WO2006023783A1 - Novel anthranilamides useful for controlling invertebrate pests - Google Patents

Novel anthranilamides useful for controlling invertebrate pests Download PDF

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Publication number
WO2006023783A1
WO2006023783A1 PCT/US2005/029639 US2005029639W WO2006023783A1 WO 2006023783 A1 WO2006023783 A1 WO 2006023783A1 US 2005029639 W US2005029639 W US 2005029639W WO 2006023783 A1 WO2006023783 A1 WO 2006023783A1
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Prior art keywords
cyano
alkyl
compound
halogen
alkoxy
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PCT/US2005/029639
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French (fr)
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George Philip Lahm
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E.I. Dupont De Nemours And Company
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Application filed by E.I. Dupont De Nemours And Company filed Critical E.I. Dupont De Nemours And Company
Priority to EP05807692A priority Critical patent/EP1789411A1/en
Priority to JP2007528063A priority patent/JP2008510721A/en
Priority to BRPI0515221-6A priority patent/BRPI0515221A/en
Priority to AU2005277228A priority patent/AU2005277228A1/en
Publication of WO2006023783A1 publication Critical patent/WO2006023783A1/en

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    • 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
    • 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
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07D401/14—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
    • 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
    • C07D403/02—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
    • C07D403/06—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 linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C07D413/06—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 linked by a carbon chain containing only aliphatic carbon atoms
    • 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

Definitions

  • This invention relates to certain anthranilamides, their //-oxides, salts and compositions suitable for agronomic and nonagronomic uses, including those uses listed below, and methods of their use for controlling invertebrate pests such as arthropods in both agronomic and nonagronomic environments.
  • invertebrate pests The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer.
  • the control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • WO 03/015519 discloses N-acyl anthranilic acid derivatives of Formula i as anthropodicides
  • R 1 is CH 3 , F, Cl or Br
  • R 2 is F, Cl, Br, I or CF 3
  • R 3 is CF 3 , Cl, Br or OCH 2 CF 3
  • R 4a is C 1 -C 4 alkyl
  • R 4 *> is H or CH 3
  • R 5 is Cl or Br.
  • This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agronomic or nonagronomic salts thereof, agricultural and nonagricultural compositions containing them and their use for controlling invertebrate pests:
  • Q is selected from the group consisting of Q-I, Q-2 and Q-3;
  • Q-I Q-2 Q-3 R 1 is X-Z-O-R 11 ;
  • X is O, S or NR 12 ;
  • Z is C2-C 4 haloalkylene or C2-C4 haloalkenylene; each R 2 is independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, halogen, cyano, nitro, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl or C 1 -C 4 haloalkylsulfonyl;
  • R 3 is H; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, cyano, nitro, hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 2 -C 4 alkoxycarbonyl, C 1 -C 4 alkylamino, C 2 -Cg dialkylamino and C 3 -C 6 cycloalkylamino;
  • R 4 is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, OH, C 1 -C 4 al
  • R 6 is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, cyano, nitro, CO 2 H, CONH 2 , hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkyl sulf in yl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C
  • R 7 is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, cyano, nitro, CO 2 H, CONH 2 , hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C 1
  • R 7 is phenyl, benzyl or phenoxy, each optionally substituted with one or more substituents selected from the group consisting of C 1 -C 4 alkyl, C 2 -C 4 alkenyl,
  • each R 10 is independently Cj-C 2 alkyl, halogen, cyano, nitro or Cj-C 2 alkoxy;
  • R 11 is C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 2 -C 8 alkoxyalkyl, C 2 -C 8 haloalkoxyalkyl, C 2 -C 8 alkoxyhaloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkyl, C 2 -C 6 haloalkyl, C 2 -C 6 haloalkyl, C 2 -C 6 haloalkyl, C 2 -C 6 haloalkyl, C 2 -C 6 haloalkyl, C 2 -C 6 haloalkyl, C 2 -C 6 haloalkyl, C 2 -C 6 hal
  • V is N or CR 13 ;
  • Y is N or CR 14 ;
  • R 13 and R 14 are independently H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, cyano, nitro, CO 2 H, CONH 2 , hydroxy, Cj-C 4 alkoxy,
  • C 1 -C 4 haloalkylsulfonyl C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, (Cj-C 4 alkyl)(C 3 -C 6 cycloalkyl)amino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -Cg dialkylaminocarbonyl or C 3 -C 6 trialkylsilyl;
  • E is CH 2 , O, S or NR 17 ;
  • R 17 is H; G 3 ; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl or phenyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, G 3 , cyano, nitro, hydroxy, C j -C 4 alkoxy, C j -C 4 haloalkoxy, CpC 4 alkylthio, C 1 -C 4 alkylsulfinyl, Cj-C 4 alkylsulfonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylcarbonyl, C 3 -C 6 trialkylsilyl and G 4 ; or R 17 is hydroxy, Cj-C 4 alkoxy, Cj-C 4 alkylamino, C 2 -Cg dialkylamino, C 3 -C 6 cycl
  • This invention also provides a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I 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.
  • This invention further provides a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I or the composition described above and a propellant.
  • This invention also provides a bait composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I or the composition described above, one or more food materials, optionally an attractant, and optionally a humectant.
  • This invention further provides a trap 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 permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
  • This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula I (e.g., as a composition described herein).
  • a biologically effective amount of a compound of Formula I e.g., as a composition described herein.
  • This invention also relates to such method wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula I 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.
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having,” “contains” or “containing,” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, a mixture, process, method, article, or apparatus 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, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or.
