CN112679467A - Heterocyclic substituted bicyclic azoles as pesticidal agents - Google Patents

Heterocyclic substituted bicyclic azoles as pesticidal agents Download PDF

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CN112679467A
CN112679467A CN202011576258.8A CN202011576258A CN112679467A CN 112679467 A CN112679467 A CN 112679467A CN 202011576258 A CN202011576258 A CN 202011576258A CN 112679467 A CN112679467 A CN 112679467A
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haloalkyl
substituted
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alkyl radical
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D·A·克拉克
B·G·弗拉加
张文明
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FMC Corp
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FMC Corp
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
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    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
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    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
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    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Abstract

Disclosed are compounds of formula 1, N-oxides or salts thereof, wherein Q is Q-2, and A, R1、m、X1、X2、X3、X4And Y2As defined in the present disclosure. Also disclosed are compositions containing the compounds of formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the invention.

Description

Heterocyclic substituted bicyclic azoles as pesticidal agents
This application is a divisional application of chinese patent application 201580079769.X entitled "heterocyclic substituted bicycloozole pesticides", filed 2016, 9, 15.
Technical Field
This invention relates to certain substituted bicycloozoles, their N-oxides, salts and compositions suitable for agricultural and non-agricultural use, and methods for their use in controlling invertebrate pests such as arthropods in both agricultural and non-agricultural environments.
Background
Control of invertebrate pests is extremely important in achieving high crop efficiency. Damage to growing and stored crops by invertebrate pests can cause significant reductions in production and thereby result in increased costs to the consumer. Control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal health is also important. For these purposes, many products are commercially available, but there is a continuing need for new compounds that are more effective, less costly, less toxic, environmentally safer, or have different sites of action.
Disclosure of Invention
The present invention is directed to compounds of formula 1 (including all geometric and stereoisomers), N-oxides, and salts thereof, and compositions containing them, and their use for controlling invertebrate pests:
Figure BDA0002864077420000011
wherein
Q is
Figure BDA0002864077420000012
A is CH, CR1Or N;
each R1Independently halogen, cyano, nitro, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio or C1-C4A haloalkylthio group;
m is 0, 1, 2 or 3;
X1、X2、X3and X4Each independently is CR2、CR3Or N, provided that (i) X1、X2、X3And X4One is CR2And (ii) X1、X2、X3And X4No more than one of is N;
R2is C (═ Z) NR6R7、N(R8)C(＝Z)R9、C(＝NR10)R11Or Qa；
Each Z is independently O or S;
each R3Independently is H, halogen, cyano, nitro, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4A haloalkoxy group;
Y1is O, S or NR4；
Y2Is N or CR5a；
Y3Is N or CR5b；
R4Is H or C1-C4An alkyl group;
R5ais H, halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4A haloalkoxy group;
R5bis H, halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4A haloalkoxy group;
R6is H, NR15R16、OR17、C(＝NR10)R11、C(O)OR21、C(O)NR15R16、C(O)R22、S(O)nR23Or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one R xSubstituted;
R7is H or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted; or
R6And R7Together with the nitrogen atom to which they are attached form a 3-to 10-membered ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Said ring being unsubstituted or substituted by up to 4RxSubstituted; or
R6And R7Taken together as S (O)pR18R19Or ═ S (═ NR)20)R18R19；
Each RxIndependently halogen, cyano, nitro, hydroxy, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkoxy, C (═ NR)10)R11、C(O)OR21、C(O)NR15R16、OC(O)R22、NR25R26、NR24C(O)R22、C(O)R22、S(O)nR23、Si(R28)3、OSi(R28)3Or Qb；
R8Is H, C (O) OR21、C(O)NR15R16、C(O)R22、S(O)nR23Or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted;
R9is H, C (═ NR)10)R11、OR21Or NR15R16(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted; or is phenyl, phenoxy or a 5-or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or is a 3-to 6-membered heterocyclic non-aromatic ring, each ring containing a ring member selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 1 carbon atom ring member is independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Each ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R10Independently is OR12、S(O)nR13Or NHR14；
Each R11Independently is H; or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted; or is C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkoxy, C (O) OR21、C(O)NR15R16、NR25R26、NR24C(O)R22、C(O)R22Or Qb；
Each R12Independently is C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C (O) R22、S(O)nR13Or Qb；
Each R13Independently is C1-C4Alkyl or C1-C4A haloalkyl group;
R14is C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C (O) R 22OR C (O) OR21(ii) a Or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R15Independently is H, C1-C6Alkyl radical, C1-C4Haloalkyl, C (O) R27Or S (O)2R27(ii) a Or is phenyl or a 5-or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R16Independently is H, C1-C6Alkyl or C1-C4A haloalkyl group; or
R15And R16Together 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 independently selected from an oxygen atom, a sulfur atom and up to 2 nitrogen atoms, of which up to 2 carbon atomsThe sub-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)2Said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
R17is C1-C4Alkyl radical, C3-C6Cycloalkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R18Independently is C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R19Independently is C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or
R18And R19Form a ring together with the sulfur atom to which they are attached;
R20is H, cyano, C1-C4Alkyl radical, C1-C4Haloalkyl or C (O) R22(ii) a Or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R21Independently is C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl or C3-C6A halocycloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R22Independently is C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl or C3-C6A halocycloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R23Independently is C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Halogenocycloalkyl, C3-C6Cycloalkylalkyl or C3-C6A halocycloalkylalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C 1-C4Alkoxy and C1-C4A haloalkoxy group;
each R24Independently is C1-C4An alkyl group;
each R25Independently is H, C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R26Independently is C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or
R25And R26Independently together with the nitrogen atom to which they are attached form a 3-to 7-membered ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S) and the sulfur atom ring member is selected from S, S (O) or S (O)2Said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of: Halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R27Independently is C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or NR29R30(ii) a Or is phenyl or a 5-or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R28Independently is C1-C6Alkyl radical, C3-C6Cycloalkyl or phenyl;
each R29Independently is H or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl groups, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R30Independently is H or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl groups, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or
R29And R30Together with the nitrogen atom to which they are attached form a 3-to 10-membered ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Said ring being unsubstituted or substituted with up to 4 substituents independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
Qais a 5-to 10-membered aromatic ring or ring system, each ring or ring system containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 3 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S) and the sulfur atom ring member is selected from S, S (O) or S (O)2Each ring or ring system being unsubstituted or substituted by at least one R xSubstituted; or is a 3-to 6-membered partially saturated ring, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Each ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each QbIndependently is phenyl, a 5-or 6-membered heterocyclic aromatic ring or a 3-to 6-membered heterocyclic non-aromatic ring, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S) and the sulfur atom ring member is selected from S, S (O) or S (O)2Each ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each n is independently 0, 1 or 2; and is
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 an invertebrate pest comprising a compound of formula 1, an N-oxide or a salt thereof and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said composition optionally further comprising at least one additional biologically active compound or agent.
The present invention further provides a spray composition for controlling an invertebrate pest comprising a compound of formula 1, an N-oxide or a salt thereof, or the composition and a propellant. The present invention also provides a bait composition for controlling invertebrate pests comprising a compound of formula 1, an N-oxide or a salt thereof or a composition described in the above examples, one or more food materials, optionally an attractant, and optionally a humectant.
The invention also provides a trap for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to allow the invertebrate pest to pass through the opening such that the invertebrate pest can access said bait composition from a location external to the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity of the invertebrate pest.
The present invention provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof (e.g., as a composition described herein). 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 a salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said 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 a seed from an invertebrate pest comprising contacting the seed 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 invention also relates to treated seeds. The invention also provides a method for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of formula 1, an N-oxide or a salt thereof (e.g., as a composition described herein). 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) for protecting an animal from an invertebrate pest.
The present invention also provides a method for increasing the vigor of a crop plant, the method comprising contacting the crop plant, the seed from which the crop plant is grown, 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 "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," "characterized by" or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process, or method that comprises a list of 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 conjunctive phrase "consisting of" excludes any unspecified elements, steps or components. If in the claims, such phrases are to be construed to mean that the claims are closed, including no material other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the subject matter of the claims, rather than immediately preceding the preamble, it is limited only to the elements mentioned in that clause; other elements are not excluded from the claims as a whole.
The conjunctive phrase "consisting essentially of" is used to define 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 to "including" and "consisting of.
Where applicants have defined the invention, or a portion thereof, in open-ended terms such as "comprising," then it should be readily understood (unless otherwise indicated) that the specification should be interpreted to describe the invention also in terms of "consisting essentially of or" consisting of.
Furthermore, 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 one of: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).
Also, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e., occurrences) of the element or component. Thus, "a" or "an" should be understood to include one or at least one and the singular forms of an element or component also include the plural unless the numerical value clearly indicates the singular.
As referred to in this disclosure, the term "invertebrate pest" includes arthropods, gastropods, nematodes and worms of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, coccidia and symphytum (symphylan). The term "gastropod" includes snails, slugs and other anomalas. The term "nematode" includes members of the phylum nematoda, such as plant-feeding nematodes and helminth nematodes that are parasitic to animals. The term "helminths" includes all parasites, such as roundworms (phylum nematoda), heartworms (phylum nematoda, class cytopenias), flukes (phylum platyphylla, class trematoda), echinoderms (phylum echinoderma) and cestodes (phylum platyphylla, class cestoda).
In the context of the present disclosure, "invertebrate pest control" refers to inhibition of invertebrate pest development (including mortality, reduced feeding, and/or mating disruption), and related expression is defined in a similar manner.
The term "agronomic" refers to the production of field crops, such as for food and fiber, and includes the growth 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 cabbage crops), fruit vegetables (e.g., tomatoes, peppers, eggplants, crucifers, and cucurbits), potatoes, sweet potatoes, grapes, cotton, woody fruits (e.g., pomes, stone fruits (stones), and citrus), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola, sunflower, and olives).
The term "non-agronomic" refers to applications other than field crops, such as horticultural crops (e.g., greenhouses, nurseries or ornamentals that do not grow in the field), residential, agricultural, commercial and industrial structures, turf (e.g., grasslands, rangelands, golf courses, lawns, sports fields, etc.), wood products, storage products, agroforestry and vegetation management, public health (i.e., human), and animal health (e.g., domesticated animals such as pets, livestock and poultry, non-domesticated animals such as wildlife).
The term "crop vigor" refers to the growth rate or biomass accumulation of a crop plant. By "increase in vigor" is meant an increase in growth or biomass accumulation in crop plants relative to untreated control crop plants. The term "crop yield" refers to the return on both quantity and quality of crop material obtained after harvesting a crop plant. By "increase in crop yield" is meant an increase in crop yield relative to untreated control crop plants.
The term "biologically effective amount" refers to an amount of a biologically active compound (e.g., a compound of formula 1) that is sufficient to produce a desired biological effect when applied to (i.e., contacted with) the invertebrate pest or its environment to be controlled, or the plant, the seed from which the plant is grown, or the locus of the plant (e.g., the growth medium) to protect the plant from the invertebrate pest or for other desired effects (e.g., to increase plant vigor).
Variable R in the structure of formula 11Is described by the numbering system shown below.
Figure BDA0002864077420000051
The wavy line in the structural fragment indicates the point of attachment of the fragment to the remainder of the molecule. For example, when the variable Q in equation 1 is defined as Q-1, the wavy line bisecting the bond in Q-1 means that Q-1 is connected to the remainder of the structure of equation 1 at that location, as shown below.
Figure BDA0002864077420000052
In structures Q-1, Q-2, Q-3, and Q-4, the variable X1、X2、X3And X4Is defined as each independently CR2、CR3Or N, provided that (i) X1、X2、X3And X4One is CR2And (ii) X1、X2、X3And X4No more than one of which is N. X1、X2、X3And X4This definition of (A) describes X1、X2、X3And X4Sixteen possible combinations of (a) are shown in the following table.
Combination of X1 X2 X3 X4
1 CR2 CR3 CR3 CR3
2 CR2 N CR3 CR3
3 CR2 CR3 N CR3
4 CR2 CR3 CR3 N
5 CR3 CR2 CR3 CR3
6 N CR2 CR3 CR3
7 CR3 CR2 N CR3
8 CR3 CR2 CR3 N
9 CR3 CR3 CR2 CR3
10 N CR3 CR2 CR3
11 CR3 N CR2 CR3
12 CR3 CR3 CR2 N
13 CR3 CR3 CR3 CR2
14 N CR3 CR3 CR2
15 CR3 N CR3 CR2
16 CR3 CR3 N CR2
In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl", includes straight-chain or branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, or the different butyl, pentyl, or hexyl isomers. "alkenyl" includes straight or branched chain alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "alkenyl" also includes polyalkenes such as 1, 2-allenyl and 2, 4-hexadienyl. "alkynyl" includes straight or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the different butynyl, pentynyl and hexynyl isomers. "alkynyl" may also include moieties made up of multiple triple bonds, such as 2, 5-hexadiynyl.
"alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, and the different butoxy, pentoxy, and hexoxy isomers. "alkylthio" includes branched or straight chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio, and hexylthio isomers.
"cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The term "halogen", alone or in compound words such as "haloalkyl", or when used in describing words such as "alkyl substituted with halogen", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", or when used in describing words such as "alkyl substituted with halogen", the alkyl may be partially or fully substituted with halogen atoms (which may be the same or different). Examples of "haloalkyl" or "alkyl substituted with halo" include F3C-、ClCH2-、CF3CH2And CF3CCl2-. The terms "halocycloalkyl", "haloalkoxy", "haloalkylthio", "haloalkenyl", "haloalkynyl" and the like are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF3O-、CCl3CH2O-、HCF2CH2CH2O-and CF3CH2O-is formed. Examples of "haloalkylthio" include CCl3S-、CF3S-、CCl3CH2S-and ClCH2CH2CH2S-。
The chemical abbreviations S (O) and S (═ O) as used herein represent sulfinyl moieties. Chemical abbreviation SO as used herein2、S(O)2And S (═ O)2Represents a sulfonyl moiety. The chemical abbreviations C (O) and C (═ O) as used herein represent carbonyl moieties. Chemical abbreviation CO as used herein 2C (O) O and C (═ O) O represent oxycarbonyl moieties. "CHO" refers to formyl.
The total number of carbon atoms in the substituents being represented by "Ci-Cj"prefix" indicates where i and j are numbers from 1 to 6. E.g. C1-C4Alkylsulfonyl represents methylsulfonyl to butylsulfonyl; c2Alkoxyalkyl represents CH3OCH2-；C3Alkoxyalkyl denotes, for example, CH3CH(OCH3)-、CH3OCH2CH2-or CH3CH2OCH2-; and C4Alkoxyalkyl denotes various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, and examples include CH3CH2CH2OCH2-and CH3CH2OCH2CH2-。
When a compound is substituted with a substituent bearing a subscript (which indicates that the number of said substituents can exceed 1), said substituents (when they exceed 1) are independently selected from the group of defined substituents, e.g., (R)1)mAnd m is 0, 1, 2 or 3. Further, when the subscript indicates a range, for example, (R)i-jThe number of substituents may then be selected from integers between i and j, inclusive. When the radical contains substituents which may be hydrogen, e.g. R3Or R4When the substituent is hydrogen, it is recognized that this is equivalent to the group being unsubstituted. When the variable groups indicate optional attachment to a single position, e.g. (R)1)mWhere m may be 0, hydrogen may be in the position even if not stated in the definition of the variable group. When one or more positions on a group are said to be "unsubstituted" or "unsubstituted," then a hydrogen atom is attached to occupy any free valence.
Unless otherwise indicated, a "ring" or "ring system" (e.g., substituent Q) as a component of formula 1a) Is carbocyclic or heterocyclic. The term "ring system" denotes two or more fused rings. The terms "bicyclic ring system" and "fused bicyclic ring system" refer to a ring system consisting of two fused rings, which may be "unilaterally fused", "bridged bicyclic" or "spirobicyclic". "unilateral fusionThe "bicyclic ring system" of (a) means a ring system in which two constituent rings have two adjacent atoms in common. A "bridged bicyclic ring system" is formed by bonding segments of one or more atoms to non-adjacent ring members of a ring. A "spirobicyclic ring system" is formed by bonding segments of two or more atoms to the same ring member of the ring. The term "fused heterobicyclic ring system" refers to a fused bicyclic ring system wherein at least one ring atom is not carbon. The term "ring member" refers to an atom or other moiety that forms the backbone of a ring or ring system (e.g., C (═ O), C (═ S), S (O), or S (O)2)。
The term "carbocyclic ring", "carbocyclic ring" or "carbocyclic ring system" denotes a ring or ring system in which the atoms forming the ring backbone are selected from carbon only. The term "heterocyclic ring", "heterocyclic ring" or "heterocyclic ring system" denotes a ring or ring system wherein at least one of the atoms forming the ring backbone is not carbon (e.g. nitrogen, oxygen or sulfur). Typically, the heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs. Unless otherwise indicated, the 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; the remaining valencies are occupied by hydrogen atoms, unless otherwise indicated. 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 or double bonds according to valence bond theory and furthermore the bonds between the atoms in the ring comprise as many double bonds as possible without cumulative double bonds (i.e. without C ═ C or 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 may accommodate a number of non-cumulative double bonds (i.e., in its fully unsaturated counterpart) between adjacent ring members greater than the number of double bonds present (i.e., in its partially unsaturated form).
Unless otherwise indicated, the heterocyclic ring and ring system may be attached through any available carbon or nitrogen via a hydrogen substituted on said carbon or nitrogen.
By "aromatic" is meant 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) pi electrons (where n is a positive integer) are associated with the ring to comply with the Huckel rule. The term "aromatic ring system" denotes a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic. When a fully unsaturated carbocyclic ring satisfies the huckel rule, then the ring is also referred to as an "aromatic ring" or "aromatic carbocyclic ring". The term "aromatic carbocyclic ring system" denotes a carbocyclic ring system wherein at least one ring of the ring system is aromatic. When the fully unsaturated heterocyclic ring satisfies the huckel 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" denotes 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 no ring in the ring system is aromatic. The term "non-aromatic heterocyclic ring system" denotes a heterocyclic ring system wherein no ring in the ring system is aromatic.
The term "optionally substituted" in relation to a heterocycle 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, the following definitions will apply unless otherwise indicated. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un) substituted". Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other.
When the substituent is a 5-or 6-membered nitrogen containing heterocycle, it may be attached to the remainder of formula 1 through any available carbon or nitrogen ring atom, unless otherwise specified. As noted above, QaMay be (especially) phenyl optionally substituted by one or more substituents selected from the group of substituents as defined in the summary of the invention. Examples of the phenyl group optionally substituted with one to five substituents are rings as shown in U-1 in example 1, wherein R isvIs as in the summary of the invention for QaR as definedxAnd r is an integer from 0 to 5.
As noted above, Q bMay be (inter alia) 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 the 5-or 6-membered unsaturated aromatic heterocyclic ring optionally substituted with one or more substituents include rings U-2 to U-61 shown in example 1, wherein R isvIs as in the summary of the invention for QbAny substituents defined, and r is an integer from 0 to 4, limited by the number of available positions on each U group. Since U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42, and U-43 have only one position available, for these U groups R is limited to the integer 0 or 1, and R is 0 means that the U group is unsubstituted and hydrogen is present in the group consisting of (R-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42, and U-43)v)rAt the indicated position.
Example 1
Figure BDA0002864077420000071
Figure BDA0002864077420000081
Figure BDA0002864077420000091
As noted above, QaMay be (inter alia) an 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 with one or more substituents include rings U-81 to U-123 shown in example 3, wherein R isvIs as in the summary of the invention for Q aAny substituent defined, and r is typically an integer from 0 to 4.
Example 3
Figure BDA0002864077420000092
Figure BDA0002864077420000101
Although R is shown in structures U-1 through U-123vGroups, it should be noted, however, that they need not be present because they are optional substituents. It should be noted that when R isvWhen attached to an atom, this is as if the atom is unsubstituted. The nitrogen atom to be substituted to fill its valence is substituted by H or RvAnd (4) substitution. It should be noted that when (R)v)rWhen the point of attachment to the U group is shown as floating, (R)v)rAny available carbon or nitrogen atom that can be attached to the U group. It should be noted that when the point of attachment on the U group is shown as floating, the U group may be attached to the remainder of formula 1 through any available carbon or nitrogen of the U group via replacement of a hydrogen atom. It should be noted that some U groups can only be substituted by less than 4RvSubstituted (e.g., U-2 to U-5, U-7 to U-48, and U-52 to U-61).
Various synthetic methods are known in the art to enable the preparation of aromatic and non-aromatic heterocycles and ring systems; for an extensive review see the eight-volume complex Heterocyclic Chemistry, A.R. Katritzky and C.W.Rees eds, Pergamon Press, Oxford [ Pegman Press, Oxford ], 1984 and the twelve-volume complex Heterocyclic Chemistry II, A.R. Katritzky, C.W.rees and E.F.V.Scriven eds, Pergamon Press, Oxford, 1996.
The compounds of the present invention may exist as one or more stereoisomers. Stereoisomers are isomers that are identical in composition but differ in the arrangement of their atoms in space, and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about a single bond, where the rotational barrier is high enough to allow separation of isomeric species. One skilled in the art will appreciate that one 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, the skilled artisan knows how to isolate, enrich and/or selectively prepare the stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see Stereochemistry of Organic Compounds [ Organic compound Stereochemistry ] of Ernest l.eiel and Samuel h.wilen, John Wiley & Sons [ John willi parent-press ], 1994.
The present invention includes all stereoisomers, conformers and mixtures thereof in all proportions and in isotopic forms, such as deuterated compounds.
Those skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides because the nitrogen requires an available lone pair to oxidize to the 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 and include the oxidation of heterocycles and tertiary amines using peroxy acids 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 widely described and reviewed in the literature, see for example: l.l.gilchist, Comprehensive Organic Synthesis [ synthetic Organic Synthesis ], volume 7, pages 748-750, s.v.ley editions, Pergamon Press; tisler and b.stanovnik, Comprehensive Heterocyclic Chemistry, volume 3, pages 18-20, edited by a.j.boulton and a.mckillop, Pergamon Press; m.r.grimett and b.r.t.keene, Advances in Heterocyclic Chemistry [ Advances in Heterocyclic Chemistry ], volume 43, pages 149-161, editors of a.r.kattritzky, Academic Press [ Academic Press ]; tisler and b.stanovnik, advanced in Heterocyclic Chemistry, volume 9, pages 285-291, editions a.r.kattritzky and a.j.boulton, Academic Press; and g.w.h.cheeseman and e.s.g.werstink, Advances in Heterocyclic Chemistry, vol 22, pages 390-392, edited by a.r.kattritzky and a.j.boulton, academic press.
One skilled in the art recognizes that salts share the biological utility of non-salt forms, as salts of compounds are in equilibrium with their corresponding non-salt forms in the environment and under physiological conditions. Thus, various salts of the compounds of formula 1 may be useful for controlling invertebrate pests. Salts of the compounds of formula 1 include acid addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acid. When the compound of formula 1 contains an acidic moiety such as a carboxylic acid or phenol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention includes compounds selected from formula 1, N-oxides and suitable salts thereof.
Compounds selected from formula 1, stereoisomers, tautomers, N-forms and salts thereof typically exist in more than one form, and thus formula 1 includes all crystalline and non-crystalline forms of the compounds represented by formula 1. Non-crystalline forms include embodiments that are solids, such as waxes and gums, and embodiments that are liquids, such as solutions and melts. Crystalline forms include embodiments that represent substantially single crystal types and embodiments that represent mixtures of polymorphs (i.e., different crystalline types). The term "polymorph" refers to a particular crystalline form of a compound that can crystallize in different crystalline forms having different molecular arrangements and/or conformations in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound within the crystal lattice. Polymorphs can differ in such chemical, physical, and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate, and bioavailability. One skilled in the art will appreciate that a polymorph of a compound represented by formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or mixture of polymorphs of the same compound represented by formula 1. The preparation and isolation of specific polymorphs of a compound represented by formula 1 can be achieved by methods known to those skilled in the art, including, for example, crystallization using selected solvents and 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 others. For a comprehensive discussion of Polymorphism, see Polymorphism in the Pharmaceutical Industry, edited by r.hilfiker, Wiley-VCH, Weinheim, 2006.
