 2-(3-pyridyl)-N-[1-(2,2,2-trifluoroethyl)]imidazo[1,2-a]pyridine-6-carboxylate amine

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

A mixture of the above prepared carboxylic acid (0.31 g, 1.30 mmol), EDC-HCl (0.27 g, 1.43 mmol), HOBt-H ₂ O (0.22 g, 1.43 mmol) and triethylamine (0.72 mL, 5.2 mmol) in DMF (10 mL) was stirred at 40° C. for 30 minutes. One-fourth of the reaction mixture volume was then removed, treated with CF ₃ CH ₂ NH ₂ (0.13 g, 1.3 mmol) and stirred overnight at 40° C. The reaction mixture was then concentrated under vacuum to remove DMF, and the residue was purified by column chromatography (silica gel eluted with 8:8:1 ethyl acetate:methanol:triethylamine) to give 43.8 mg of the title compound, a compound of the present invention.

Synthesis Example 5

Preparation of methyl 2-[[2-(3-pyridyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate (Compound 42)

Step A: Preparation of methyl 4-nitro-[(3-pyridylimino)methyl]benzoate

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

Step B: Preparation of methyl 2-(3-pyridyl)-2H-indazole-5-carboxylate

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

Step C: Preparation of 2-(3-pyridyl)-2H-indazole-5-carbonyl chloride

The methyl ester (4.1g, 16mmol) prepared in step B is dissolved in methanol (150mL), added in 50% sodium hydroxide in water (7.1mL), and the reaction mixture is heated to reflux for 4 hours.Then the reaction mixture is cooled to room temperature, and desolventizing is removed under reduced pressure.The crude product is acidified with 1N HCl aqueous solution, and the gained precipitate is separated by filtration, washed with diethyl ether, and dried overnight at 60 ℃ under reduced pressure.Then the crude carboxylic acid is dissolved in thionyl chloride (60mL) again, and the reaction mixture is heated to 75 ℃.Then the reaction mixture is cooled to room temperature, and desolventizing is removed under reduced pressure.Crude phosgene is used for the next step without further purification.

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

The acyl chloride (200mg, 0.836mmol) prepared in step C is merged with the hydrazinocarboxylate (82mg, 0.91mmol) in dichloromethane (5mL).The reaction mixture is cooled to 0 ℃, and triethylamine (360 μl, 2.51mmol) is added dropwise.The reaction is warmed to room temperature and stirred overnight.Then the reaction mixture is cooled and quenched with saturated sodium bicarbonate aqueous solution.Separate the two layers, and the water layer is extracted three times with dichloromethane.The organic layer combined is dried over magnesium sulfate, filtered and concentrated under reduced pressure.By silica gel chromatography (20%-80% ethyl acetate/hexane) purification of the obtained crude solid to produce the title compound as white solid, compound of the present invention.

Synthesis Example 6

Preparation of 2-(3-pyridyl)-N-[(tetrahydro-2-furanyl)methyl]pyrazolo[1,5-a]pyridine-5-carboxamide (Compound 467)

Step A: Preparation of 3-(dimethoxymethyl)-5-(3-pyridyl)-1H-pyrazole

Hexamethyldisilane lithium (55mL of 1.0M solution in tetrahydrofuran, 55 mmoles) is added to a solution of 3-acetylpyridine (5.5mL, 50 mmoles), dimethoxymethyl acetate (6.7mL, 55 mmoles) and anhydrous tetrahydrofuran (100mL) cooled at -45°C. The resulting reaction mixture is warmed to 25°C within 1 hour and stirred at this temperature for 3 hours. The reaction mixture is then concentrated under reduced pressure, and the residue is suspended in methanol (50mL) and concentrated under reduced pressure. The resulting residue is suspended in methanol (150mL) and treated with hydrazine monohydrate (2.62mL, 55 mmoles) and glacial acetic acid (6.29mL, 110 mmoles), and the reaction mixture is heated under reflux for 14 hours. The resulting reaction mixture is cooled to 25°C and concentrated under reduced pressure. The residue is distributed between ethyl acetate (200mL) and 1N sodium hydroxide aqueous solution (100mL). The layers were separated, and the organic layer was washed sequentially with 1N aqueous sodium hydroxide solution (50 mL) and brine (50 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give 8.83 g of the title compound as a beige solid.

¹ H NMR (CDCl ₃ ): δ10.5(br s,1H)9.03(d,1H),8.57(dd,1H),8.09(dt,1H),7.34(dd,1H),6.65(s,1H ),5.63(s,1H),3.39(s,6H).

Step B: Preparation of 5-(3-pyridyl)-1H-pyrazole-3-carbaldehyde

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

Step C: Preparation of ethyl 2-(3-pyridyl)pyrazolo[1,5-a]pyridine-5-carboxylate

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

¹ H NMR (CDCl ₃ ): δ9.20(d,1H),8.63(dd,1H),8.50(d,1H),8.33(d,1H),8.27(dt,1H),7.43-7.35(m ,2H),7.05(s,1H),4.43(q,2H),1.44(t,3H).

Step D: Preparation of 2-(3-pyridyl)-N-[(tetrahydro-2-furanyl)methyl]pyrazolo[1,5-a]pyridine-5-carboxylate Amide

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

¹ H NMR (CDCl ₃ ): δ9.19(d,1H),8.63(dd,1H),8.51(d,1H),8.26(dt,1H),8.03(s,1H),7.39(dd,1H ),7.16(dd,1H),7.00(s,1H),6.60(br s,1H),4.10(qd,1H),3.93(dt,1H),3.89-3.76(m,2H),3.38-3.29 (m,1H),2.11-2.02(m,1H),2.00-1.83(m,3H).

Synthesis Example 7

Preparation of N-(1-cyano-1-methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide (Compound 636)

Step A: Preparation of 2-(3-pyridyl)-2H-indazole-4-carbonitrile

A solution of 4-bromo-2-(3-pyridyl)-2H-indazole (6.0 g, 21.9 mmol), zinc cyanide (3.85 g, 21.9 mmol) and tetrakis(triphenylphosphine)palladium(0) (2.53 g, 2.2 mmol) in degassed N-methylpyrrolidone (60 mL) was heated to 110° C. for 2 hours under a nitrogen atmosphere. The reaction mixture was cooled and stirred by Filter the pad and The pad was washed with ethyl acetate (200 mL). The combined organic filtrates were washed with water (4×100 mL), dried over sodium sulfate, filtered and concentrated. The resulting crude solid was triturated with 40% ethyl acetate/hexanes, isolated by filtration and dried to yield the title compound as a tan solid which was used in the next step without further purification. ¹ H NMR (500 MHz, DMSO-d ₆ ) δ ppm 9.60 (d, J=1.10 Hz, 1 H), 9.42 (m, 1 H), 8.71 (m, 1 H), 8.59 (m, 1 H), 8.17 (m, 1 H), 7.84 (m, 1 H), 7.69 (m, 1 H), 7.52 (m, 1 H).

Step B: Preparation of 2-(3-pyridyl)-2H-indazole-4-carboxylic acid

To 2-(3-pyridyl)-2H-indazole-4-nitrile (2.5g, 11.4mmol) in ethanol (100mL) and water (28mL) solution, add solid KOH (12.7g, 227mmol). Gained solution is heated to reflux and continues 4 hours. After being cooled to room temperature, ethanol is removed under reduced pressure. Remaining aqueous solution is washed with dichloromethane (3x100mL), and is acidified to pH 4 with concentrated HCl, cools in ice bath to form white precipitate simultaneously. This solid is separated by filtration, and is dried to produce the title compound (2.7g) as off-white solid. ¹ H NMR (500MHz, DMSO-d ₆ ) δppm 13.22 (br s, 1H), 9.39 (m, 1H), 9.31 (d, J = 0.95Hz, 1H), 8.68 (m, 1H), 8.58 (m, 1H), 8.05 (m, 1H), 7.88 (m, 1H), 7.65 (m, 1H), 7. 48(m,1H).

Step C: Preparation of N-(1-cyano-1-methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide

At 0°C, a solution of 2-(3-pyridyl)-2H-indazole-4-carboxylic acid (2.0 g, 8.4 mmol) in acetonitrile (40 mL) was treated with propylphosphonic anhydride (50 wt% in ethyl acetate, 8.96 mL, 15 mmol), 2-amino-2-methylpropionitrile (1.4 g, 16.8 mmol), triethylamine (2.5 g, 25 mmol) and 4-dimethylaminopyridine (0.002 g, 0.01 mmol). The reaction mixture was stirred at 0°C for 30 minutes, warmed to room temperature, and then heated to 40°C for 2 hours. The reaction mixture was cooled to room temperature and the solvent was removed in vacuo. The residue was distributed between ethyl acetate and water, each phase was separated, and the aqueous phase was washed with ethyl acetate (3 × 100 mL). The combined organic layer was dried over sodium sulfate, filtered and concentrated. The crude residue was purified by normal phase column chromatography (silica gel, 0-100% ethyl acetate/hexanes) to give 1.45 g of the title compound, a compound of the present invention, as a white solid. ¹ H NMR (500 MHz, CDCl ₃ ) δ ppm 9.29 (m, 1H), 9.17 (d, J=0.95 Hz, 1H), 8.67-8.71 (m, 1H), 8.30 (m, 1H), 8.00 (m, 1H), 7.50 (m, 1H), 7.33-7.42 (m, 2H), 6.29 (s, 1H), 1.89 (s, 6H).

Specific compounds of Formula 1 prepared by the methods and variations as described in the foregoing Schemes 1-13 and Synthesis Examples 1-7 are shown in the following Index Table.

Abbreviations used in the Index Tables may include: Cmpd means compound, t is tert, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, Bu is butyl, c-Pr is cyclopropyl, c-Pn is cyclopentyl, c-Hx is cyclohexyl, t-Bu is tert-butyl, Ph is phenyl, OMe is methoxy, SMe is methylthio, and _SO2Me means methylsulfonyl. A wavy line or "-" in a structural fragment indicates the point of attachment of the fragment to the remainder of the molecule. In the column titled "Analytical Data", an asterisk (*) means that NMR data are provided in Index Table O; a single number indicates a mass spectrum parent peak (M+1); and a numerical range indicates a melting point range.

Index Table A

* ¹ H NMR data see Index Table O.

Index Table B

X ⁴ is CH

^X4 is N

Compound No. R A Analyze the data 173 -C(O)NHCH ₂ (tetrahydro-2-furanyl) CH *

* ¹ H NMR data see Index Table O.

Index Table C

Compound No. R A Analyze the data 428 -C(O)NHCH ₂ CF ₃ CH * 429 -C(O)NH(cyclopropyl) CH * 430 -C(O)NHCH ₂ (2-pyrimidinyl) CH * 431 -C(O)NHNHCO ₂ Me CH * 432 -C(O)NHCH ₂ CH ₂ SMe CH * 433 -C(O)NHCH ₂ CH(OMe) ₂ CH * 434 -C(O)NHCH(Me)CF ₃ CH * 435 -C(O)NHCH ₂ CHF ₂ CH * 436 -C(O)NHCH(CH ₂ OMe) ₂ CH * 437 -C(O)NHCH ₂ (tetrahydro-2-furanyl) CH *

* ¹ H NMR data see Index Table O.

Index Table D-1

Compound No. R X Analyze the data 135 -C(O)NHNHCO ₂ Me Cl * 136 -C(O)NHCH ₂ CF ₃ Cl * 137 -C(O)NHCH ₂ (2-pyrimidinyl) Cl * 142 -C(O)NH(cyclopropyl) H * 438 -C(O)NHCH ₂ (tetrahydro-2-furanyl) Cl *

* ¹ H NMR data see Index Table O.

Index Table D-2

Compound No. R X Analyze the data 668 -C(O)NHCH ₂ CF ₃ Cl * 669 -C(O)NHCH ₂ CF ₃ F *

* ¹ H NMR data see Index Table O.

Index Table E

R ^b is H

Compound No. ^R X ³ A Analyze the data 77 -C(O)(1-pyrrolidinyl) CH CH * 78 -C(O)NHCH ₂ CF ₃ CH CH * 79 -C(O)N(Me) ₂ CH CH * 80 -C(O)NH(2-pyrimidinyl) CH CH * 81 -C(O)NH(isopropyl) CH CH * 82 -NHC(O)O(tert-butyl) CH CH * 83 -NHC(O)(2-pyridyl) CH CH * 84 -C(O)NHCH ₂ CH ₂ SMe CH CH * 85 -C(O)NHCH ₂ CH ₂ S(tert-butyl) CH CH * 160 -C(O)NH(cyclobutyl) CH CH * 161 -C(O)NHCH ₂ (tetrahydro-2-furanyl) CH CH * 162 -C(O)NHNHCO ₂ Me CH CH * 163 -C(O)NH(cyclopropyl) CH CH *

^Ra is H

* ¹ H NMR data see Index Table O.

Index Table F

* ¹ H NMR data see Index Table O.