  • a condition A or B is satisfied by any one of the following: 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).
  • 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. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.
  • a composition of the present invention comprises a biologically effective amount of "a" compound of Formula I which should be read that the composition includes one or at least one compound of Formula I.
  • 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, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkylene denotes a straight-chain or branched alkanediyl.
  • alkylene examples include CH 2 , CH 2 CH 2 , CH(CH 3 ), CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ) and the different butylene isomers.
  • alkenylene denotes a straight-chain or branched alkenediyl containing one olefinic bond.
  • Alkynylene denotes a straight-chain or branched alkynediyl containing one triple bond.
  • alkynylene examples include C ⁇ C, CH 2 C ⁇ C, C ⁇ CCH 2 and the different butynylene isomers.
  • Alkoxy includes, for example, methoxy, ethoxy, ra-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkoxyalkoxy denotes alkoxy substitution on alkoxy.
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group.
  • alkylsulfinyl examples include CH 3 S(O)-, CH 3 CH 2 S(O)-, CH 3 CH 2 CH 2 S(O)-, (CH 3 ) 2 CHS(O> and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.
  • alkylsulfonyl examples include CH 3 S(O) 2 -, CH 3 CH 2 S(O) 2 -, CH 3 CH 2 CH 2 S(O) 2 -, (CH 3 ) 2 CHS(O) 2 -, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • Alkylamino alkylamino
  • dialkylamino and the like, are defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • cycloalkylamino includes the same groups linked through a nitrogen atom such as cyclopentylamino and cyclohexylamino.
  • alkylcycloalkylamino denotes a branched or straight-chain alkyl group and another cycloalkyl group both bonded to a nitrogen atom such as methylcyclopentylamino and ethylcyclohexylamino.
  • halogen either alone or in compound words such as “haloalkyl” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C-, ClCH 2 -, CF 3 CH 2 - and CF 3 CCl 2 -.
  • haloalkynyl examples include HC ⁇ CCHCl-, CF 3 C ⁇ C-, CC1 3 C ⁇ C- and FCH 2 C ⁇ CCH 2 -.
  • haloalkoxy examples include CF 3 O-, CCl 3 CH 2 O-, HCF 2 CH 2 CH 2 O- and CF 3 CH 2 O-.
  • haloalkylthio examples include CCl 3 S-, CF 3 S-, CCl 3 CH 2 S- and ClCH 2 CH 2 CH 2 S-.
  • haloalkylsulfinyl examples include CF 3 S(O)-, CCl 3 S(O)-, CF 3 CH 2 S(O)- and CF 3 CF 2 S(O)-.
  • haloalkylsulfonyl examples include CF 3 S(O) 2 -, CCl 3 S(O) 2 -, CF 3 CH 2 S(O) 2 - and CF 3 CF 2 S(O) 2 -.
  • Haloalkoxyalkyl denotes haloalkoxy substitution on an alkyl moiety.
  • haloalkoxyalkyl include CF 3 OCH 2 -, CCl 3 CH 2 OCH 2 CH 2 -, HCF 2 CH 2 CH 2 O(CH 3 )CH- and CF 3 CH 2 OCH 2 CH 2 -, and other straight-chain or branched haloalkyl moieties bonded to a straight-chain or branched alkyl groups.
  • haloalkoxyhaloalkyl include CF 3 OCH 2 -, CCl 3 CH 2 OCH 2 CH 2 -, HCF 2 CH 2 CH 2 O(CH 3 )CH- and CF 3 CH 2 OCH 2 CH 2 -, and other straight-chain or branched haloalkyl moieties bonded to a straight-chain or branched alkyl groups.
  • haloalkoxyhaloalkyl include CF 3 OCH 2 -, CCl 3 CH 2 OCH 2 CH 2 -, HCF 2 CH 2 CH 2 O(CH 3 )CH- and CF 3
  • alkoxyhaloalkyl and the like, are defined analogously to the term “haloalkoxyalkyl”.
  • Trialkylsilyl includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom such as trimethylsilyl, triethylsilyl and t-butyl-dimethylsilyl.
  • the total number of carbon atoms in a substituent group is indicated by the "Cj-C;" prefix where i and j are numbers from 1 to j.
  • Cj -C 4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 2 alkylaminoalkyl designates CH 3 NHCH 2 -
  • C 3 alkylaminoalkyl designates, for example, CH 3 (CH 3 NH)CH-, CH 3 NHCH 2 CH 2 - or CH 3 CH 2 NHCH 2 -
  • C4 alkylaminoalkyl designates the various isomers of an alkyl group substituted with an alkylamino group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 NHCH 2 - and CH 3 CH 2 NHCH 2 CH 2 -.
  • alkylcarbonyl denotes alkylcarbonyl substitution on an alkyl moiety.
  • alkoxycarbonyl-alkyl alkylaminocarbonylalkyl, and the like, are defined analogously to the term “alkylcarbonylalkyl".
  • Ci-C 4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents, e.g., (R 2 ) n , n is 1, 2, 3 or 4.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethydioxirane
  • the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • aromatic ring system denotes fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied for the ring system).
  • aromatic carbocyclyl includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied).
  • nonaromatic carbocyclyl denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the H ⁇ ckel rule is not satisfied by any of the rings in the ring system.
  • aromatic heterocyclyl includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied).
  • nonaromatic heterocyclyl denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the H ⁇ ckel rule is not satisfied by any of the rings in the ring system.
  • the heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • optionally substituted in connection with aromatic ring groups refers to groups that are unsubstituted or have at least one non-hydrogen substituent. Commonly, the number of optional substituents (when present) ranges from one to four.