Embodiments of the present invention as described in the summary of the invention include those described below. In the following examples, reference to "a compound of formula 1" includes the definitions of the substituents specified in the summary of the invention, unless otherwise defined in the examples.
Example 1A compound of formula 1, wherein Q is Q-1, Q-2 or Q-3.
Embodiment 2. Compounds of formula 1, wherein Q is Q-1, Q-2 or Q-3, and Y3Is CR5b。
Embodiment 3. Compounds of formula 1, wherein Q is Q-1 or Q-2.
Embodiment 4. the compound of formula 1, wherein Q is Q-1.
Embodiment 5. Compounds of formula 1, wherein Q is Q-1, and Y1Is O or S.
Embodiment 6. Compounds of formula 1, wherein Q is Q-1, and Y1Is S.
Embodiment 7. Compounds of formula 1, wherein Q is Q-1, and Y1Is O.
Embodiment 8. the compound of formula 1, wherein Q is Q-2.
Embodiment 9A compound of formula 1, wherein Q is Q-2, and Y2Is CR5a。
Embodiment 10. the compound of formula 1 or any of embodiments 1-9, wherein A is CH, CR1Or N, and R1Is a halogen.
Embodiment 11. the compound of embodiment 10, wherein A is CH, CF, or N.
The compound of example 10, wherein a is CF or N.
Embodiment 12. the compound of embodiment 10, wherein a is CH or CF.
The compound of embodiment 10, wherein a is CH.
The compound of example 10, wherein a is N.
Embodiment 15. the compound of formula 1 or any of embodiments 1-9, wherein m is 1, and R1Is C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or halogen.
Embodiment 16. the compound of embodiment 15, wherein R1Is CF3OMe, Me, or F.
An embodiment 17. the compound of embodiment 16, wherein R1Is CF3OMe, Me, or F, and is in the 4-position.
Embodiment 18. the compound of embodiment 17, wherein R1Is CF3And is in the 4-position.
Embodiment 19. the compound of formula 1 or any one of embodiments 1-9, wherein m is 0.
Embodiment 20. the compound of formula 1 or any of embodiments 1-19, wherein X1Is CR2And X2、X3And X4Each independently is CR3(ii) a Or X2Is CR2And X1、X3And X4Each independently is CR3。
Embodiment 21. the compound of embodiment 20, wherein X1Is CR2And X2、X3And X4Each independently is CR3。
Embodiment 22. the compound of embodiment 20, wherein X2Is CR2And X 1、X3And X4Each independently is CR3。
Embodiment 23. the compound of formula 1 or any of embodiments 1-22, wherein each R3Independently H or halogen.
Embodiment 24. the compound of embodiment 23, wherein each R3Independently H or F.
Embodiment 25. the compound of embodiment 24, wherein each R3Is H.
Embodiment 26. the compound of formula 1 or any of embodiments 1-25, wherein R2Is C (═ Z) NR6R7、C(＝NR10)R11Or Qa。
Embodiment 27. the compound of formula 1 or any of embodiments 1-25, wherein R2Is C (═ NR)10)R11。
Embodiment 28. the compound of formula 1 or any of embodiments 1-25, wherein R2Is C (═ NR)10)R11；R10Is C1-C4An alkoxy group; and R is11Is quilt S (O)nR23Substituted C1-C4An alkyl group.
Embodiment 29. the compound of formula 1 or any of embodiments 1-25, wherein R2Is C (═ Z) NR6R7Or Qa。
Embodiment 30. the compound of formula 1 or any of embodiments 1-25, wherein R2Is C (═ Z) NR6R7。
Embodiment 31. the compound of formula 1 or any of embodiments 1-25, wherein R2Is C (═ O) NR6R7。
Embodiment 32. the compound of formula 1 or any of embodiments 1-25, wherein R2Is C (═ S) NR6R7。
Embodiment 33. the compound of formula 1 or any of embodiments 1-25, wherein R 2Is C (═ O) NR6R7(ii) a And R is6Is H, C (O) OR21、C(O)R22Or C1-C6An alkyl group.
Embodiment 35. the compound of formula 1 or any of embodiments 1-25, wherein R2Is C (═ O) NR6R7(ii) a And R is6H, C (O) OMe, C (O) Me or methyl.
Embodiment 36. the compound of formula 1 or any of embodiments 1-25, wherein R2Is C (═ O) NR6R7(ii) a And R is6Is H.
Embodiment 36a. the compound of formula 1 or any one of embodiments 1-25, wherein R2Is C (═ O) NR6R7(ii) a And R is6Is C (O) OMe.
Embodiment 36b. a compound of formula 1 or any one of embodiments 1-25, wherein R2Is C (═ O) NR6R7(ii) a And R is6Is C (O) Me.
Embodiment 36c. compounds according to formula 1 or any of embodiments 1-25, wherein R2Is C (═ O) NR6R7(ii) a And R is6Is methyl.
Embodiment 37. the compound of formula 1 or any of embodiments 1-25, wherein R2Is Qa。
Embodiment 38. the compound of formula 1 or any of embodiments 1-25, wherein R2Is Qa(ii) a And QaIs a 5-or 6-membered aromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from an oxygen atom, a sulfur atom and up to 3 nitrogen atoms, each ringIs unsubstituted or substituted by at least one R xAnd (3) substituted.
Embodiment 39. the compound of formula 1 or any of embodiments 1-25, wherein R2Is Qa(ii) a And QaIs a 5-or 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from an oxygen atom, a sulfur atom and up to 3 nitrogen atoms, each ring being unsubstituted or substituted by at least one RxAnd (3) substituted.
The compound of embodiment 39, wherein the heteroaromatic ring is a 5-membered heteroaromatic ring.
The compound of embodiment 40, wherein the heteroaromatic ring is a 5-membered heteroaromatic ring having a nitrogen atom at the 2-position.
The compound of embodiment 39, wherein the heteroaromatic ring is a 6-membered heteroaromatic ring.
An embodiment 43. the compound of embodiment 42, wherein the heteroaromatic ring is a 6-membered heteroaromatic ring having a nitrogen atom at the 2-position.
Embodiment 44. the compound of embodiment 43, wherein the heteroaromatic ring is C-substituted with a nitrogen atom at the 2-position1-C4A haloalkyl-substituted 6-membered heteroaromatic ring.
Embodiment 45. the compound of embodiment 44, wherein the heteroaromatic ring is substituted with CF and has a nitrogen atom at the 2-position3A substituted 6-membered heteroaromatic ring.
Embodiments of the invention, including examples 1-45 above as well as any other examples described herein, can be combined in any manner, and the description of the variables in the examples refers 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. Furthermore, embodiments of the present invention, including the above embodiments 1-45 as well as 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 by:
example a. a compound according to formula 1, wherein
X1Or X2Is CR2。
A compound as in example A, wherein
Q is Q-1 or Q-2.
The compound of embodiment B, wherein
Q is Q-1; and is
Y1Is O or S.
The compound of embodiment C, wherein
Q is Q-2; and is
Y2Is CR5a。
The compound of any one of embodiments A-D, wherein
A is CH or CF; and is
m is 0.
Example F. a compound according to formula 1, wherein
A is CH or CF;
m is 0;
q is Q-2;
Y2is CR5a；
X1Is CR2And X2、X3And X4Each is CH; or X2Is CR2And X1、X3And X4Is CH; r 2Is C (═ Z) NR6R7Or Qa。
Example g. a compound according to formula 1, wherein
A is CH or CF;
m is 0;
q is Q-2;
Y2is CR5a；
X1Is CR2And X2、X3And X4Each is CH;
R2is C (═ Z) NR6R7Or Qa。
Example h. a compound according to formula 1, wherein
A is CH or CF;
m is 0;
q is Q-2;
Y2is CR5a；
X2Is CR2And X1、X3And X4Is CH;
R2is C (═ Z) NR6R7Or Qa。
The compound of formula 1, wherein
A is CH;
m is 0;
q is Q-2;
Y2is CR5a；
R5aIs H;
X1is CR2And X2、X3And X4Each is CH; or X2Is CR2And X1、X3And X4Is CH; r2Is C (O) NR6R7(ii) a And is
R6Is H.
Example j. a compound according to formula 1, wherein
A is CH;
m is 0;
q is Q-2;
Y2is CR5a；
R5aIs H;
X1is CR2And X2、X3And X4Each is CH;
R2is C (O) NR6R7(ii) a And is
R6Is H.
Example K. a compound according to formula 1, wherein
A is CH;
m is 0;
q is Q-2;
Y2is CR5a；
R5aIs H;
X2is CR2And X1、X3And X4Is CH;
R2is C (O) NR6R7(ii) a And is
R6Is H.
The combination of examples 1-45 is shown by:
embodiment A1. A compound of formula 1, wherein
Q is Q-2;
a is CH, CR1Or N;
each R1Independently halogen, cyano, nitro, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio or C 1-C4A haloalkylthio group;
m is 0 or 1;
X1、X2、X3and X4Each independently is CR2、CR3Or N, provided that (i) X1、X2、X3And X4One is CR2And (ii) X1、X2、X3And X4No more than one of is N;
R2is C (═ Z) NR6R7、N(R8)C(＝Z)R9、C(＝NR10)R11Or Qa；
Each Z is independently O or S;
each R3Independently is H, halogen, cyano, nitro, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4A haloalkoxy group;
Y2is N or CR5a；
R5aIs H, halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4A haloalkoxy group;
R6is H, NR15R16、OR17、C(＝NR10)R11、C(O)OR21、C(O)NR15R16、C(O)R22、S(O)nR23Or Qb(ii) a Or is
C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted;
R7is H or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted; or
R6And R7Together with the nitrogen atom to which they are attached form a 3-to 10-membered ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Said ring being unsubstituted or substituted by up to 4R xSubstituted; or
R6And R7Taken together as S (O)pR18R19Or ═ S (═ NR)20)R18R19；
Each RxIndependently halogen, cyano, nitro, hydroxy, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkoxy, C (═ NR)10)R11、C(O)OR21、C(O)NR15R16、OC(O)R22、NR25R26、NR24C(O)R22、C(O)R22、S(O)nR23、Si(R28)3、OSi(R28)3Or Qb；
R8Is H, C (O) OR21、C(O)NR15R16、C(O)R22、S(O)nR23Or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted;
R9is H, C (═ NR)10)R11、OR21Or NR15R16(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted; or is phenyl, phenoxy or a 5-or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or is a 3-to 6-membered heterocyclic non-aromatic ring, each ring containing a ring member selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 1 carbon atom ring member is independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O) 2Each ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R10Independently is OR12、S(O)nR13Or NHR14；
Each R11Independently is H; or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted; or is C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkoxy, C (O) OR21、C(O)NR15R16、NR25R26、NR24C(O)R22、C(O)R22Or Qb；
Each R12Independently is C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C (O) R22、S(O)nR13Or Qb；
Each R13Independently is C1-C4Alkyl or C1-C4A haloalkyl group;
R14is C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C (O) R22OR C (O) OR21(ii) a Or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R15Independently is H, C1-C6Alkyl radical, C1-C4Haloalkyl, C (O) R27Or S (O)2R27(ii) a Or is phenyl or a 5-or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted by at least one Substituted with one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R16Independently is H, C1-C6Alkyl or C1-C4A haloalkyl group; or
R15And R16Together with the nitrogen atom to which they are attached form a 3-to 7-membered ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
R17is C1-C4Alkyl radical, C3-C6Cycloalkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C 1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R18Independently is C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro,C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R19Independently is C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or
R18And R19Form a ring together with the sulfur atom to which they are attached;
R20is H, cyano, C1-C4Alkyl radical, C1-C4Haloalkyl or C (O) R22(ii) a Or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R21Independently is C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl or C3-C6A halocycloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R22Independently is C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl or C3-C6A halocycloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R23Independently is C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Halogenocycloalkyl, C3-C6Cycloalkylalkyl or C3-C6A halocycloalkylalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R24Independently is C1-C4An alkyl group;
each R25Independently is H, C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C 1-C4Alkoxy and C1-C4A haloalkoxy group;
each R26Independently is C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, halogen,Cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or
R25And R26Independently together with the nitrogen atom to which they are attached form a 3-to 7-membered ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S) and the sulfur atom ring member is selected from S, S (O) or S (O)2Said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R27Independently is C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or NR29R30(ii) a Or is phenyl or a 5-or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R28Independently is C1-C6Alkyl radical, C3-C6Cycloalkyl or phenyl;
each R29Independently is H or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl radicals each being unsubstitutedSubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R30Independently is H or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl groups, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or
R29And R30Together with the nitrogen atom to which they are attached form a 3-to 10-membered ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O) 2Said ring being unsubstituted or substituted with up to 4 substituents independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
Qais 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, a,S (O) or S (O)2Each ring or ring system being unsubstituted or substituted by at least one RxSubstituted; or is a 3-to 6-membered partially saturated ring, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Each ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each QbIndependently is phenyl, a 5-or 6-membered heterocyclic aromatic ring or a 3-to 6-membered heterocyclic non-aromatic ring, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S) and the sulfur atom ring member is selected from S, S (O) or S (O)2Each ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each n is independently 0, 1 or 2; and
p is 1 or 2.
Example b1. the compound of example a1, wherein
R2Is C (═ O) NR6R7Or Qa。
Embodiment c1. the compound of embodiment B1, wherein
X1Is CR2And X2、X3And X4Each independently is CR3(ii) a Or X2Is CR2And X1、X3And X4Each independently is CR3(ii) a And is
QaIs a 5-or 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from an oxygen atom, a sulfur atom and up to 3 nitrogen atoms, each ring being unsubstituted or substituted by at least one R xAnd (3) substituted.
The compound of embodiment C1, wherein
A is CH or CR1(ii) a And is
Each R1Independently of one another is halogen, cyano, C1-C4Alkyl radical, C1-C4Alkoxy or C1-C4An alkylthio group.
Example E1. the compound of example D1, wherein
A is CH or CR1(ii) a And is
Each R1Independently cyano, F, CH3、OCH3Or SCH3。
Embodiment F1. the compound of embodiment E1, wherein
m is 0; and is
A is CH or CF.
Specific examples include compounds of formula 1 (compound number reference index tables a-N) selected from the group consisting of:
n- (1-methylethyl) -2- (3-pyridinyl) -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);
methyl 2- [ [2- (3-pyridinyl) -2H-indazol-5-yl ] carbonyl ] hydrazinecarboxylate (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-pyridyl) -2H-indazole-5-carboxamide (Compound 76).
Additional specific embodiments include compounds of formula 1 selected from the group consisting of (compound number reference 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 present invention are characterized by favorable metabolic and/or soil residue patterns and exhibit activity against a broad spectrum of agronomic and non-agronomic invertebrate pests.
It is particularly noteworthy that for reasons of invertebrate pest control spectrum and economic importance, protection of crops from damage or injury caused by invertebrate pests by controlling invertebrate pests is an embodiment of the present invention. The compounds of the 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 properties or systemic properties in plants.
Also noteworthy as embodiments of the present invention are compositions comprising a compound described in any one of the preceding embodiments, and 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, said composition optionally further comprising at least one additional biologically active compound or agent.
Also of note as an embodiment of the present invention is a composition for controlling an invertebrate pest comprising the compound of any one of the preceding embodiments, as well as any other embodiment 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, the composition optionally further comprising at least one additional biologically active compound or agent. Embodiments of the present invention further include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound as described in any of the preceding embodiments (e.g., as a composition described herein).
Embodiments of the 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 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 an invertebrate pest comprising a biologically effective amount of a compound as described in any of the preceding embodiments and a propellant. Embodiments of the invention further include a bait composition for controlling an invertebrate pest comprising a biologically effective amount of a compound as described in any of the preceding embodiments, one or more food materials, optionally an attractant, and optionally a humectant. Embodiments of the invention also include a device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to allow the invertebrate pest to pass through the opening such that the invertebrate pest can access said bait composition from a location external to the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity of the invertebrate pest.
Embodiments of the invention also include methods for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound 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 of any of the preceding embodiments.
Embodiments of the present invention also include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of formula 1, an N-oxide or a salt thereof (e.g., as a composition described herein) provided that the methods are not methods of pharmaceutical 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 a salt thereof and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent, provided that the methods are not methods of pharmaceutical treatment of the human or animal body by therapy.
The compounds of formula 1 may be prepared by one or more of the following methods and variations as described in schemes 1-13. Unless otherwise indicated, the substituents in the compounds of the following formulae 1 to 23 are as defined in the summary above. The compounds of formulae 1a-1g are a different subset of the compounds of formula 1, and all substituents of formulae 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 methanesulfonate, 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 prepared from a transition metal such as Pd (e.g., Pd (OAc)2Or Pd2(dba)3And mono-or bidentate ligands such as PPh3、PCy3、Pt-Bu32-dicyclohexylphosphine-2, 4, 6-triisopropylbiphenyl, 4, 5-bisdiphenylphosphine-9, 9-dimethylxanthene, 2-dicyclohexylphosphine-2 ', 6 ' -dimethoxybiphenyl and 1,1 ' -bis (diphenylphosphino) ferrocene. Typical bases used include carbonates such as sodium 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.
Scheme 1
Figure BDA0002864077420000181
Compounds of formula 1a (formula 1 wherein Q is Q-1, Q-3 or Q-4) can also be prepared as shown in scheme 2 by coupling a compound of formula 4 with a compound of formula 5 (wherein LG is a suitable leaving group such as Cl, Br, I, Tf or Nf) in the presence of a catalyst and a suitable ligand. Various catalysts may be used in the process of scheme 2, and these catalysts may be formed from transition metal species such as copper or Pd (e.g., complexes such as Pd (OAc)2Or Pd2(dba)3) And ligand production. Typical ligands may be monodentate or bidentate and include PPh3、PCy3、Pt-Bu32-dicyclohexylphosphine-2, 4, 6-triisopropylbiphenyl, 4, 5-bisdiphenylphosphine-9, 9-dimethylxanthene, 2-dicyclohexylphosphine-2 ', 6 ' -dimethoxybiphenyl and 1,1 ' -bis (diphenylphosphino) ferrocene. Typical bases used include carbonates such as sodium or cesium carbonate, phosphates such as potassium triphosphate, amines such as ethyldiisopropylamine, or alkoxides such as sodium tert-butoxide. Additives, e.g. molecular sieves, Bu4N+Br-Or copper or silver salts (e.g., AgOAc) may be beneficial. Typical reaction 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. For example, see Chemical Communications ]2011, 47(17), p 5043-5045; journal of the American Chemical Society [ national Society of Chemicals ]]2010, 132(11), pages 3674-3675; heterocycles]2011, 83(6), pages 1371-1376; U.S. patent application publication 20090076266; bulletin of the Chemical Society of Japan [ Notification of the Japanese Society of chemistry]1998, 71(2), pp.467-473; tetrahedron Letters]2008, 49(10), pages 1598-1600; and Tetrahedron Letters 2010, 51(42), pages 5624-5627.
Scheme 2
Figure BDA0002864077420000182
The compound of formula 2 wherein LG is halogen can be reacted with a halogen source such as CuBr2Or BnNEt3 +Br-By using ON in the presence of+Sources such as isoamyl nitrite or tert-butyl nitrite or nitrous acid treatment are prepared from the corresponding amines. Preferred reaction conditions include aqueous or organic solvents such as THF or acetonitrile, and reaction temperatures in the range from 0 ℃ to the boiling point of the solvent.
Compounds of formula 2 wherein LG is Cl or Br can also be prepared by using halogenating agents such as POCl3、PCl5、PBr3Or SOCl2The treatment is prepared from the corresponding hydroxy compound. Compounds of formula 2 wherein LG is OMS or OTf can also be prepared by using MsCl or Tf2The O treatment is prepared from the corresponding hydroxy compound.
The compound of formula 4 can be prepared by reacting with ON+Sources such as isoamyl nitrite or tert-butyl nitrite treatments are prepared from the corresponding amine compounds. Preferred reaction conditions include ethereal solvents such as THF at temperatures in the range from ambient temperature to the boiling point of the solvent.
The compound of formula 6 can be prepared by electrophilic halogenation of the corresponding compound 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 a temperature in the range of ambient temperature up to the boiling point of the solvent (scheme 3).
Scheme 3
Figure BDA0002864077420000191
The 2-aminobenzothiazoles of formula 8 may be prepared from ortho-unsubstituted anilines and thiocyanate anions of formula 9 (where M is K)+、Na+Or Bu4N+) Preparation, as shown in scheme 4. The reaction can be carried out in a single step, for example in acetic acid, or via an intermediate thiourea, followed by oxidation. Suitable oxidant packageIncluding bromine.
Scheme 4
Figure BDA0002864077420000192
The compound of formula 1b can be prepared from the compound 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 is in the range from 80 ℃ to the boiling point of the solvent.
Scheme 5
Figure BDA0002864077420000193
The compounds of formula 10 are schiff bases and can be prepared by methods known in the art (see, e.g., March, j., Advanced Organic Chemistry, Wiley, 1992, pages 896-898).
Compounds of formula 1c can be prepared from compounds of formula 11 by the method shown in scheme 6 over copper (II) catalysts such as Cu (OAc)2Or CuBr2By oxidation of a compound of formula 11 with molecular oxygen or a peroxide such as t-butyl hydroperoxide. Typical reaction conditions include an alcohol solvent such as t-amyl alcohol, DMF, NMP or aqueous ammonia, and the reaction temperature is from 60 ℃ to the boiling point of the solvent.
Scheme 6
Figure BDA0002864077420000201
The 2-amino azo compounds of formula 11 can be prepared by reaction of an aniline of formula 9 with a diazonium salt of formula 12 by methods known in the art (see, e.g., March, J., Advanced Organic Chemistry, Wiley, 1992, pp. 525-526). The compound of formula 11 may also be prepared by reaction of an aryl nitroso compound of formula 13 with a diamine of formula 14 in a solvent such as acetic acid. These two methods are shown in scheme 7.
Scheme 7
Figure BDA0002864077420000202
Compounds of formula 1d can be prepared by condensation of compounds of formula 14 (where Lg is a suitable leaving group such as Cl or Br) with an aminopyridine or an aminodiazine of formula 16, as shown in scheme 8. Typical reaction conditions include an alcoholic solvent such as ethanol or toluene, and the reaction temperature is in the range from ambient temperature to the boiling point of the solvent. The pyridine nitrogen may optionally be protected as BH 3An adduct, an N-oxide, or a 2-or 6-halopyridine derivative.
Scheme 8
Figure BDA0002864077420000203
The compounds of formula 1e can be prepared by cycloaddition of a 2-aminopyridine of formula 15 with an aryl nitrile of formula 16 as shown in scheme 9 (see, e.g., Journal of the American Chemical Society 2009, 131(42), pages 15080-15081, and WO 2013041472).
Scheme 9
Figure BDA0002864077420000204
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, e.g., j.het Chem [ journal of heterocyclic chemistry ]1970, 7, p 1019). Compounds of formula 17 can be prepared by the methods described in WO 2008006540 and j. org. chem. [ journal of organic chemistry ],1966, page 251.
Scheme 10
Figure BDA0002864077420000211
The intermediate of formula 18 can be prepared by the method shown in scheme 11 by treating the 2-aminopyridine of formula 15 with an isocyanate followed by hydroxylamine and a suitable base such as triethylamine.
Scheme 11
Figure BDA0002864077420000212
The compound of formula 1 wherein Q is Q-4 can also be prepared by the method described in synthetic example 6.
The 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 oxidizing agent as shown in scheme 12. The reaction being carried out in a base such as K 2CO3In a suitable solvent such as water or DMF, and by addition of a copper salt (e.g., CuI or CuCl)2) And preferably a suitable ligand such as 1, 10-phenanthroline. Typical reaction temperatures range from 70 ℃ to the boiling point of the solvent.
Scheme 12
Figure BDA0002864077420000213
The compounds of formula 1f can also be prepared as shown in the second reaction of scheme 12 by reacting a 2-halothioamide of formula 21 with a base such as KOtBu, NaH, DBU or Cs 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-phenanthroline2CO3By cyclization of (a). The reaction may also be carried out from Pd species (e.g. from Pd)2(dba)3And (t-Bu)2P-o-biphenyl preparation), bases such as Cs2CO3In a suitable solvent such as 1, 2-dimethoxyethane or dioxane. Typical reaction temperatureIn the range from 80 ℃ to the boiling point of the solvent. For copper and Pd catalyzed reactions, the halogen substituent on the compound of formula 21 is preferably Br or I. For example, see Journal of Organic Chemistry]2006, 71(5), pages 1802-1808; tetrahedron Letters]2003, 44(32), pp 6073-6077; synthetic Communications]1991, 21(5), pages 625 to 33; and european patent application No. 450420.