Index Table G

Compound No. R Analyze the data 158 -NHC(O)(cyclobutyl) * 159 -NHC(O)(cyclopropyl) * 439 -C(O)NHCH ₂ (2-pyrimidinyl) * 440 -C(O)NH(tetrahydro-2-furanyl) * 441 -C(O)NH(isopropyl) * 442 -C(O)N(Pr)CH ₂ (cyclopropyl) * 443 -C(O)NHCH ₂ CF ₂ CF ₃ * 444 -C(O)N(Me)(Cyclopropyl) * 445 -C(O)NHCH ₂ CH(OMe) ₂ * 446 -C(O)NHCH ₂ (cyclopropyl) * 447 -C(O)NH(cyclopropyl) * 448 -C(O)NHNHCO ₂ Me * 449 -C(O)NHCH ₂ CH ₂ CF ₃ *

* ¹ H NMR data see Index Table O.

Index Table H

Compound No. R Analyze the data 200 -C(O)(1-pyrrolidinyl) * 201 -C(O)NH(isopropyl) *

* ¹ H NMR data see Index Table O.

Index Table I

Compound No. R Analyze the data 450 -C(O)NHCH ₂ CH ₂ SMe * 451 -C(O)NHCH ₂ CH(OMe) ₂ * 452 -C(O)N(Me) ₂ * 453 -C(O)NHCH ₂ CF ₃ * 454 -C(O)NH(tert-butyl) *

* ¹ H NMR data see Index Table O.

Index Table J

Compound No. R Analyze the data 455 -C(O)NHCH ₂ CH(OMe) ₂ 327 456 -C(O)NHCH ₂ (tetrahydro-2-furanyl) 323 457 -C(O)NHCH ₂ CF ₃ 321 458 -C(O)NHCH ₂ (2,2-difluorocyclopropyl) 329

* ¹ H NMR data see Index Table O.

Index table K

Compound No. R Analyze the data 459 -C(O)NHNHCO ₂ Me 313 460 -C(O)NHCH ₂ CF ₃ 322.5

Index Table L

Compound No. R Analyze the data 461 -C(O)NHCH ₂ CF ₃ 322.5

Index Table M

Compound No. R Analyze the data 467 -C(O)NHCH ₂ (tetrahydro-2-furanyl) *

* ¹ H NMR data see Index Table O.

Index Table N

* ¹ H NMR data see Index Table O.

Index Table O

^a1 H NMR data are in ppm downfield from tetramethylsilane. Couplings are assigned by (s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet, (dd)-doublet of doublet, (dt)-doublet of triplet, (br)-broad singlet.

Examples of intermediates useful in the preparation of the compounds of the present invention are shown in Tables I-1 to I-16. The following abbreviations are used in the following tables: Me means methyl, Et means ethyl, Ph means phenyl, C(O) means carbonyl and CHO means formyl.

Table I-1

A is CH

R R -COOH -C(O)OMe -C(O)OEt Cyano -C(O)Cl -C(O)OPh -C(O)O(4-nitrophenyl) -C(O)Me -CHO Cl Br I -OS(O) ₂ CF _{3 NH2} Nitro

A is for CF

R R -COOH -C(O)OMe -C(O)OEt Cyano -C(O)Cl -C(O)OPh -C(O)O(4-nitrophenyl) -C(O)Me -CHO Cl Br I -OS(O) ₂ CF _{3 NH2} Nitro

A is N

Table I-2

A is CH

R R -COOH -C(O)OMe -C(O)OEt Cyano -C(O)Cl -C(O)OPh -C(O)O(4-nitrophenyl) -C(O)Me -CHO Cl Br I -OS(O) ₂ CF _{3 NH2} Nitro

A is for CF

R R -COOH -C(O)OMe -C(O)OEt Cyano -C(O)Cl -C(O)OPh -C(O)O(4-nitrophenyl) -C(O)Me -CHO Cl Br I -OS(O) ₂ CF _{3 NH2} Nitro

A is N

R R -COOH -C(O)OMe -C(O)OEt Cyano -C(O)Cl -C(O)OPh -C(O)O(4-nitrophenyl) -C(O)Me -CHO Cl Br I -OS(O) ₂ CF _{3 NH2} Nitro

Table I-3

A is CH

A is for CF

R R -COOH -C(O)OMe -C(O)OEt Cyano -C(O)Cl -C(O)OPh -C(O)O(4-nitrophenyl) -C(O)Me -CHO Cl Br I -OS(O) ₂ CF _{3 NH2} Nitro

A is N

R R -COOH -C(O)OMe -C(O)OEt Cyano -C(O)Cl -C(O)OPh -C(O)O(4-nitrophenyl) -C(O)Me -CHO Cl Br I -OS(O) ₂ CF _{3 NH2} Nitro

Table I-4

A is CH

R R -COOH -C(O)OMe -C(O)OEt Cyano -C(O)Cl -C(O)OPh -C(O)O(4-nitrophenyl) -C(O)Me -CHO Cl Br I -OS(O) ₂ CF _{3 NH2} Nitro

A is for CF

A is N

R R -COOH -C(O)OMe -C(O)OEt Cyano -C(O)Cl -C(O)OPh -C(O)O(4-nitrophenyl) -C(O)Me -CHO Cl Br I -OS(O) ₂ CF _{3 NH2} Nitro

Table I-5

Table I-5 is the same as Table I-1, except that the structure shown under the heading " Table 1-1 " is replaced with the structure shown above.

Table I-6

Table I-6 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

Table I-7

Table I-7 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

Table I-8

Table I-8 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

Table I-9

Table I-9 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

Table I-10

Table I-10 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

Table I-11

Table I-11 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

Table I-12

Table I-12 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

Table I-13

Table I-13 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

Table I-14

Table I-14 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

Table I-15

Table I-15 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

Table I-16

Table I-16 is the same as Table I-1, except that the structure shown under the title " Table I-1 " is replaced with the structure shown above.

The following compounds in Tables 1 to 24d can be prepared by the procedures described herein together with methods known in the art. In the following tables the following abbreviations may be used: t means tertiary, s means secondary, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means thiomethoxy, SEt means ethylthio, -CN means cyano, Ph means phenyl, Py means pyridyl, _-NO2 means nitro, S(O)Me means methylsulfinyl, and S(O) _2Me means methylsulfonyl.

The "-" at the beginning of a fragment definition indicates the point of attachment of the fragment to the rest of the molecule; for example, " _-CH2CH2OMe " indicates the fragment 2- _methoxyethyl . Cyclic fragments are indicated by using two "-"s within parentheses; for example, the fragment 1 _{- pyrrolidinyl is indicated by "N(-CH2CH2CH2CH2- )} " where the nitrogen atom is bonded to the two terminal carbon atoms of the four-carbon chain, as _shown below.

Table 1a

A is CH

A is for CF

A is N

Table 1b

A is CH

A is for CF

A is N

Table 1c

A is CH

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

A is for CF

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

A is N

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

Table 1d

A is CH

A is for CF

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

A is N

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

Table 1e

A is CH

A is for CF

A is N

Table 1f

A is CH

A is for CF

A is N

Table 2a

A is CH

A is for CF

A is N

Table 2b

A is CH

A is for CF

A is N

Table 2c

A is CH

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

A is for CF

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

A is N

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

Table 2d

A is CH

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

A is for CF

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

A is N

R R N(-CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH(OMe)CH ₂ -) N(-CH ₂ CH ₂ CF ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CF ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ SCH ₂ CH ₂ -) N(-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -) N(-CH ₂ CH ₂ OCH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(C(O)(c-Pr))CH ₂ CH ₂ -) N(-CH ₂ CH ₂ N(Me)CH ₂ CH ₂ -) N( _-CH2C (Me) _2N =CH-) N(-CH ₂ CH ₂ CH ₂ CH(CF ₃ )CH ₂ -) N(CH ₂ C≡CH) ₂ N(Et) ₂ N(Pr) _CH2 (c-Pr) N(Et)(c-Hexyl) N(-CHC(O)SCH ₂ CH ₂ -)

Table 2e

A is CH

A is for CF

A is N

Table 2f

A is CH

A is for CF

A is N

Table 3a

Table 3a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 3c

Table 3c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 3e

Table 3e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 4a

Table 4a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 4c

Table 4c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 4e

Table 4e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 5a

Table 5a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 5b

Table 5b is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 5c

Table 5c is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 5d

Table 5d is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 5e

Table 5e is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 5f

Table 5f is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 6a

Table 6a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 6c

Table 6c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 6e

Table 6e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 7a

Table 7a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 7c

Table 7c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 7e

Table 7e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 8a

Table 8a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 8c

Table 8c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 8e

Table 8e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 9a

Table 9a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 9c

Table 9c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 9e

Table 9e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 10a

Table 10a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 10b

Table 10b is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 10c

Table 10c is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 10d

Table 10d is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 11a

Table 11a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 11b

Table 11b is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 11c

Table 11c is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 11d

Table 11d is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 12a

Table 12a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 12c

Table 12c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 12e

Table 12e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 13a

Table 13a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 13c

Table 13c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 13e

Table 13e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 14a

Table 14a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 14c

Table 14c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 14e

Table 14e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 15a

Table 15a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 15c

Table 15c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 15e

Table 15e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 16a

Table 16a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 16c

Table 16c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 16e

Table 16e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 17a

Table 17a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 17c

Table 17c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 17e

Table 17e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 18a

Table 18a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 18c

Table 18c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 18e

Table 18e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 19a

Table 19a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 19c

Table 19c is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 19e

Table 19e is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 20a

Table 20a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 20b

Table 20b is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 21a

Table 21a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 21b

Table 21b is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 22a

Table 22a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 22b

Table 22b is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 23a

Table 23a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 23b

Table 23b is the same as Table 1e, except that the structure shown under the heading " Table 1e " is replaced with the structure shown above.

Table 24a

Table 24a is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 24b

Table 24b is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

Table 24c

Table 24c is the same as Table 1a, except that the structure shown under the heading " Table 1a " is replaced with the structure shown above.

Table 24d

Table 24d is the same as Table 1c, except that the structure shown under the heading " Table 1c " is replaced with the structure shown above.

The compounds of the present invention will generally be used as invertebrate pest control active ingredients in compositions (i.e., formulations) wherein at least one additional component is selected from the group consisting of surfactants, solid diluents, and liquid diluents, used as carriers. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, the mode of application, and environmental factors such as soil type, moisture, and temperature.

Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates and/or suspoemulsions) and the like that may optionally be thickened into gels. General types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates and suspoemulsions. General types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.

The general types of solid compositions are dusts, powders, granules, pellets, pellets, pastilles, tablets, filled films (including seed coatings), etc., which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed by film-forming solutions or flowable suspensions are particularly useful for seed treatment. The active ingredient can be (micro) encapsulated and further formed into a suspension or solid formulation; alternatively, the entire formulation of the active ingredient can be encapsulated (or "coated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granular formulations. High-strength compositions are mainly used as intermediates for further formulations.

Sprayable formulations are usually dispersed in suitable media before spraying. Such liquid and solid formulations are formulated in spray media, usually water, but occasionally another suitable medium is easy to dilute as aromatic hydrocarbons or paraffin hydrocarbons or vegetable oils. The scope of spray volume can be from about one liter to several thousand liters per hectare, but more typically in the scope of about ten to several hundred liters per hectare. Sprayable formulations can be mixed with water or another suitable medium in the groove, for carrying out leaf treatment by air or ground application, or for being applied to the growth medium of plant. Liquid and dry formulations can be directly metered into the drip irrigation system, or metered into the furrow during planting. Liquid and solid formulations can be applied to the seeds of crops and other desired vegetation as seed treatment agents before planting, so as to protect the root and other plant parts and/or leaves under the ground in the development by systemic absorption.

The formulation will generally contain effective amounts of active ingredient, diluent and surfactant totaling up to 100 weight percent within the following approximate ranges.

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

Liquid diluents include, for example, water, N,N-dimethylalkaneamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerol, triacetin, sorbitol, aromatic hydrocarbons, dearomatized aliphatic compounds, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-heptanone. -hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactic acid esters, dibasic esters, alkyl and aryl benzoates, γ-butyrolactone, and alcohols which may be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, tridecanol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycerides of saturated and unsaturated fatty acids (generally _C6 - _C22 ), such as plant seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil (maize oil), peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil and palm kernel oil), animal fats (e.g., tallow, lard, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, which can be obtained by hydrolysis of glycerides from plant and animal sources and purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd ed., Interscience, New York, 1950.

The solid and liquid compositions of the present invention typically include one or more surfactants. When added to a liquid, a surfactant (also known as a "surfactant") typically changes, most often reduces, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, the surfactant can be used as a wetting agent, dispersant, emulsifier or defoaming agent.

Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants that can be used in the compositions of the present invention include, but are not limited to, alcohol alkoxylates, such as those based on natural and synthetic alcohols (which may be branched or linear) and prepared from alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean oil, castor oil and rapeseed oil; alkylphenol alkoxylates, such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and trans-block polymers in which the terminal blocks are prepared from propylene oxide. ; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerides, lanolin-based derivatives, polyethoxylated esters (such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitan fatty acid esters and polyethoxylated glycerol fatty acid esters); other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (PEGs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.

Useful anionic surfactants include, but are not limited to, alkylaryl sulfonic acids and salts thereof; carboxylated alcohol or alkylphenol ethoxylates; diphenylsulfonate derivatives; lignin and lignin derivatives, such as lignin sulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonates; phosphates, such as phosphates of alcohol alkoxylates, phosphates of alkylphenol alkoxylates, and phosphates of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfates; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides, such as N,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecylbenzene and tridecylbenzene; sulfonates of polycondensed naphthalene; sulfonates of naphthalene and alkylnaphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives, such as dialkylsulfosuccinates.