  • Examples of 5- or 6-membered nonaromatic carbocyclic or heterocyclic rings optionally substituted with R 10 (or R 1 ⁇ ) include those illustrated as G-I through G-35 in Exhibit 1. Note that the attachment point on these G groups is illustrated as floating, the G group can be attached to the remainder of Formula I through any available carbon or nitrogen of the G group by replacement of a hydrogen atom.
  • R 1 ⁇ (or R 1 ⁇ ) can be attached to any carbon or nitrogen by replacement of a hydrogen atom (said substituents are not illustrated in Exhibit 1 since they are optional substituents).
  • Q 2 may be selected from O, S, NH or substituted N.
  • G 2 is a phenyl ring, a phenoxy ring, a 5-membered heteroaromatic ring or a 6-membered heteroaromatic ring, each ring optionally substituted with 1 to 3 substituents independently selected from R 9 (or R 18 ).
  • R 9 or R 18
  • An example of phenyl optionally substituted with R 9 (or R 18 ) is the ring illustrated as U-I in Exhibit 2, wherein R v is R 9 (or R 18 ) and r is an integer from 1 to 3.
  • Examples of 5- or 6-membered heteroaromatic rings optionally substituted with R 9 (or R 18 ) include the rings U-2 through U-53 illustrated in Exhibit 2 wherein R v is R 9 (or R 18 ) and r is an integer from 1 to 3.
  • R v groups are shown in the structures U-I through U-53, it is noted that they do not need to be present since they are optional substituents. Note that when R v is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or R v . Note that some U groups can only be substituted with less than 3 R v groups (e.g. U-16 through U-21, U-32 through U-34 and U-40 can only be substituted with one R v ). Note that when the attachment point between (R v ) r and the U group is illustrated as floating, (R v ) r can be attached to any available carbon atom of the U group. Note that when the attachment point on the U group is illustrated as floating, the U group can be attached to the remainder of Formula I through any available carbon of the U group by replacement of a hydrogen atom.
  • Embodiment 1 A compound of Formula I wherein R 11 is C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 3 -Cg cycloalkyl, C2-C4 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C4 alkoxyhaloalkyl, C 1 -C 4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C 3 -Cg halocycloalkyl or C2-C4 haloalkoxyhaloalkyl.
  • Embodiment 2 A compound of Embodiment 1 wherein R 11 is C 1 -C4 alkyl or C 1 -C 4 haloalkyl.
  • Embodiment 3 A compound of Embodiment 2 wherein R 11 is methyl, ethyl, CH2CF3,
  • Embodiment 4 A compound of Embodiment 3 wherein R 1 Ms CF 3 .
  • Embodiment 5 A compound of Formula I wherein X is O.
  • Embodiment 6. A compound of Formula I wherein Z is C 2 haloalkylene.
  • Embodiment 7. A compound of Embodiment 6 wherein R 1 is -X-CF 2 CHFO-R 11 .
  • Embodiment 8. A compound of Embodiment 7 wherein R 1 is -OCF 2 CHFO-R 11 .
  • Embodiment 9. A compound of Embodiment 8 wherein R 1 is -OCF 2 CHFOCF 3 .
  • Embodiment 10 A compound of Formula I wherein W is N, CH, CF, CCl, CBr or CL Embodiment 11. A compound of Embodiment 10 wherein W is N, CH, CF or CCl. Embodiment 12. A compound of Formula I wherein each R 2 is independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, halogen, cyano, nitro, C 1 -C 4 alkoxy, or C1-C4 haloalkoxy; and n is 1, 2 or 3.
  • Embodiment 13 A compound of Embodiment 12 wherein each R 2 is independently H,
  • n 1 or 2.
  • Embodiment 14 A compound of Formula I wherein R 3 is H or C 1 -C 4 alkyl.
  • Embodiment 15 A compound of Embodiment 14 wherein R 3 is H.
  • Embodiment 16 A compound of Formula I wherein R ⁇ is H or C 1 -C4 alkyl.
  • Embodiment 17 A compound of Embodiment 16 wherein R 4 is H.
  • Embodiment 18 A compound of Formula I wherein R 5 is H; or C 1 -Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl or C 3 -Cg cycloalkyl, each optionally substituted with one or more substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, OCH 3 and S(O) p CH 3 ; and p is 0, 1, or 2.
  • Embodiment 19 A compound of Embodiment 18 wherein R 5 is H, methyl, ethyl, i- propyl or t-butyl.
  • Embodiment 20 A compound of Formula I wherein R ⁇ is H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl or C 1 -C 4 haloalkylsulfonyl.
  • Embodiment 21 A compound of Embodiment 20 wherein R ⁇ is CH 3 , CF 3 , OCHF 2 , S(O) q CF 3 , S(O) q CHF 2 , cyano or halogen; and q is 0, 1, or 2.
  • Embodiment 22 A compound of Embodiment 21 wherein R 6 is F, Cl, Br, I, CH3 or
  • Embodiment 23 A compound of Embodiment 22 wherein R 6 is Cl or CH3.
  • Embodiment 24 A compound of Formula I wherein R 7 is H, C j -Cg alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl,
  • Embodiment 26 A compound of Embodiment 25 wherein R 7 is Cl, Br or cyano.
  • Embodiment 27 A compound of Embodiment 26 wherein R 7 is Cl or cyano.
  • Embodiment 28 A compound of Formula I wherein R 13 is H, CH 3 , halogen or cyano.
  • Embodiment 29. A compound of Formula I wherein V is CR 13 .