The 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. Typical oxidizing agents used in the process include bromine or iodine, DDQ and K3Fe(CN)6. See, for example, Tetrahedron]2007, 63(41), pages 10276-10281; synthesis]2007, (6), 819-823; and U.S. patent application publication 20120215154.
The three methods described in scheme 12 can be used to prepare compounds wherein X is1-X4Is a carbon atom, or wherein X1-X4Compounds in which one is nitrogen (see, e.g., J.Heterocyclic Chem. [ journal of heterocyclic chemistry ]]2009, 46, page 1125, and references cited therein).
Intermediates used in the preparation of compounds of formula 1 and compounds of formula 1 wherein Z is S can be prepared by reaction with, for example, the Law reagent (CAS No. 19172-47-5), Belleau reagent (CAS No. 88816-02-8), or P2S5Sulfurizing the corresponding compound in which Z is O. The sulfurization reaction is generally carried out in a solvent such as toluene, xylene or dioxane, and at an elevated temperature from 80 ℃ to the boiling point of the solvent.
Wherein R is2Is C (O) NR6R7The compound of formula 1 can be prepared by carbonylation wherein R2Is halogen (preferably Br or I) or wherein R2Is a sulfonate (e.g., triflate or perfluorobutanesulfonate). The reaction is carried out at a carbon monoxide source, such as carbon monoxide gas or Mo (CO), at a pressure of between atmospheric pressure and 25 bar, optionally under microwave heating, and generally at an elevated temperature in the range of from 80 ℃ to 160 ℃ 6In the presence of (a). Typical reaction solvents include DMF, NMP,Toluene or ether solvents such as THF or dioxane.
Wherein R is2Is QaThe compounds of formula 1 (a) can be prepared as shown in scheme 13. The method of scheme 13 is similar to the method described in scheme 1. M is a suitable metal or metalloid such as Mg, Zn or B species, and R2Corresponds to LG in scheme 1 and is a suitable leaving group, for example Cl, Br, I, Tf or Nf.
Scheme 13
Figure BDA0002864077420000221
Wherein R is2Is QaAnd QaVia QaThe compound of formula 1 in which the nitrogen atom in (a) is bonded to Q can be prepared by a method similar to scheme 13. In this process, M in the compound of formula 23 is hydrogen. The coupling reagents include a copper (I) salt, such as CuI, and a suitable ligand, such as trans-bis (N, N-dimethyl-1, 2-cyclohexanediamine typical reaction conditions include a solvent, such as toluene or dioxane, and the elevated reaction temperature is in the range from 80 ℃ to the boiling point of the solvent.
It will be appreciated that certain of the reagents and reaction conditions described above for preparing the 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, 2 nd edition; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, additional conventional synthetic steps not described in detail may be required to complete the synthesis of the compound of formula 1 after the reagents depicted in the various schemes are introduced. One skilled in the art will also recognize that it may be desirable to perform the combination of steps shown in the above schemes in a different order than the specific sequence presented for the preparation of the compound of formula 1.
One skilled in the art will also recognize that the compounds of formula 1 and intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. Accordingly, the following synthetic examples are to be construed as merely illustrative, and not limitative of the disclosure in any way whatsoever. The steps in the synthetic examples below illustrate the procedure for each step in the overall synthetic transformation, and the starting materials for each step do not have to be prepared by specific preparative trials whose procedures are described in other examples or steps. Percentages are by weight, except for chromatographic solvent mixtures or unless otherwise indicated. Parts and percentages of chromatographic solvent mixtures are by volume unless otherwise indicated.1The H NMR spectrum is reported in ppm downfield from tetramethylsilane. "s" means singlet, "d" means doublet, "t" means triplet, "q" means quartet, "m" means multiplet, "dd" means doublet, "dt" means doublet triplet, "br s" means broad singlet. DMF means N, N-dimethylformamide. The compound numbers refer to the index tables A-N.
Synthesis example 1
Preparation of N- [2- (methylthio) ethyl ] -2- (3-pyridyl) -7-benzothiazolecarboxamide (compound 84)
Step A: preparation of 3- [ (aminothiomethyl) amino group]Benzoic acid ethyl ester
Ethyl 3-aminobenzoate (35.25g, 213.6mmol) was dissolved in chlorobenzene (250mL) and cooled to-10 ℃. Concentrated sulfuric acid (5.93mL) was added, followed by KSCN (21.76g) and 18-crown-6 (600mg), and the reaction mixture was heated at 100 ℃ for 14 hours. Hexane was added to the cooled mixture and the precipitated solid was isolated by filtration. The solid was slurried in a mixture of water and hexane, and the slurry was stirred for 1 hour. The solid was isolated by filtration and dried under vacuum overnight to give the title compound as a gray solidCompound (40.7 g).1H NMR(DMSO-d6) Delta 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).
And B: preparation of ethyl 2-amino-7-benzothiazolecarboxylate
The product of step A was taken up in chloroform (300mL) and acetic acid (200mL) and bromine (21mL) in chloroform (100mL) were added dropwise over 1.5 hours. The reaction mixture was then heated at 70 ℃ for 4 hours, cooled, filtered, and the isolated solid was washed with 50mL1:1 acetone/chloroform. Adding the solid to Na 2CO3(25g) In a solution in water (400mL) and stirred for 20 minutes. The suspension was filtered and the isolated solid was washed with water and dried under vacuum overnight to give the title compound (6.73g) as a white solid. The organic filtrate was concentrated and reslurried in 100ml of 1:1 chloroform/acetone and treated as described above to give an additional 8.1g of a white solid (90% purity, remaining 10% being regioisomeric benzothiazole).1H NMR(DMSO-d6)δ:7.66(dd,J＝7.7,0.9Hz,1H),7.60(s,1H),7.57(dd,1H),7.35(t,J＝7.8Hz,1H),4.37(q,J＝7.1Hz,2H),1.36(t,J＝7.1Hz,3H)。
And C: preparation of ethyl 2-chloro-7-benzothiazolecarboxylate
The product of step B (7.97g, 9:1 mixture of regioisomers, 35.9mmol) was added portionwise to tert-butyl nitrite (7.1mL) and CuCl at 65 ℃ over 45 min2(5.31g) in a mixture of acetonitrile (360 mL). After stirring for a further 15 minutes, the cooled mixture was extracted 6 times with hexane. The combined extracts were concentrated to give the title compound (5.85g) as a yellow solid. The acetonitrile layer was diluted with water (200mL), extracted with hexane, and the hexane fraction was filtered through a pad of silica gel eluting with butyl chloride to give an additional 0.55g of product upon concentration.1H NMR(CDCl3)δ:8.14(d,2H),7.58(t,1H),4.49(q,J＝7.1Hz,2H),1.47(t,J＝7.2Hz,3H)。
Step D: preparation of 2- (3-pyridinyl) -7-benzothiazolecarboxylic acid
The product of step C (6.2g, mixture of regioisomers of 9: 1) was reacted with 3-pyridylboronic acid (3.79g), PPh 3(1.35g) and Na2CO3(5.44g) were combined in toluene (100mL), water (25mL), and ethanol (15mL), and the reaction mixture was bubbled with nitrogen for 5 minutes. Adding Pd2dba3(588mg) and the reaction mixture was heated at reflux for 4 h. The cooled reaction mixture was diluted with water, extracted twice with dichloromethane and the combined organic extracts were over MgSO4Dried 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 (25mL) yielded the ethyl ester of the title compound as the single desired regioisomer (5.65 g).1H NMR(CDCl3)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 product obtained above was dissolved in ethanol (100mL) and treated with 1N NaOH solution (24.8 mL). The reaction mixture was heated at reflux for 1.5 h, then cooled, neutralized with concentrated HCl (2.0mL), and concentrated. The residue was dried in vacuo to give a mixture of the title compound and NaCl, which was used in the next step without further purification.
Step E: preparation of N- [2- (methylthio) ethyl]-2- (3-pyridinyl) -7-benzothiazolecarboxamide
Thionyl chloride (40mL) was added to the product of step D (0.55g) 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.
With dichloromethane (5mL), MeSCH2CH2NH2Crude acid chloride (containing 120 mol% NaCl, 114mg, 0.3mmol) was treated (33. mu.L) and triethylamine (125. mu.L) and the reaction mixture was then stirred at ambient temperature for 14 hours. The reaction mixture was washed with saturated NaHCO3Diluting with an aqueous solutionExtracted twice with dichloromethane and over MgSO4And (5) drying. The combined organic layers were concentrated and the residue was purified by column chromatography (silica gel eluting with 30% ethyl acetate to 100% ethyl acetate in hexanes) to give 65mg of the title compound, a compound of the invention.1H NMR(CDCl3)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-pyridinyl) -N- (2,2, 2-trifluoroethyl) -6-benzothiazolecarboxamide (Compound 127)
Step A: preparation of 2- (5-fluoro-3-pyridinyl) -6-benzothiazolecarboxylic acid
4-amino-3-iodobenzoic acid methyl ester (1.93g, 6.96mmol) was reacted with K2CO3(1.92g)、S8(668mg)、CuCl2-2H2O (119mg), 1, 10-phenanthroline (125mg) and 5-fluoro-3-pyridinecarboxaldehyde (957mg) in H2O (30mL) and the reaction mixture was heated at reflux for 16 hours. The cooled reaction mixture was filtered and the filtrate was taken up with NH4Cl (1.49 g). The reaction mixture was stirred at ambient temperature for 10 minutes, filtered, and the solid was dried in vacuo to give a grey solid. The solid was suspended in dioxane, the suspension was heated to reflux, cooled and filtered to isolate the solid. The solid was washed with diethyl ether to give the title compound (0.66 g). 1H NMR(DMSO-d6)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)。
And B: preparation of 2- (5-fluoro-3-pyridinyl) -N- (2,2, 2-trifluoroethyl) -6-benzothiazolecarboxamide
Thionyl chloride (5mL) was added to the product of step a (0.66g) and the mixture was heated at reflux for 16 h. The reaction mixture was then cooled and concentrated. The resulting residue was suspended in toluene and concentrated to afford the crude acid chloride, which was used without further purification.
The crude acid chloride (103mg, 0.31mmol) was purified with dichloromethane (5mL), triethylamine (131. mu.L) and CF3CH2NH2(29 μ L) and the reaction mixture was stirred at ambient temperature for 3 days. The reaction mixture was washed with saturated NaHCO3The aqueous solution was diluted, extracted twice with dichloromethane and over MgSO4And (5) drying. The combined organic layers were concentrated and the residue was purified by column chromatography (silica gel eluting with 20% to 40% ethyl acetate in hexanes) to give the title compound, a compound of the invention (52mg) as a white solid.1H NMR(CDCl3)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-pyridinyl) -2H-indazole-4-carboxamide (Compound 8)
Step A: preparation of N- [ (2-bromo-6-fluorophenyl) methylene]-3-pyridylamine
A solution of 2-bromo-6-fluorobenzaldehyde (5g, 24.6mmol) and 3-aminopyridine (2.7g, 29.5mmol) in EtOH (4mL) 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 hexane) to afford the title compound (4.5g) as an orange solid. 1H NMR(CDCl3)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)。
And B: preparation of 4-bromo-2- (3-pyridyl) -2H-indazole
The product of step A (4.5g, 16.1mmol) and NaN3A solution of (1.2g, 19.3mmol) in DMF (20mL) was heated to 90 ℃ for 24 hours. The cooled mixture was diluted with water and extracted 3 times with dichloromethane. The combined organic layers were dried (MgSO)4) Filtered, concentrated, and the residue purified by column chromatography (silica gel eluted with 0-30% ethyl acetate in hexanes) to give as yellow colorTitle compound as a solid (4.0 g).1H NMR(CDCl3)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)。
And C: preparation of N- (1-methylethyl) -2- (3-pyridinyl) -2H-indazole-4-carboxamide
The product of step B (200mg, 0.727mmol), isopropylamine (183. mu.L, 2.18mmol), trans-bis (acetoxy) bis [ o- (di-o-tolylphosphino) bis]Benzyl radical]Palladium (II) (17mg, 0.018mmol), tri-tert-butylphosphonium tetrafluoroborate (10.5mg, 0.036mmol), molybdenum hexacarbonyl (192mg, 0.727mmol), 1, 8-diazabicycloundec-7-ene (473. mu.L, 2.18mmol), and DMF (5mL) were placed in a microwave vial and irradiated at 160 ℃ for 40 min. The reaction mixture was then cooled to room temperature and passed
Figure BDA0002864077420000241
The pad is filtered. The filtrate was taken up with saturated NaHCO3The solution was diluted and extracted with dichloromethane. The organic layer was dried (MgSO4) Filtered, concentrated, and the residue 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 (45mg) as a white solid. 1H NMR(CDCl3)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-pyridinyl) -N- [1- (2,2, 2-trifluoroethyl) ] imidazo [1,2-a ] pyridine-6-carboxamide (Compound 457)
Step A: preparation of 2- (3-pyridyl) imidazo [1,2-a]Pyridine-6-carboxylic acid methyl ester
Following the procedure described in U.S. patent application publication No. 20110189794, solid sodium bicarbonate (5.52g, 65.7mmol) was added to a mixture of methyl 6-aminonicotinate (5.0g, 33mmol) in ethanol (140mL) at 60 deg.C followed by 3- (bromoacetyl) pyridine hydrogen bromide (10.16g, 36.2 mmol). The resulting mixture was heated to reflux for 9 hours. The reaction mixture was then cooled, concentrated, and to the resulting residue were added saturated aqueous sodium bicarbonate (50mL) and dichloromethane (50 mL). The aqueous phase was extracted with dichloromethane (5X 30 mL). The combined organic phases were concentrated and purified by column chromatography (silica gel eluted with ethyl acetate) to give the title compound.
And B: preparation of 2- (3-pyridinyl) -N- [1- (2,2, 2-trifluoroethyl)]Imidazo [1,2-a ]]Pyridine-6-carboxylic acid amides Amines as pesticides
A mixture of the ester prepared in step A (0.4g, 2.4mmol) and aqueous NaOH (1N, 7.1mL, 7.1mmol) was stirred in methanol (10mL) 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 1N 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.
The carboxylic acid (0.31g, 1.30mmol) prepared above, EDC-HCl (0.27g, 1.43mmol), HOBt-H2A mixture of O (0.22g, 1.43mmol) and triethylamine (0.72mL, 5.2mmol) in DMF (10mL) was stirred at 40 ℃ for 30 min. Then one quarter of the reaction mixture volume was removed, using CF3CH2NH2(0.13g, 1.3mmol) and stirred at 40 ℃ overnight. The reaction mixture was then concentrated in vacuo to remove DMF and the residue was purified by column chromatography (silica gel eluted with 8:8:1 ethyl acetate: methanol: triethylamine) to give 43.8mg of the title compound, a compound of the invention.
Synthesis example 5
Preparation of methyl 2- [ [2- (3-pyridinyl) -2H-indazol-5-yl ] carbonyl ] hydrazinecarboxylate (Compound 42)
Step A: preparation of 4-nitro- [ (3-pyridylimino) methyl]Benzoic acid methyl ester
A solution of methyl 3-formyl-4-nitrobenzoate (5g, 25mmol) and 3-aminopyridine (2.7g, 30mmol) in ethanol (4mL) 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 (eluting with 0-40% ethyl acetate/hexanes) to provide 4.5g of the title product as an orange solid.
And B: preparation of methyl 2- (3-pyridyl) -2H-indazole-5-carboxylate
A solution of the product of step A (4.5g, 16mmol) and sodium azide (1.2g, 19mmol) in DMF (20mL) was heated to 90 ℃ for 16 hours. The reaction mixture was then cooled to room temperature and diluted with water. The resulting two layers were separated and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over magnesium sulfate, filtered and concentrated under reduced pressure. The resulting crude solid was purified by silica gel chromatography (0-30% ethyl acetate/hexane) to provide 4.0g of the title product as a yellow solid.
And C: preparation of 2- (3-pyridyl) -2H-indazole-5-carbonyl chloride
The methyl ester prepared in step B (4.1g, 16mmol) was dissolved in methanol (150mL), 50% sodium hydroxide in water (7.1mL) was added, and the reaction mixture was heated to reflux for 4 hours. The reaction mixture was then cooled to room temperature and the solvent was removed under reduced pressure. The crude product was acidified with 1N aqueous HCl and the resulting precipitate was isolated by filtration, washed with diethyl ether and dried under reduced pressure at 60 ℃ overnight. The crude carboxylic acid was then redissolved in thionyl chloride (60mL) and the reaction mixture was heated to 75 ℃. The reaction mixture was then cooled to room temperature and the solvent was removed under reduced pressure. The crude phosgene was used in the next step without further purification.
Step D: preparation of 2- [ [2- (3-pyridinyl) -2H-indazol-5-yl]Carbonyl radical]Hydrazine carboxylic acid methyl ester
The acid chloride prepared in step C (200mg, 0.836mmol) was combined with hydrazinocarboxylic acid ester (82mg, 0.91mmol) in dichloromethane (5 mL). The reaction mixture was cooled to 0 ℃ and triethylamine (360. mu.l, 2.51mmol) was added dropwise. The reaction was allowed to warm to room temperature and allowed to stir overnight. The reaction mixture was then cooled and quenched with saturated aqueous sodium bicarbonate. The two layers were separated and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over magnesium sulfate, filtered and concentrated under reduced pressure. The resulting crude solid was purified by silica gel chromatography (20% to 80% ethyl acetate/hexanes) to yield the title compound, a compound of the invention, as a white solid.
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-pyridinyl) -1H-pyrazole
Lithium hexamethyldisilazide (55mL of a 1.0M solution in tetrahydrofuran, 55 mmol) was added to a cooled solution of 3-acetylpyridine (5.5mL, 50 mmol), dimethoxyacetic acid methyl ester (6.7mL, 55 mmol) and anhydrous tetrahydrofuran (100mL) at-45 ℃. The resulting reaction mixture was warmed to 25 ℃ over 1 hour and stirred at that temperature for 3 hours. The reaction mixture was then concentrated under reduced pressure, and the residue was suspended in methanol (50mL) and concentrated under reduced pressure. The resulting residue was suspended in methanol (150mL) and treated with hydrazine monohydrate (2.62mL, 55 mmol) and glacial acetic acid (6.29mL, 110 mmol) and the reaction mixture was heated at reflux for 14 h. The resulting reaction mixture was cooled to 25 ℃ and concentrated under reduced pressure. The residue was partitioned between ethyl acetate (200mL) and 1N aqueous sodium hydroxide (100 mL). The layers were separated and the organic layer was washed successively with 1N aqueous sodium hydroxide solution (50mL) and brine (50mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give 8.83g of the title compound as an off-white solid.
1H NMR(CDCl3):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)。
And B: preparation of 5- (3-pyridinyl) -1H-pyrazole-3-carbaldehyde
To a solution of the product from step a (715mg, 3.3 mmol) and chloroform (5mL) was added a solution of trifluoroacetic acid (2.5mL) and water (2.5 mL); the temperature of the reaction mixture was kept below 5 ℃ with an ice water bath. The reaction mixture was then stirred at 0 ℃ to 5 ℃ for 2 hours, treated with triethylamine (5mL) at 0 ℃, stirred for 15 minutes, treated with water (10mL), and filtered to isolate a brown solid. The solid was washed with chloroform (20mL) and water (20mL) and air dried to give 605mg of the title compound as a pale beige solid, which was used in the next step without further purification.
And C: preparation of 2- (3-pyridinyl) pyrazolo [1,5-a]Pyridine-5-carboxylic acid ethyl ester
A mixture of the product from step B (596mg, 3.4 mmol), ethyl 4-bromocrotonate (75%, 0.95mL, 5.2 mmol), anhydrous potassium carbonate (1.42g, 10.3 mmol), and anhydrous N, N-dimethylformamide (17mL) was stirred at 25 ℃ 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 (3 ×), brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give the crude product. The product obtained was purified by MPLC on a 24g silica gel column eluted with 0 to 100% ethyl acetate in hexane to give the title compound (105mg) as a pale beige solid.
1H NMR(CDCl3):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-carboxylic acid methyl ester Amides of carboxylic acids
To a solution of the product from step C (31mg, 0.11 mmol), tetrahydrofurfuryl amine (0.12mL, 1.2 mmol) and dry toluene (2.3mL) was added trimethylaluminum (0.6mL of a 2.0M solution in toluene, 1.2 mmol). The resulting solution was stirred at 25 ℃ for 2 hours, at 80 ℃ for 2 hours, and then cooled to 0 ℃ and carefully treated with water (3 mL). The resulting reaction mixture was stirred at 25 ℃ for 15 minutes, treated with saturated aqueous sodium potassium tartrate solution (2mL), stirred for 30 minutes, and then partitioned between dichloromethane and water. The organic layer was separated, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to isolate a brown residue, which was triturated with diethyl ether to give the title compound, the compound of the invention (15mg), as an off-white solid.
1H NMR(CDCl3):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-pyridyl) -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 (6.0g, 21.9mmol), zinc cyanide (3.85g, 21.9mmol) and tetrakis (triphenylphosphine) palladium (0) (2.53g, 2.2mmol) in degassed N-methylpyrrolidinone (60mL) was heated to 110 ℃ under a nitrogen atmosphere for 2 hours. The reaction mixture is cooled and passed through
Figure BDA0002864077420000261
Filtering with a pad, and filtering
Figure BDA0002864077420000262
The pad was washed with ethyl acetate (200 mL). The combined organic filtrates were washed with water (4 × 100mL), dried over sodium sulfate, filtered and concentrated. The resulting crude solid was triturated with 40% ethyl acetate/hexanes, isolated by filtration and dried to give the title compound as a tan solid, which was used in the next step without further purification.1H NMR(500MHz,DMSO-d6)δppm 9.60(d,J＝1.10Hz,1H),9.42(m,1H),8.71(m,1H),8.59(m,1H),8.17(m,1H),7.84(m,1H),7.69(m,1H),7.52(m,1H)。
And B: preparation of 2- (3-pyridyl) -2H-indazole-4-carboxylic acid
To a solution of 2- (3-pyridyl) -2H-indazole-4-carbonitrile (2.5g, 11.4mmol) in ethanol (100mL) and water (28mL) was added solid KOH (12.7g, 227 mmol). The resulting solution was heated to reflux for 4 hours. After the mixture is cooled to the room temperature,ethanol was removed under reduced pressure. The remaining aqueous solution was washed with dichloromethane (3 × 100mL) and acidified to pH 4 with concentrated HCl while cooling in an ice bath to form a white precipitate. The solid was isolated by filtration and dried to give the title compound (2.7g) as an off-white solid.1H NMR(500MHz,DMSO-d6)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)。
And C: preparation of N- (1-cyano-1-methylethyl) -2- (3-pyridyl) -2H-indazole-4-carboxamide
A solution of 2- (3-pyridyl) -2H-indazole-4-carboxylic acid (2.0g, 8.4mmol) in acetonitrile (40mL) was treated with propylphosphonic anhydride (50 wt% in ethyl acetate, 8.96mL, 15mmol), 2-amino-2-methylpropanenitrile (1.4g, 16.8mmol), triethylamine (2.5g, 25mmol), and 4-dimethylaminopyridine (0.002g, 0.01mmol) at 0 ℃. The reaction mixture was stirred at 0 ℃ for 30 minutes, warmed to room temperature, and then heated to 40 ℃ for 2 hours. The reaction mixture was cooled to room temperature and the solvent was removed in vacuo. The residue was partitioned between ethyl acetate and water, the phases were separated and the aqueous phase was washed with ethyl acetate (3 × 100 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated. The crude residue was purified by normal phase column chromatography (silica gel, 0-100% ethyl acetate/hexane) to give 1.45g of the title compound, a compound of the present invention, as a white solid. 1H NMR(500MHz,CDCl3)δppm 9.29(m,1H),9.17(d,J＝0.95Hz,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 synthetic examples 1-7 are shown in the following index table.