Useful cationic surfactants include, but are not limited to, amides and ethoxylated amides; amines such as N-alkylpropylenediamine, tripropylenetriamine and dipropylenetetramine, and ethoxylated amines, ethoxylated diamines, and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); amine salts such as ammonium acetate and diamine salts; quaternary ammonium salts such as quaternary ammonium salts, ethoxylated quaternary salts, and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

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

The compositions of the present invention may also contain formulation aids and additives known to those skilled in the art as auxiliary formulations (some of which may also be considered to act as solid diluents, liquid diluents or surfactants). Such formulation aids and additives may control: pH (buffers), foaming during processing (defoamers, such as polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), microbial growth in containers (antimicrobial agents), product freezing (antifreeze agents), color (dye/pigment dispersions), elution (film formers or adhesives), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetate, polyvinyl acetate copolymers, polyvinyl pyrrolidone-vinyl acetate copolymers, polyvinyl alcohol, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include McCutcheon's Second Volume: Functional Materials, International and North American Annual Editions, published by The Manufacturing Confectioner Publishing Co., a division of McCutcheon; and those listed in PCT Publication WO 03/024222.

The compound of formula 1 and any other active ingredient are usually incorporated into the composition of the present invention by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions including emulsifiable concentrates can be prepared by simply mixing these ingredients. If the solvent of the liquid composition intended to be used as an emulsifiable concentrate is immiscible with water, an emulsifier is usually added to emulsify the solvent containing the active ingredient when diluted with water. The active ingredient slurry with a particle size of up to 2,000 μm can be wet-milled using a media grinder to obtain particles with an average particle size of less than 3 μm. The aqueous slurry can be made into a finished suspension concentrate (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry preparations generally require a dry grinding process that produces an average particle size in the range of 2 to 10 μm. Dusts and powders can be prepared by blending and usually by grinding (e.g., with a hammer mill or fluid energy mill). Granules and spherical agents can be prepared by spraying the active substance on a preformed granule carrier or by agglomeration techniques. See, Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp. 147-48; Perry's Chemical Engineer's Handbook, 4th ed., McGraw-Hill, New York, 1963, pp. 8-57 et seq., and WO 91/13546. Pellets may be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules may be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

For further information on the formulation field, see T. S. Woods, "The Formulator's Toolbox-Product Forms for Modern Agriculture," in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, eds. T. Brooks and T. R. Roberts, Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, column 6, lines 16 to column 7, line 19, and Examples 10-41; U.S. 3,309,192, column 5, lines 43 to column 7, line 62, and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; U.S. 2,891,855, column 3, lines 66 to column 5, line 17, and Examples 1-4; Klingman, Weed Control as a Science, John Wiley & Sons, New York, 1961, pp. 81-96; Hance et al., Weed Control Handbook, 8th ed., Blackwell Scientific Publications [Blackwell Scientific Publishers], Oxford, 1989; and Developments in formulation technology [Development of formulation technology], PJB Publishing Company [PJB Publications], Richmond, UK, 2000.

In the following examples, all formulations were prepared in a conventional manner. Compound numbers refer to compounds in Index Tables A-N. Without further elaboration, it is believed that one skilled in the art can utilize the present invention to its maximum extent using the foregoing description. Therefore, the following examples should be construed as merely illustrative and not limiting of the present disclosure in any way. Unless otherwise indicated, percentages are by weight.

Example A

High Strength Concentrate

Compound 8 98.5%

Silica aerogel 0.5%

Synthetic amorphous fine silica 1.0%

Example B

Wettable powder

Example C

Granules

Compound 16 10.0%

Attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. 90.0% No. 25-50 sieve)

Example D

Extruded pellets

Example E

Emulsifiable concentrates

Compound 41 10.0%

Polyoxyethylene sorbitan hexaoleate 20.0%

C ₆ -C ₁₀ fatty acid methyl ester 70.0%

Example F

Microemulsion

Example G

Seed treatment

Example H

Fertilizer sticks

Example I

Suspension concentrate

Example J

Emulsion in water

Example K

Oil dispersion

Example L

Suspension emulsion

Compounds of the present invention show activity against a wide spectrum of invertebrate pests. These harmful organisms include invertebrates that inhabit various environments, such as plant leaves, roots, soil, crops or other foods, building structures or animal skins that are harvested. These harmful organisms include, for example, leaves (including leaves, stems, flowers and fruits), seeds, timber, textile fibers or animal blood or tissues for food, and thereby, for example, growing or storing agronomic crops, forests, greenhouse crops, ornamental plants, nursery crops, stored food or fiber products, or houses or other structures or their contents, or invertebrates that are harmful to animal health or public health. It will be appreciated by those skilled in the art that not all compounds are equally effective for all growth stages of all harmful organisms.

Therefore, these compounds and compositions of the present invention can be used agriculturally to protect field crops from phytophagous invertebrate pests, and also non-agriculturally to protect other horticultural crops and plants from phytophagous invertebrate pests. This utility includes protecting crops and other plants (i.e. agronomy and non-agronomy) that have been introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide favorable traits. Examples of such traits include herbicide resistance, phytophagous pest resistance (e.g., insects, mites, aphids, spiders, nematodes, snails, plant pathogenic fungi, bacteria and viruses), improved plant growth, tolerance to adverse growth conditions such as high and low temperatures, high or low soil moisture and high salinity, increased flowering or fruiting, higher harvest yields, faster maturation, higher quality and/or nutritional value of harvested products, or improved storage or processing characteristics of harvested products. Transgenic plants can be modified to express a variety of traits. Examples of plants containing traits provided by genetic engineering or mutagenesis include varieties of corn, cotton, soybean, and potato expressing the insecticidal Bacillus thuringiensis toxin, such as YIELD and INVICTARR2 PRO ^TM and various corn, cotton, soybean and rapeseed varieties tolerant to herbicides such as Roundup Liberty and As well as crops expressing N-acetyltransferase (GAT) to provide resistance to glyphosate herbicides, or crops containing HRA genes that provide resistance to herbicides that inhibit acetolactate synthase (ALS). The compounds and compositions of the present invention can interact synergistically with traits introduced by genetic engineering or modified by mutagenesis to enhance the phenotypic expression or effectiveness of the traits or to improve the invertebrate pest control effectiveness of the compounds and compositions of the present invention. In particular, the compounds and compositions of the present invention can interact synergistically with the phenotypic expression of proteins or other natural products that are toxic to invertebrate pests to provide more than additive control of these pests.

Composition of the present invention can also optionally include plant nutrients, for example, include at least one fertilizer composition of plant nutrients selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc and molybdenum.It is noteworthy that the composition comprising at least one fertilizer composition, the fertilizer composition includes at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnesium.The composition further comprising at least one plant nutrient of the present invention can be in the form of liquid or solid.It is noteworthy that the solid preparation in the form of granule, small rod or tablet.The solid preparation comprising fertilizer composition can be prepared by mixing the compound of the present invention or composition with the fertilizer composition and formulation ingredients and then preparing the preparation by a method such as granulation or extrusion.Alternately, solid preparation can be prepared by spraying the solution or suspension of the compound of the present invention or composition in a volatile solvent onto the fertilizer composition in the form of a dimensionally stable mixture (for example, granule, small rod or tablet) prepared before, and then evaporating the solvent to prepare.

Non-agricultural use refers to the control of invertebrate pests in areas other than crop plant fields. The non-agricultural use of the compounds and compositions of the present invention includes the control of invertebrate pests in stored grains, beans and other foods and textiles such as clothing and carpets. The non-agricultural use of the compounds and compositions of the present invention also includes the control of invertebrate pests in ornamental plants, forests, courtyards, roadsides and railroad lands, and turf such as lawns, golf courses and pastures. The non-agricultural use of the compounds and compositions of the present invention also includes the control of invertebrate pests in houses and other buildings that may be occupied by humans and/or companions, farms, pastures, zoos or other animals. The non-agricultural use of the compounds and compositions of the present invention also includes the control of pests such as termites that may damage the wood or other structural materials used in buildings.

The non-agricultural uses of the compounds and compositions of the present invention also include protecting human and animal health by controlling parasitic or invertebrate pests that spread infectious diseases. The control of animal parasites includes controlling external parasites that parasitize on the surface of the host animal body (e.g., shoulders, armpits, abdomen, inner thighs) and internal parasites that parasitize inside the host animal body (e.g., stomach, intestines, lungs, veins, subcutaneous, lymphatic tissue). External parasites or pests that spread diseases include, for example, chiggers, ticks, lice, mosquitoes, flies, mites and fleas. Internal parasites include heartworms, hookworms and worms. The compounds and compositions of the present invention are suitable for systemic and/or non-systemic control of parasites on animals or infections. The compounds and compositions of the present invention are particularly suitable for combating external parasites or pests that spread diseases. The compounds and compositions of the present invention are suitable for combating parasites that infest agricultural working animals such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, hens, turkeys, ducks, geese and bees; pet animals and livestock such as dogs, cats, pet birds and ornamental fish; and so-called laboratory animals such as hamsters, guinea pigs, rats and mice. By combating these parasites, mortality and performance decline (in meat, milk, wool, skin, eggs, honey, etc.) are reduced, so the application of a composition comprising the compounds of the present invention allows more economical and simple animal breeding.

Examples of agronomic or non-agronomic invertebrate pests include eggs, larvae and adults of the order Lepidoptera, such as armyworms, sugar moths, geometrids and heliothines of the family Noctuidae (e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioides Lefebvre), Southern Armyworm (Spodoptera eridania Cramer), fall armyworm (Spodoptera frugiperda J.E. Smith), beet armyworm (Spodoptera exigua Hübner), cotton leafworm (Spodoptera littoralis Boisduval), yellow striped armyworm (Spodoptera ornithogalli Guenée), black cutworm (Agrotis ipsilon Hufnagel), velvet bean caterpillar (Anticarsiagemmatalis Hübner), green fruitworm (Lithophane antennata Walker), cabbage armyworm (Barathra brassicae Linnaeus), soybean looper (Pseudoplusia includens Walker), cabbage looper (Trichoplusia ni Hübner), tobacco budworm (Heliothis virescens Fabricius); borers, sheath moths, webworms, coneworms, cabbage worms and skeletonizers from the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hübner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae: Pyralinae) such as sodworm (Herpetogramma licarsisalis Walker), sugarcane borer (Chilo infuscatellus Snellen), tomato smallborer (Neoleucinodes elegantalis Guenée), green leafroller (Cnaphalocrocis medinalis), grape leaffolder (Desmiafuneralis Hübner), melon worm (Diaphania nitidalis Stoll), cabbage center grub (Hellualahydralis Guenée), yellow stem borer (Scirpophaga incertulas Walker), early shoot borer (Scirpophaga infuscatellus Snellen), white stem borer (Scirpophaga innotata Walker), top shoot borer (Scirpophaga nivella Fabricius), dark-headed rice borer (Chilopolychrysus Meyrick), striped rice borer (Chilo suppressalis Walker), cabbage cluster caterpillar (Crocidolomiabinotalis English); leaf rollers, aphids, seed and fruit insects of the family Cirrhidae (e.g., codling moth (Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck), citrus false codling moth (Cryptophlebia leucotreta Meyrick), citrus borer (Ecdytolopha aurantiana Lima), redbanded leafroller (Argyrotaenia velutinana Walker), obliquebanded leafroller (Choristoneura rosaceana Harris), light brown applemoth (Epiphyas postvittana Walker), European grape berry moth (Eupoecilia ambiguella Hübner), apple bud moth (Pandemis pyrusana Kearfott), omnivorous leafroller (Platynotastultana Walsingham), barred fruit-tree tortrix (Pandemis cerasana Hübner), apple brown tortrix (Pandemis heparana Denis &Schiffermüller); and many other economically important Lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophoragossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus), peach fruit borer (Carposina niponensis Walsingham), peach twig borer (Anarsia lineatella Zeller), potato tuberworm (Phthorimaea operculella Zeller), spotted teniform leafminer (Lithocolletis blancardella Fabricius), Asiatic apple leafminer (Lithocolletis ringoniella Matsumura), rice leaffolder (Lerodea eufala Edwards), apple leafminer (Leucoptera scitella Zeller); eggs, nymphs and adults of the order Blattale, including cockroaches from the families Blattaria and Blattaria (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella Germanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius), smoky brown cockroach (Periplaneta fuliginosa Service), Australian cockroach (Periplaneta australasiae Fabr.), lobster cockroach (Nauphoeta cinerea Olivier), and smooth cockroach (Symplocepallens Stephens); eggs, leaf-feeding, fruit-feeding, root-feeding, seed-feeding and vesicle-feeding larvae and adults of the order Coleoptera, including weevils from the families Anthribidae, Bruchidae and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus), annual bluegrass weevil (Listronotus maculicollis Dietz), bluegrass weevil (Listronotus billbug (Sphenophorus parvulus Gyllenhal), hunting billbug (Sphenophorus venatus vestitus), Denver billbug (Sphenophorus cicatristriatus Fahraeus); flea beetles, cucumber leaf beetles, rootworms, leaf beetles, potato beetles, and leaf miners of the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera LeConte); beetles and other beetles from the family Scarabaeidae (e.g., Japanese beetle (Popillia japonica Newman), oriental beetle (Popillia japonica Newman), beetle (Anomala orientalis Waterhouse, Exomalaorientalis (Waterhouse) Baraud), northern masked chafer (Cyclocephalaborealis Arrow), southern masked chafer (Cyclocephalaimmaculata Olivier or C.lurida Bland), dung beetle and white grub (Aphodius species), black turfgrass ataenius (Ataenius spretulus Haldeman), green June beetle (Cotinisnitida Linnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/June beetles (Phyllophaga species) and European chafer (Rhizotrogus majalis Razoumowsky); skin beetles from the family Dermestidae; wireworms from the family Corytidae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae.