  • Embodiment 30. A compound of Embodiment 29 wherein V is CH.
  • Embodiment 31. A compound of Formula I wherein R 14 is H, CH 3 , halogen or cyano.
  • Embodiment 32. A compound of Formula I wherein Y is CR 14 .
  • Embodiment 33 A compound of Embodiment 32 wherein Y is CH, CF, CCl or CBr.
  • Embodiment 34 A compound of Embodiment 33 wherein Y is CH.
  • Embodiment 35 A compound of Formula I wherein L is a linking chain of one to three carbon atoms, optionally substituted with one to three substituents independently selected from R 15 .
  • Embodiment 36 A compound of Formula I wherein each R 15 is independently H, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.
  • Embodiment 39 A compound of Embodiment 38 wherein L is CH 2 .
  • Embodiment 40 A compound of Formula I wherein Q is Q-2 or Q-3.
  • Embodiment 41 A compound of Formula I wherein Q is Q-I or Q-3.
  • Embodiment 42 A compound of Formula I wherein Q is Q-I or Q-2.
  • Embodiment 43 A compound of Formula I wherein Q is Q-I.
  • Embodiment 44 A compound of Formula I wherein Q is Q-2.
  • Embodiment 45 A compound of Formula I wherein Q is Q-3.
  • Embodiment A A compound of Formula I wherein W is N, CH, CF, CCl, CBr or CI; each R 2 is independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, halogen, cyano, nitro,
  • n 1, 2 or 3;
  • R 3 is H or C 1 -C 4 alkyl;
  • R 4 is H or C 1 -C 4 alkyl
  • R 5 is H; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, each optionally substituted with one or more substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, OCH3 and S(COpCH 3 ; p is O, 1, or 2;
  • R 6 is CH 3 , CF 3 , OCHF 2 , S(O) p CF 3 , S(O) p CHF 2 , cyano or halogen;
  • R 7 is H, F, Cl, Br, I, cyano or CF 3 ;
  • Y is CR 13 ;
  • R 13 is H, CH 3 , halogen or cyano;
  • Y is CR 14 ;
  • R 14 is H, CH 3 , halogen or cyano.
  • Embodiment B A compound of Embodiment A wherein
  • X is O
  • Z is C 2 haloalkylene; and R 11 is C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.
  • Embodiment C A compound of Embodiment B wherein
  • W is N, CCl, CF or CH;
  • R 2 is H, Cl, F or Br; n is 1 or 2;
  • R 3 and R 4 are H
  • R 5 is H, methyl, ethyl, /-propyl or t-butyl
  • R 6 is F, Cl, Br, I, CH 3 or CF 3 ;
  • R 7 is Cl, Br or cyano; V is CH;
  • Y is CH, CF, CCl or CBr.
  • Embodiment D A compound of Embodiment C wherein
  • R 1 is -OCF 2 CHF-O-R 11 ;
  • R 11 is methyl, ethyl, CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 Br, CF 2 CF 2 CF 3 or CF(CF 3 ) 2 .
  • Embodiment E A compound of Embodiment D wherein
  • R 1 is -OCF 2 CHFOCF 3 ;
  • Embodiment F A compound of Embodiment B wherein
  • Q is Q-2;
  • W is N, CCl, CF or CH;
  • R 2 is H, Cl, F or Br; n is 1 or 2; R 3 and R 4 are H;
  • R 5 is H, methyl, ethyl, /-propyl or t-butyl;
  • R 6 is F, Cl, Br, I, CH 3 or CF 3 ;
  • R 7 is Cl, Br or cyano
  • Y is CH
  • Embodiment G A compound of Embodiment F wherein
  • R 1 is -OCF 2 CHF-O-R 11 ; and R 11 is methyl, ethyl, CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 Br, CF 2 CF 2 CF 3 or
  • Embodiment H A compound of Embodiment G wherein R 1 is -OCF 2 CHFOCF 3 ;
  • Y is CH
  • R 6 is Cl or CH 3 ;
  • R 7 is Cl or CN.
  • Embodiment I A compound of Embodiment B wherein Q is Q-3;
  • W is N, CCl, CF or CH;
  • R 2 is H, Cl, F or Br; n is 1 or 2;
  • R 3 and R 4 are H;
  • R 5 is H, methyl, ethyl, /-propyl or t-butyl;
  • R 6 is F, Cl, Br, I, CH 3 or CF 3 ;
  • R 7 is Cl, Br or cyano
  • Y is CH
  • Embodiment J A compound of Embodiment I wherein
  • R 1 is -OCF 2 CHF-O-R 11 ;
  • R 11 is methyl, ethyl, CH 2 CF 3 , CF 3 , CF 2 CF 3 , CF 2 CF 2 Br, CF 2 CF 2 CF 3 or CF(CF 3 ) 2 .
  • Embodiment K A compound of Embodiment J wherein R 1 is -OCF 2 CHFOCF 3 . Y is CH;
  • R 6 is Cl or CH 3 ; and R 7 is Cl or cyano.
  • compositions for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding Embodiments, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent.
  • Embodiments of the 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 of any of the preceding Embodiments (e.g., as a composition described herein).
  • Embodiments of the invention also include a composition comprising a compound of any of the preceding Embodiments, in the form of a soil drench liquid formulation.
  • Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the soil with a liquid composition as a soil drench comprising a biologically effective amount of a compound of any of the preceding Embodiments.