Abbreviations used in the index table may include: cmpd means the compound, t is t, c is ring, 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 t-butyl, Ph is phenyl, OMe is methoxy, SMe is methylthio, andSO2me means methylsulfonyl. The wavy line or "-" in the structural fragment indicates the point of attachment of the fragment to the remainder of the molecule. In the column entitled "analytical data", the asterisks (—) mean that the NMR data is provided in the index table O; the single number represents the mass spectrum parent peak (M + 1); and the numerical ranges indicate melting point ranges.
Index table A
Figure BDA0002864077420000271
Figure BDA0002864077420000272
Figure BDA0002864077420000281
Figure BDA0002864077420000291
Figure BDA0002864077420000301
*1See index table O for H NMR data.
Index table B
Figure BDA0002864077420000311
4X is CH
Figure BDA0002864077420000312
Figure BDA0002864077420000321
Figure BDA0002864077420000331
Figure BDA0002864077420000341
Figure BDA0002864077420000351
Figure BDA0002864077420000361
4X is N
Compound numbering R A Analyzing data
173 -C(O)NHCH2(tetrahydro-2-furanyl) CH *
*1See index table O for H NMR data.
Index table C
Figure BDA0002864077420000362
Compound numbering R A Analyzing data
428 -C(O)NHCH2CF3 CH *
429 -C (O) NH (cyclopropyl) CH *
430 -C(O)NHCH2(2-pyrimidinyl) CH *
431 -C(O)NHNHCO2Me CH *
432 -C(O)NHCH2CH2SMe CH *
433 -C(O)NHCH2CH(OMe)2 CH *
434 -C(O)NHCH(Me)CF3 CH *
435 -C(O)NHCH2CHF2 CH *
436 -C(O)NHCH(CH2OMe)2 CH *
437 -C(O)NHCH2(tetrahydro-2-furanyl) CH *
*1See index table O for H NMR data.
Index Table D-1
Figure BDA0002864077420000363
Compound numbering R X Analyzing data
135 -C(O)NHNHCO2Me Cl *
136 -C(O)NHCH2CF3 Cl *
137 -C(O)NHCH2(2-pyrimidinyl) Cl *
142 -C (O) NH (cyclopropyl) H *
438 -C(O)NHCH2(tetrahydro-2-furanyl) Cl *
*1See index table O for H NMR data.
Index Table D-2
Figure BDA0002864077420000371
Compound numbering R X Analyzing data
668 -C(O)NHCH2CF3 Cl *
669 -C(O)NHCH2CF3 F *
*1See index table O for H NMR data.
Index table E
Figure BDA0002864077420000372
bR is H
Compound numbering Ra X3 A Analyzing data
77 -C (O) (1-pyrrolidinyl) CH CH *
78 -C(O)NHCH2CF3 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)NHCH2CH2SMe CH CH *
85 -C(O)NHCH2CH2S (tert-butyl) CH CH *
160 -C (O) NH (cyclobutyl) CH CH *
161 -C(O)NHCH2(tetrahydro-2-furanyl) CH CH *
162 -C(O)NHNHCO2Me CH CH *
163 -C (O) NH (cyclopropyl) CH CH *
aR is H
Figure BDA0002864077420000373
Figure BDA0002864077420000381
*1See index table O for H NMR data.
Index table F
Figure BDA0002864077420000382
Figure BDA0002864077420000383
Figure BDA0002864077420000391
*1H NMR dataSee index table O.
Index table G
Figure BDA0002864077420000392
Compound numbering R Analyzing data
158 -NHC (O) (cyclobutyl) *
159 -NHC (O) (cyclopropyl) *
439 -C(O)NHCH2(2-pyrimidinyl) *
440 -C (O) NH (tetrahydro-2-furanyl) *
441 -C (O) NH (isopropyl)Base) *
442 -C(O)N(Pr)CH2(cyclopropyl) *
443 -C(O)NHCH2CF2CF3 *
444 -C (O) N (Me) (cyclopropyl) *
445 -C(O)NHCH2CH(OMe)2 *
446 -C(O)NHCH2(cyclopropyl) *
447 -C (O) NH (cyclopropyl) *
448 -C(O)NHNHCO2Me *
449 -C(O)NHCH2CH2CF3 *
*1See index table O for H NMR data.
Index table H
Figure BDA0002864077420000393
Compound numbering R Analyzing data
200 -C (O) (1-pyrrolidinyl) *
201 -C (O) NH (isopropyl) *
*1See index table O for H NMR data.
Index table I
Figure BDA0002864077420000394
Compound numbering R Analyzing data
450 -C(O)NHCH2CH2SMe *
451 -C(O)NHCH2CH(OMe)2 *
452 -C(O)N(Me)2 *
453 -C(O)NHCH2CF3 *
454 -C (O) NH (tert-butyl) *
*1See index table O for H NMR data.
Index table J
Figure BDA0002864077420000401
Compound numbering R Analyzing data
455 -C(O)NHCH2CH(OMe)2 327
456 -C(O)NHCH2(tetrahydro-2-furanyl) 323
457 -C(O)NHCH2CF3 321
458 -C(O)NHCH2(2, 2-Difluorocyclopropyl) 329
*1See index table O for H NMR data.
Index table K
Figure BDA0002864077420000402
Compound numbering R Analyzing data
459 -C(O)NHNHCO2Me 313
460 -C(O)NHCH2CF3 322.5
Index table L
Figure BDA0002864077420000403
Compound numbering R Analyzing data
461 -C(O)NHCH2CF3 322.5
Index table M
Figure BDA0002864077420000404
Compound numbering R Analyzing data
467 -C(O)NHCH2(tetrahydro-2-furanyl) *
*1See index table O for H NMR data.
Index table N
Figure BDA0002864077420000405
Figure BDA0002864077420000411
*1See index table O for H NMR data.
Index table O
Figure BDA0002864077420000412
Figure BDA0002864077420000421
Figure BDA0002864077420000431
Figure BDA0002864077420000441
Figure BDA0002864077420000451
Figure BDA0002864077420000461
Figure BDA0002864077420000471
Figure BDA0002864077420000481
Figure BDA0002864077420000491
Figure BDA0002864077420000501
Figure BDA0002864077420000511
Figure BDA0002864077420000521
Figure BDA0002864077420000531
Figure BDA0002864077420000541
Figure BDA0002864077420000551
Figure BDA0002864077420000561
Figure BDA0002864077420000571
Figure BDA0002864077420000581
Figure BDA0002864077420000591
Figure BDA0002864077420000601
Figure BDA0002864077420000611
Figure BDA0002864077420000621
Figure BDA0002864077420000631
a1H NMR data is in ppm downfield from tetramethylsilane. Coupling is specified by(s) -singlet, (d) -doublet, (t) -triplet, (m) -multiplet, (dd) -doublet, (dt) -doublet 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
Figure BDA0002864077420000632
A is CH
R R
-COOH -C(O)OMe
-C(O)OEt Cyano radical
-C(O)Cl -C(O)OPh
-C (O) O (4-nitrophenyl) -C(O)Me
-CHO Cl
Br I
-OS(O)2CF3 NH2
Nitro radical
A is CF
R R
-COOH -C(O)OMe
-C(O)OEt Cyano radical
-C(O)Cl -C(O)OPh
-C (O) O (4-nitrophenyl) -C(O)Me
-CHO Cl
Br I
-OS(O)2CF3 NH2
Nitro radical
A is N
Figure BDA0002864077420000633
Figure BDA0002864077420000641
TABLE I-2
Figure BDA0002864077420000642
A is CH
R R
-COOH -C(O)OMe
-C(O)OEt Cyano radical
-C(O)Cl -C(O)OPh
-C (O) O (4-nitrophenyl) -C(O)Me
-CHO Cl
Br I
-OS(O)2CF3 NH2
Nitro radical
A is CF
R R
-COOH -C(O)OMe
-C(O)OEt Cyano radical
-C(O)Cl -C(O)OPh
-C (O) O (4-nitrophenyl) -C(O)Me
-CHO Cl
Br I
-OS(O)2CF3 NH2
Nitro radical
A is N
R R
-COOH -C(O)OMe
-C(O)OEt Cyano radical
-C(O)Cl -C(O)OPh
-C (O) O (4-nitrophenyl) -C(O)Me
-CHO Cl
Br I
-OS(O)2CF3 NH2
Nitro radical
TABLE I-3
Figure BDA0002864077420000643
A is CH
Figure BDA0002864077420000644
Figure BDA0002864077420000651
A is CF
R R
-COOH -C(O)OMe
-C(O)OEt Cyano radical
-C(O)Cl -C(O)OPh
-C (O) O (4-nitrophenyl) -C(O)Me
-CHO Cl
Br I
-OS(O)2CF3 NH2
Nitro radical
A is N
R R
-COOH -C(O)OMe
-C(O)OEt Cyano radical
-C(O)Cl -C(O)OPh
-C (O) O (4-nitrophenyl) -C(O)Me
-CHO Cl
Br I
-OS(O)2CF3 NH2
Nitro radical
TABLE I-4
Figure BDA0002864077420000652
A is CH
R R
-COOH -C(O)OMe
-C(O)OEt Cyano radical
-C(O)Cl -C(O)OPh
-C (O) O (4-nitrophenyl) -C(O)Me
-CHO Cl
Br I
-OS(O)2CF3 NH2
Nitro radical
A is CF
Figure BDA0002864077420000653
Figure BDA0002864077420000661
A is N
R R
-COOH -C(O)OMe
-C(O)OEt Cyano radical
-C(O)Cl -C(O)OPh
-C (O) O (4-nitrophenyl) -C(O)Me
-CHO Cl
Br I
-OS(O)2CF3 NH2
Nitro radical
TABLE I-5
Figure BDA0002864077420000662
Table I-5 is the same as Table I-1, except under the heading "TABLE 1-1The structure shown "below" is replaced with the structure shown above.
TABLE I-6
Figure BDA0002864077420000663
Table I-6 is the same as Table I-1, except under the heading "TABLE I-1The structure shown "below" is replaced with the structure shown above.
TABLE I-7
Figure BDA0002864077420000664
Table I-7 is the same as Table I-1, except under the heading "TABLE I-1The structure shown "below" is replaced with the structure shown above.
TABLE I-8
Figure BDA0002864077420000665
Table I-8 is the same as Table I-1, except under the heading "TABLE I-1The structure shown "below" is replaced with the structure shown above.
TABLE I-9
Figure BDA0002864077420000666
Table I-9 is identical to Table I-1, except for in the title "TABLE I-1The structure shown "below" is replaced with the structure shown above.
TABLE I-10
Figure BDA0002864077420000671
Table I-10 is identical to Table I-1, except for in the title "TABLE I-1The structure shown "below" is replaced with the structure shown above.
TABLE I-11
Figure BDA0002864077420000672
Table I-11 is identical to Table I-1, except for the title "TABLE I-1The structure shown "below" is replaced with the structure shown above.
TABLE I-12
Figure BDA0002864077420000673
Table I-12 is identical to Table I-1, except for in the title "TABLE I-1The structure shown "below" is replaced with the structure shown above.
TABLE I-13
Figure BDA0002864077420000674
Table I-13 is identical to Table I-1, except for in the title "TABLE I-1The structure shown "below" is replaced with the structure shown above.
TABLE I-14
Figure BDA0002864077420000675
Table I-14 is identical to Table I-1, except for in the title "TABLE I-1The structure shown "below" is replaced with the structure shown above.
TABLE I-15
Figure BDA0002864077420000676
Table I-15 is identical to Table I-1, except for in the title "TABLE I-1The structure shown "below" is replaced with the structure shown above.
TABLE I-16
Figure BDA0002864077420000677
Table I-16 is the same as Table I-1, except under the heading "TABLE I-1The structure shown "below" is replaced with the structure shown above.
The following compounds in tables 1 to 24d may be prepared by the procedures described herein together with methods known in the art. The following abbreviations may be used in the following tables: t means tertiary, s means secondary, i means iso, c means ring, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, sat means ethylthio, -CN means cyano, Ph means phenyl, Py means pyridyl, -NO2Meaning nitro, S (O) Me means methylsulfinyl, and S (O)2Me means methylsulfonyl.
The "-" at the beginning of the fragment definition indicates the point of attachment of the fragment to the rest of the molecule; for example, "-CH2CH2OMe "represents the fragment 2-methoxyethyl. Cyclic fragments are represented by using the two "-" in parentheses; for example, the fragment 1-pyrrolidinyl is represented by "N (-CH) 2CH2CH2CH2- "denotes wherein the nitrogen atom is bonded to the two terminal carbon atoms of the four carbon chain, as shown below.
Figure BDA0002864077420000681
TABLE 1a
Figure BDA0002864077420000682
A is CH
Figure BDA0002864077420000683
Figure BDA0002864077420000691
A is CF
Figure BDA0002864077420000692
Figure BDA0002864077420000701
A is N
Figure BDA0002864077420000702
Figure BDA0002864077420000711
Figure BDA0002864077420000721
TABLE 1b
Figure BDA0002864077420000722
A is CH
Figure BDA0002864077420000723
Figure BDA0002864077420000731
A is CF
Figure BDA0002864077420000732
Figure BDA0002864077420000741
A is N
Figure BDA0002864077420000742
Figure BDA0002864077420000751
TABLE 1c
Figure BDA0002864077420000761
A is CH
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
A is CF
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
A is N
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
TABLE 1d
Figure BDA0002864077420000762
A is CH
Figure BDA0002864077420000763
Figure BDA0002864077420000771
A is CF
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
A is N
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
TABLE 1e
Figure BDA0002864077420000772
A is CH
Figure BDA0002864077420000773
Figure BDA0002864077420000781
A is CF
Figure BDA0002864077420000782
Figure BDA0002864077420000791
A is N
Figure BDA0002864077420000792
Figure BDA0002864077420000801
TABLE 1f
Figure BDA0002864077420000811
A is CH
Figure BDA0002864077420000812
Figure BDA0002864077420000821
A is CF
Figure BDA0002864077420000822
Figure BDA0002864077420000831
A is N
Figure BDA0002864077420000832
Figure BDA0002864077420000841
TABLE 2a
Figure BDA0002864077420000842
A is CH
Figure BDA0002864077420000843
Figure BDA0002864077420000851
A is CF
Figure BDA0002864077420000852
Figure BDA0002864077420000861
A is N
Figure BDA0002864077420000862
Figure BDA0002864077420000871
Figure BDA0002864077420000881
TABLE 2b
Figure BDA0002864077420000882
A is CH
Figure BDA0002864077420000883
Figure BDA0002864077420000891
A is CF
Figure BDA0002864077420000892
Figure BDA0002864077420000901
A is N
Figure BDA0002864077420000902
Figure BDA0002864077420000911
TABLE 2c
Figure BDA0002864077420000912
A is CH
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
A is CF
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
A is N
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
TABLE 2d
Figure BDA0002864077420000921
A is CH
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
A is CF
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
A is N
R R
N(-CH2CH2CH2-) N(-CH2CH(OMe)CH2-)
N(-CH2CH2CF2CH2CH2-) N(-CH2CH2CH2CF2CH2-)
N(-CH2CH2CH2CH2-) N(-CH2CH2SCH2CH2-)
N(-CH2CH2CH2CH2CH2-) N(-CH2CH2OCH2CH2-)
N(-CH2CH2N(C(O)(c-Pr))CH2CH2-) N(-CH2CH2N(Me)CH2CH2-)
N(-CH2C(Me)2N＝CH-) N(-CH2CH2CH2CH(CF3)CH2-)
N(CH2C≡CH)2 N(Et)2
N(Pr)CH2(c-Pr) N (Et) (c-hexyl)
N(-CHC(O)SCH2CH2-)
TABLE 2e
Figure BDA0002864077420000931
A is CH
Figure BDA0002864077420000932
Figure BDA0002864077420000941
A is CF
Figure BDA0002864077420000942
Figure BDA0002864077420000951
A is N
Figure BDA0002864077420000952
Figure BDA0002864077420000961
TABLE 2f
Figure BDA0002864077420000962
A is CH
Figure BDA0002864077420000963
Figure BDA0002864077420000971
A is CF
Figure BDA0002864077420000972
Figure BDA0002864077420000981
A is N
Figure BDA0002864077420000982
Figure BDA0002864077420000991
TABLE 3a
Figure BDA0002864077420001001
Table 3a is the same as Table 1a except under the heading "TABLE 1aThe structure shown below is shown aboveThe structure of (1) is replaced.
TABLE 3c
Figure BDA0002864077420001002
Table 3c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 3e
Figure BDA0002864077420001003
Table 3e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 4a
Figure BDA0002864077420001004
Table 4a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 4c
Figure BDA0002864077420001005
Table 4c is the same as Table 1c except under the heading " TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 4e
Figure BDA0002864077420001006
Table 4e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 5a
Figure BDA0002864077420001011
Table 5a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 5b
Figure BDA0002864077420001012
Table 5b is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 5c
Figure BDA0002864077420001013
Table 5c is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 5d
Figure BDA0002864077420001014
Table 5d is the same as Table 1a, except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 5e
Figure BDA0002864077420001015
Table 5e is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 5f
Figure BDA0002864077420001021
Table 5f is the same as Table 1a, except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 6a
Figure BDA0002864077420001022
Table 6a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 6c
Figure BDA0002864077420001023
Table 6c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 6e
Figure BDA0002864077420001024
Table 6e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 7a
Figure BDA0002864077420001025
Table 7a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 7c
Figure BDA0002864077420001031
Table 7c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 7e
Figure BDA0002864077420001032
Table 7e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 8a
Figure BDA0002864077420001033
Table 8a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 8c
Figure BDA0002864077420001034
Table 8c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 8e
Figure BDA0002864077420001035
Table 8e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 9a
Figure BDA0002864077420001036
Table 9a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 9c
Figure BDA0002864077420001041
Table 9c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 9e
Figure BDA0002864077420001042
Table 9e is the same as Table 1e, except under the heading "TABLE 1e The structure shown "below" is replaced with the structure shown above.
TABLE 10a
Figure BDA0002864077420001043
Table 10a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 10b
Figure BDA0002864077420001044
Table 10b is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 10c
Figure BDA0002864077420001045
Table 10c is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 10d
Figure BDA0002864077420001051
Table 10d is the same as Table 1a, except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 11a
Figure BDA0002864077420001052
Table 11a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 11b
Figure BDA0002864077420001053
Table 11b is the same as Table 1a, except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 11c
Figure BDA0002864077420001054
Table 11c is the same as Table 1a, except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 11d
Figure BDA0002864077420001055
Table 11d is the same as Table 1a, except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 12a
Figure BDA0002864077420001056
Table 12a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 12c
Figure BDA0002864077420001061
Table 12c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 12e
Figure BDA0002864077420001062
Table 12e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 13a
Figure BDA0002864077420001063
Table 13a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 13c
Figure BDA0002864077420001064
Table 13c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 13e
Figure BDA0002864077420001065
Table 13e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 14a
Figure BDA0002864077420001066
Table 14a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 14c
Figure BDA0002864077420001067
Table 14c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 14e
Figure BDA0002864077420001071
Table 14e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 15a
Figure BDA0002864077420001072
Table 15a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 15c
Figure BDA0002864077420001073
Table 15c is the same as Table 1c, except under the heading " TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 15e
Figure BDA0002864077420001074
Table 15e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 16a
Figure BDA0002864077420001075
Table 16a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 16c
Figure BDA0002864077420001076
Table 16c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 16e
Figure BDA0002864077420001077
Table 16e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 17a
Figure BDA0002864077420001081
Table 17a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 17c
Figure BDA0002864077420001082
Table 17c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 17e
Figure BDA0002864077420001083
Table 17e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 18a
Figure BDA0002864077420001084
Table 18a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
Table 18c
Figure BDA0002864077420001085
Table 18c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 18e
Figure BDA0002864077420001086
Table 18e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 19a
Figure BDA0002864077420001087
Table 19a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
Table 19c
Figure BDA0002864077420001091
Table 19c is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
TABLE 19e
Figure BDA0002864077420001092
Table 19e is the same as Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
Watch 20a
Figure BDA0002864077420001093
Table 20a is the same as table 1a,except in the title "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 20b
Figure BDA0002864077420001094
Table 20b is identical to Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 21a
Figure BDA0002864077420001095
Table 21a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 21b
Figure BDA0002864077420001096
Table 21b is identical to Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 22a
Figure BDA0002864077420001097
Table 22a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 22b
Figure BDA0002864077420001101
Table 22b is identical to Table 1e, except under the heading " TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 23a
Figure BDA0002864077420001102
Table 23a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 23b
Figure BDA0002864077420001103
Table 23b is identical to Table 1e, except under the heading "TABLE 1eThe structure shown "below" is replaced with the structure shown above.
TABLE 24a
Figure BDA0002864077420001104
Table 24a is the same as Table 1a except under the heading "TABLE 1aThe structure shown "below" is replaced with the structure shown above.
TABLE 24b
Figure BDA0002864077420001105
Table 24b is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" is replaced with the structure shown above.
Table 24c
Figure BDA0002864077420001106
Table 24c is the same as Table 1a except under the heading "TABLE 1aThe structure shown belowThe structure shown above is substituted.
Table 24d
Figure BDA0002864077420001111
Table 24d is the same as Table 1c, except under the heading "TABLE 1cThe structure shown "below" 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, as carriers. The formulation or composition ingredients are selected to be consistent with the physical characteristics 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, which optionally can be thickened into gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates and suspoemulsions. Common types of non-aqueous liquid compositions are emulsifiable concentrates, micro-emulsifiable concentrates, dispersible concentrates and oil dispersions.
The general types of solid compositions are powders, granules, pellets, granules, lozenges, tablets, filled films (including seed coatings), and the like, which may be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. The active ingredient may be (micro-) encapsulated and further formed into a suspension or solid formulation; alternatively, the entire formulation of the active ingredient may be encapsulated (or "coated"). Encapsulation may control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granule formulations. The high strength compositions are mainly used as intermediates for further formulations.
Sprayable formulations are typically dispersed in a suitable medium prior to spraying. Such liquid and solid formulations are formulated to be readily dilutable in a spray medium, usually water, but occasionally another suitable medium like aromatic or paraffinic hydrocarbons or vegetable oils. The spray volume may range from about one to several thousand liters per hectare, but more typically ranges from about ten to several hundred liters per hectare. The sprayable formulation may be mixed with water or another suitable medium in a tank for foliar treatment by air or ground application, or for application to the growing medium of the plant. The liquid and dry formulations can be metered directly into the drip irrigation system or into the furrow during planting. Liquid and solid formulations may be applied as seed treatments to the seeds of crops and other desired vegetation prior to planting in order to protect the developing roots and other sub-surface plant parts and/or foliage by systemic absorption.
The formulation will generally contain an effective amount of active ingredient, diluent and surfactant, in total up to 100 weight percent, within the following approximate ranges.
Figure BDA0002864077420001112
Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starches, dextrins, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid Diluents are described in Handbook of Insecticide Dust Diluents and Carriers, Watkins et al, 2 nd edition, Dorland Books, codeville, new jersey.
Liquid diluents include, for example, water, N, N-dimethylalkanamides (e.g., N, N-dimethylformamide), limonene, dimethyl sulfoxide, N-Alkyl pyrrolidones (e.g., N-methyl pyrrolidone), 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, N-paraffin, isoparaffin), alkylbenzenes, alkylnaphthalenes, glycerol, triacetin, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate, other esters such as alkylated lactates, dibasic esters, alkyl and aryl benzoates, ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, N-paraffin, isoparaffin), alkylbenzenes, Gamma-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, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include saturated and unsaturated fatty acids (typically C) 6-C22) Such as vegetable seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil (corn oil), peanut oil, sunflower oil, grape seed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal-derived fats (e.g., beef tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, wherein the fatty acids may be obtained by hydrolysis of glycerides from plant and animal sources and may be purified by distillation. Typical liquid diluents are listed in Marsden, Solvents Guide [ solvent Guide ]]2 nd edition, Interscience, new york, 1950.
The solid and liquid compositions of the present invention typically include one or more surfactants. Surfactants (also referred to as "surface active agents") generally alter, most often reduce, the surface tension of liquids when added to liquids. Surfactants can be used as wetting agents, dispersing agents, emulsifying agents, or defoaming agents, depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule.
Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful in the compositions of the present invention include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from 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 ethoxylates 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 end 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, glycerol esters, lanolin-based derivatives, polyethoxylated esters (such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters); other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; a silicone-based surfactant; and sugar derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.
Useful anionic surfactants include, but are not limited to: alkyl aryl sulfonic acids and salts thereof; carboxylated alcohol or alkylphenol ethoxylates; a diphenyl sulfonate derivative; lignin and lignin derivatives, such as lignosulfonates; maleic or succinic acid or anhydrides thereof; olefin sulfonates; phosphate esters such as alcohol alkoxylate phosphate esters, alkylphenol alkoxylate phosphate esters, and styrylphenol ethoxylate phosphate esters; a protein-based surfactant; a sarcosine derivative; styrylphenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; amine and amide sulfonates such as N, N-alkyl taurates; benzene, cumene, toluene, xylene, and the sulfonates of dodecylbenzene and tridecylbenzene; a sulfonate of condensed polynaphthalene; sulfonates of naphthalene and alkylnaphthalenes; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.
Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propylene diamine, tripropylene triamine and dipropylene tetramine, and ethoxylated, ethoxylated 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 salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxide and bis- (2-hydroxyethyl) -alkylamine oxide.
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 The McCutcheon division, The Manufacturing conditioner Publishing Co. [ Emulsifiers and Detergents for McCutcheon ], annual and International specifications [ U.S. and International annual edition ]; sisely and Wood, Encyclopedia of Surface Active Agents [ surfactant Encyclopedia ], Chemical publication. And a.s.davidson and b.milwidsky, Synthetic Detergents, seventh edition, john wily father, new york, 1987.
The compositions of the present invention may also contain formulation adjuvants and additives known to those skilled in the art as co-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 (buffer), foaming during processing (antifoam agents such as polyorganosiloxanes), sedimentation of the active ingredient (suspending agents), viscosity (thixotropic thickeners), microbial growth in the container (antimicrobials), product freezing (antifreeze), color (dye/pigment dispersion), elution (film former or sticker), evaporation (evaporation retarder), and other formulation attributes. Film formers include, for example, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include The second volume of McCutcheon published by The subsection of McCutcheon, The Manufacturing conditioner Publishing co: functional Materials [ Functional Materials ], international and north american year versions; and those listed in PCT publication WO 03/024222.
The compound of formula 1 and any other active ingredient are typically incorporated into the compositions 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 the ingredients. If the solvent of the liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the solvent containing the active ingredient upon dilution with water. Slurries of active ingredient having a particle size of up to 2,000 μm can be wet-milled using a media mill to give particles having an average particle size of less than 3 μm. The aqueous slurry can be made into a finished suspension concentrate (see, e.g., U.S.3,060,084) or further processed by spray drying to form water dispersible granules. Dry formulations typically require a dry milling process, which results in an average particle size in the range of 2 to 10 μm. Powders and powders may be prepared by blending and typically by grinding (e.g. with a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active substance onto a preformed granule carrier or by agglomeration techniques. See, Browning, "Agglomeration ]", Chemical Engineering, 12.4.1967, pages 147-48; perry's Chemical Engineers ' Handbook [ Parry's Handbook of Chemical Engineers ], 4 th edition, McGraw-Hill [ McGray Hill group ], New York, 1963, pages 8-57 and beyond, and WO 91/13546. Spheroids may be prepared as described in U.S.4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S.4,144,050, U.S.3,920,442 and DE 3,246,493. Tablets may be prepared as taught in U.S.5,180,587, U.S.5,232,701 and U.S.5,208,030. Membranes may be prepared as taught in GB 2,095,558 and u.s.3,299,566.
For further information on The field of formulation, see "The formulations's Toolbox-Product Forms for model Agriculture analysis" in The Food-environmental Challenge [ Pesticide Chemistry and Bioscience, formulation kit-Modern agricultural Product form ], editions of t.brooks and t.r.roberts, Proceedings of The 9th International conference on Pesticide Chemistry [ ninth International conference on Pesticide Chemistry ], The Royal Society of Chemistry [ chemical Society ], cambridge, 1999, p.120. 133. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S. Pat. No. 3,309,192, column 5, column 43 to column 7, column 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, line 66 to column 5, line 17 and examples 1-4; klingman, Weed Control as a Science, john william, new york, 1961, pages 81-96; hance et al, Weed Control Handbook, 8 th edition, Blackwell Scientific Publications, blakewell Scientific publishers, oxford, 1989; and development in formulation technology, PJB publishing company [ PJB Publications ], Riekan, UK, 2000.
In the following examples, all formulations were prepared in a conventional manner. The compound numbers refer to the compounds in the index tables A-N. Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. Accordingly, the following examples are to be construed as merely illustrative, and not limitative of the disclosure in any way whatsoever. Percentages are by weight unless otherwise indicated.
Example A
High strength concentrate
Compound 898.5%
0.5 percent of silicon dioxide aerogel
Synthetic amorphous Fine silica 1.0%
Example B
Wettable powders
Figure BDA0002864077420001131
Example C
Granules
Compound 1610.0%
Attapulgite granule (low volatile matter, 0.71/0.30 mm; U.S. S. 90.0% No.25-50 sieve)
Example D
Extrusion spheronization agent
Figure BDA0002864077420001132
Figure BDA0002864077420001141
Example E
Emulsifiable concentrate
Compound 4110.0%
Polyoxyethylene sorbitol hexaoleate 20.0%
C6-C10Fatty acid methyl ester 70.0%
Example F
Microemulsion
Figure BDA0002864077420001142
Example G
Seed treatment
Figure BDA0002864077420001143
Example H
Fertilizer bar
Figure BDA0002864077420001144
Example I
Suspension concentrates
Figure BDA0002864077420001145
Example J
Emulsions in water
Figure BDA0002864077420001146
Figure BDA0002864077420001151
Example K
Oil dispersion
Figure BDA0002864077420001152
Example L
Suspoemulsion
Figure BDA0002864077420001153
The compounds of the present invention exhibit activity against a broad spectrum of invertebrate pests. These pests include invertebrates that inhabit various environments such as, for example, plant leaves, roots, soil, harvested crops or other food, building structures, or animal skin. These pests include invertebrates which feed, for example, on leaves (including leaves, stems, flowers and fruits), seeds, wood, textile fibres or animal blood or tissue and thereby cause damage or harm to, for example, growing or stored agronomic crops, forests, greenhouse crops, ornamentals, nursery crops, stored food or fibre products, or houses or other structures or their contents, or are harmful to animal health or public health. It will be understood by those skilled in the art that not all compounds are equally effective at all growth stages of all pests.
Thus, these compounds and compositions of the invention are useful in agriculture to protect field crops from planting Feeding invertebrate pests and also non-agriculturally for protecting other horticultural crops and plants from plant-feeding invertebrate pests. This utility includes the protection of crops and other plants (i.e., agronomic and nonagronomic) that have been genetically engineered (i.e., transgenic) to introduce or modified genetic material by mutagenesis to provide advantageous traits. Examples of such traits include herbicide tolerance, resistance to phytophagous pests (e.g. insects, mites, aphids, spiders, nematodes, snails, phytopathogenic fungi, bacteria and viruses), improved plant growth, increased tolerance to adverse growth conditions such as high and low temperature, high or low soil moisture and high salinity, increased flowering or fruiting, higher harvest yield, faster maturation, higher quality and/or nutritional value of the harvested product, or improved storage or processing characteristics of the harvested product. Transgenic plants can be modified to express a variety of traits. Examples of plants containing traits provided by genetic engineering or mutagenesis include various maize, cotton, soybean and potato varieties expressing insecticidal Bacillus thuringiensis toxins such as Yield
Figure BDA0002864077420001154
And
Figure BDA0002864077420001157
INVICTA RR2 PROTMand herbicide tolerant varieties of corn, cotton, soybean and rapeseed such as Roundup
Figure BDA0002864077420001155
Liberty
Figure BDA0002864077420001156
And
Figure BDA0002864077420001158
and a crop plant expressing an N-acetyltransferase (GAT) to provide resistance to glyphosate herbicide, or a crop plant containing an HRA gene that provides resistance to an herbicide that inhibits acetolactate synthase (ALS). The compounds and compositions of the invention may interact synergistically with traits introduced by genetic engineering or modified by mutagenesisThereby enhancing phenotypic expression or effectiveness of the trait or increasing the invertebrate pest control effectiveness of the compounds and compositions of the invention. In particular, the compounds and compositions of the present invention may synergistically interact with the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide above-additive control of these pests.
The compositions of the present invention may also optionally comprise a plant nutrient, for example, a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of note are compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from the group consisting of nitrogen, phosphorus, potassium, sulfur, calcium, and magnesium. The composition of the invention further comprising at least one phytonutrient may be in liquid or solid form. Of note are solid formulations in the form of granules, rods or tablets. Solid formulations comprising a fertilizer composition may be prepared by mixing a compound or composition of the invention with the fertilizer composition and formulation ingredients and then preparing the formulation by methods such as granulation or extrusion. Alternatively, solid formulations may be prepared by spraying a solution or suspension of the compound or composition of the invention in a volatile solvent onto a previously prepared fertilizer composition in the form of a dimensionally stable mixture (e.g., granules, slugs or tablets), and then evaporating the solvent.
Non-agronomic use refers to invertebrate pest control in areas other than crop plant fields. Non-agronomic uses of the compounds and compositions of the present invention include the control of invertebrate pests in stored cereals, legumes and other food products, as well as textiles such as clothing and carpets. Non-agronomic uses of the compounds and compositions of the present invention also include invertebrate pest control in ornamentals, forests, patios, roadside and railroad grounds, and turf such as lawns, golf courses and rangelands. Non-agronomic uses of the compounds and compositions of the present invention also include invertebrate pest control in houses and other buildings that may be occupied by humans and/or companions, farms, pastures, zoos or other animals. Non-agronomic uses of the compounds and compositions of the present invention also include the control of pests such as termites that may damage wood or other structural materials used in buildings.
Non-agronomic uses of the compounds and compositions of the present invention also include the protection of human and animal health by controlling invertebrate pests that are parasitic or that transmit infectious diseases. Control of animal parasites includes control of external parasites that are parasitic to the surface of the body of the host animal (e.g., shoulder, axilla, abdomen, inside thigh) and internal parasites that are parasitic to the interior of the body of the host animal (e.g., stomach, intestine, lung, vein, subcutaneous, lymphoid tissue). External parasites or pests that transmit 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 invention are suitable for systemic and/or non-systemic control of parasite infestations or infections on animals. The compounds and compositions of the present invention are particularly useful against external parasites or pests that transmit diseases. The compounds and compositions of the present invention are useful against infesting agricultural work animals such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, hens, turkeys, ducks, geese and bees; pet animals and domestic animals such as dogs, cats, pet birds, and aquarium fish; and parasites of so-called laboratory animals such as hamsters, guinea pigs, rats and mice. By combating these parasites, mortality and performance degradation (in terms of meat, milk, wool, skin, eggs, honey, etc.) is reduced, so that the application of a composition comprising the compounds of the invention allows more economical and simple rearing of animals.
Examples of agronomic or non-agronomic invertebrate pests include eggs, larvae and adults of the order lepidoptera, such as armyworms, sugar moths, loopers and cotton bollworms (heliotropins) (e.g., pink stem borer (pink stem borer) (diaphania grandiflorus (Sesamia incognita Walker)), corn borer (corn stem borer) (Sesamia nonagrioides Lefebvre), Southern Armyworm (Southern Arstem) (Southern Armillaria viridis Cramer (Spodoptera), fall Armyworm (fall Armyworm) (Spodoptera frugiperda), Spodoptera frugiperda (Spodoptera frugiperda), Spodoptera litura (Spodoptera frugiperda (Spodoptera), Spodoptera litura heterosporum (Spodoptera), Spodoptera litura heterospodoptera (Spodoptera), Spodoptera litura (Spodoptera litura), Spodoptera litura (Spodoptera frugiperda (Spodoptera), Spodoptera litura (Spodoptera litura) and Spodoptera (Spodoptera litura), Spodoptera litura (Spodoptera litura) and Spodoptera frugiperda (Spodoptera) in the family, Spodoptera variety (Spodoptera) and Spodoptera variety (Spodoptera litura), and Spodoptera, Cabbage loopers (cabbage loopers) (Barathra brassica Linnaeus), soybean loopers (soybean loopers) (pseudopluvialis Walker), cabbage loopers (cabbage loopers) (Trichoplusia ni Hubner), oriental tobacco budworms (tobaco budworm) (helicoptera Fabricius)); borers, coleoptera, nodulus, coneworms, cabbage worms and cutworm (skilonizers) from the family of borer, e.g., European corn borer (European corn borer) (Ostrinia nubilalis hebner), navel orange borer (navelo orangeworm) (amylois tranthitis Walker), corn root knot borer (corn root worm) borer (corn root borer) (corn root grass borer (crambe california Clemens)), meadow moth (soderbelm) borer (soderbelm borer) (moth family: subfamily of soderbornidae) such as meadow borer (sod worm) (rice leaf borer), petiolus pyralis (petiolatus grunnis), sugarcane borer (sugarbeet borer) (grapevines greenbris) (grapevines) (Ostrinia borer), sugarcane borer (cabbage borer) (grapevines greenfly) (Diaphania punctifera), sugarcane borer (cabbage borer (cantonensis) (grapevines) (Ostrinia green leaf borer (grapevines) (grapevines) (Diaphania borer (grapevis)) Cabbage core grub (cabbage center grub) (helualahydality guene), rice stem borer (yellow stem borer) (scirphaga incertulas Walker), early young shoot borer (early shoot bore borer) (sugarcane borer (scirphaga incertulas Snellen)), white stem borer (white stem borer) (rice stem borer (scirphaga incerta Walker)), top young shoot borer (top shoot borer) (sugarcane white stem borer (scirphagella Fabricius)), black head rice borer (dark-headed borrei) (Chilo multichrysick medick), striped rice stem borer (stringella ostrinia) (Chilo punctifera), and cabbage borer (Chilo fascicularia punctifera) (ostrinia), ostrinia (Chilo punctifera), ostrinia nubilalis (Chilo punctifera), ostrinia (Chilo punctifera corpalis) (ostrinia fascialis), ostrinia nubilalis (chilus punctifera (chilus), ostrinia nubilalis) (ostrinia nubilalis), ostrinia nubilalis (chilus punctifera (chilus), ostrinia nubilalis), ostrinia (chilus punctifera (chilus domestica), ostrinia nubilalis) (ostrinia nubilalis), ostrinia; leaf rollers, aphids, seed insects and fruit insects of the family tortricidae (e.g. codling moth (codling moth) (codling moth (Cydia pomonella Linnaus)), grape leaf roller (grapple berry moth) (Endopiza virens Clemens)), pear fruit moth (Oriental fruit moth (Grapholitta mosaic Busck)), citrus pseudoapple moth (citrus false) codling moth (apple leaf roller) (Cryptophylloxera) citrus (citrus borteus), citrus longibrachiata (apple leaf roller)), red leaf roller (Red leaf roller) (Argyriana nigra (European leaf roller)), apple leaf roller (cabbage leaf roller) (apple leaf roller)), and fruit moth (cabbage leaf roller) (apple leaf roller (cabbage leaf roller)), and fruit moth (cabbage leaf roller) (apple leaf roller) (European leaf roller) (Rose leaf roller) (European leaf roller)) Apple leafroll (apple budworm) (Pandemis pyrusana carambola), omnivorous leafroll (omnivorous leaf roller) (platinostastultan Walsingham), grape brown leaf roller (grape brown leaf roller) (Pandemis cerana hubner), apple brown leaf roller (apple brown leaf roller) (Pandemis hepes & schifformer)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus)), pink bollworm (ping bollworm) (Cotton bollworm (Pectinophora gossypiella Saunders)), gypsy moth (gypsy molt) (Lymantria dispar Linnaeus), small fruit borer (peach fruit borer) (Carposina niponensis Walsingham), peach fruit borer (peach fruit borer) (apple leaf miner)), cabbage (potato leaf moth) (Phyllodendron punctatus), leaf miner (apple leaf miner)), leaf miner (apple leaf miner) (apple leaf miner)), leaf miner (apple leaf miner) (leaf miner (apple leaf miner)), and leaf miner (leaf miner) (leaf miner)) Nymphs and adults, including cockroaches from the families of the blattaceae and blattaceae (e.g., oriental cockroaches (Oriental Cockroach) (Oriental cockroaches Linnaeus), Asiatic cockroaches (Asian cockroaches) (Blatella asahinaci Mizukubo), Germanic cockroaches (German cockroaches) (Blattella germanica Linnaeus), brown banded cockroaches (brown banded cockroaches) (Succinia Fabricius), American cockroaches (American cockroaches) (Periplaneta americana (Australia Linnaeus)), brown cockroaches (brown cockroaches) (Brown cockroaches) (Symphora glabra bunkeri), and Blattella (Fabricola bunela) cockroaches (Fabricola buntoria), cockroaches (Fabricola bunolo cockroaches) (Fabricola bunolo) and Blattella fusca (Fabricola) order, larval and adult species including weevils (e.g., boll weevils) (e.g., cotton weevils (bollweevils) from the family Caryopteraceae (Anthribidae), Viridae (Bruchidae) and Bispidae (Curculoideae), rice weevils (rice water weevils) (Rice water weevils Kuschel), cereal weevils (cereal weevils) (cereal weevils Linnaeus), rice weevils (rice weevils) (rice water weevils), cereal weevils (cereal weevils), cereal grass weevils (Sphenomorphus Linnaeus) and vesicle tissues of the family (Choristidae family) Yellow melon leaf beetles, root beetles, leaf beetles, potato beetles and leaf miners (e.g., Colorado potato beetle (potato beetle) (leptotricha decemlineata Say)), western corn rootworm (western corn rootworm) (western corn rootworm (Diabrotica virgifera northern corn)), scarab and other beetles (e.g., Japanese beetle (Japanese beetle) (Popillia japonica Newman)), oriental beetle (oriental beetle) (oriental tortoise) (southern insect oriensis (northern tortoise)), yellow beetle (northern tortoise) bark (southern yellow beetle), southern yellow beetle (southern yellow beetle), southern yellow beetle (yellow beetle) and southern yellow beetle (northern yellow beetle) (southern yellow beetle (yellow beetle)), southern yellow beetle (northern yellow beetle) (southern yellow beetle (yellow beetle)), southern yellow beetle (yellow beetle) and southern yellow beetle (yellow beetle) (southern yellow beetle) (yellow beetle and white beetle (yellow beetle) (southern yellow beetle) (northern yellow beetle) (yellow beetle and white beetle) (yellow beetle) (southern yellow beetle) (yellow beetle) and yellow beetle (yellow beetle) and yellow beetle) (yellow beetle) and yellow beetle) (yellow beetle) and yellow beetle (yellow beetle) species) (yellow beetle) and yellow beetle (, Green June beetles (green June beetles) (cottonida Linnaeus), asian garden beetles (Asiatic garden beetles) (maladerastana auraw), June/June beetles (May/June beetles) (spica spp. (phyllophoga) species), and European chafer (European chafer) (rhizoctonia mangosteens (rhizogus majalis Razoumowsky)); bark beetles from the family bark beetles; wireworms from the family click beetle; bark beetles from the family bark beetle (Scolytidae) and flour beetles from the family Tenebrionidae (Tenebrionidae).
In addition, agronomic and non-agronomic pests include: eggs, adults and larvae of the order dermaptera, including earwigs from the family earwigidae (e.g. europaea earwig (European earwig) (centipede (Forficula auricularia Linnaeus)), black earwigs (black earwig) (chelidol mori), eggs, larvae, adults and nymphs from the family ceyloviridae, such as ceylon bugs (bunt bugs) from the family ceyloviridae, cicadas from the family cicadae, leafhoppers from the family phyllophiocladidae (leaffophthirius) (e.g. phyllopodera (Empoasca) species) from the family hemiptera, bed bugs from the family cimicidae (e bugs) from the family armoraceae), bed bugs (e bugs from the family cerambycidae and the family femoraceae, bed bugs from the family cicadae, carpopodidae, bemisia delphacidae from the family trichinae, bemisia delphacidae from the family trichodinidae (dictyoporaceae), bemisia rubelluscas from the family trichidae (trichidae bugs, bevaccaria bugs from the family trichodinidae, bevaccaria), stinkbugs from the family of stinkbugs, stinkbugs from the family of stinkbugs (chinch bugs) (e.g., hair stinkbugs (hair chinch bugs) (brissus americana bugs montan) and southern stinkbugs (southern stinkbugs Barber) and other stinkbugs from the family of stinkbugs (seed bugs), cicadas from the family of lypocladium, squash fringed stinkbugs from the family of lygus, and red stinkbugs and cotton swarms (cotton stainers) from the family of red stinkbugs.