In addition, agronomic and non-agronomic pests include: eggs, adults and larvae of the order Dermoptera, including earwigs from the family Acrididae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius); eggs, larvae, adults and nymphs of the orders Hemiptera and Homoptera, such as plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers from the family Cicadidae (e.g., Empoasca species), bed bugs from the family Cimex lectularius Linnaeus), planthoppers from the families of Cicadidae and Delphacidae, treehoppers from the family of Membracidae, psyllids from the family of Psyllidae, whiteflies from the family of Alyssidae, aphids from the family of Aphididae, phylloxera from the family of Phylloxera, mealybugs from the family of Mealycopodidae, scales from the families of Coccidae, Coccidae, and Coccidae, web bugs from the family of Lachnophoridae, stink bugs from the family of Pentatomidae, chinch bugs from the family of Pentatomidae (e.g., hairy chinch bug (Blissus leucopterushirtus Montandon) and southern chinch bug (Blissus insularis Barber), and other seed bugs from the family of Pentatomidae. bugs, cicadas from the family Cicadidae, pumpkin bugs from the family Pseudostellaria, and red bugs and cottonstainers from the family Pseudostellaria.

Agronomic and non-agronomic pests also include: eggs, larvae, nymphs and adults of the order Acarina (Mites), such as spider mites and red mites of the family Tetranychidae (e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychusmcdanieli McGregor); flat mites of the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor); rust mites and aphid mites in the family Mycophoridae, and other leaf-feeding mites and mites of importance to human and animal health, namely, dust mites in the family Epidermoptidae, hair follicle mites in the family Demodicidae, and grain mites in the family Glycyphagidae; ticks in the family Ixodidae, commonly known as hard ticks (e.g., deer ticks (Ixodes scapularis Say), Australian paralysis ticks (Ixodes holocyclus Neumann), American dog ticks (Dermacentor variabilis Say), lone star ticks (Amblyommaamericanum Linnaeus), and ticks in the family Cryptorchidae, commonly known as soft ticks (e.g., relapsing fever ticks tick (Ornithodoros turicata), common fowl tick (Argas radiatus); scab mites and itch mites in the families Itch, Pyreniformes, and Sarcoptera; eggs, adults, and larvae of the order Orthoptera, including grasshoppers, locusts, and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas, American grasshoppers (e.g., Schistocerca americana Drury), desert locusts (Schistocerca gregaria Forskal), migratory locusts (Locustamigratoria Linnaeus), bush locusts (E.g., locust (Zonocerus species), house cricket (Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket (Scapteriscusvicinus Scudder) and southern mole cricket (Scapteriscusborellii Giglio-Tos); eggs, adults and larvae of Diptera, including leaf miners (e.g., Liriomyza species, such as serpentinevegetable leafminer (Liriomyza sativae Blanchard), midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella spp.), frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fanniacanicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya species, Phormia species) and other fly pests, horse flies (e.g., Tabanus species), bot flies (e.g., Gastrophilus species, Oestrus species), cattle grubs (e.g., Hypoderma species), deer flies (e.g., flies (e.g., Chrysops species), sheep ticks (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes species, Anopheles species, Culex species), black flies (e.g., Prosimulium species, Simulium species), biting midges, sand flies, sciarids and other Nematocera; eggs, adults, and larvae of the order Thysanoptera, including onion thrips (Thrips tabaci Lindeman), flowerthrips (Frankliniella species), and other leaf-feeding thrips; insect pests of the order Hymenoptera, including ants of the family Formicidae, including the Florida carpenter ant (Camponotus floridanus Buckley), red carpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), white-footed ant (Technomyrmex albipes fr. Smith), big headed ants (Pheidole species), ghost ant (Tapinoma melanocephalum Fabricius); Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus )) and odorous house ant (Tapinoma sessileSay). Other Hymenoptera, including bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodiprion species); Cephus species); Isoptera, including insect pests of the Termitidae (e.g., Macrotermes species, Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes species), and Rhinotermitidae (e.g., Reticulitermes species, Coptotermes species, Heterotermes tenuis Hagen) families, the eastern subterranean termite (Reticulitermes species), and the eastern subterranean termite (Coptotermes species). flavipes Kollar), western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder), powder post termite (Cryptotermes brevis Walker), drywood termite (Incisitermes snyderi Light), southeastern subterranean termite (Reticulitermes virginicus Banks), western drywood termite (Incisitermes minor Hagen), arboreal termites, such as termites of the genus Nasutitermes and other termites of economic importance; insect pests of the order Thysanura, such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the order Trichophagus, including head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicolaovis Schrank), short-nosed cattle louse (Haematopinus usysternus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus), and other sucking and chewing parasitic lice that attack humans and animals; insect pests of the order Siphonoptera, including the oriental rat flea (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea (Human flea) flea) (Pulex irritans Linnaeus) and other fleas that afflict mammals and birds. Additional arthropod pests covered include spiders of the order Araneae, such as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectusmactans Fabricius), and centipedes of the order Scolopendra, such as the house centipede (Scutigera coleoptrata Linnaeus).

Examples of invertebrate pests in stored grain include larger grain borer (Prostephanus truncatus), lesser grain borer (Rhyzoperthadominica), rice weevil (Stiophilus oryzae), maize weevil (Stiophilus zeamais), cowpea weevil (Callosobruchus maculatus), red flour beetle (Tribolium castaneum), granary weevil (Stiophilus granarius), Indian meal moth (Plodia interpunctella), Mediterranean flour beetle (Ephestia spp.), kuhniella) and the long-horned flat or rusty grain beetle (Cryptolestis ferrugineus).

The compounds of the invention may be active against members of the classes Nematoda, Cestoda, Trematoda, and Acanthocephala, including members of the economically important orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida, such as, but not limited to, economically important agricultural pests (i.e., root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, nematodes, etc.) and animal and human health pests (i.e. all economically important trematodes, tapeworms and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).

The compounds of the invention may have activity against pests in the order Lepidoptera (e.g., Alabama argillacea Hübner (cotton leaf worm), Archipsargyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilosuppressalis Walker (rice stem borer), Cnaphalocrosismedinalis Guenée (rice leaf roller), Crambuscaliginosellus Clemens (corn root webworm), Crambusteterrellus Zincken (bluegrass moth), and Crambus caliginosellus Clemens (corn root webworm). webworm), Cydia pomonellaLinnaeus(codling moth), Earias insulana Boisduval(spiny bollworm), Earias vittella Fabricius(spotted bollworm), Helicoverpa armigera Hübner(American bollworm), Helicoverpa zea Boddie(corn earworm), Heliothis virescens Fabricius(tobacco budworm), Herpetogrammalicarsisalis Walker(sod webworm), Lobesia botrana Denis & Schiffermüller(grape berry leaf roller), moth), Pectinophoragossypiella Saunders (pink bollworm), Phyllocnistiscitrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hübner (beetarmyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J.E. Smith) (fall armyworm), Trichoplusia ni Hübner (cabbage looper), and Tuta absoluta Meyrick (tomato leafminer).

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

The compounds of the invention are also active against members from the order Hemiptera, including: Acrosternum hilare Say (green stink bug), Anasa tristis DeGeer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Cimex lectularius Linnaeus (bed bug), Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich- ) (cotton stainer), Euschistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus species (complex of seed bugs), Halymorpha halys )(brown marmorated stink bug), Leptoglossus corculus Say(leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois(American tarnished plant bug), Nezara viridula Linnaeus(Southern green stink bug), Oebalus pugnax Fabricius(rice stink bug), Oncopeltus fasciatus Dallas(large milkweed bug), Pseudatomoscelisseriatus Reuter(cotton fleahopper). Other insect orders controlled by the compounds of the present invention include the order Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilaxna varivestis Mulsant (Mexican bean beetle), and Thrips tabaci Lindeman (onion thrips). beetle) and wireworms of the genera Agriotes, Athous or Limonius).

It should be noted that some contemporary classification systems place Homoptera in the suborder Hemiptera.

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

The compound of the present invention can also be used to increase the vigor of crop plants. The method includes contacting crop plants (for example, leaves, flowers, fruits or roots) or the seeds of the crop plants with the compound of formula 1 with an amount (i.e. biologically effective amount) sufficient to achieve the desired plant vigor effect. Typically, the compound of formula 1 is applied with a prepared composition. Although the compound of formula 1 is usually directly applied to crop plants or their seeds, it can also be applied to the location of crop plants, i.e. the environment of crop plants, particularly close enough to allow the compound of formula 1 to migrate to the environmental part on crop plants. The location associated with the method most commonly includes a growth medium (i.e., a medium providing nutrients to plants), typically the soil in which plants are grown. Therefore, in order to increase the vigor of crop plants, the treatment of crop plants includes contacting the location of crop plants, the seeds of growing and planting crops or crop plants with the compound of formula 1 of biologically effective amount.

Increased crop vigor can result in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by superior seed germination, crop emergence, and crop stand; (b) enhanced crop growth as demonstrated by rapid and healthy leaf growth (e.g., as measured by leaf area index), plant height, tiller number (e.g., for rice), root mass, and overall dry weight of the vegetative body of the crop; (c) improved crop yield as demonstrated by flowering time, flowering duration, number of flowers, total biomass accumulation (i.e., yield), and/or product grade marketability of fruit or grain (i.e., yield quality); (d) enhanced ability of crops to tolerate or prevent infection by plant diseases and infestation by arthropod, nematode, or mollusk pests; and (e) increased ability of crops to tolerate environmental stresses, such as exposure to extreme heat, suboptimal moisture, or phytotoxic chemicals.

The compounds of the present invention can increase the vigor of treated plants by killing phytophagous invertebrate pests or preventing them from feeding in the plant's environment compared to untreated plants. In the absence of such control of phytophagous invertebrate pests, the pests reduce plant vigor by consuming plant tissue or sap, or transmitting plant pathogens such as viruses. Even in the absence of phytophagous invertebrate pests, the compounds of the present invention can increase plant vigor by altering the metabolism of the plant. In general, if the plant is grown in a non-ideal environment, i.e., contains one or more aspects that are not conducive to the plant achieving its full genetic potential that it should exhibit in an ideal environment, then the vigor of the crop plant will be most significantly increased by treating the plant with the compounds of the present invention.

It is noteworthy that the method for increasing the vigor of crop plants, wherein the crop plants grow in an environment including phytophagous invertebrate pests. It is also noteworthy that the method for increasing the vigor of crop plants, wherein the crop plants grow in an environment not including phytophagous invertebrate pests. It is also noteworthy that the method for increasing the vigor of crop plants, wherein the crop plants grow in an environment including an amount of moisture less than the ideal amount of moisture supporting the growth of crop plants. It is noteworthy that the method for increasing the vigor of crop plants, wherein the crop is rice. It is also noteworthy that the method for increasing the vigor of crop plants, wherein the crop is maize (corn). It is also noteworthy that the method for increasing the vigor of crop plants, wherein the crop is soybean.

The compounds of the present invention may also be mixed with one or more other biologically active compounds or agents to form multi-component pesticides, imparting even broader agronomic and non-agronomic benefits, including insecticides, fungicides, nematicides, bactericides, miticides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or insect pathogenic bacteria, viruses or fungi. The present invention therefore also relates to a composition comprising a biologically effective amount of a compound of formula 1, at least one additional component and at least one additional biologically active compound or agent, the at least one additional component being selected from the group consisting of a surfactant, a solid diluent and a liquid diluent. For mixtures of the invention, the other biologically active compounds or agents can be formulated together with the compounds of the invention (including compounds of Formula 1) to form a premix, or the other biologically active compounds or agents can be formulated separately from the compounds of the invention (including compounds of Formula 1) and the two formulations combined together (e.g., in a spray tank) prior to administration, or alternatively, applied sequentially.