  • Embodiments of the invention also include a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of 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 of 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 permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
  • Scheme 3 depicts an alternate preparation for benzoxazinones of Formula 2 involving coupling of an acid chloride of Formula 7 with an isatoic anhydride of Formula 6 to provide the Formula 2 benzoxazinone directly.
  • Solvents such as pyridine or pyridine/acetonitrile are suitable for this reaction.
  • the acid chlorides of Formula 7 are available from the corresponding acids of Formula 4 by known methods such as chlorination with thionyl chloride or oxalyl chloride.
  • the benzoxazinone of Formula 2 is prepared directly via coupling of a carboxylic acid of Formula 4 with an anthranilic acid of Formula 5.
  • This method affords very good yields of the benzoxazinone and is illustrated with greater detail in Example 1.
  • anthranilic acids of Formula 5 are available commercially or by a variety of known methods. As shown in Scheme 5, anthranilic acids of Formula 5b containing an R 7 substituent of chloro, bromo or iodo can be prepared by direct halogenation of an unsubstituted anthranilic acid of Formula 5a with ⁇ f-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or iV-iodosuccinimide (NIS) respectively in solvents such as N,iV-dimethylformamide.
  • NCS N-chlorosuccinimide
  • NPS N-bromosuccinimide
  • NIS iV-iodosuccinimide
  • the anthranilic acids of Formula 5b represent intermediates for a preferred set of compounds of Formula I.
  • Cyanoanthranilic acids of Formula 5c can be prepared from haloanthranilic acids of Formula 5b as outlined in Scheme 6. Reaction of a haloanthranilic acid of Formula 5b (wherein R 7 is bromo or iodo) with a metal cyanide (e.g., cuprous cyanide, zinc cyanide, or potassium cyanide), optionally with or without a suitable palladium catalyst (e.g., tetrakis(triphenylphosphine)palladium(0) or dichlorobis(triphenylphosphine) palladium(II)) and optionally with or without a metal halide (e.g., cuprous iodide, zinc iodide, or potassium iodide) in a suitable solvent such as acetonitrile, N,N-dimethylformamide or N- methylpyrrolidinone, optionally at temperatures ranging from room temperature to the reflux temperature of the solvent, afford
  • Anthranilic acids of Formula 5, where one or both of Y and Z are selected from N, are available by a variety of known methods; see e.g., PCT Patent Publication WO 2002/070483.
  • isatoic anhydrides of Formula 6 wherein Y and V are CH can be achieved from isatins of Formula 9 as outlined in Scheme 7.
  • Isatins of Formula 9 are available from aniline derivatives of Formula 8 following literature procedures such as F. D. Popp, Adv. Heterocycl. Chem. 1975, 18, 1-58 and J. F. M. Da Silva et al., Journal of the Brazilian Chemical Society 2001, 12(3), 273-324.
  • Oxidation of isatin 9 with hydrogen peroxide generally affords good yields of the corresponding isatoic anhydride 6 (G. Reissenweber and D. Mangold, Angew. Chem. Int. Ed. Engl. 1980, 19, 222-223).
  • Isatoic anhydrides are also available from the anthranilic acids 5 via many known procedures involving reaction of 5 with phosgene or a phosgene equivalent.
  • Pyrazole acids 4a represent a preferred set of pyrazole acids for the synthesis of compounds of Formula I.
  • Their preparation involves reaction of a 5-hydroxypyrazole of Formula 10 with a substituted trifluoroethylene 11 in the presence of a base such as sodium hydroxide or potassium hydroxide in polar solvents such as dimethylsulfoxide, N,N- dimethylformamide or N-methylpyrrolidinone. Cosolvents such as toluene, tetrahydrofuran, dioxane and the like may be used.
  • the reaction is generally conducted in the range of 0 0 C to room temperature. This method affords very good yields of the pyrazole ester of Formula 12.
  • the pyrazole ester of Formula 12 is converted to the acid of Formula 4a by conventional hydrolytic methods and is illustrated with greater detail in Example 1.
  • Compounds of Formula I, where Q is Q-3 can be prepared directly by treatment of Formula I compounds, where Q is Q-I, with dehydrating reagents such as phosphoryl chloride, thionyl chloride and oxalyl chloride.
  • dehydrating reagents such as phosphoryl chloride, thionyl chloride and oxalyl chloride.
  • the reaction can be run neat or in solvents such as dichloromethane, dichloroethane, chloroform, benzene, toluene, xylene, tetrahydrofuran, dioxane and chlorobenzene at temperatures ranging from 0 0 C to the reflux temperature of the solvent.
  • solvents such as dichloromethane, dichloroethane, chloroform, benzene, toluene, xylene, tetrahydrofuran, dioxane and chlorobenzene at temperatures ranging from 0 0 C to the reflux
  • Q is Q-I; R 3 and R 4 is H
  • Step B Preparation of ethyl 2-(3-chloro-2-pyridinyl)-2,5-dihvdro-5-oxo-lH-pyrazole-
  • Step C Preparation of ethyl l-(3-chloro-2-pyridinyl)-3-Fl,l,2-trifluoro- 2-(trifluoromethoxy)ethoxyl-lH-pyrazole-5-carboxylate
  • Step D Preparation of l-(3-chloro-2-pyridinyl)-3-ri.l,2-trifluoro-
  • Step H Preparation of l-(3-chloro-2-pyridinyl)-N-r4-cvano-2-methyl-
  • Et means ethyl
  • i-Pr means isopropyl
  • Bu means butyl
  • CN means cyano
  • 2-C1-4-F means 2- chloro-4-fluoro.