Agronomic and non-agronomic pests also include: eggs, larvae, nymphs and adults of the order acarina (mites), such as tetranychidae (spider mites) and red mites (e.g. red mites (European red mite) (Panonychus ulmi Koch)), tetranychidae (two spotted spider mite (Tetranychus urticae Koch)), tetranychidae (mcdaniella mackeri McGregor)), brachyprus (flat mites) in the family gracilidae (e.g. grape short-fibrous mite (brachypus flat mite) (breviper short-fibrous McGregor)), (aphid and mite in the family gallinaceae), and other leaves of aphid and mites of the family gallinae and those of the species acarina and mites which have an important influence on the health of humans and animals, i.e. the species acarina (e.g. dermabrasion tick (mite), which is often called epididyma (acarus gramineus, pycidomycosis (black tick (mite), in the family chaetophycidomyidae (e.g. mite), and mites (epididyma (epididae (acarus gramineus, pycida (acarus (pycidus) in the family), which are often called glochirophagidae (epididae (black ticks, pycidomycosis) and mites) Australian paraplegia (Australian paralytic tick (Ixodes holocystis Neumann)), American dog tick (Dermacentor variabilis Say)), lone tick (lone star tick) (Amblyomma americanum Linnaeus) and tick of the Cryptoridae family, commonly referred to as soft ticks (e.g., recurrent heat tick (recurrent heat tick) (Ornithiosorb tritici), common chicken tick (Argas radiatus)); scabies in the Psychotridae, Psychotridae and Sarcophagidae families Mites (scab mites) and itch mites (itch mites); eggs, adults and larvae of the order orthoptera, including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanophagus sanguinipes Fabricius), Crataegus crispa (e.g., Melanophagus sanguinipes), Melanophagus crispa (e.g., Melanophagus sanguineus), Melanophagus americanus (e.g., Schistocaryopsis americanus (Schiocarpus), locusts (desert locustus) and Gracilaria (e.g., Gracilaria viridula), Graphoma microorgens (Migratory locustus), locusts (Bulocustus) (e zoticus species), Graphomopsis (e.g., Gracilaria viridula), Gracilaria gallica (Gracilaria), Gracilaria gallica) and Gracilaria (e), Gracilaria gigantiacuminata (Gracilaria), Gracilaria pseudophagostigmatis (Graves) (e), Gracilaria gigantica (Gracilaria), and Gracilaria pseudophacidula (e.g., Graves (Gracilaria) of the order, Midges (midges), fruit flies (fruit flies) (trypanosomatidae (Tephritidae)), straw flies (fruit flies) (e.g. swedish straw flies (Oscinella front Linnaeus)), soil maggots (soil maggers), house flies (house flies) (e.g. house flies (Musca domestica Linnaeus)), house flies (house flies) (e.g. houseflies (fancia canicola Linnaeus)), house flies (house flies) (e.g. house flies (fancia canicola Linnaeus)), house flies (f.febrile stinus)), stable flies (stable flies) (e.g. stable flies (Stomoxys calceis Linnaeus)), fall flies (flies), horn flies), blowflies (blowflies), and other species (e.g. flies) of the genus cophaga), and species (e.g. blowflies) (e.g. blowflies, pest species of the genus cophagus), and other species (e.g. blowflies) (e.g. blowflies (bils, species of the genus cophagecodina), species (blowflies) (e.g. blowflies, species of the genus coporiganla, blowflies (blowflies) (e.g. blowflies, species of the genus blowflies (blowflies) of the genus blowflies (blowflies) of the species of the genus blowflies (blowflies of the genus blowflies of the species of the genus cophagus, blowflies of the genus blowflies, Deer flies (deer flies) (e.g., deer flies (Chrysops) species), sheep ticks (kes) (e.g., sheep lice flies (Melophagus ovinus Linnaeus)) and other subclasses of the short horn (Brachycera), mosquitoes (e.g., Aedes (Aedes) species, Anopheles (Anopheles) species, Culex (Culex) species), gnats (black flies) (e.g., Aragnat genus (Prosimulium) species, gnats (Simulium) species), biting midges (biting midges), sand flies (sand flies), Octopus mosquitoes (scabarids) and other Sitoptera species (Nematocera); eggs, adults, and larvae of the order thysanoptera, including Thrips tabaci (Thrips tabaci Lindeman), Thrips floribunda (Thrips species), and other leaf-fed Thrips; insect pests of the order hymenoptera, including ants of the family formicaceae, including the Florida carpenter ant (the Florida carpenter ant) (Florida bow back ant (Camponotus floridanus Buckley)), red wood ant (red carpenter ant) (red wood ant (Camponotus ferugineus Fabricius)), black wood ant (black carpenter ant) (black wood ant (Camponotus pennyformis De Geer)), white foot ant (white-foot ant) (technical foot ant (smith)), big head ant (big head ant) (pholiod species), ghost ant (g nest ant) (taproot acid ant (tappings bee), etc.); pharaoh (Pharaoh ant) (Monomorium pharaonis Linnaeus), Formica fusca (little fire ant (Walmannia aurora Roger)), Formica fusca (fire ant) (Solenopsis geminata Fabricius), Pyrenopsis invicta (red imported fire ant) (Solenopsis invicta Buren (Solenopsis Buren)), Argentina (Argentina ant) (Iridogyrex Mayr), Terminalia (Crazy ant) (Paralichia longifolia) Lance), and Atractylis ovata (Fabricius) or Lagena (Fabricius) Linnaeus (Terminalia Linnaeus (corn), or Ant (Lagena) Linnaeus (corn), or Lagena (Lagenaria (corn) or Lagenaria (corn)
Figure BDA0002864077420001181
) And fragrant family ants (odorous house ant) (family ants (Tapinoma sessile Say)). Other hymenopterans, including bees (including carpenter beets), hornets (hornets), wasps (yellow bees), wasps (wasps), and wasps (sawflies) (neodendrophilus (Neodiprion) species); stemona (Cephus) species); insect pests of the order Isoptera, including the family Begonidae (Termitidae) (e.g., macrotermites (Macrotermes) species, Odontotermes (Odontottermes obesus Rambur)), the family Wood termitaceae (Kalotteridae) (e.g., dump sand termites (Cryptotermes) species)) And the family of the rhinotermites (rhizotetramites) (e.g., the species of the genus Reticulitermes, the species of the genus Coptotermes, the family of the genus Heterotermites (Heterotermites tenuis Hagen)), the family of the eastern subterranean termites (the eastern subterranean termites) (the species of the woody termites flavipes Kollar), the western subterranean termites (the species of the western subterranean termites) (the species of the western termites), the family of the Termite (the species of the woody termites), the family of the Taiwan lacto termites (the species of the woody termites of the western termites), the family of the western termites (the species of the woody termites of the northern termites), the western Stem white termites (the species of the western termites), the western termites (the species of the western termites), the West Dry termites (the white termites) and white termites (the family of the western termites) (the white termites), the family of the white termites (the family of the genus, the family of the genus, the genus of the family of the genus of the family of the genus of the species of the genus, the family of the species (the family of the genus Hoptotermes), the genus of the, Arborescent termites (arboreal termites) such as termites of species like termites (natutitermes) and other termites of economic significance; insect pests of the order thysanoptera, such as silverfish (chlamydia sacchara linaeus) and chlamydomonas domestica (firefly Packard); insect pests of the order mallophaga, including head lice (Pediculus humanus capitis De Geer)), body lice (body louse) (body lice (Pediculus humanus Linnaeus)), chicken body lice (chicken body louse) (Menacanthus striatus Nitszch), dog bite louse (dog biting louse) (Trichoplusis canis De Geer)), fluffy lice (fluff louse) (Goniochotus gallinae De Geer)), sheep body louse (sheep lice (Bovicola ovula schranium)), short-nosed cattle lice (short-nosed louse) (Haematoporus nipponensis grus nipponensis kuntzi (and other types of sucking lice of cattle); insect pests of the order Siphonaptera include the eastern rat flea (the Orthosiphon aristatus), Xenopsylla cheopis Rothschild, Cat flea (cat flea) (Ctenocephalides felis Bouche), dog flea (dog flea) (Ctenocephalides canicum) Fleas (Ctenocephalides cantis), chicken fleas (hen flea) (chicken horny flea (Ceratophyllus gallinae Schrank)), stinktight fleas (fowl horny fleas (Echidnogagana gallinae Westwood)), human fleas (human flea) (human fleas (Pulex irutans Linnaeus)), and other fleas afflicting mammals and birds. Additional arthropod pests covered include: aranea of the Aranea order, e.g. the brown recise spider (Loxosceles recissa Gertsch)&Mulaik)) and the black widow spider (the black widow spider) (Latrodectus mammus Fabricius), as well as the centipedes of the order Scutigera, such as Scutigera (the housefly centipede) (Scutigera colestipulus (Scutigera coleophila Linnaeus)).
Examples of invertebrate pests in stored grains include bark beetles (large grain beetles), bark beetles (bark beetles), rice weevils (rice weevils), maize weevils (maize weevils), bean weevils (cowpea), red rice beetles (red rice weevils), red rice beetles (red rice flour), grain weevils (grain wheat flour), grain borers (grain borers), red rice borers (red rice borers), grain borers (grain borers), red rice borers (Indian rice borers), and red rice borers (pink rice borers) and red rice borers (red rice borers) in stored grains.
The compounds of the invention may have activity against members of the classes Nematoda (Nematoda), Cestoda (Cestoda), Trematoda (Trematoda) and Acanthocephala (Acanthocephala), including economically important members of the order Strongylida (Strongylida), ascarida (ascarida), urocanida (oxurida), rhabdida (rhabdida), urocanida (Spirurida) and urocanida (enopha), such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne (Meloidogyne), root rot nematodes (leiomycots) in the genus Pratylenchus, root rot nematodes (Nematoda) in the genus trichotheca (trichoderma), root rot nematodes (tres) in the genus trichoderma (trichoderma), healthy roots (stubbros) in the genus trichoderma) and healthy pests (trichomonas), such as human and adult pests (trichomonas), human nematode), and adult pests (trichomonas), such as trichomonas canis (trichomonas), trichomonas sp) Dirofilaria immitis Leidy in dogs, cestode pelagina lobata (Anoplocephala perfoliata) in horses, Fasciola hepatica (Fasciola hepatica Linnaeus) in ruminants, etc.
The compounds of the invention may have activity against pests in the order lepidoptera (e.g. cotton leafworm (Alabama argillacea Hubner) (cotton leafworm (cotton leaf word) fruit tree yellow leaf moth (Archips argyrophylla Walker) (fruit tree leaf moth (fruit tree leaf roller)), A. rosana Linnaeus (European leaf moth (European leaf roller)) and other species of yellow leaf moth (Archie), Chilo suppressalis (Chilo supressalis Walker) (rice stem borer (rice stem borner)), Cnaphalocrocis medinalis guenee (apple stem borer (moth)), yellow leaf borer (yellow leaf borer)), corn rootworm (Cramberlis nubilalis) (corn rootworm (corn borer), yellow leaf borer (apple borer leaf borer)), corn rootworm (corn borer (yellow rice stem borer), corn borer (yellow rice borer) (yellow rice borer), yellow rice borer (yellow rice borer) (corn borer), yellow rice borer (yellow rice borer) rice borer (yellow rice borer) rice borer (yellow rice borer, Heliothis virescens (Earria virescens Fabricius) (spotlike (spottedbollworm)), Heliothis gossypii (Helicoverpa armigera Hubner) (American bollworm (America bollworm)), Heliothis virescens (Helicoverpa zea (corn earworm)), Heliothis virescens (Heliothis virescens) (tobacco budworm (Tobacco budworm)), Heliothis virescens Walker (grass borer (soderbworm), Heliothis virescens (Lobesia botricius) (Linteus punctatus (Linteus)), Heliothis virescens (Linteus flavipes), Heliothis virescens (Linteus punctatus (Linteus), Heliothis virescens gossypiella (Linteus), Helicoverpa virescens (Linteus) and Linteus punctatus (Linteus), Helicoverpa virescens (Linteus) (Linteus punctatus (Linteus), Linteus punctatus (Linteus punctatus) (Linteus punctatus (Linteus) and Linteus punctatus (Linteus) Pieris (Linteus) Pieris (Linteus) A (Linteus) A) and Piteus punctifera (Linteus Plutella) A) and Piteus (Linteus Plutella) Miyas (Linteus Plutella) and Piteus (Linteus pluteus (, Spodoptera exigua (Spodoptera exigua hubner) (beet armyworm), Spodoptera litura Fabricius (Spodoptera litura (tobaco cutword, clustericatiplantrum)), Spodoptera frugiperda (Spodoptera frugiperda j.e.smith) (fall armyworm), Trichoplusia ni hubner (Trichoplusia ni hubner) (cabbage looper), and Trichosta sativa (Tuta agglomerk) (tomato leaf miner).
The compounds of the invention have significant activity against members from the homoptera, including: pea aphid (Achythos pisum Harris) (pea aphid)), black bean aphid (Aphis craccivora Koch) (bean aphid (cowpea aphid)), beet aphid (Aphis fabae Scopoli) (broad bean aphid (black bean aphid)), cotton aphid (Aphis gossypii Glover) (cotton aphid (melon aphid)), apple aphid (Aphis pomi Geer) (apple aphid)), pear green (apple spore opa) (Aphis spiracla Aphis), apple ditch Nephophora Aphis japonica (apple aphid) (tussilago aphid (apple aphid)), apple green (apple aphid), apple aphid (apple aphid), apple ditch apple aphid (apple aphid), apple aphid (apple aphid) (strawberry aphid) (Dynasalis (apple aphid)), apple aphid (apple aphid) and apple aphid (apple aphid), etc.) (strawberry) Tail of green peach (Hyalopterus pruni Geoffroy) (medium aphid), radish aphid (Lipaphis erysipelas Kaltenbach) (radish aphid (turnip aphid)), ductus gracilis (metaaphid), ductus meretrix (rhizomorph) of potato (metaaphid), ductus persicae (Myzus persicae) (peach-leaf aphid, green peach), stem aphid (lettuce grain), stem aphid (lettuce grain), stem aphid (cabbage aphid), stem aphid (stem aphid) of stem aphid), stem aphid (stem aphid), stem aphid (stem aphid of stem aphid (stem aphid), stem aphid (stem aphid) of stem aphid (stem), stem aphid (stem aphid) of stem aphid (stem aphid) of stem aphid (stem aphid of stem) of phils grandis Rondani (binary wheat aphid), Sitobion avenae Fabricius (Sitobion avenae aphid), Sitobion maduratus (sitobis grandis aphid), sitobis major burkton (sitobis alfa aphid), binary orange aphid (toxptartea aurantii Boyer de Fonscolome) (binary orange aphid), and green orange aphid (toxptata citrida kirkalky) (brown orange aphid (brown citrus aphid)); globulus (Adelges) species (ballaphids (adelgids)); hickory root nodule aphid (Phylloxera devastatrix Pergande) (pecan root nodule aphid (pecan Phylloxera)); bemisia tabaci (Bemisia tabaci Gennadius) (Tobacco whitefly, sweet potato whitefly), Bemisia argentata (Bemisia argentati Belllows)&Perring) (silverleaf whitefly)), citrus whitefly (dialeures citri Ashmead) (citrus whitefly)), and greenhouse whitefly (greenhouse whitefly)); potato leafhoppers (Empoasca fabae Harris) (potato leafhoppers), Laodelphax striatellus (small brown planthopper), leafhoppers (Macrolestes quadralinesis wheels) (aster leafhoppers), leafhoppers (Nephoteix cincticeps Uhler) (green leafhoppers), and leafhoppers (Nephoteix nigrostreatus)
Figure BDA0002864077420001201
) (rice leafhoppers), Nilapavata lugens
Figure BDA0002864077420001202
) (brown planthopper), corn wax cicada (peregrine maindisc ash) (corn planthopper), Sogatella furcifera Horvath) (white-backed planthopper), rice planthopper (sogatedes oriicola Muir) (rice planthopper), apple leafhopper (typhlobaba mcmateum McAtee) (white leafhopper (white apple leaf hopper)), grape leafhopper (erythoontoneura) species (grape leafhopper)); sedum cicada (Magicidada septindecoim Linnaeus) (periodic cicada)(ii) a Icerya purchassia Maskell (cottony cushione)), pyricularia pyricularis (quadrastichus perniciosus Comstock) (San Jose scale)); mealybugs gluteus (Planococcus citri Risso) (citrus mealybug); the genus Lecanicillium (Pseudococcus) species (other Lecanicillium lineages); psyllids (pear psyllids), persimmon psyllid (Trioza dioxapyri ash) (persimmons psyllid).
The compounds of the invention also have activity against members from the order hemiptera, including: stinkbug (Acrosternum italicum Say) (green stink bug), squash stinkbug (Anasa tristis De Geer) (pumpkin insect (squash bug)), stinkbug (Blissus leucopterus Say) (stink bug), temperate bugs (Cimex leucopterus Linnaeus) (bed bug)), stinkbug (Corytuca gossypii Fabricius) (cotton bug)), stinkbug (Cyrtopeltis modesta dist) (tomato bug)), red cotton wing (Dysdercus sutureus herrichum-
Figure BDA0002864077420001203
) (Cotton seed stink bugs), stinkbug (Euschistus servus Say) (Brown stink bugs (brown stink bugs)), Eurystus variolius Palisot de Beauvois (one-spotted stink bugs)), Graptosthitus species (Long stink complexes), and tea bug (Halymorpha toxins)
Figure BDA0002864077420001204
) (brown Marble stink bug), root and stink bug (Leptoglossosus coricus Say) (leaf-leaved pine seed bug), Lygus lineolaris (Lygus lineolaris de Beauvois) (tarnished plant bug), Oryza sativa Linnaeus (Southern green stink bug), Oryza sativa (Oebalus pugnoides Fabricius) (rice stink), Oryza sativa (Oynaud horse lace fleur) (Cotton seed bug), and Oryza sativa (Black horse muscle bug) (Cotton seed bug). ByOther insect orders which the compounds of the invention control include Thysanoptera (Thysanoptera) (e.g.Frankliniella occidentalis Perganide) (western flower Thrips), Franklinis citrifolia Moulton (citrus Thrips), Thrips glycines (soybean Thrips), and Thrips tabaci Lindeman (onion Thrips), and Coleoptera (Coleoptera), e.g.Leptospira fruticosa (maize mosaic screw), Murraya koenigii (Colorado potato), Pieris meyensis (Epsilosis variola), and Muconopsis (Agileria), and Muconopsis (Marinothrips).
It should be noted that some contemporary taxonomies classify homopterans into the sub-orders hemiptera.
It is notable that the compounds according to the invention are used for controlling Frankliniella occidentalis (western flower thrips). Of note is the use of the compounds of the present invention for the control of potato leafhoppers (potato leafhoppers). It is noteworthy that the compounds of the invention are used for controlling the cotton aphid (cotton aphid) cotton aphid (Aphis gossypii). Of note is the use of the compounds of the present invention for the control of green peach aphid (green peach aphid). Of note is the use of the compounds of the present invention for controlling sweet potato whitefly (Bemisia tabaci).
The compounds of the invention may also be used to increase the vigor of crop plants. The method comprises contacting a crop plant (e.g., leaf, flower, fruit, or root), or seed from which the crop plant is growing, with a compound of formula 1 in an amount (i.e., a biologically effective amount) sufficient to achieve the desired plant vigor effect. Typically, the compound of formula 1 is administered in a formulated composition. Although the compound of formula 1 is typically applied directly to the crop plant or to the seed thereof, it may also be applied to the locus of the crop plant, i.e. to the environment of the crop plant, in particular to parts of the environment which are sufficiently close to allow the compound of formula 1 to migrate to the crop plant. The locus with which the method is associated most often comprises a growth medium (i.e. a medium which provides nutrients to the plant), usually the soil in which the plant is grown. Thus, treatment of crop plants to increase the vigor of the crop plants comprises contacting the crop plants, the seeds from which the crop plants are grown, or the locus of the crop plants with a biologically effective amount of a compound of formula 1.
Increasing crop vigor may result in one or more of the following observed effects: (a) such as optimal crop cultivation from excellent seed germination, crop emergence and crop standing display; (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 nutrients for the crop; (c) improved crop yield as demonstrated by flowering time, duration of flowering, number of flowers, total biomass accumulation (i.e., yield), and/or product grade marketability (i.e., yield quality) of the fruit or grain; (d) enhanced crop tolerance or the ability to prevent plant disease infections and arthropod, nematode or mollusc pest infestation; and (e) increased crop ability to withstand environmental stresses, such as exposure to extreme heat, suboptimal moisture, or phytotoxic chemicals.
The compounds of the present invention may increase the vigor of treated plants compared to untreated plants by killing phytophagous invertebrate pests or preventing their feeding in the environment of the plant. In the absence of such control by phytophagous invertebrate pests, the pests reduce plant vigor by consuming plant tissue or juice, or transmitting plant pathogens such as viruses. The compounds of the present invention may increase plant vigor by altering the metabolism of the plant, even in the absence of phytophagous invertebrate pests. In general, if a 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.
Of note are methods for increasing the vigor of a crop plant, wherein the crop plant is grown in an environment comprising a phytophagous invertebrate pest. Also of note are methods for increasing the vigor of a crop plant, wherein the crop plant is grown in an environment that does not include a phytophagous invertebrate pest. Also of note are methods for increasing the vigor of a crop plant, wherein the crop plant is grown in an environment that includes an amount of moisture that is less than the ideal amount of moisture to support growth of the crop plant. Of note are methods for increasing the vigor of a crop plant, wherein the crop is rice. Also of note are methods for increasing the vigor of a crop plant, wherein the crop is maize (corn). Also of note are methods for increasing the vigor of a crop plant, 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, including insecticides, fungicides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and root-growth stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, viruses or fungi to form multi-component pesticides, conferring an even broader spectrum of agronomic and non-agronomic utility. 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 selected from the group consisting of surfactants, solid diluents and liquid diluents, and at least one additional biologically active compound or agent. For the mixtures of the invention, the other biologically active compounds or agents may be formulated together with the compounds of the invention (including the compounds of formula 1) to form a premix, or the other biologically active compounds or agents may be formulated separately from the compounds of the invention (including the compounds of formula 1) and the two formulations combined together prior to administration (e.g., in a spray can), or alternatively, administered sequentially.
Such biological activity of the compounds of the invention may be formulatedExamples of compounds or agents are insecticides, such aS abamectin (abamectin), acephate, acequinocyl, acetamiprid, fluthrin, pyriproxyfen (afidopyropen) ([ (3S,4R,4aR,6S,6aS,12R,12aS,12bS) -3- [ (cyclopropylcarbonyl) oxy]-1,3,4,4a,5,6,6a,12,12a,12 b-decahydro-6, 12-dihydroxy-4, 6a,12 b-trimethyl-11-oxo-9- (3-pyridinyl) -2H, 11H-naphtho [2,1-b ] o]Pyrano [3,4-e ] s]Pyran-4-yl]Methyl cyclopropane carboxylate), sulfafurazoate, amitraz, avermectin (avermectin), azadirachtin, glutethion, benfuracarb, benfurathion, bifenthrin, bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbarfan, cartap, varroan, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos-methyl, chromafenozide, chlorfenapyr (cloventezin), clothianidin, cyantranilide (3-bromo-1- (3-chloro-2-pyridyl) -N- [ 4-cyano-2-methyl-6- [ (methylamino) carbonyl]Phenyl radical]-1H-pyrazole-5-carboxamide), Cyclobromantraniliprole (3-bromo-N- [ 2-bromo-4-chloro-6- [ [ (1-cyclopropylethyl) amino group]Carbonyl radical]Phenyl radical]-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxamide), cycloprothrin, cycloxaprid ((5S,8R) -1- [ (6-chloro-3-pyridyl) methyl group ]-2,3,5,6,7, 8-hexahydro-9-nitro-5, 8-epoxy-1H-imidazo [1,2-a ]]Azepine), cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, permethrin, dimehypo, dimethoate, dinotefuran, phenetole, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin, fenitrothion, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flosoquin (2-ethyl-3, 7-dimethyl-6- [4- (trifluoromethoxy) phenoxy ] phenoxy]-4-quinolinylcarbonate methyl ester), flonicamid, flubendiamide, flucythrinate, pyrimethanil, flufenoxuron, flubendiamide ((alpha E) -2- [ [ 2-chloro-4- (trifluoromethyl) phenoxy ] phenacyl]Methyl radical]-methyl α - (methoxymethylene) phenylacetate), fluensulfone (5-chloro-2- [ (3,4, 4-trifluoro-3-buten-1-yl) sulfonyl group]Thiazole), cyano thioether insecticides (fluhexafon), fluopyramAmide, fluprirole (1- [2, 6-dichloro-4- (trifluoromethyl) phenyl) ]-5- [ (2-methyl-2-propen-1-yl) amino]-4- [ (trifluoromethyl) sulfinyl group]-1H-pyrazole-3-carbonitrile), fluoropyrafuranone (4- [ [ (6-chloro-3-pyridinyl) methyl group](2, 2-Difluoroethyl) amino]-2(5H) furanone), fluvalinate, tau-fluvalinate, disulfoton, varacetamidine, fosthiazate, chlorfenapyr, heptafluthrin (2, 2-dimethyl-3- [ (1Z) -3,3, 3-trifluoro-1-propen-1-yl)]Cyclopropanecarboxylic acid [2,3,5, 6-tetrafluoro-4- (methoxymethyl) phenyl]Methyl ester), hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soap, isoxathion, lufenuron, malathion, meperfluthrin ((1R,3S) -3- (2, 2-dichlorovinyl) -2, 2-dimethylcyclopropanecarboxylic acid [2,3,5, 6-tetrafluoro-4- (methoxymethyl) phenyl ] cyclopropanecarboxylic acid]Methyl ester), metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, metofluthrin, methoxyfenozide, metofluthrin, monocrotophos, monoflurothrin (3- (2-cyano-1-propen-1-yl) -2, 2-dimethylcyclopropanecarboxylic acid [2,3,5, 6-tetrafluoro-4- (methoxymethyl) phenyl ] cyclopropanecarboxylic acid]Methyl ester), nicotine, nitenpyram, thifluzamide, novaluron, noviflumuron, oxamyl, parathion, methyl parathion, prometharine, phorate, vozaphos, phosmet, phosphamidon, pirimicarb, profenofos, proffluthrin, propargite, propylphenthrin (protifenbute), pyfluumide (1,3, 5-trimethyl-N- (2-methyl-1-propionyl) -N- [3- (2-methylpropyl) -4- [2,2, 2-trifluoro-1-methoxy-1- (trifluoromethyl) ethyl ]Phenyl radical]-1H-pyrazole-4-carboxamide), pymetrozine, pyrazinecarboxamide (pyrafluprole), pyrethrin, pyridaben, pyridalyl, neoquinazoline (m-diazabenzene) insecticides (pyrifluquinazon), pyriminostrobin ((alpha E) -2- [ [ [2- [ (2, 4-dichlorophenyl) amino group]-6- (trifluoromethyl) -4-pyrimidinyl]Oxy radical]Methyl radical]-methyl alpha- (methoxymethylene) phenylacetate), pyriftalid (pyriproxyfen), pyriproxyfen, rotenone, linalodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, thioprofos, sulfoxaflor (N- [ methyl-oxidized [1- [6- (trifluoromethyl) -3-pyridyl) -pyriftalid)]Ethyl radical]-λ4-sulfonyl subunit]Cyanamide), tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin,Terbufos, chlorfenvinphos, chrysanthemum flower, tetrafluoethrin (2,2,3, 3-tetramethyl cyclopropane carboxylic acid [2,3,5, 6-tetrafluoro-4- (methoxy methyl) phenyl group]Methyl ester), cyantraniliprole, thiacloprid, thiamethoxam, thiodicarb, dimehypo, tioxazafen (3-phenyl-5- (2-thienyl) -1,2, 4-oxadiazole), tolfenpyrad, tetrabromthrin, triazamate, trichlorfon, triflumylpyrimidine (2, 4-dioxo-1- (5-pyrimidinylmethyl) -3- [3- (trifluoromethyl) phenyl ] pyriproxyfen ]-2H-pyrido [1,2-a]Pyrimidinium inner salts), triflumuron, bacillus thuringiensis delta-endotoxin, entomopathogenic bacteria, entomopathogenic viruses, and entomopathogenic fungi.