Examples of such biologically active compounds or agents with which the compounds of the present invention can be formulated are insecticides such as abamectin, acefenamid, acetamiprid, acrinathrin, afidopyropen ([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl] methylcyclopropanecarboxylate), sulfanilamide, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, chlorpyrifos, bifenthrin, bifenazate, bistrifluan, borate, buprofezin, cadusafos, carbaryl, carbofuran, cartap, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorpyrifos-methyl, chlorfenapyr, clofentezin, clothianidin, cyantraniliprole (3-bromo-1-(3-chloro-2-pyridyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide), cyclobromobenzene (3-bromo-N-[2-bromo-4-chloro-6-[ [(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide), cypermethrin, cyclohexidine ((5S,8R)-1-[(6-chloro-3-pyridyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-epoxy-1H-imidazo[1,2-a]azepine), cyfluthrin, cyfluthrin, β-cyfluthrin, cyhalothrin, γ-cyhalothrin, λ-cyhalothrin, cypermethrin, α-cypermethrin, ζ-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, tetrafluthrin, dimethoate, dimethoate, dimethoate, benzylpenicillin, Emamectin, endosulfan, cypermethrin, ethiprole, etoxazole, fenbutatin, fenitrothion, fenthiocarb, fenoxycarb, cypermethrin, cypermethrin, fipronil, flometoquin (2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolyl carbonate methyl ester), flonicamid, flubendiamide, flucythrinate, flufenoxuron, flufenoxuron ((αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)phenylacetic acid methyl ester), flufensulfone (5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole) , cyanothioether insecticides (fluhexafon), fluopyram, flupiprole (1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile), flupyrone (4-[[(6-chloro-3-pyridyl)methyl](2,2-difluoroethyl)amino]-2(5H)furanone), fluvalinate, τ-fluvalinate, flufenacet, flufenacet, thiamethoxam, thiophanate-methyl, chlorfenapyr, heptafluthrin (2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclohexane propanecarboxylic acid [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl] methyl ester), hexaflumuron, hexathiazox, hydrazone, imidacloprid, indoxacarb, insecticidal soap, isofenphos, fenthion, malathion, chlorfluthrin ((1R,3S)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl] methyl ester), metaflumizone, snail antagonist, methamidophos, methidathion, methiodicarb, methomyl, methoprene, methoxychlor, methoxyfluthrin, methoxyfenozide, methoxyfluthrin, monocrotophos, monofluorothrin (3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl] methyl ester propanecarboxylic acid [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl ester), nicotine, nitenpyram, nitrothiazole, fluazifop, noviflumuron, oxamyl, parathion, methyl parathion, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide (1,3,5-trimethyl-N-(2-methyl-1-propionyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide), pyridine Aphidone, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyrimidine ((αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)phenylacetic acid methyl ester), pyriprole, pyriproxyfen, rotenone, ryanodine, flutosan, ethyl spinosad, spinosad, spirodiclofen, spiromesifen, spirotetramat, thioprofen, sulfonecarb (N-[methyloxy[1-[6-(trifluoromethyl)-3-pyridinyl]ethyl]-λ ⁴ [-sulfonylidene] cyanamide), fenpyrad, tebufenpyrad, diflubenzuron, tefluthrin, terbufos, chlorpyrifos, pyrethroid, tetrafluthrin (2,2,3,3-tetramethylcyclopropanecarboxylic acid [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl] methyl ester), flucyanamide, thiacloprid, thiomethoxam, thiodicarb, dimethoate, tioxazafen (3-phenyl-5-(2-thienyl)-1,2,4-oxadiazole), tolfenpyrad, tralomethrin, trichlorfon, triflumezopyrim (2,4-dioxo-1-(5-pyrimidinylmethyl)-3-[3-(trifluoromethyl)phenyl]-2H-pyrido[1,2-a]pyrimidinium inner salt), thiofluanid, Bacillus thuringiensis delta-endotoxin, insect pathogenic bacteria, insect pathogenic viruses and insect pathogenic fungi.

Of note are insecticides such as abamectin, acetamiprid, acralthrin, pyraclostrobin, amitraz, avermectin, azadirachtin, benfuracarb, sulfamethoxam, bifenthrin, buprofezin, cadusafosfos, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyproconazole, cyfluthrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cyfluthrin, cypermeth ... - Cypermethrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, benfenpyroxil, emamectin, endosulfan, cypermethrin, ethiprole, efenproxil, etoxazole, fenitrothion, fenthiocarb, fenoxycarb, cypermethrin, fipronil, flometoquin, flonicamid, flubendiamide, flufenoxuron, flutoxifen, fluthiamethoxam, flupiprole, Flupyralidone, fluvalinate, flumethrin, thiamethoxam, heptafluthrin, hexaflumuron, hydrazone, imidacloprid, indoxacarb, lufenuron, chlorfluthrin, metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide, metofluthrin, monofluorothrin, nitenpyram, thiazole, isoflurane, oxamyl, pyflubumide, pymetrozine, and chlorpyrifos. Pyrethroids, pyridaben, pyridalyl, cypermethrin, lyanodine, ethyl spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfonecarb, tebuconazole, pyrethroids, tetrafluthrin, thiacloprid, thiomethoxam, thiodicarb, dimethoate, tralomethrin, triazolam, triflumuron, Bacillus thuringiensis delta-endotoxin, all strains of Bacillus thuringiensis and all strains of nuclear polyhedrosis virus.

One example of a biological agent for admixture with the compounds of the invention includes insect pathogenic bacteria such as Bacillus thuringiensis, and encapsulated delta-endotoxins of Bacillus thuringiensis such as those obtained from Methods of preparation and Biological insecticides ( and is a trademark of Mycogen Corporation, Indianapolis, Indiana, USA); insect pathogenic fungi such as Metarhizium; and insect pathogenic (both naturally occurring and genetically modified) viruses, including baculoviruses, nuclear polyhedrosis viruses (NPVs) such as Helicoverpa zea nuclear polyhedrosis virus (HzNPV), Anagrapha falcifera nuclear polyhedrosis virus (AfNPV); and granuloviruses (GVs) such as Cydia pomonella granulovirus (CpGV).

Of particular note are combinations in which other invertebrate pest control active ingredients belong to a different chemical class from the compound of Formula 1 or have a different site of action therefrom. In some cases, a combination with at least one other invertebrate pest control active ingredient having a similar control spectrum but a different site of action will be particularly advantageous for resistance management. Therefore, the composition of the present invention may further comprise a biologically effective amount of at least one additional invertebrate pest control active ingredient having a similar control spectrum but belonging to a different chemical class or having a different site of action. These additional biologically active compounds or agents include, but are not limited to, acetylcholinesterase (AChE) inhibitors such as the carbamate methomyl, oxamyl, thiodicarb, triazolam and the organophosphate chlorpyrifos; GABA-gated chloride channel antagonists such as the cyclopentadiene insecticides dieldrin and endosulfan, and the phenylpyrazoles ethiprole and fipronil; sodium channel modulators such as the pyrethroids bifenthrin, cypermethrin, β-cypermethrin, cyhalothrin, λ-cyhalothrin, cypermethrin, bromide Cypermethrin, transfluthrin, cypermethrin, metofluthrin and profluthrin; nicotinic acetylcholine receptor (nAChR) agonists such as the neonicotinoids acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nitrothiazide, thiacloprid and thiamethoxam, and sulfonecarb; nicotinic acetylcholine receptor (nAChR) allosteric activators such as the spinosads and spinosads; chloride channel activators such as avermectins abamectin and emamectin; juvenile hormone mimetics such as benzylpyridin. ethers, methoprene, fenoxycarb and pyriproxyfen; selective homopteran feeding blockers such as pymetrozine and flonicamid; mite growth inhibitors such as etoxazole; mitochondrial ATP synthase inhibitors such as propargite; uncouplers of oxidative phosphorylation via proton gradient disruption such as chlorfenapyr; nicotinic acetylcholine receptor (nAChR) channel blockers such as the nereistoxin analog cartap; chitin biosynthesis inhibitors such as the benzoylurea flufenoxuron, hexaflumuron, lufenuron, noflubenzuron, nobifenuron and cyfluthrin urea, and buprofezin; dipteran molting disruptors such as cyromazine; ecdysone receptor agonists such as the diacylhydrazide methoxyfenozide and fenbumid; true octopamine receptor agonists such as amitraz; mitochondrial complex III electron transport inhibitors such as hydrazone; mitochondrial complex I electron transport inhibitors such as pyridabenz; voltage-dependent sodium channel blockers such as indoxacarb; acetyl CoA carboxylase inhibitors such as tetronic acid and 1,5-dihydro-4-hydroxy-2H-pyrrol-2-one (tetramic acid) spirodiclofen, spiromesifen and spirotetramat; mitochondrial complex II electron transport inhibitors such as the β-ketonitriles pyraclostrobin and cyfluthrin; ryanodine receptor modulators such as the anthranilic acid diamides chlorantraniliprole, cyantraniliprole and cyantraniliprole, diamides such as flubendiamide, and ryanodine receptor ligands such as ryanodine; compounds in which the target site responsible for the biological activity is unknown or uncharacterized, such as azadirachtin, bifenazate, pyridalyl, new quinazoline (meta-diazine) class insecticides and triflubenzuron; insect midgut membrane microbial disruptors such as Bacillus thuringiensis and the delta-endotoxins they produce and Bacillus sphaericus and biological agents, including nuclear polyhedrosis viruses (NPV) and other naturally occurring or genetically modified insecticidal viruses.

Additional examples of biologically active compounds or agents that can be formulated with the compounds of the present invention are fungicides such as acibenzolar-S-methyl, 4-dodecyl-2,6-dimethylmorpholine (aldimorph), pyraclostrobin, anthracene, dithiocarb, pentoconazole, azoxystrobin, bensulfuron (including bensulfuron-M), oxadiazine, benomyl, benthiavalicarb (including benthiavalicarb-isopropyl), benzovindiflupyr, 3-benzo[b]thiophen-2-yl-5,6-dihydro-1, 4,2-thiazine 4-oxide (bethoxazin), binacarb, biphenyl, triadimefon, bifenthrin, blasticidin, boscalid, fumarole, pyrimidine, butyrate, carboxin, cyproconazole, captan, captan, carbendazim, chlorpyrifos, chlorothalonil, chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate, syringostyrin, cyazofamid, flutolanil, cymoxanil, cyproconazole, cyproconazole, cyprodinil, dichlorvos, dichlorocyanamide, chloranil, chlorfenapyr, ethoprop, difluanid, dimethomorph, dimethomorph, dimethomorph, dimethomorph, dimethomorph, dimethomorph (including dimethomorph-M), diclofenac, dithianon, dithiolane, dodecanone, docodine, econazole , ethoconazole, dichlorvos, enoxastrobin (also known as enestroburin), epoxiconazole, ethaboxam, ethocyanin, oxathiapiprolin ... Flutriafol, fluoxapyrab, folpet, tetrachlorophthalide (also known as phthalide), phthalide, furalaxyl, forabi, hexaconazole, oxamexazole, biguanide salt, imazalil, amide, amide, alkylbenzene sulfonate standard, biguanide octylamine triacetate, iodicarb, cyproconazole, isofetamid, isofetamidoprop, isoproconazole, propineb, rice blast, pyraclostrobin, isothiopyrad, kasugamycin, kesuoxin, mancozeb, mandestrobin, maneb, mapanipyrin, oxadiazine, metalaxyl (including high-efficiency metalaxyl/metalaxyl-M), metconazole, sulfamethoxam, Senlian, benzylpyrazone, mefenamic acid, myclobutanil, naftitine, ferric ammonium arsenate (ferric methylarsate), flubendiamide, octhilamide, furamide, oxamyl, oxathiapiprolin, oxolinic acid, oximidazole, oxycarboxin, oxytetracycline, penconazole, pencuron, penflufenamic acid, penthiopyrad, perfurazoate, phosphorous acid (including its salts, such as triethyl aluminum), picoxystrobin, powdery mildew, polyoxin, thiabendazole, prochloraz, propymidone, propamocarb, propiconazole, methyl propineb, propoxyquin, thiocarb, prothioconazole, pyraclostrobin, azole Aminostim, pyraclostrobin, pyraclostrobin, pyraclofos, pyributacarb, pyributacarb, pyriofenone, perisoxazole, pyrimidine, pyributacarb, pyrrolnitrin, pyroquilon, quinconazole, quinmethionate, quinoxyfen, pentachloronitrobenzene, silthiopyrad, fluazifop, silfluazole, spiroxafil, streptomycin, sulfur, tebuconazole, tebufloquin, teclofthalam, kekurot, tetranitrobenzene, terbinafine, fluconazole, thiabendazole, thiofuran, thiophanate-methyl The invention also includes the following: chloranil, thiram, thiamethoxam, tolprocarb, tolylfluanid, triadimefon, triadimenol, myclobutanil, tripyraclostrobin, tribasic copper sulfate, chlorpyrifos-butyl, tridemorph, trifloxystrobin, triflumizole, trimoprhamide, trifloxystrobin, trimethoprim-butyl, triclosan, trimethoprim-butyl, triclosan, trimethoprim-butyl, triclosan, trimethoprim-butyl, triclosan, valinate (also known as valifenal), valinate (also known as valifenal), vinclozolin, mancozeb, ziram, zoxanil and 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazole nematicides such as fluopyram, spirotetramat, thiodicarb, thiothiazolyl, abamectin, iprodione, fluensulfone, dimethyl disulfide, tioxazafen, 1,3-dichloropropylene (1,3-D), metamidine (sodium and potassium), dazomet, chloropicrin, fenamiphos, chloranil, cadusaphos, terbufos, imicyafos, oxamyl, carbofuran, tioxazafen, Bacillus firmus (Bacillus firmus and Pasteuria nishizawae; bactericides such as streptomycin; acaricides such as amitraz, chlorpyrifos, chlorfenapyr, cypermethrin, dicofol, cyfluthrin, etoxazole, fenazaquin, fenbutatin, cypermethrin, fenpyrad, hexathiapiprolin, propargite, pyridaben and tebufenpyrad.