  • R 1 is OCF 2 CFHOCF 3
  • Compounds of this invention can generally be used as a formulation or composition with a carrier suitable for agronomic and nonagronomic uses comprising at least one of a liquid diluent, a solid diluent or a surfactant.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredients, mode of application and environmental factors such as soil type, moisture and temperature.
  • Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels.
  • Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films (including seed treatment), and the like which can be water-dispersible ("wettable") or water-soluble.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated”). Encapsulation can control or delay release of the active ingredient.
  • Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions can be primarily used as intermediates for further formulation.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
  • Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, iV,iV-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, glycerol esters, poly- oxyethylene/polyoxypropylene block copolymers, and alkylpolyglycosides where the number of glucose units, referred to as degree of polymerization (D.P.), can range from 1 to 3 and the alkyl units can range from Cg-C ⁇ (see Pure and Applied Chemistry 72, 1255- 1264).
  • degree of polymerization D.P.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Liquid diluents include, for example, water, iV,N-dimethylformamide, dimethyl sulfoxide, ⁇ f-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, glycerine, triacetine, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4- hydroxy-4-methyl-2-pentanone, acetates and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
  • Useful formulations of this invention can also contain materials known as formulation aids including antifoams, film formers and dyes and are well known to those skilled in the
  • Antifoams can include water dispersible liquids comprising polyorganosiloxanes such as Rhodorsil® 416.
  • the film formers can include polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes.
  • Dyes can include water dispersible liquid colorant compositions such as Pro-lzed® Colorant Red.
  • formulation aids include those listed herein and those listed in McCutcheon's 2001, Volume 2: Functional Materials, published by MC Publishing Company and PCT Publication WO 03/024222.
  • Solutions can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S.
  • 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 can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Wettable Powder active ingredient 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
  • Granule active ingredient 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
  • Extruded Pellet active ingredient 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
  • Example E Microemulsion active ingredient 5.0% triacetine 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%.
  • Example F Seed Treatment active ingredient 20.00% polyvinylpyrrolidone-vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water 65.75%.
  • POE 20 stearyl alcohol
  • Compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and nonagronomic invertebrate pests.
  • Compounds of this invention are also characterized by favorable foliar and or soil-applied systemicity in plants exhibiting translocation to protect foliage and other plant parts not directly contacted with invertebrate pest control compositions comprising the present compounds.
  • invertebrate pest control means inhibition of invertebrate pest development (including mortality) that causes significant reduction in feeding or other injury or damage caused by the pest; related expressions are defined analogously.
  • invertebrate pest includes arthropods, gastropods and nematodes of economic importance as pests.
  • arthropod includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
  • gastropod includes snails, slugs and other Stylommatophora.
  • nematode includes all of the helminths, such as: roundworms, heartworms, and phytophagous nematodes (Nematoda), flukes (Tematoda), Acanthocephala, and tapeworms (Cestoda). Those skilled in the art will recognize that not all compounds are equally effective against all pests. Compounds of this invention display activity against economically important agronomic and nonagronomic pests.
  • agronomic refers to the production of field crops such as for food and fiber and includes the growth of corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye, rice, maize), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (berries, cherries) and other specialty crops (e.g., canola, sunflower, olives).
  • wheat e.g., wheat, oats, barley, rye, rice, maize
  • leafy vegetables e.g., lettuce, cabbage, and other cole crops
  • fruiting vegetables e.g., tomatoes, pepper, eggplant, crucifers and cucurbits
  • potatoes e.g., sweet potatoes, grapes, cotton, tree fruits (e.g.
  • nonagronomic refers to other horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential and commercial structures in urban and industrial settings, turf (commercial, golf, residential, recreational, etc.), wood products, stored product agro-forestry and vegetation management public health (human) and animal health (pets, livestock, poultry) applications.
  • turf commercial, golf, residential, recreational, etc.
  • wood products stored product agro-forestry and vegetation management public health (human) and animal health (pets, livestock, poultry) applications.
  • Agronomic or nonagronomic pests include larvae of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., fall armyworm (Spodoptera fugiperda J. E.
  • agronomic and nonagronomic pests include: adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forf ⁇ cula auricularia Linnaeus), black earwig (Chelisoches mono Fabricius)); adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g.
  • Empoasca spp. from the family Cicadellidae, planthoppers from the families Fulgoroidae and Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, cinch bugs (e.g., Blissus spp.) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae.
  • insects are also included are adults and larvae of the order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdanieli McGregor)); flat mites in the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e.
  • Tetranychidae e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdaniel
  • femoralis Stein stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium s
  • Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider ⁇ Loxosceles reclusa Gertsch & Mulaik) and the black widow spider ⁇ Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede ⁇ Scutigera coleoptrata Linnaeus).
  • Compounds of the present invention also have activity on members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e.
  • Compounds of the invention show particularly high activity against pests in the order Lepidoptera (e.g., Alabama argillacea H ⁇ bner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera H ⁇ bner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco bud
  • Compounds of this invention also have activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp.
  • Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower thrip), Scirthothrips citri Moulton (citrus thrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaci Lindeman (onion thrip); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius).
  • Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower thrip), Scirthothrips citri Moulton (citrus thrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaci Lindeman (onion thrip
  • Coleoptera e.g.
  • compounds of this invention for controlling silverleaf whitefly (Bemisia argentifoli ⁇ ). Of note is use of compounds of this invention for controlling western flower thrip ⁇ Frankliniella occidentalis). Of note is use of compounds of this invention for controlling potato leafhopper (Empoasca fabae). Of note is use of compounds of this invention for controlling corn planthopper ⁇ Peregrinus maidis). Of note is use of compounds of this invention for controlling cotton melon aphid (Aphis gossypii). Of note is use of compounds of this invention for controlling green peach aphid (Myzus persicae).