Of note are insecticides such as abamectin, acetamiprid, flupropathrin, pyriproxyfen, amitraz, abamectin, azadirachtin, benfuracarb, sulcotine, bifenthrin, buprofezin, cadusafos, carbaryl, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyromanil, cycloprothrin, cyfluthrin, beta-cyfluthrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, ben ether, emamectin, endosulfan, esfenproplis, etoxazole, fenthion, fenoxycarb, fenvalerate, metaflumetofenapyr, flufenapyr, flufena, Flubendiamide, flufenoxuron, flutriafol, fluthiacet, flupirrolide, flupyradifurone, cyfluthrin, vaboxamidine, fosthiazate, hexflufluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiocarb, methomyl, methoprene, flumethrin, monofluthrin, nitenpyram, thiflubenzuron, oxamyl, pyflubiude, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, pyrethroids, tefluthrin, thiacloprid, thiamethoxam, thiodicarb, dimehypo, tetrabromthrin, triazamate, trifluoropyrimidine, 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 a compound of the invention includes entomopathogenic bacteria such as bacillus thuringiensis, and encapsulated delta-endotoxins of bacillus thuringiensis such as bacillus thuringiensis
Figure BDA0002864077420001231
Prepared by the method
Figure BDA0002864077420001232
And
Figure BDA0002864077420001233
biological insecticides (
Figure BDA0002864077420001234
And
Figure BDA0002864077420001235
is a trademark of Mycogen Corporation, Indianapolis, Indiana, USA (Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi such as Metarrhizium anisopliae; and entomopathogenic (both naturally occurring and genetically modified) viruses, including baculovirus, Nuclear Polyhedrosis Virus (NPV) such as Helicoverpa zea (Helicoverpa zea) nuclear polyhedrosis virus (HzNPV), apiacea (anagrena falcifera) nuclear polyhedrosis virus (AfNPV); and Granulosis Viruses (GV), such as codling moth (Cydia pomonella) granulosis virus (CpGV).
Of particular note are combinations wherein the other invertebrate pest control active ingredient belongs to a different chemical class or has a different site of action than the compound of formula 1. In certain instances, a combination with at least one other invertebrate pest control active ingredient having a similar control spectrum but a different site of action would be particularly advantageous for resistance management. Thus, the compositions of the present invention may further comprise a biologically effective amount of at least one additional invertebrate pest control active ingredient having a similar spectrum of control but belonging to a different chemical class or having a different site of action. These additional biologically active compounds or agents include, but are not limited to, acetylcholinesterase (AChE) inhibitors such as carbamate methomyl, oxamyl, thiodicarb, triazamate, and the organophosphate chlorpyrifos; GABA-gated chloride channel antagonists such as the cyclopentadiene class of pesticides dieldrin and endosulfan, and the phenylpyrazole class of ethiprole and fipronil; sodium channel modulators such as bifenthrin pyrethroids, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, deltamethrin, tetramethrin, esfenvalerate, metofluthrin, and proffluthrin; nicotinic acetylcholine receptor (nAChR) agonists such as neonicotinoid acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nitroethimide thiazole, thiacloprid and thiamethoxam, and sulfoxaflor; nicotinic acetylcholine receptor (nAChR) allosteric activators such as the spinosyns spinetoram and spinosyns; chloride channel activators such as abamectin and emamectin; juvenile hormone mimics such as benchol, methoprene, fenoxycarb, and pyriproxyfen; selective feeding blockers of the order homoptera, 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 nereistoxin analog cartap; chitin biosynthesis inhibitors such as benzoylurea flufenoxuron, hexaflumuron, lufenuron, diphenylthiourea, noviflumuron and triflumuron, and buprofezin; dipteran molting disruptors, such as cyromazine; ecdysone receptor agonists such as dihydrazide and tebufenozide; octopamine receptor agonists such as amitraz; mitochondrial complex III electron transport inhibitors such as hydramethylnon; mitochondrial complex I electron transport inhibitors such as pyridaben; 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 β -ketonitrile pyrauxifen and cyflumetofen; ryanodine receptor modulators, such as anthranilic diamides chlorantraniliprole, cyantraniliprole, and cyantraniliprole, diamides, such as flubendiamide, and ryanodine receptor ligands, such as ryanodine; compounds in which the target site responsible for biological activity is unknown or uncharacterized, such as azadirachtin, bifenazate, pyridalyl, neoquinazoline (m-diazabenzene) insecticides, and trifluorobenzene pyrimidine; insect midgut membrane microbial disruptors such as bacillus thuringiensis and their delta-endotoxins produced as well as bacillus sphaericus and biologicals, including Nuclear Polyhedrosis Virus (NPV) and other naturally occurring or genetically modified insecticidal viruses.
Further examples of biologically active compounds or agents that can be formulated with the compounds of the invention are: fungicides, such as acibenzolar-S-methyl, 4-dodecyl-2, 6-dimethylmorpholine (aldimorph), ametoctradin, hymexazol, penconazole, azoxystrobin, benalaxyl (including benalaxyl-M), mefenox, benomyl, benthiavalicarb (including benthiavalicarb-isoprox)), benzovindiflupyr (benzovindifiumbr), 3-benzo [ b ] thiophen-2-yl-5, 6-dihydro-1, 4, 2-thiazine 4-oxide (betaxazin), binapacryl, biphenyltriazolyl alcohol, bixafen, blasticidin, boscalid, bromuconazole, bupirizole, bupirimate, butrymate, carboxin, cyprodinil, captafol, captan, carbendazid, diclofen, chlorothalonil, carbendazim, chlozolinate, ethirimol, carbendate, carbendazim, ethiprole, benomyl, benomy, Copper oxychloride, copper sulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocyanide, diclofenamate, niclosamide, diethofencarb, difenoconazole, difluorine, metidine, dimethomorph, dodemodin, econazole, epoxiconazole, fenamiphos, enoxastrobin (also known as enestroburin), epoxiconazole, ethaboxam, ethirimycin, hymexazol, famoxadone, fenamidone, dimethomofenamidone, fenamidoxim, fenamidol, fenbuconazole, furanilide, fenhexamid, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamide, fenpropitin acetate, fentin hydroxide, flumizone, methazone, metofenapyr, fluquinconazole, fludioxonil, fenpyroxapyroxad, fenpropiconazole, fenpropimorph, fenpropiconazole, flufenamidone, fludioxonil, flumorph, fluopicolide, fluopyram, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, fluthiabendazole (fluthianil), flutolanil, flutriafol, fluxapyroxad, folpet, tetrachlorophthalide (also known as phthalide), fuberidazole, furalaxyl, frazopyr, hexaconazole, hymexazol, biguanide salts, imazalil, amidazole, alkylbenzene sulfonate standards, iminoctadine triacetate, iodocarb, ipconazole, iprodione (isoflutamide), iprobenfos, iprodione, propineb, isoprothiolane, isopyramid, kasugamycin, cuckooxin, mancozeb, mandipropamid, mandesrobinin, manshibon, maprotipyrin, mepanipyrimethanil, imazapyr, imazamethamidone, metalaxyl (including hymexazol/mefenoxamine), metrafoxanil, fenbuconazole, metiram, metominostrobin, fenpropiconazole, fenpyroxim, fenpropineb, flutriafolacin, fluazinaxate, flutriafolacinone (including fluazinaxaprop-methyl), fluazinaxaprop-N), flutriafolacin, flutriafol, Flufenacet, octreotide, furamectin, orysastrobin, oxadixyl, fluthiazopyr (Oxathiapaprolin), oxolinic acid, oxpoconazole, carboxin, oxytetracycline, penconazole, pencycuron, penflufen, penthiopyrad, oryzamate (perfurazole), phosphorous acid (including salts thereof, such as aluminum fosetyl), picoxystrobin, fluazinam, polyoxin, thiabendazole, prochloraz, procymidone, propamocarb, propiconazole, zineb-methyl, proquinclorac, prothioconazole, pyraclostrobin, pirfenicol, pyributicarb, pyribenzoxim (pyribenzoxim), pyribenzoxim (pyribenzoxim-ethyl), penflufenapyr, fluquindoxine, flufenadine (flufenamate), fluquindoxine, thiflufenadine, thiflufenamide, teclofthalam, kukukuro, tetraoxy nitrobenzene, terbinafine, flutriazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, tolcumate, tolprocarb, tolylfluanid, triadimefon, triadimenol, pyrimethanil, triazoxide, tribasic copper sulfate, cloxystrobin, tridemorph, trifloxystrobin, triflumizole, trimopramide tricyclazole, trifloxystrobin, triforin, triticonazole, uniconazole, validamycin, propamocarb (valenalate) (also known as valifinal), propamocarb (also known as valifinal), vinclozolin, zineb, ziram, zoxamide, and 1- [4- [4- [5- (2, 6-difluorophenyl) -4, 5-dihydro-3-isoxazolyl ] -2-thiazolyl ] -1-piperidinyl ] -2- [ 5-trifluoromethyl-3-H) -1-pyrazole-1-2- [4- [5- (1H) -3-trifluoromethyl ] -1H ] -1-pyrazole 1-yl ] ethanone; nematicides such as fluopyram, spirotetramat, thiodicarb, fosthiazate, abamectin, iprodione, fluensulfone (flunsulfone), dimethyldisulfide, tioxazafen, 1, 3-dichloropropene (1,3-D), metam (sodium and potassium), dazomet, trichloronitromethane, fenamiphos, ethoprophos, cadusafos, terbufos, neonicotinophos (imicyafos), oxamyl, carbarfan, tioxazafen, Bacillus firmus (Bacillus firmus) and pasteurella (Pasteuria nishizawa); bactericides such as streptomycin; acaricides such as amitraz, mefenpyr, beclomethazine, cyhexatin, dicofol, dichlorfen, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad.
In certain instances, the combination of a compound of the present invention with other biologically active (particularly invertebrate pest control) compounds or agents (i.e., active ingredients) may result in a more than additive (i.e., synergistic) effect. It has been desirable to reduce the amount of active ingredient released in the environment while ensuring effective pest control. Such combinations may be advantageously used to reduce crop production costs and reduce environmental load when synergistic effects of the invertebrate pest control active ingredients occur at application rates, thereby imparting agronomically satisfactory levels of invertebrate pest control.
The compounds of the invention and compositions thereof may be applied to plants genetically transformed to express proteins 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 exogenously applied invertebrate pest control effect of the compounds of the invention may act synergistically with the expressed toxin protein.
General references to such agricultural protectants (i.e., insecticides, fungicides, nematicides, acaricides, herbicides, and biologicals) include The Pesticide Manual, 13 th edition, c.d.s.tomlin editions, British Crop Protection Council, Farnham, Surrey, u.k., 2003, and The BioPesticide Manual, 2 nd edition, l.g.coating editions, British Crop Protection Council, Farnham, Surrey, u.k., 2001.
For embodiments in which one or more of these different mixing components are used, the weight ratio of these different mixing components (total) to the compound of formula 1 is typically between about 1:3000 and about 3000: 1. Of note is a weight ratio of between about 1:300 and about 300:1 (e.g., a ratio of between about 1:30 and about 30: 1). The biologically effective amount of the active ingredient necessary for the desired spectrum of biological activity can be readily determined by one skilled in the art by simple experimentation. It will be apparent that the inclusion of these additional components may extend the invertebrate pest control spectrum beyond that of the compound of formula 1 alone.
Table a lists specific combinations of compounds of formula 1 with other invertebrate pest control agents, illustrating the mixtures, compositions and methods of the invention. The first column of table a lists specific invertebrate pest control agents (e.g., "abamectin" 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 examples of the weight ratio ranges for the invertebrate pest control agent that may be applied relative to the compound of formula 1 (e.g., "50: 1 to 1: 50" by weight abamectin relative to the compound of formula 1). Thus, for example, the first row of table a specifically discloses that the combination of the compound of formula 1 and abamectin may be administered in a weight ratio of between 50:1 and 1: 50. The remaining rows of table a will be similarly constructed. It is further noted that table a lists specific combinations of compounds of formula 1 with other invertebrate pest control agents, exemplifies the mixtures, compositions and methods of the invention and includes additional examples of weight ratio ranges for application rates.
TABLE A
Figure BDA0002864077420001241
Figure BDA0002864077420001251
Figure BDA0002864077420001261
Of note are compositions of the present invention wherein at least one additional biologically active compound or agent is selected from the group of invertebrate pest control agents listed in table a above.
The weight ratio of the compound comprising a compound of formula 1, an N-oxide thereof, or a salt thereof, to the additional invertebrate pest control agent is typically between 1000:1 and 1:1000, one embodiment between 500:1 and 1:500, another embodiment between 250:1 and 1:200, and another embodiment between 100:1 and 1: 50.
Listed in tables B1 through B10 below are examples of specific compositions comprising compounds of formula 1 (compound numbers refer to compounds in tables a-N) and additional invertebrate pest control agents.
TABLE B1
Figure BDA0002864077420001262
Figure BDA0002864077420001271
TABLE B2
Table B2 is the same as 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 the additional invertebrate pest control agent abamectin.
TABLE B3
Table B3 is the same as 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 the additional invertebrate pest control agent abamectin.
TABLE B4
Table B4 is the same as 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 the same as 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 the additional invertebrate pest control agent abamectin.
TABLE B6
Table B6 is the same as 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 the additional invertebrate pest control agent abamectin.
TABLE B7
Table B7 is the same as 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 the additional invertebrate pest control agent abamectin.
TABLE B8
Table B8 is the same as 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 the same as 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 the same as 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 through B10 generally combine the compound of formula 1 with other invertebrate pests in the ratios specified in table a.
Listed in tables C1 through C10 below are specific mixtures comprising compounds of formula 1 (compound No. (cmpd.no.) compounds indexed in tables a-N) and additional invertebrate pest control agents. 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 the mixture of compound 8 and abamectin of the index table a administered at a weight ratio of 100 parts compound 1 to 1 part abamectin.
TABLE C1
Figure BDA0002864077420001281
Figure BDA0002864077420001291
TABLE C2
Table C2 is the same as 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 at a weight ratio of 100 parts compound 1 to 1 part abamectin.
TABLE C3
Table C3 is the same as 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 at a weight ratio of 100 parts compound 1 to 1 part abamectin.
TABLE C4
Table C4 is the same as 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 at a weight ratio of 100 parts compound 1 to 1 part abamectin.
TABLE C5
Table C5 is the same as 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 at a weight ratio of 100 parts compound 1 to 1 part abamectin.
TABLE C6
Table C6 is the same as 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 at a weight ratio of 100 parts compound 1 to 1 part abamectin.
TABLE C7
Table C7 is the same as 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 at a weight ratio of 100 parts compound 1 to 1 part abamectin.
TABLE C8
Table C8 is the same as 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 at a weight ratio of 100 parts compound 1 to 1 part abamectin.
TABLE C9
Table C9 is the same as 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 at a weight ratio of 100 parts compound 1 to 1 part abamectin.
TABLE C10
Table C10 is the same as 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 a compound of formula 1 (compound No. (cmpd.no.) reference table a-N) and an additional fungicide.
TABLE D1
Figure BDA0002864077420001301
Figure BDA0002864077420001311
(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 the same as 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 the same as 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 the same as 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 the same as 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 the same as 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 the same as 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 the same as 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 the same as 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 the same as 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 locus of an insult to the agronomic and/or nonagronomic locus, to the area to be protected, or directly to the pest to be controlled.
Accordingly, the present invention includes a method for controlling an invertebrate pest in agronomic and/or non-agricultural applications comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more compounds of the invention or with a composition comprising at least one such compound or a composition comprising at least one such compound and a biologically effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a compound of the invention and a biologically effective amount of at least one additional biologically active compound or agent include granular compositions wherein the additional active compound is present on the same particles as the compound of the invention or on particles separate from those of the compound of the invention.
To effect contact with a compound or composition of the invention to protect a field crop from an invertebrate pest, the compound or composition is typically applied to the crop seed prior to planting, to the foliage (e.g., leaves, stems, flowers, fruits) of the crop plant, or to soil or other growth medium prior to or after planting the crop.
One example of a method of contacting is by spraying. Alternatively, a granular composition comprising a compound of the invention may be applied to the foliage of a plant or to the soil. The compounds of the present invention may also be effectively delivered by plant uptake by contacting the plant with a composition comprising the compounds of the present invention applied as a soil drench, granular formulation into soil, nursery box treatment or transplant soak as a liquid formulation. Of note are compositions of the present invention in the form of a soil drench liquid formulation. Also of note is a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of the invention or with a composition comprising a biologically effective amount of a compound of the invention. Of further note is such a method wherein the environment is soil and the composition is applied to the soil as a soil drench formulation. It is also noteworthy that the compounds of the present invention are also made effective by topical application to the affected locus. Other methods of contact include administering the compounds or compositions of the present invention by direct and residual spray, aerial spray, gel, seed coat, microencapsulation, systemic absorption, bait, ear tag, bolus, nebulizer, fumigant, aerosol, powder, and many other methods. One example of a method of contacting is a dimensionally stable fertilizer granule, bar, or tablet comprising a compound or composition of the present invention. The compounds of the present invention may also be impregnated into materials used to manufacture invertebrate pest control devices (e.g., insect control nets).
The compounds of the invention are useful for the treatment of 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. A transgene defined by its specific location in the plant genome is referred to as a transformation or transgenic event.
Genetically modified plants and seed cultivars that may be treated according to the invention include those that are resistant to one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinization, etc.), or those that comprise other desirable characteristics. Plants and seeds may be genetically modified to exhibit traits such as herbicide tolerance, insect resistance, modified oil characteristics, or drought tolerance. Useful genetically modified plants and seeds comprising a single genetic 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 table Z below: tol, tolerance, res, resistance, SU sulfonylureas, ALS acetolactate synthase, HPPD 4-hydroxyphenylpyruvate dioxygenase, NA unavailable?
Watch Z
Figure BDA0002864077420001321
Figure BDA0002864077420001331
Figure BDA0002864077420001341
Figure BDA0002864077420001351
Figure BDA0002864077420001361
Figure BDA0002864077420001371
Figure BDA0002864077420001381
Figure BDA0002864077420001391
Figure BDA0002864077420001401
Figure BDA0002864077420001411
Figure BDA0002864077420001421
Figure BDA0002864077420001431
Argentine, Polish and eggplant
Treatment of genetically modified plants and seeds with the compounds of the invention may result in superadditive or synergistic effects. For example, a reduction in application rates, an expansion of the activity spectrum, an increase in tolerance to biotic/abiotic stress or an increase in storage stability may be greater than would be expected from an additive effect from a simple application of the compounds of the invention on genetically modified plants and seeds only.
The compounds of the present invention may also be used in seed treatments to protect seeds from invertebrate pests. In the context of the present disclosure and claims, treating seed means contacting the seed with a biologically effective amount of a compound of the present invention typically formulated as a composition of the present invention. The seed treatment protects the seed from invertebrate soil pests and may also protect the roots of seedlings developed from the germinating seed and other plant parts in contact with the soil as a whole. The seed treatment may also provide protection to the leaves by translocating the compound of the invention or the second active ingredient in the developing plant. Seed treatments can be applied to all types of seeds, including those that will germinate to form transgenic plants to express a particular trait. Representative examples include those expressing proteins toxic to invertebrate pests, such as bacillus thuringiensis toxins, or those expressing herbicide resistance, such as glyphosate acetyltransferases that provide glyphosate resistance. Seed treatment agents with the compounds of the present invention may also increase the vigor of plants grown from seeds.
One method of seed treatment is by spraying or dusting the seed with the compounds of the invention (i.e., as a formulated composition) prior to sowing the seed. Compositions formulated for seed treatment generally comprise a film former or binder. Thus, 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-forming agent or binder. Seeds may be coated by spraying a flowable suspension concentrate directly into a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wet powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water may be sprayed on the seeds. The method is particularly useful for applying a film coating to seeds. Various coating equipment and methods are available to those skilled in the art. Suitable methods include those described in p.kosters et al, Seed Treatment: Progress and processes [ Seed Treatment: progression and prospect ], 1994BCPC monograph No. 57 and those listed in 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, soybean, cotton, cereals (e.g., wheat, oats, barley, rye, and rice), potato, vegetables, and oilseed rape.
Other insecticides that can be formulated with the compounds of formula 1 to provide mixtures useful for seed treatment include abamectin, acetamiprid, fluthrin, amitraz, abamectin, azadirachtin, monosultap, bifenthrin, buprofezin, cadusafos, sevin, carbarfuran, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfluthrin, beta-cyfluthrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, ben ether, emamectin, endosulfan, fenvalerate, ethiprole, etofenprox, etoxazole, fenoxycarb, pentaphne, fipronil, flonicamid, flufenamid, flubendiamide, fenobucfenamide, and the like, Flufenoxuron, fluvalinate, varacetamidine, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide, nitenpyram, nitro-ethylurea thiazole, novaluron, oxamyl, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, liar, lialidine, spinetoram, spinosad, spirodiclofen, spirotetramat, sulfoxaflor, tebufenozide, chrysanthemum, thiacloprid, thiamethoxam, thiodicarb, dimehypo, tetrabromthrin, triazamate, triflumuron, bacillus thuringiensis delta-endotoxin, all strains of bacillus thuringiensis and all strains of nuclear polyhedrosis virus.
Fungicides which can be formulated with the compounds of formula 1 to provide mixtures useful for seed treatment include amisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, fluazinam, fludioxonil, fluquinconazole, fluopyram, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam, metconazole, myclobutanil, paclobutrazol, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, epoxiconazole, silthiopham, tebuconazole, thiabendazole, thiophanate-methyl, thiram, trifloxystrobin and triticonazole.
Compositions comprising compounds of formula 1 useful for seed treatment may further comprise bacteria and fungi having the ability to provide protection from phytopathogenic fungi or the harmful effects of bacteria and/or earthy animals such as nematodes. Bacteria exhibiting nematicidal properties may include, but are not limited to, Bacillus firmus (Bacillus firmus), Bacillus cereus (Bacillus cereus), Bacillus subtilis (Bacillus subtilis), and Bacillus punctatus (Pasteurella penetrans). A suitable Bacillus firmus strain is as BioNem TMThe commercially available strain CNCM I-1582 (GB-126). A suitable Bacillus cereus strain is strain NCMM I-1592. Both strains of bacillus are disclosed in US 6,406,690. Other suitable bacteria exhibiting nematicidal activity are Bacillus amyloliquefaciens (B. amyloliquefaciens) IN937a andbacillus subtilis strain GB 03. Bacteria exhibiting fungicidal properties may include, but are not limited to, bacillus pumilus (b.puminus) strain GB 34. Fungal species exhibiting nematicidal properties may include, but are not limited to, Myrothecium verrucaria, Paecilomyces lilacinus and Purpureocillium lilacinum.
The seed treatment may also comprise one or more nematicides of natural origin, such as elicitor proteins known as hypersensitive proteins (harpins), which are isolated from certain bacterial plant pathogens, such as fire blight pear. Examples are as N-HibitTMHarpin-N-Tek seed treatment technology available to Gold CST
The seed treatment may also include one or more species of legume root nodule bacteria, such as the micro symbiotic nitrogen fixing bacteria Bradyrhizobium japonicum. These inoculants may optionally comprise one or more Lipid Chitooligosaccharides (LCOs), which are Nod (Nod) factors produced during the initiation of nodulation on the roots of leguminous plants by rhizobia bacteria. For example,
Figure BDA0002864077420001441
Brand seed treatment Technology combined with LCO promoter Technology in combination with an inoculantTM。
The seed treatment may further comprise one or more isoflavones, which may increase the level of root colonization by the mycorrhizal fungi. Mycorrhizal fungi improve plant growth by enhancing root uptake of nutrients such as water, sulfate, nitrate, phosphate and metals. Examples of isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperetin, naringenin, and pratensein. Formononetin as mycorrhizal inoculant product such as PHC
Figure BDA0002864077420001442
The active ingredient in AG is available.