In some cases, the combination of the compounds of the present invention with other biologically active (particularly invertebrate pest control) compounds or agents (i.e., active ingredients) can result in greater than additive (i.e., synergistic) effects. Reducing the amount of active ingredients released into the environment while ensuring effective pest control has always been desirable. When synergistic effects of invertebrate pest control active ingredients occur at the application rate, thereby imparting an agronomically satisfactory level of invertebrate pest control, such combinations can be advantageously used to reduce crop production costs and reduce environmental loads.

The compounds of the invention and compositions thereof can be applied to plants that have been genetically transformed to express proteins that are toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxin). Such application can provide a broader spectrum of plant protection and is advantageous for resistance management. The invertebrate pest control effects of exogenously applied compounds of the invention can act synergistically with the expressed toxin protein.

General references to these agricultural protectants (i.e., insecticides, fungicides, nematicides, miticides, herbicides and biological agents) include The Pesticide Manual, 13th edition, C.D.S. Tomlin, ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd edition, L.G. Copping, ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.

For embodiments in which one or more of these various admixture components are used, the weight ratio of these various admixture components (total amount) to the compound of Formula 1 is generally between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (e.g., ratios between about 1:30 and about 30:1). One skilled in the art can readily determine the biologically effective amount of the active ingredient necessary for the desired spectrum of biological activity by simple experimentation. It will be apparent that the inclusion of these additional components can expand the spectrum of invertebrate pest control beyond that provided by the compound of Formula 1 alone.

Table A lists the specific combination of the compound of Formula 1 with other invertebrate pest control agents, illustrating the mixture, composition and method of the present invention. The first column of Table A lists specific invertebrate pest control agents (e.g., "abamedin" in the first row). The second column of Table A lists the mode of action (if known) or chemical class of the invertebrate pest control agent. The third column of Table A lists one or more embodiments of the weight ratio range of the compound of Formula 1 relative to the compound of Formula 1 (e.g., abamedin is "50:1 to 1:50" by weight relative to the compound of Formula 1) at which the invertebrate pest control agent can be applied. Therefore, for example, the first row of Table A specifically discloses that the combination of the compound of Formula 1 and abamedin can be applied at a weight ratio between 50:1 and 1:50. The remaining rows of Table A will be similarly constructed. It is further worth noting that Table A lists the specific combination of the compound of Formula 1 with other invertebrate pest control agents, illustrating the mixture, composition and method of the present invention, and includes additional embodiments of the weight ratio range of the application rate.

Table A

Of note are compositions of the present invention wherein at least one additional biologically active compound or agent is selected from the invertebrate pest control agents listed in Table A above.

The weight ratio of the compound comprising the compound of Formula 1, its N-oxide or salt thereof to the additional invertebrate pest control agent is typically between 1000:1 and 1:1000, one embodiment is between 500:1 and 1:500, another embodiment is between 250:1 and 1:200, and another embodiment is between 100:1 and 1:50.

Listed below in Tables B1 to B10 are examples of specific compositions comprising compounds of Formula 1 (compound numbers refer to compounds in Index Tables A-N) and additional invertebrate pest control agents.

Table B1

Table B2

Table B2 is identical to Table B1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 14. For example, the first mixture in Table B2 is designated B2-1 and is a mixture of compound 14 and an additional invertebrate pest control agent, abamectin.

Table B3

Table B3 is identical to Table B1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 16. For example, the first mixture in Table B3 is designated B3-1 and is a mixture of compound 16 and an additional invertebrate pest control agent, abamectin.

Table B4

Table B4 is identical to Table B1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 19. For example, the first mixture in Table B4 is designated B4-1 and is a mixture of compound 19 and the additional invertebrate pest control agent abamectin.

Table B5

Table B5 is identical to Table B1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 41. For example, the first mixture in Table B5 is designated B5-1 and is a mixture of compound 41 and an additional invertebrate pest control agent, abamectin.

Table B6

Table B6 is identical to Table B1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 42. For example, the first mixture in Table B6 is designated B6-1 and is a mixture of compound 42 and an additional invertebrate pest control agent, abamectin.

Table B7

Table B7 is identical to Table B1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 51. For example, the first mixture in Table B7 is designated B7-1 and is a mixture of compound 51 and an additional invertebrate pest control agent, abamectin.

Table B8

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

Table B9

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

Table B10

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

The specific mixtures listed in Tables B1 to B10 generally combine the compound of Formula 1 with the other invertebrate pest agents in the ratios specified in Table A.

Listed in Tables C1 to C10 below are specific mixtures comprising a compound of Formula 1 (compound number (Cmpd. No.) refers to the compound in Index Tables A-N) and an additional invertebrate pest control agent. Tables C1 to C10 further list typical specific weight ratios of the mixtures of Tables C1 to C10. For example, the first weight ratio entry in the first row of Table C1 specifically discloses a mixture of Compound 8 of Index Table A and Abamectin applied at a weight ratio of 100 parts of Compound 1 to 1 part of Abamectin.

Table C1

Table C2

Table C2 is identical to Table C1, except that each reference to Compound 8 in the column heading "Compound No." is replaced with a reference to Compound 14. For example, the first weight ratio entry in the first row of Table C2 specifically discloses a mixture of Compound 14 and abamectin administered in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C3

Table C3 is identical to Table C1, except that each reference to Compound 8 in the column heading "Compound No." is replaced with a reference to Compound 16. For example, the first weight ratio entry in the first row of Table C3 specifically discloses a mixture of Compound 16 and abamectin administered in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C4

Table C4 is identical to Table C1, except that each reference to Compound 8 in the column heading "Compound No." is replaced with a reference to Compound 19. For example, the first weight ratio entry in the first row of Table C4 specifically discloses a mixture of Compound 19 and abamectin administered in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C5

Table C5 is identical to Table C1, except that each reference to Compound 8 in the column heading "Compound No." is replaced with a reference to Compound 41. For example, the first weight ratio entry in the first row of Table C5 specifically discloses a mixture of Compound 41 and abamectin administered in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C6

Table C6 is identical to Table C1, except that each reference to Compound 8 in the column heading "Compound No." is replaced with a reference to Compound 42. For example, the first weight ratio entry in the first row of Table C6 specifically discloses a mixture of Compound 42 and abamectin administered in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C7

Table C7 is identical to Table C1, except that each reference to Compound 8 in the column heading "Compound No." is replaced with a reference to Compound 51. For example, the first weight ratio entry in the first row of Table C7 specifically discloses a mixture of Compound 51 and abamectin administered in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C8

Table C8 is identical to Table C1, except that each reference to Compound 8 in the column heading "Compound No." is replaced with a reference to Compound 54. For example, the first weight ratio entry in the first row of Table C8 specifically discloses a mixture of Compound 54 and abamectin administered in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C9

Table C9 is identical to Table C1, except that each reference to Compound 8 in the column heading "Compound No." is replaced with a reference to Compound 55. For example, the first weight ratio entry in the first row of Table C9 specifically discloses a mixture of Compound 55 and abamectin administered in a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Table C10

Table C10 is identical to Table C1, except that each reference to Compound 8 in the column heading "Compound No." is replaced with a reference to Compound 76. For example, the first weight ratio entry in the first row of Table C10 specifically discloses a mixture of Compound 76 and abamectin administered at a weight ratio of 100 parts Compound 1 to 1 part abamectin.

Listed in Tables D1 to D10 below are examples of specific compositions comprising compounds of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Tables A-N) and additional fungicides.

Table D1

(a) 1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone

Table D2

Table D2 is identical to Table D1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 14. For example, the first mixture in Table D2 is designated D2-1 and is a mixture of compound 14 and the additional fungicide thiabendazole.

Table D3

Table D3 is identical to Table D1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 16. For example, the first mixture in Table D3 is designated D3-1 and is a mixture of compound 16 and the additional fungicide thiabendazole.

Table D4

Table D4 is identical to Table D1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 19. For example, the first mixture in Table D4 is designated D4-1 and is a mixture of compound 19 and the additional fungicide thiabendazole.

Table D5

Table D5 is identical to Table D1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 41. For example, the first mixture in Table D5 is designated D5-1 and is a mixture of compound 41 and the additional fungicide thiabendazole.

Table D6

Table D6 is identical to Table D1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 42. For example, the first mixture in Table D6 is designated D6-1 and is a mixture of compound 42 and the additional fungicide thiabendazole.

Table D7

Table D7 is identical to Table D1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 51. For example, the first mixture in Table D7 is designated D7-1 and is a mixture of compound 51 and the additional fungicide thiabendazole.

Table D8

Table D8 is identical to Table D1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 54. For example, the first mixture in Table D8 is designated D8-1 and is a mixture of compound 54 and the additional fungicide thiabendazole.

Table D9

Table D9 is identical to Table D1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 55. For example, the first mixture in Table D9 is designated D9-1 and is a mixture of compound 55 and the additional fungicide thiabendazole.

Table D10

Table D10 is identical to Table D1 except that each reference to compound 8 in the column heading "Compound No." is replaced with a reference to compound 76. For example, the first mixture in Table D10 is designated D10-1 and is a mixture of compound 76 and the additional fungicide thiabendazole.

In agronomic and nonagronomic applications, invertebrate pests are controlled by applying a biologically effective amount of one or more compounds of the invention, usually in the form of a composition, to the pest environment, including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly to the pest to be controlled.

Thus, the present invention includes a method for controlling invertebrate pests in agronomic and/or non-agricultural applications, comprising contacting the invertebrate pests or their environment with a biologically effective amount of one or more compounds of the present invention or with a composition comprising at least one such compound or a composition comprising at least one such compound and a biologically effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a compound of the present invention and a biologically effective amount of at least one additional biologically active compound or agent include granular compositions, wherein the additional active compound is present on the same particles as the compounds of the present invention or on particles separate from those particles of the compounds of the present invention.

To achieve contact with the compounds or compositions of the invention to protect field crops from invertebrate pests, the compounds or compositions are typically applied to crop seeds prior to planting, to the foliage (e.g., leaves, stems, flowers, fruits) of crop plants, or to the soil or other growth medium before or after planting the crop.

One embodiment of a contact method is by spraying. Alternatively, a granular composition comprising the compound of the present invention can be applied to plant leaves or in the soil. The compound of the present invention can also be effectively delivered by plant absorption by contacting the plant with a composition comprising the compound of the present invention applied as a soil drench as a liquid formulation, a granular formulation into the soil, a nursery box treatment, or a transplant soak. It is worth noting that the composition of the present invention is in the form of a soil drench liquid formulation. It is also worth noting that a method for preventing and controlling invertebrate pests includes contacting the invertebrate pest or its environment with a biologically effective amount of the compound of the present invention or with a composition comprising a biologically effective amount of the compound of the present invention. It is further worth noting that this method, wherein the environment is soil and the composition is applied to the soil as a soil drench formulation. It is also worth noting that the compound of the present invention is also effective by topical application to the site of the infestation. Other contact methods include applying the compound or composition of the present invention by direct spraying and retention spraying, aerial spraying, gel, seed coating, microencapsulation, systemic absorption, bait, ear tag, bolus, sprayer, fumigant, aerosol, powder, and many other methods. One example of a contacting method is a dimensionally stable fertilizer granule, stick or tablet comprising a compound or composition of the invention. The compounds of the invention may also be impregnated into materials used to make invertebrate pest control devices (eg, insect screens).

The compounds of the present invention can be used to treat all plants, plant parts and seeds. Plant and seed varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which a heterologous gene (transgene) has been stably integrated into the plant or seed genome. Transgenics defined by their specific position in the plant genome are referred to as transformation or transgenic events.

Genetically modified plant and seed cultivars that can be treated according to the present invention include those that resist one or more biological stresses (harmful organisms, such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinization, etc.), or those that contain other desired characteristics. Plants and seeds can be genetically modified to express traits, such as herbicide tolerance, insect resistance, modified oil characteristics, or drought tolerance. Useful genetically modified plants and seeds including a single gene transformation event or a combination of transformation events are listed in Table Z. Additional information for the genetic modifications listed in Table Z can be obtained from the following databases:

http://www2.oecd.org/biotech/byidentifier.aspx

http://www.aphis.usda.go

http://gmoinfo.jrc.ec.europa.eu

The following abbreviations are used in the following Table Z: tol. is tolerance, res. is resistance, SU is sulfonylurea, ALS is acetolactate synthase, HPPD is 4-hydroxyphenylpyruvate dioxygenase, and NA is not available?

Table Z

*Argentina, **Poland, #Eggplant

Treatment of genetically modified plants and seeds with the compounds of the invention may result in superadditive or synergistic effects. For example, reduced application rates, expanded activity spectrum, increased tolerance to biotic/abiotic stresses, or enhanced storage stability may be greater than would be expected from the additive effects of simply applying the compounds of the invention to genetically modified plants and seeds.