  • One or more compounds of this invention can also be mixed with one or more "other" biologically active compounds or agents where "other" biologically active compounds or agents do not include compounds of Formula I.
  • Such "other" biologically active compounds or agents include insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators such as rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agronomic and nonagronomic utility.
  • the present invention also pertains to a composition
  • a composition comprising a biologically effective amount of a compound of Formula I and an effective amount of at least one additional biologically active compound or agent and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent.
  • insecticides such as abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, binfenazate, buprofezin, carbofuran, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, diofenolan, emamectin, endosulfan, e
  • insecticides such as abamectin, acephate,
  • Compounds of this invention and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin).
  • proteins toxic to invertebrate pests such as Bacillus thuringiensis toxin.
  • the effect of the exogenously applied invertebrate pest control compounds of this invention may be synergistic with the expressed toxin proteins.
  • insecticides and acaricides for mixing with compounds of this invention include pyrethroids such as acetamiprid, cypermethrin, cyhalothrin, cyfluthrin, beta-cyfluthrin, esfenvalerate, fenvalerate and tralomethrin; carbamates such as fenothicarb, methomyl, oxamyl and thiodicarb; neonicotinoids such as clothianidin, imidacloprid and thiacloprid; neuronal sodium channel blockers such as indoxacarb; insecticidal macrocyclic lactones such as spinosad, abamectin, avermectin and emamectin; ⁇ -aminobutyric acid (GABA) antagonists such as endosulfan, ethiprole and fipronil; insecticidal ureas such as fluf
  • biological agents for mixing with compounds of this invention include Bacillus thuringiensis and Bacillus thuringiensis delta endotoxin as well as naturally occurring and genetically modified viral insecticides including members of the family Baculoviridae as well as entomophagous fungi.
  • mixtures include a mixture of a compound of this invention with cyhalothrin; a mixture of a compound of this invention with beta-cyfluthrin; a mixture of a compound of this invention with esfenvalerate; a mixture of a compound of this invention with methomyl; a mixture of a compound of this invention with imidacloprid; a mixture of a compound of this invention with thiacloprid; a mixture of a compound of this invention with indoxacarb; a mixture of a compound of this invention with abamectin; a mixture of a compound of this invention with endosulfan; a mixture of a compound of this invention with ethiprole; a mixture of a compound of this invention with fipronil; a mixture of a compound of this invention with flufenoxuron; a mixture of a compound of this invention with pyriproxyfen; a mixture of a compound of this invention with pymet
  • compositions of the present invention can further comprise a biologically effective amount of at least one additional invertebrate pest control compound or agent having a similar spectrum of control but a different mode of action.
  • a plant protection compound e.g., protein
  • a biologically effective amount of a compound of invention can also provide a broader spectrum of plant protection and be advantageous for resistance management.
  • Invertebrate pests are controlled in agronomic and nonagronomic applications by applying a composition comprising a compound of this invention, in a biologically effective amount, to the environment of the pests, including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • Agronomic applications include protecting a field crop from invertebrate pests typically by applying a composition or a mixture of the invention to the seed of the crop before the planting, to the foliage, stems, flowers and/or fruit of crop plants, or to the soil or other growth medium before or after the crop is planted.
  • Nonagronomic applications refer to invertebrate pest control in the areas other than fields of crop plants.
  • Nonagronomic applications include control of invertebrate pests in stored grains, beans and other foodstuffs, and in textiles such as clothing and carpets.
  • Nonagronomic applications also include invertebrate pest control in ornamental plants, forests, in yards, along roadsides and railroad rights of way, and on turf such as lawns, golf courses and pastures.
  • Nonagronomic applications also include invertebrate pest control in houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo or other animals.
  • Nonagronomic applications also include the control of pests such as termites that can damage wood or other structural materials used in buildings.
  • Nonagronomic applications also include protecting human and animal health by controlling invertebrate pests that are parasitic or transmit infectious diseases. Such pests include, for example, chiggers, ticks, lice and fleas.
  • the present invention further comprises a method for controlling an invertebrate pest in agronomic and/or nonagronomic applications, comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the compounds of the invention, or with a composition comprising at least one such compound or a composition comprising at least one such compound and a biologically effective amount of at least one additional biologically active compound or agent.
  • 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 granule as the compound of the invention or on granules separate from those of the compound of the invention.
  • a method of contact is by spraying.
  • a granular composition comprising a compound of the invention can be applied to the plant foliage or the soil.
  • Compounds of this invention can also be effectively delivered through plant uptake by contacting the plant with a composition comprising a compound of this invention applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants.
  • a method for controlling an invertebrate pest comprising contacting the soil environment of the invertebrate pest with a biologically effective amount of a compound of the present invention.
  • compounds of this invention also effective by topical application to the locus of infestation.
  • Other methods of contact include application of a compound or a composition of the invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • the compounds of this invention can also be impregnated into materials for fabricating invertebrate control devices (e.g. insect netting).
  • the compounds of this invention can be incorporated into a bait composition that is consumed by an invertebrate pest or used within a device such as a trap, bait station, and the like.
  • a bait composition can be in the form of granules which comprise (a) active ingredients, namely a biologically effective amount of a compound of Formula I, an N- oxide, or salt thereof; (b) one or more food materials; optionally (c) an attractant, and optionally (d) one or more humectants.