The seed treatment may also include one or more plant activators that cause systemic acquired resistance in plants upon contact by a pathogen. An example of a plant activator that causes such a protective mechanism is acibenzolar-S-methyl.
The treated seed typically comprises the compounds of the present invention in an amount of from about 0.1g to 1kg per 100kg of seed (i.e., from about 0.0001% to 1% by weight of the seed prior to 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 consumed 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 a salt thereof; (b) one or more food ingredients; optionally (c) an attractant, and optionally (d) one or more humectants. Of note are granule or bait compositions comprising between about 0.001% to 5% active ingredient, about 40% to 99% food material and/or attractant; and optionally from about 0.05% to 10% of a wetting agent effective at controlling soil invertebrate pests at very low application rates, especially by ingestion and not by direct contact lethal doses of the active ingredient. Some food ingredients may serve as both a food source and an attractant. The food material includes 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 odorants and flavors, such as fruit or plant extracts, spices, or other animal or plant components, pheromones, or other agents known to attract targeted invertebrate pests. Examples of humectants (i.e., water retention agents) are ethylene glycol and other polyols, glycerin, 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 an invertebrate pest may comprise a bait composition of the 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 such that the invertebrate pest may 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 locus of potential or known activity of the invertebrate pest.
One embodiment of the present invention relates to a method for controlling an invertebrate pest comprising 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.
While spray compositions formed by diluting a sufficient concentration of the pesticidal composition of the present invention with water may provide sufficient efficacy to control invertebrate pests, a separately formulated adjuvant product may also be added to the spray can mixture. These additional adjuvants are commonly referred to as "spray adjuvants" or "tank-mix adjuvants" and include any substance that is mixed in the spray tank to improve the performance of the pesticide or to alter the physical characteristics of the spray mixture. The adjuvant may be a surfactant, emulsifier, petroleum-based crop oil, crop-derived seed oil, acidulant, buffer, thickener, or defoamer. Adjuvants are used to enhance efficacy (e.g., bioavailability, adhesion, permeability, coverage uniformity, and protection durability), or to minimize or eliminate spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization, and degradation. Adjuvants are selected with regard to the nature, formulation and target of the active ingredient (e.g. crop, insect pest) in order to obtain optimum performance.
Among spray adjuvants, oils (including crop oils, crop oil concentrates, vegetable oil concentrates, and methylated seed oil concentrates) are most commonly used to enhance the efficacy of pesticides, possibly by promoting more uniform and consistent spray deposition. In situations where phytotoxicity, which 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 contain an oil-based spray aid. However, in cases where phytotoxicity caused by the oil-based spray aid is not commercially significant, spray compositions prepared from the compositions of the present invention may also contain an oil-based spray aid, which may potentially further increase control of invertebrate pests, as well as rain-resistance.
Products identified as "crop oils" typically contain 95% to 98% paraffinic or naphtha-based petroleum oil and 1% to 2% of one or more surfactants that act as emulsifiers. Products identified as "crop oil concentrates" typically consist of 80% to 85% emulsifiable petroleum-based oil and 15% to 20% nonionic surfactant. A product correctly identified as a "vegetable oil concentrate" typically consists of 80% to 85% vegetable oil (i.e., seed oil or fruit oil, most commonly from cotton, linseed, soybean or sunflower) and 15% to 20% nonionic surfactant. Adjuvant performance can be improved by replacing the vegetable oil with methyl esters of fatty acids commonly derived from vegetable oils. Examples of methylated seed oil concentrates include
Figure BDA0002864077420001455
Concentrate (UAP-Loveland Products, Inc.) and Premium MSO methylated spray oil (Helena Chemical Company).
The amount of adjuvant added to the spray mixture typically does not exceed about 2.5% by volume, and more typically the amount is from about 0.1% to about 1% by volume. The application rate of the adjuvant added to the spray mixture is generally between about 1 and 5 liters per hectare. Representative examples of spray aids include:
Figure BDA0002864077420001451
(Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons;
Figure BDA0002864077420001452
(Helena chemical Co.) polyalkylene oxide-modified heptamethyltrisiloxane and
Figure BDA0002864077420001453
(BASF) 83% of a 17% surfactant blend in paraffin-based mineral oil.
The compounds of the invention may be administered without other adjuvants, but the most common administration is to administer a formulation comprising one or more active ingredients with suitable carriers, diluents and surfactants, possibly in combination with food, depending on the envisaged end use. One method of application involves spraying an aqueous dispersion or refined oil solution of the compounds of the present invention. Combinations with spray oils, spray oil concentrates, viscosity-extending agents, adjuvants, other solvents, and synergists such as piperonyl butoxide, generally enhance compound efficacy. For non-agronomic uses, such sprays may be applied from spray containers such as cans, bottles or other containers, with the aid of a pump or by releasing them from a pressurized container, such as a pressurized aerosol spray can. Such spray compositions may take a variety of forms, such as a spray, mist, foam, mist, or dust mist. Thus, such spray compositions may further comprise a propellant, a foaming agent, and the like, as the case may be. Of note are spray compositions comprising a biologically effective amount of a compound or composition of the invention and a carrier. One embodiment of such a spray composition comprises a biologically effective amount of a compound or composition of the invention and a propellant. Representative propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butenes, pentanes, isopentanes, neopentanes, pentenes, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing. Of note are spray compositions (and methods of using such spray compositions dispensed from a spray container) for controlling at least one invertebrate pest selected from the group consisting of: mosquitoes, black mosquitoes, stable flies, deer flies, horse flies, wasps, hornets, ticks, spiders, ants, gnats, and the like, either alone or in combination.
Biological examples of the invention
The following tests demonstrate the control efficacy of the compounds of the present invention against specific pests. By "control efficacy" is meant inhibition of development of invertebrate pests (including mortality) resulting in significantly reduced feeding. However, the pest control protection provided by the compounds is not limited to these species. Compound descriptions are found in index tables a-N.
Formulations and spray methodologies for testing A-F
A mixture containing 10% acetone, 90% water and 300ppm of acetone was used
Figure BDA0002864077420001454
Test compounds were formulated from a solution of Spreader Lo-Foam Formula nonionic surfactant comprising an alkylaryl polyoxyethylene, free fatty acid, ethylene glycol, and isopropanol (Loveland Industries, Inc. Greeley, Colorado, USA). The formulated compounds were applied as 1mL of liquid through a SUJ2 sprayer nozzle (Spraying Systems co. wheaton, Illinois, USA) with 1/8JJ custom bodies positioned 1.27cm (0.5 inch) above the top of each test unit. Test compounds were sprayed at the indicated 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 inoculators were pre-infested with approximately 50 new larvae distributed via corn cob crumbs into the test unit. After dispersal into the test cell, the larvae were moved to the test plants.
Test compounds were formulated and sprayed at 250ppm and/or 50 ppm. After spraying the formulated test compounds, each test cell was allowed to dry for 1 hour and then a black masking lid was placed on top. The test cells were kept in a growth chamber at 25 ℃ and 70% relative humidity for 6 days. Plant feeding damage was then assessed visually based on the consumed leaves, and larval mortality was assessed.
Of the compounds of formula 1 tested at 250ppm, the following provide a very good to excellent level 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 50ppm, the following provide very good to excellent levels of control efficacy (40% or less feeding damage, and/or 100% mortality): 735, and 824.
Test B
To evaluate the control of potato leafhoppers (potato leafhoppers) (Empoasca fabae (Harris)) by contact and/or systemic means, the test unit consists of a small open container with 5-6 day old Soleil bean plants inside (showing primary leaves). White sand was added to the top of the soil and a piece of primary leaf was cut off before applying the test compound.
Test compounds were formulated and sprayed at 250ppm and/or 50 ppm. After spraying the formulated test compounds, the test units were allowed to dry for 1 hour before they were post-infested with 5 potato leafhoppers (18-21 day old adults). A black, masking lid was placed on top of the test cell and the test cell was held in a growth chamber at 24 ℃ and 70% relative humidity for 6 days. Insect mortality was then visually assessed for each test unit.
In the compounds of formula 1 tested at 250ppm, the following resulted in a mortality of at least 80%: 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.
In the compounds of formula 1 tested at 50ppm, the following resulted in a mortality of at least 80%: 301. 309, 375, 380, 382, 386, 387, 388, 648, 836, 837, 842, 843, and 855.
Test C
In order to assess the control of green peach aphid (green peach aphid) (Myzus persicae (Sulzer)) by contact and/or systemic means, the test unit consists of a small open container with 12-15 day old radish plants inside. The test plants were pre-infested by placing 30-40 aphids on a leaf cut from the cultivated plant (leaf cutting method). As the leaves dehydrate, aphids move on the test plants. After pre-insult, the soil of the test cell was covered with a layer of sand.
Test compounds were formulated and sprayed at 250ppm and/or 50 ppm. After spraying the formulated test compounds, each test cell was allowed to dry for 1 hour and then a black masking lid was placed on top. The test cells were maintained in a growth chamber at 19-21 ℃ and 50% -70% relative humidity for 6 days. Insect mortality was then visually assessed for each test unit.
In the compounds of formula 1 tested at 250ppm, the following resulted in a mortality of at least 80%: 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, 378, 338, 340, 341, 343, 350, 376, 351, 375, 353, 354, 377, 364, 363, 382, 380, 363, 380, 363, 380, 150, 388. 393, 400, 401, 402, 403, 404, 409, 410, 411, 412, 413, 415, 416, 419, 439, 440, 442, 443, 444, 445, 446, 447, 448, 449, 455, 456, 462, 463, 464, 500, 501, 502, 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, 631, 636, 637, 638, 639, 640, 641, 642, 645, 647, 648, 658, 667, 720, 721, 722, 723, 724, 726, 727, 729, 731, 732, 733, 734, 735, 736, 738, 746, 747, 824, 764, 815, 819, 828, 826, 827, 643, 830, 831, 832, 836, 839, 838, 845, 849, 845, 833, 849, 844, 736, 738, 748, 747, 849, 844, 849, and 849, 844, 849, 844, and 849, 849.
In the compounds of formula 1 tested at 50ppm, the following resulted in a mortality of at least 80%: 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, 334, 335, 336, 338, 340, 342, 343, 344, 345, 346, 348, 350, 351, 352, 353, 354, 366, 374, 375, 376, 378, 380, 382, 387, 388, 401, 402, 403, 404, 412, 410, 447, 415, 413, 503, 455, 444, 501, 600, 501, 443, 502, 443, 444, 440, 444, 440, 444, 440, 444, 440, 601. 604, 605, 606, 608, 609, 613, 614, 615, 616, 617, 619, 623, 626, 629, 630, 631, 636, 637, 638, 639, 640, 641, 642, 643, 644, 645, 646, 647, 648, 649, 650, 652, 654, 655, 656, 658, 659, 660, 661, 669, 683, 684, 685, 686, 695, 696, 720, 722, 723, 724, 726, 731, 732, 735, 736, 738, 744, 746, 747, 748, 758, 759, 764, 765, 766, 832, 865, 775, 780, 800, 801, 802, 803, 805, 806, 807, 808, 76815, 818, 819, 821, 823, 825, 826, 827, 828, 830, 831, 832, 833, 836, 837, 609, 840, 844, 843, 845, 843, 855, 863, 855, 863, and 863.
Test D
In order to evaluate the control of the cotton aphid (cotton aphid) (aphid gossypii (Glover)) by contact and/or systemic means, the test unit consists of a small open container with 6-7 day old cotton plants inside. The plants were pre-infested with 30-40 insects located on one leaf according to the leaf cutting method and the soil of the test cell was covered with a layer of sand.
Test compounds were formulated and sprayed at 250ppm and/or 50 ppm. After spraying, the test cells were kept in a growth chamber at 19 ℃ and 70% relative humidity for 6 days. Insect mortality was then visually assessed for each test unit.
In the compounds of formula 1 tested at 250ppm, the following resulted in a mortality of at least 80%: 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, 746, 765, 815, 819, 824, 831, 833, 836, 839, 840, 841, 844, 848, 850, and 858.
In the compounds of formula 1 tested at 50ppm, the following resulted in a mortality of at least 80%: 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
In order to evaluate the control of western flower thrips (frankliniella occidentalis (Pergande)) by contact and/or systemic means, the test unit consisted of a small open container with 5-7 day old Soleil bean plants inside.
Test compounds were formulated and sprayed at 250ppm 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 masking lid was placed on top and the test unit was held at 25 ℃ and 45% -55% relative humidity for 6 days.
Of the compounds of formula 1 tested at 250ppm, 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 50ppm, the following provide 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 sweet potato whitefly (Bemisia tabaci (genodus)) by contact and/or systemic means, the test unit consisted of a small open container with 12-14 day old cotton plants inside. Prior to spray application, two cotyledons were removed from the plants, leaving one true leaf for assay. Adult whiteflies were allowed to lay eggs on the plants and then removed from the test unit. Cotton plants infested with at least 15 eggs were subjected to the spray test.
Test compounds were formulated and sprayed at 250ppm and/or 50 ppm. After spraying, the test cell was allowed to dry for 1 hour. The cylinder was then removed and the unit was taken out to the growth chamber and held at 28 ℃ and 50% -70% relative humidity for 13 days. Insect mortality was then visually assessed for each test unit.
In the compounds of formula 1 tested at 250ppm, the following resulted in a mortality of at least 50%: 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.
In the compounds of formula 1 tested at 50ppm, the following resulted in a mortality of at least 50%: 326. 648, 818, 824, 833, 836, 837, 839, 843, 849, 850, and 855.

Claims (15)

1. A compound selected from formula 1, an N-oxide or a salt thereof,
Figure FDA0002864077410000011
wherein
Q is
Figure FDA0002864077410000012
A is CH;
each R1Independently halogen, cyano, nitro, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy radical, C1-C4Haloalkoxy, C1-C4Alkylthio or C1-C4A haloalkylthio group;
m is 0, 1, 2 or 3;
X1、X2、X3and X4Each independently is CR2、CR3Or N, provided that(i)X1、X2、X3And X4One is CR2And (ii) X1、X2、X3And X4No more than one of is N;
R2is C (═ Z) NR6R7、N(R8)C(＝Z)R9、C(＝NR10)R11Or Qa；
Each Z is independently O or S;
each R3Independently is H, halogen, cyano, nitro, C1-C4Alkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4A haloalkoxy group;
Y2is CR5a；
R5aIs H, halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy or C1-C4A haloalkoxy group;
R6is H, NR15R16、OR17、C(＝NR10)R11、C(O)OR21、C(O)NR15R16、C(O)R22、S(O)nR23Or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted;
R7is H or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one R xSubstituted; or
R6And R7Together 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 atomOne 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)2Said ring being unsubstituted or substituted by up to 4RxSubstituted; or
R6And R7Taken together as S (O)pR18R19Or ═ S (═ NR)20)R18R19；
Each RxIndependently halogen, cyano, nitro, hydroxy, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkoxy, C (═ NR)10)R11、C(O)OR21、C(O)NR15R16、OC(O)R22、NR25R26、NR24C(O)R22、C(O)R22、S(O)nR23、Si(R28)3、OSi(R28)3Or Qb；
R8Is H, C (O) OR21、C(O)NR15R16、C(O)R22、S(O)nR23Or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted;
R9is H, C (═ NR)10)R11、OR21Or NR15R16(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted; or is phenyl, phenoxy or a 5-or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, halogen, Cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or is a 3-to 6-membered heterocyclic non-aromatic ring, each ring containing a ring member selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 1 carbon atom ring member is independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Each ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R10Independently is OR12、S(O)nR13Or NHR14；
Each R11Independently is H; or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl, each unsubstituted or substituted by at least one RxSubstituted; or is C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkoxy, C (O) OR21、C(O)NR15R16、NR25R26、NR24C(O)R22、C(O)R22Or Qb；
Each R12Independently is C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C (O) R22、S(O)nR13Or Qb；
Each R13Independently is C1-C4Alkyl or C1-C4A haloalkyl group;
R14is C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C (O) R 22OR C (O) OR21(ii) a Or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R15Independently is H, C1-C6Alkyl radical, C1-C4Haloalkyl, C (O) R27Or S (O)2R27(ii) a Or is phenyl or a 5-or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R16Independently is H, C1-C6Alkyl or C1-C4A haloalkyl group; or
R15And R16Together 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 independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
R17is C1-C4Alkyl radical, C3-C6Cycloalkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R18Independently is C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R19Independently is C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or
R18And R19Form a ring together with the sulfur atom to which they are attached;
R20is H, cyano, C1-C4Alkyl radical, C1-C4Haloalkyl or C (O) R22(ii) a Or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R21Independently is C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl or C3-C6A halocycloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R22Independently is C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl or C3-C6A halocycloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R23Independently is C1-C4Alkyl radical, C1-C4Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Halogenocycloalkyl, C3-C6Cycloalkylalkyl or C3-C6A halocycloalkylalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C 1-C4Alkoxy and C1-C4A haloalkoxy group;
each R24Independently is C1-C4An alkyl group;
each R25Independently is H, C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R26Independently is C1-C4Alkyl or C1-C4A haloalkyl group; or is phenyl, unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or
R25And R26Independently together with the nitrogen atom to which they are attached form a 3-to 7-membered ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Said ring being unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C 1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R27Independently is C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy or NR29R30(ii) a Or is phenyl or a 5-or 6-membered heterocyclic aromatic ring, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R28Independently is C1-C6Alkyl radical, C3-C6Cycloalkyl or phenyl;
each R29Independently is H or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl groups, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each R30Independently is H or Qb(ii) a Or is C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C2-C6Alkenyl or C2-C6Alkynyl groups, each unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C 1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group; or
R29And R30Together 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 (═ C)O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Said ring being unsubstituted or substituted with up to 4 substituents independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
Qais a 5-to 10-membered aromatic ring or ring system, each ring or ring system containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 3 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O)2Each ring or ring system being unsubstituted or substituted by at least one RxSubstituted; or is a 3-to 6-membered partially saturated ring, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S), and the sulfur atom ring member is selected from S, S (O) or S (O) 2Each ring is unsubstituted or substituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each QbIndependently is phenyl, a 5-or 6-membered heterocyclic aromatic ring or a 3-to 6-membered heterocyclic non-aromatic ring, each ring containing a ring member selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring members are independently selected from C (═ O) and C (═ S) and the sulfur atom ring member is selected from S, S (O) or S (O)2Each ring being unsubstituted or substituted bySubstituted with at least one substituent independently selected from the group consisting of: halogen, cyano, nitro, C1-C4Alkyl radical, C3-C6Cycloalkyl radical, C1-C4Haloalkyl, C1-C4Alkoxy and C1-C4A haloalkoxy group;
each n is independently 0, 1 or 2; and is
p is 1 or 2.
2. The compound of claim 1, wherein
X1Is CR2And X2、X3And X4Each independently is CR3(ii) a Or X2Is CR2And X1、X3And X4Each independently is CR3。
3. The compound of claim 1 or 2, wherein m is 0.
4. The compound of claim 1, having the formula:
Figure FDA0002864077410000031
wherein A is CH and R is selected from-CH2(2-pyrimidinyl), -CH2CHF2、-CH2CF3、-CH2CH2SMe、-CH2CH2CN, 1-methylcyclopropyl, -C (Me)2CN or-CH2CH(OMe)2。
5. A composition comprising a compound according to any preceding claim and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
6. The composition of claim 5, further comprising at least one additional biologically active compound or agent.
7. The composition of claim 6, wherein the at least one additional biologically active compound or agent is selected from the group consisting of: abamectin, acephate, chlorfenapyr, acetamiprid, flupropathrin, cyprodinil, sulfasalazine, amitraz, abamectin, azadirachtin, glutethion, benfuracarb, monosulfur, bifenthrin, bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl, carbarfuran, cartap, vadiamin, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos-methyl, chromafenozide, chlorfenapyr, clothianidin, cyantraniliprole, cycloprothrin, cyflufen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, diafenthiuron, diazinon, diafenprox, Diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinotefuran, benchol, emamectin, endosulfan, esfenvalerate, ethiprole, effenprox, etoxazole, fenbutatin, fenitrothion, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flucythrinate, pyrimethanil, flufenoxuron, flutriafol, flupyraclostrobin, flupyrazamide, flupirfenidone, tau-fluvalinate, flufenphos, vamiprid, fosthiazate, chlorfenapyr, hexfluafluorofen, hexaflumuron, hexythiazox, imidacloprid, indoxacarb, chlorfenapyr, lufenuron, malathion, cyhalothrin, flumethrin, metaflumizone, glufosfamid, methidathion, methoxyfenozide, thiacloprid, thiabendazole, thia, Monocrotophos, monoflurothrin, nicotine, nitenpyram, nifedipine, noviflumuron, oxamyl, parathion, methyl parathion, promastilin, phorate, phosmet, phosphamidon, pirimicarb, profenofos, proffluthrin, propargite, propylbifenthrin, pyfluumide, pyllumide, pymetrozine, pyrazinofloxacin, pyrafluprole, pyrethrin, pyridaben, pyridalyl, rotenone, linalodine, silafluofluthrin, spinetoram, spirodiclofen, spirotetramat, thiopropaphos, sulfoxaflor, tebufenozide, tebufenpyrad, tefluthrin, tebufenozide, tebuf, Triazamate, trichlorfon, triflumylpyrimidine, triflumuron, Bacillus thuringiensis delta-endotoxin, entomopathogenic bacteria, entomopathogenic viruses and/or entomopathogenic fungi.
8. The composition of claim 6, wherein the at least one additional biologically active compound or agent is selected from the group consisting of: abamectin, acetamiprid, flupropathrin, pyridalyl, amitraz, abamectin, azadirachtin, benfuracarb, bensulin, bifenthrin, buprofezin, cadusafos, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyromanil, cycloprothrin, cyfluthrin, beta-cyfluthrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, ben, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenicol, fenitrothion, fenoxycarb, fenvalerate, fipronil, meturon, metquiflolan, flonicamid, flufenamid, flufenamate, flufenoxuron, flufenozide, flufenoxad, flufenoxa, Fluensulfone, flupirrole, flupirfuranone, cyfluthrin, vaboxamidine, fosthiazate, hextafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide, metofluthrin, monoflurothiorin, nitenpyram, nitroethylurea thiazole, novaluron, oxamyl, pyfluubumide, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriminostrobin, linalodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, pyrethroids, tefluthrin, thiacloprid, thiamethoxam, thiodicarb, dimehypo, tetrabromthrin, triazamate, triflumuron, bacillus thuringiensis delta-endotoxin, all strains of bacillus thuringiensis, and all strains of nuclear polyhedrosis virus.
9. The composition of claim 6, wherein the at least one additional biologically active compound or agent is selected from the group consisting of: cyromaniliprole, cyhalodiamide, cyantraniliprole and chlorantraniliprole.
10. The composition of any one of claims 6-9, 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.
11. A method of protecting a field crop from an invertebrate pest comprising contacting the seed of the crop prior to planting, the foliage of the crop or soil or other growth medium prior to or after planting of the crop with a pesticidally effective amount of the compound of any one of claims 1-4 or the composition of any one of claims 5-10.
12. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of any one of claims 1-4 or a composition of any one of claims 5-10 provided that the method is not a method of treatment of the human or animal body by treatment.
13. The method of claim 12, wherein the environment is a plant or a seed.
14. A treated seed comprising the compound of any one of claims 1-4 in an amount of 0.0001% to 1% by weight of the seed prior to treatment.
15. A compound having the formula:
Figure FDA0002864077410000051
wherein A is CH, CF or N, and R is selected from: -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)2CF3、NH2Or a nitro group;
or the compound has the formula:
Figure FDA0002864077410000052
wherein:
(i) a is CH and R is selected from the group consisting of-C (O) OMe, -C (O) OEt, cyano, -C (O) OPh, -C (O) O (4-nitrophenyl), -C (O) Me, -CHO, Cl, Br, I, -OS (O)2CF3、NH2Or nitro, or
(ii) A is CF or N, and R is selected from-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)2CF3、NH2Or a nitro group.
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