The compounds of the present invention can also be used in seed treatments to protect seeds from invertebrate pests. In the context of the present disclosure and claims, treating seeds means contacting the seeds with a biologically effective amount of the compounds of the present invention, which are typically formulated into the compositions of the present invention. The seed treatment protects the seeds from invertebrate soil pests and can also protect the roots and other soil-contacted plant parts of the seedlings developed from the germinating seeds in general. The seed treatment can also provide protection to the leaves by translocating the compounds of the present invention or the second active ingredient in the developing plants. The seed treatment can be applied to all types of seeds, including those that will germinate to form transgenic plants to express specific traits. Representative examples include those that express proteins that are toxic to invertebrate pests, such as Bacillus thuringiensis toxins, or those that express herbicide resistance, such as glyphosate acetyltransferase that provides glyphosate resistance. Seed treatments with the compounds of the present invention can also increase the vigor of plants grown from seeds.

One method of seed treatment is to spray or dust the seeds with the compound of the present invention (i.e., as a formulated composition) before sowing the seeds. The composition formulated for seed treatment generally comprises a film former or an adhesive. Therefore, typically, the seed coating composition of the present invention comprises a biologically effective amount of a compound of formula 1, an N-oxide or salt thereof, and a film former or an adhesive. Seed coating can be performed by spraying a flowable suspension concentrate directly into a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wet powders, solutions, suspoemulsions, emulsifiable concentrates, and emulsions in water can be sprayed on seeds. The method is particularly useful for applying film coatings to seeds. Those skilled in the art may use various coating equipment and methods. Suitable methods include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects [seed treatment: progress and prospects], 1994 BCPC monograph No. 57 and the references listed therein.

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

Other insecticides that can be formulated with the compounds of Formula 1 to provide mixtures useful for seed treatment include abamectin, acetamiprid, acralthrin, amitraz, avermectin, azadirachtin, sulfanil, bifenthrin, buprofezin, cadusafos, carbaryl, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfluthrin, beta-cyfluthrin, flucythrin, gamma-cyfluthrin, lambda-cyfluthrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, benzylpyrene, emamectin, endosulfan, cypermethrin, ethiprole, fenthiocarb, fenoxycarb, cypermethrin , fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate, flumethrin, famoxadone, hexamethonium, hydrazone, imidacloprid, indoxacarb, lufenuron, metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide, nitenpyram, nithiazole, bispyribac, oxamyl, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, lyanodine, ethyl spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfone cypermethrin, tebuconazole, pyrethroids, thiamethoxam, thiodicarb, dimethoate, tralomethrin, triazolam, triflumuron, Bacillus thuringiensis delta-endotoxin, all strains of Bacillus thuringiensis and all strains of nuclear polyhedrosis virus.

Fungicides that can be formulated with the compounds of Formula 1 to provide mixtures useful for seed treatment include indazolesulfuron, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, fluazinam, fludioxonil, fluquinconazole, fluopyram, fluoxastrobin, flutriafol, fluopyram, ipconazole, iprodione, metalaxyl, metalaxyl-M, metconazole, myclobutrazol, paclobutrazol, pentocyclanil, picoxystrobin, prothioconazole, pyraclostrobin, flutoxafen, sithiopyrad, tebuconazole, thiabendazole, methylthiophanate, thiram, trifloxystrobin and trichlorfon.

Compositions comprising compounds of Formula 1 useful for seed treatment may further comprise bacteria and fungi having the ability to provide protection from harmful effects of plant pathogenic fungi or bacteria and/or soil-born animals such as nematodes. Bacteria exhibiting nematicidal properties may include but are not limited to Bacillus firmus, Bacillus cereus, Bacillus subtiliis and Pasteuria penetrans. Suitable Bacillus firmus strains are commercially available strains CNCM I-1582 (GB-126) as BioNem ^TM . Suitable Bacillus cereus strains are strains NCMM I-1592. Both Bacillus strains are disclosed in US 6,406,690. Other suitable bacteria exhibiting nematicidal activity are Bacillus amyloliquefaciens IN937a and Bacillus subtilis strain GB03. Bacteria that exhibit fungicidal properties may include, but are not limited to, B. pumilus strain GB 34. Fungal species that exhibit nematicidal properties may include, but are not limited to, Myrothecium verrucaria, Paecilomyces lilacinus, and Purpureocillium lilacinum.

Seed treatments may also include one or more naturally derived nematicides, such as elicitor proteins known as harpins, which are isolated from certain bacterial plant pathogens such as Erwinia amylovora. An example is Harpin-N-Tek Seed Treatment Technology available as N-Hibit ^™ Gold CST

Seed treatments may also include one or more legume root nodulation bacterial species, such as the microsymbiotic nitrogen-fixing bacterium Bradyrhizobium japonicum. These inoculants may optionally contain one or more lipid chitosan oligosaccharides (LCOs), which are nodulation (Nod) factors produced by Rhizobium bacteria during the initiation of nodule formation on the roots of legumes. For example, brand seed treatment technology incorporates LCO Promoter Technology ^™ in combination with an inoculant.

Seed treatments may also include one or more isoflavones, which may increase the level of root colonization by mycorrhizal fungi. Mycorrhizal fungi improve plant growth by enhancing root uptake of nutrients such as water, sulfates, nitrates, phosphates, and metals. Examples of isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperidin, naringenin, and tricholoma. Formononetin is used as a mycorrhizal inoculant product such as PHC The active ingredients in AG are available.

Seed treatments may also include one or more plant activators that induce systemic acquired resistance in plants after exposure to pathogens. An example of a plant activator that induces such a protective mechanism is acibenzolar-S-methyl.

Treated seeds generally contain the compound of the invention in an amount of from about 0.1 g to 1 kg per 100 kg of seeds (i.e., from about 0.0001% to 1% by weight of the seeds before treatment). Flowable suspensions formulated for seed treatment typically contain from about 0.5% to about 70% active ingredient, from about 0.5% to about 30% film-forming binder, from about 0.5% to about 20% dispersant, from 0% to about 5% thickener, from 0% to about 5% pigment and/or dye, from 0% to about 2% defoamer, from 0 to about 1% preservative, and from 0% to about 75% volatile liquid diluent.

The compounds of the present invention may be incorporated into bait compositions that are eaten by invertebrate pests or used in devices such as traps, bait stations, and the like. Such bait compositions may be in the form of granules comprising (a) an active ingredient, i.e., a biologically effective amount of a compound of Formula 1, an N-oxide or salt thereof; (b) one or more food materials; optionally (c) an attractant, and optionally (d) one or more wetting agents. It is noteworthy that granules or bait compositions comprising between about 0.001%-5% active ingredient, about 40%-99% food materials and/or attractants; and optionally about 0.05%-10% wetting agents, which can effectively control soil invertebrate pests at very low application rates, especially at doses of active ingredients that are lethal by ingestion rather than by direct contact. Some food materials can be used as both a food source and an attractant. Food materials include carbohydrates, proteins, and lipids. Examples of food materials are vegetable powders, sugars, starches, animal fats, vegetable oils, yeast extracts, and milk solids. Examples of attractants are flavor enhancers and flavors, such as fruit or plant extracts, spices, or other animal or plant components, pheromones, or other agents known to attract target invertebrate pests. Examples of humectants (i.e., water retainers) are ethylene glycol and other polyols, glycerol, and sorbitol. Of note are bait compositions (and methods of using such bait compositions) for controlling at least one invertebrate pest selected from the group consisting of ants, termites, and cockroaches. A device for controlling invertebrate pests, the device may include a bait composition of the present invention and a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to allow the invertebrate pest to pass through the opening so that the invertebrate pest can approach the bait composition from a location external to the housing, and wherein the housing is further adapted to be placed in or near a location of potential or known activity of the invertebrate pest.

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

Although the spray composition formed by diluting the insecticidal composition of the present invention at a sufficient concentration with water can provide sufficient efficacy in controlling invertebrate pests, separately formulated adjuvant products can also be added to the spray tank mixture. These additional adjuvants are generally referred to as "spray adjuvants" or "tank-mix adjuvants", and include any material mixed in the spray tank to improve the performance of the pesticide or to change the physical properties of the spray mixture. The adjuvant can be a surfactant, an emulsifier, a crop oil based on petroleum, a seed oil derived from a crop, an acidulant, a buffer, a thickener, or a defoamer. Adjuvants are used to enhance efficacy (e.g., bioavailability, adhesion, permeability, uniformity of coverage, and durability of protection), or minimize or eliminate spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization, and degradation. In order to obtain optimal performance, the adjuvant is selected with respect to the characteristics, formulation, and target (e.g., crops, insect pests) of the active ingredient.

Among spray adjuvants, oils (including crop oils, crop oil concentrates, vegetable oil concentrates, and methylated seed oil concentrates) are most commonly used to improve the efficacy of pesticides, which may be achieved by promoting more uniform and consistent spray deposition. In cases where phytotoxicity that may be caused by oils or other water-immiscible liquids is important, spray compositions prepared from the compositions of the present invention will generally not include oil-based spray adjuvants. However, in cases where phytotoxicity caused by oil-based spray adjuvants is commercially insignificant, spray compositions prepared from the compositions of the present invention may also include oil-based spray adjuvants, which can potentially further increase the control of invertebrate pests, as well as rainfastness.

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

The amount of adjuvant added to the spray mixture is usually no more than about 2.5% by volume, and more usually the amount is from about 0.1% to about 1% by volume. The application rate of adjuvant added to the spray mixture is usually between about 1 liter and 5 liters per hectare. Representative examples of spray adjuvants include: (Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons; (Helena Chemical Company) polyoxyalkylene-modified heptamethyltrisiloxane and (BASF) 17% surfactant blend in 83% paraffinic mineral oil.

The compound of the present invention can be applied without other adjuvants, but the most common application is to apply a preparation comprising one or more active ingredients with suitable carriers, diluents and surfactants, and may be combined with food according to the envisioned end use. A method of application involves spraying an aqueous dispersion or refined oil solution of the compound of the present invention. Combinations with spray oil, spray oil concentrate, sticking agents, adjuvants, other solvents and synergists such as piperonyl butoxide generally enhance compound efficacy. For non-agricultural purposes, such sprays can be applied from spray containers such as cans, bottles or other containers by means of a pump or by releasing it from a pressurized container such as a pressurized aerosol spray can. Such spray compositions can take a variety of forms, such as spray, mist, foam, smoke or dust. Therefore, according to the specific circumstances, such spray compositions can further include propellants, foaming agents, etc. It is worth noting that the spray composition comprising a biologically effective amount of the compound of the present invention or composition and a carrier. An embodiment of such a spray composition comprises a biologically effective amount of the compound of the present invention or composition and a propellant. Representative propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butylene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing. Of note are spray compositions (and methods of using such spray compositions dispensed from spray containers) for controlling at least one invertebrate pest selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like, alone or in combination.

Biological Examples of the Invention

The following tests demonstrate the control efficacy of the compounds of the present invention for specific harmful organisms. "Control efficacy" means the inhibition (including mortality) of invertebrate pest development resulting in a significant reduction in feeding. However, the harmful organism control protection provided by the compounds is not limited to these species. See Index Tables A-N for compound descriptions.

Formulations and spray methodology for tests A-F

Use a mixture containing 10% acetone, 90% water and 300ppm The test compound was prepared with a solution of Spreader Lo-Foam Formula nonionic surfactant, which includes alkylaryl polyoxyethylene, free fatty acids, ethylene glycol and isopropyl alcohol (Loveland Products, Inc. Greeley, Colorado, USA). The prepared compound was applied with 1 mL of liquid by a SUJ2 sprayer nozzle (Spraying Systems Co. Wheaton, Illinois, USA) with a 1/8 JJ custom body positioned 1.27 cm (0.5 inch) above the top of each test unit. The test compound was sprayed at a specified rate, and each test was repeated three times.

Test A

To evaluate the control of diamondback moth (Plutella xylostella (L.)), the test unit consisted of a small open container with 12-14 day old mustard plants inside. The test unit was pre-infested with about 50 newborn larvae distributed into it via corn cob crumbs using an inoculator. After being dispersed into the test unit, the larvae moved onto the test plants.

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

Of the compounds of Formula 1 tested at 250 ppm, the following provided very good to excellent levels of control efficacy (40% or less feeding damage, and/or 100% mortality): 309, 501, 502, 344, 431, 466, 609, 658, 673, 720, 734, 735, 750, 819, 820, 822, 824, 844 and 859.

Of the compounds of Formula 1 tested at 50 ppm, the following provided very good to excellent levels of control efficacy (40% or less feeding damage, and/or 100% mortality): 735 and 824.

Test B

To evaluate control of potato leafhopper (Empoasca fabae (Harris)) by contact and/or systemic means, the test unit consisted of a small open container with 5-6 day old Soleil bean plants (primary leaves showing) inside. White sand was added to the top of the soil and one primary leaf was cut off before application of the test compound.

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

Of the compounds of Formula 1 tested at 250 ppm, the following caused at least 80% mortality: 21, 130, 131, 133, 300, 301, 309, 366, 367, 368, 370, 375, 380, 382, 386, 387, 388, 409, 466, 636, 646, 648, 664, 685, 802, 824, 827, 836, 837, 842, 843, 855, and 859.

Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 301, 309, 375, 380, 382, 386, 387, 388, 648, 836, 837, 842, 843, and 855.

Test C

To evaluate the control of green peach aphid (Myzus persicae (Sulzer)) by contact and/or systemic means, the test unit consisted of a small open container with 12-15 day old radish plants inside. The plants were pre-infested by placing 30-40 aphids on a leaf cut from a cultivated plant on the leaves of the test plants (cut leaf method). As the leaves dehydrated, the aphids moved on the test plants. After pre-infestation, the soil of the test unit was covered with a layer of sand.

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

Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1, 6, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 24, 25, 26, 27, 28, 34, 35, 36, 37, 39, 41, 42, 44, 46, 49, 51, 52, 53, 54, 55, 56, 57, 58, 60, 61, 62, 63, 64, 66, 67, 68, 69, 70, 72, 73, 74, 75, 76, 78, 79, 81, 84, 85, 86, 92, 96, 97, 98, 100, 102, 106, 111, 114 、117、118、121、122、124、125、131、132、133、160、161、162、163、173、300、301、308、309、320、321、322、323、324、326、329、330、331、332、333、334、335、336、338、340、341、342、343、344、345、346、348、350、351、352、353、354、363、364、366、370、372、374、375、376、377、378、380、381、382、387、3 88, 393, 400, 401, 402, 403, 404, 409, 410, 411, 412, 413, 415, 416, 419, 439, 440, 442, 443, 444, 445, 446, 447, 448, 449, 455, 456, 462, 463, 464, 50 0, 501, 502, 503, 600, 601, 603, 604, 605, 606, 608, 609, 610, 611, 612, 613, 614, 615, 616, 617, 618, 619, 621, 623, 624, 626, 627, 628, 629, 630, 63 1, 636, 637, 638, 639, 640, 641, 642, 643, 645, 647, 648, 658, 667, 720, 721, 722, 723, 724, 726, 727, 729, 731, 732, 733, 734, 735, 736, 738, 746, 747, 748, 764, 765, 815, 819, 824, 826, 827, 828, 830, 831, 832, 833, 836, 837, 838, 839, 840, 841, 843, 844, 845, 848, 849, 850, 852, 855, 856, 857, and 858.

Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 6, 7, 8, 10, 11, 12, 13, 14, 16, 17, 18, 19, 21, 24, 25, 26, 27, 28, 34, 35, 36, 37, 39, 41, 42, 46, 49, 51, 52, 53, 54, 55, 56, 57, 58, 60, 62, 63, 64, 66, 67, 68, 69, 73, 75, 76, 78, 81, 84, 85, 86, 96, 121, 122, 124, 125, 131, 132, 133, 160, 161, 162, 163, 300, 308,309,320,322,323,324,325,326,329,330,331,332,333,334,335,336,338,340,342,343,344,345,346,348,350,351,352,353,354,366,3 74, 375, 376, 378, 380, 382, 387, 388, 401, 402, 403, 404, 409, 410, 411, 412, 413, 415, 419, 440, 443, 444, 445, 446, 447, 448, 455, 462, 463 ,464,500,501,502,503,600,601,604,605,606,608,609,613,614,615,616,617,619,623,626,629,630,631,636,637,638,639,640,641,642, 7 731, 732, 735, 736, 738, 744, 746, 747, 748, 758, 759, 764, 765, 766, 767, 771, 775, 780, 800, 801, 802, 803, 804, 805, 806, 807, 808, 815, 818, 819, 821, 823, 825, 826, 827, 828, 830, 831, 832, 833, 836, 837, 839, 840, 841, 843, 844, 845, 848, 849, 850, 852, 855, 856, 857, 858, 863, 864, and 865.

Test D

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

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

Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 6, 7, 8, 11, 12, 14, 16, 19, 21, 24, 25, 37, 39, 40, 41, 51, 52, 54, 55, 58, 62, 63, 64, 66, 67, 68, 69, 70, 79, 96, 131, 133, 160, 161, 309, 323, 336, 342, 345, 348, 350, 351, 353, 366, 401, 403, 412, 419, 440 , 444, 447, 455, 462, 464, 500, 501, 503, 600, 605, 606, 608, 609, 612, 613, 614, 615, 616, 617, 618, 621, 623, 631, 636, 638, 639, 645, 667, 721, 724, 727, 728, 734, 735, 746, 765, 815, 819, 824, 831, 833, 836, 839, 840, 841, 844, 848, 850, and 858.

Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 80% mortality: 6, 8, 14, 16, 19, 21, 24, 39, 41, 42, 51, 52, 54, 55, 58, 67, 76, 131, 133, 323, 348, 351, 401, 403, 601, 605, 606, 608, 609, 613, 614, 615, 616, 617, 623 , 631, 636, 644, 645, 647, 649, 654, 655, 656, 657, 658, 683, 684, 685, 686, 695, 721, 724, 735, 736, 737, 738, 765, 775, 804, 818, 819, 821, 825, 826, 833, 839, 840, 841, 844, 855, 858 and 865.

Test E

For evaluation of control of western flower thrips (Frankliniellla occidentalis (Pergande)) by contact and/or systemic means, the test units consisted of small open containers with 5-7 day old Soleil bean plants inside.

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

Of the compounds of Formula 1 tested at 250 ppm, the following provided very good to excellent levels of control efficacy (30% or less plant damage and/or 100% mortality): 13, 64, 68, 70, 72, 131, 132, 133, 314, 340, 348, 367, 409, 410, 415, 464, 504, 601, 604, 609, 612 , 613, 615, 616, 617, 618, 619, 620, 622, 623, 624, 625, 631, 636, 637, 638, 720, 721, 722, 733, 778, 819, 828, 833, 836, 837, 838, 839, 840, 841, 843, 844, 845, 849, 850 and 855.

Of the compounds of Formula 1 tested at 50 ppm, the following provided very good to excellent levels of control efficacy (30% or less plant damage and/or 100% mortality): 615, 616, 646, 655, 657, 669, 685, 686, 695, 696, 769, 774, 776, 780, 836, 839, 855 and 865.

Test F

In order to evaluate the control of sweetpotato whitefly (Bemisia tabaci (Gennadius)) by contact and/or systemic means, the test unit consists of a small open container with 12-14 day old cotton plants inside. Before spray application, two cotyledons are removed from the plants, leaving one true leaf for determination. Adult whiteflies are allowed to lay eggs on the plants and then removed from the test unit. Cotton plants infested with at least 15 eggs are subjected to the spray test.

The test compound was formulated and sprayed at 250 ppm and/or 50 ppm. After spraying, the test unit was allowed to dry for 1 hour. The cylinder was then removed and the unit was taken to a growth chamber and maintained at 28°C and 50%-70% relative humidity for 13 days. The insect mortality of each test unit was then visually evaluated.

Of the compounds of Formula 1 tested at 250 ppm, the following caused at least 50% mortality: 8, 42, 58, 63, 64, 68, 72, 321, 324, 326, 330, 334, 339, 340, 348, 349, 360, 366, 368, 402, 403, 412, 456, 463, 606, 610, 636, 639, 726, 809, 824, 833, 836, 837, 839, 840, 841, 843, 844, 845, 849, 850, 852, 855, 856, 857.

Of the compounds of Formula 1 tested at 50 ppm, the following caused at least 50% mortality: 326, 648, 818, 824, 833, 836, 837, 839, 843, 849, 850, and 855.

Claims (11)

1. A compound selected from formula 1, an N-oxide or salt thereof,

Wherein the method comprises the steps of

Q is

A is CH;

each of X ¹ and X ² is independently CR ³,X³ is CR ²,X⁴ is CR ³ or N;

R ² is C (=z) NR ⁶R⁷;

Each Z is independently O or S;

Each R ³ is independently H, halogen, cyano, nitro, C ₁-C₄ alkyl, C ₁-C₄ haloalkyl;

y ² is CR ^5a;

r ^5a is H or halogen;

R ⁶ is H, NR ¹⁵R¹⁶、C₁-C₆ alkyl, or C ₃-C₆ cycloalkyl;

R ⁷ is H, C ₁-C₆ alkyl, or C ₃-C₆ cycloalkyl;

Each R ¹⁵ is independently H, C ₁-C₆ alkyl, C ₁-C₄ haloalkyl, or C (O) R ²⁷;

Each R ¹⁶ is independently H, C ₁-C₆ alkyl or C ₁-C₄ haloalkyl; and

Each R ²⁷ is independently C ₁-C₆ alkyl, C ₁-C₆ haloalkyl, C ₁-C₆ alkoxy, or C ₁-C₆ haloalkoxy.

2. A composition comprising a compound of claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

3. The composition of claim 2, further comprising at least one additional biologically active compound or agent.

4. The composition of claim 3, wherein the at least one additional biologically active compound or agent is selected from the group consisting of: abamectin, acephate, chlorfenapyr, acetamiprid, trifluralin, pyripyropene, sulfamethazine, amitraz, avermectin, azadirachtin, valphos, carbosulfan, dimefon, trifloxysulfuron bifenthrin, bifenazate, bistrifluron, borate, buprofezin, fenphos, carbaryl, cartap, chlorantraniliprole, chlorpyrifos, and chlorpyrifos bifenthrin, bifenazate, bistrifluron, borate, buprofezin, fenphos, carbaryl, and the like carbafuran, cartap, valproate, chlorantraniliprole, chlorpyrifos Tetrafipronil, dimehypo, dimethoate, dinotefuran, benomyl, emamectin, endosulfan, fenvalerate, ethiprole, eplerenone, etoxazole, fenbutatin oxide, fenitrothion, benfocarb, fenitrothion, fenpropidium, and mixtures thereof benomyl, fenpropathrin, fenvalerate, fipronil, flometoquin, flonicamid, fipronil, fluvalinate, pyrimethanil, flufenoxuron, flufenpyrad, fluthiamethoxam sulfone, fluopyram benxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide fenvalerate, pyrimethanil, flufenoxuron, flufenacet, fluthiamethoxam sulfone, fluopyram, bifenthrin, monocrotophos, monofluorothrin, nicotine, nitenpyram, novaluron, bisbenzofluorourea, polyfluorourea, oxamyl, parathion methyl parathion, chlorpyrifos, methamphetamine, valphos, phos, triazamate, and the like methyl parathion, chlorpyrifos, phorate, phoxim phosphorus iminothiolate, phosphamidon, pirimicarb, profenofos, profenothrin spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, thiophos, triamcinolone acetonide, tebufenozide, tebufenpyrad Fungicide, tefluthrin, terbufos, flucyantraniliprole, chlorpyrifos, plague, tefluthrin, thiacloprid thiamethoxam, thiodicarb, dimehypo, tioxazafen, tolfenpyrad, tetrabromothrin, triazamate, trichlorfon, triflumuron, bacillus thuringiensis (Bacillus thuringiensis) delta-endotoxin, entomopathogenic bacteria, entomopathogenic viruses and/or entomopathogenic fungi.

5. The composition of claim 3, wherein the at least one additional biologically active compound or agent is selected from the group consisting of: abamectin, acetamiprid, flumethrin, pyripyropene, amitraz, avermectin, azadirachtin, carbosulfan, monosulfuron, bifenthrin, buprofezin, fenphos, carbaryl, carbosulfan, and carbosulfan, and combinations thereof cartap, chlorantraniliprole, chlorpyrifos, clothianidin, cyantraniliprole, cyclomethidat, etofenprox, cyhalothrin, beta-cyhalothrin, cyhalothrin cartap, chlorantraniliprole, chlorpyrifos, clothianidin, cyantraniliprole Cyantraniliprole, beta-cyhalothrin, cyhalothrin Fluofenacin, fluthiamethoxam sulfone, flupiprole, flupyrafungon, flufenthrinate, valicarb, fosthiazate, heptafluthrin, hexaflumuron, triadimefon, imidacloprid, indoxacarb, lufenuron, bifenthrin, fenhalothrin, fenbufenpyrad metaflumizone, methiocarb, methoprene, methoxyfenozide, methoprene, monofluorothrin, nitenpyram, niflumic thiazole, bisphenylfluorourea, oxamyl, pyflubumide, pymetrozine metaflumizone, methiocarb, methoprene, methoxyfenozide, methoprene, bifenthrin, and the like monofluorothrin, nitenpyram, nitroethylurea thiazole, bisbenzofururon, oxamyl, pyflubumide, pymetrozine, all strains of bacillus thuringiensis and all strains of nucleopolyhedrovirus.

6. The composition of claim 3, wherein the at least one additional biologically active compound or agent is selected from the group consisting of: cyclobromothalamide flucyantraniliprole cyantraniliprole and chlorine and (3) antraniliprole.

7. The composition of any one of claims 3-6, wherein the weight ratio of the compound of formula 1 to the at least one biologically active compound or agent is from 1:3000 to 3000:1.

8. A method of protecting a field crop from invertebrate pests, the method comprising contacting the crop seed prior to planting, the crop leaf, or the soil or other growth medium prior to or after planting with a pesticidally effective amount of a compound of claim 1 or a composition of any of claims 2-7.

9. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound as claimed in claim 1 or a composition as claimed in any of claims 2 to 7, provided that the method is not a method of treating a human or animal body by therapy.

10. The method of claim 9, wherein the environment is a plant or seed.

11. The method of claim 10, wherein the treated seed comprises the compound of claim 1 in an amount of 0.0001% to 1% by weight of the seed prior to treatment.