  • granules or bait compositions which comprise between about 0.001-5% active ingredients, about 40-99% food material and/or attractant; and optionally about 0.05-10% humectants, which are effective in controlling soil invertebrate pests at very low application rates, particularly at doses of active ingredient that are lethal by ingestion rather than by direct contact.
  • Some food materials can function both as a food source and an attractant.
  • Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids.
  • attractants are odorants and flavorants, such as fruit or plant extracts, perfume, or other animal or plant component, pheromones or other agents known to attract a target invertebrate pest.
  • humectants i.e. moisture retaining agents, are glycols and other polyols, glycerine and sorbitol.
  • a bait composition (and a method utilizing such a bait composition) used to control at least one invertebrate pest selected from the group consisting of ants, termites and cockroaches.
  • a device for controlling an invertebrate pest can comprise the present bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
  • the compounds of this invention can be applied without other adjuvants, but most often application will be of a formulation comprising one or more active ingredients with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • One method of application involves spraying a water dispersion or refined oil solution of a compound of the present invention.
  • Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy.
  • sprays can be applied from spray containers such as a can, a bottle or other container, either by means of a pump or by releasing it from a pressurized container, e.g., a pressurized aerosol spray can.
  • Such spray compositions can take various forms, for example, sprays, mists, foams, fumes or fog.
  • Such spray compositions thus can further comprise propellants, foaming agents, etc. as the case may be.
  • a spray composition comprising a biologically effective amount of a compound or a composition of the present invention and a carrier.
  • a spray composition comprises a biologically effective amount of a compound or a composition of the present invention and a propellant.
  • propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing.
  • a spray composition (and a method utilizing such a spray composition dispensed from a spray container) used to control at least one invertebrate pest selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like, including individually or in combinations.
  • the rate of application required for effective control i.e. "biologically effective amount" will depend on such factors as the species of invertebrate to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like.
  • Control efficacy represents inhibition of invertebrate pest development (including mortality) that causes significantly reduced feeding.
  • the pest control protection afforded by the compounds is not limited, however, to these species.
  • Index Table A for compound descriptions. The following abbreviations are used in the Index Tables which follow: i is iso, Me is methyl, Pr is propyl, z ' -Pr is isopropyl, and CN is cyano.
  • the abbreviation “Ex.” stands for "Example” and is followed by a number indicating in which example the compound is prepared.
  • test unit For evaluating control of fall armyworm (Spodoptera frugiperda) the test unit consisted of a small open container with a 4-5-day-old corn (maize) plant inside. This was pre-infested (using a core sampler) with 10-15 1-day-old larvae on a piece of insect diet.
  • Test compounds were formulated using a solution containing 10% acetone, 90% water and 300 ppm X-77TM Spreader Lo-Foam Formula non-ionic surfactant containing alkylarylpolyoxyethylene, free fatty acids, glycols and isopropanol (Loveland Industries, Inc. Greeley, Colorado, USA).
  • the formulated compounds were applied in 1 mL of liquid through a SUJ2 atomizer nozzle with 1/8 JJ custom body (Spraying Systems Co. Wheaton, Illinois, USA) positioned 1.27 cm (0.5 inches) above the top of each test unit. All experimental compounds in these tests were sprayed at 10 ppm replicated three times.
  • each test unit was allowed to dry for 1 hour and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 25 0 C and 70% relative humidity. Each test unit was then visually assessed for insect mortality.
  • test unit For evaluating control of potato leafhopper ⁇ Empoasca fabae Harris) through contact and/or systemic means, the test unit consisted of a small open container with a 3-4 day old corn plant. White sand was added to the top of the soil prior to application and misted with water to form a sand crust.
  • Test compounds were formulated as described for Test A and sprayed at 50 ppm and replicated three times. After spraying, the test units were allowed to dry for 1 hour before they were post-infested with 5 potato leafhoppers (18 to 21 day old adults). A black, screened cap was placed on the top of the cylinder. The test units were held for 6 days in a growth chamber at 20 °C and 70% relative humidity. Each test unit was then visually assessed for insect mortality. Of the compounds tested, the following resulted in at least 80% mortality: 3 and 7.

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Abstract

Disclosed are compounds of Formula (I), including all geometric and stereoisomers, N oxides, and salts thereof formula (I) wherein Q is selected from the group consisting of formulae (Q-1), (Q-2) and (Q-3); R1 is X-Z-O-R11; X is O, S or NR12; Z is C2-C4 haloalkylene or C2-C4 haloalkenylene; and R2, R3, R4, R5, R6, R7, R11, R12 and n are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula I 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

NOVEL ANTHRANILAMIDES USEFUL FOR CONTROLLING INVERTEBRATE PESTS
FIELD OF THE INVENTION This invention relates to certain anthranilamides, their //-oxides, salts and compositions suitable for agronomic and nonagronomic uses, including those uses listed below, and methods of their use for controlling invertebrate pests such as arthropods in both agronomic and nonagronomic environments.
BACKGROUND OF THE INVENTION The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action.
WO 03/015519 discloses N-acyl anthranilic acid derivatives of Formula i as anthropodicides
Figure imgf000002_0001
» wherein, inter alia, R1 is CH3, F, Cl or Br; R2 is F, Cl, Br, I or CF3; R3 is CF3, Cl, Br or OCH2CF3; R4a is C1-C4 alkyl; R4*> is H or CH3; and R5 is Cl or Br.
SUMMARY OF THE INVENTION
This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agronomic or nonagronomic salts thereof, agricultural and nonagricultural compositions containing them and their use for controlling invertebrate pests:
Figure imgf000003_0001
I wherein
Q is selected from the group consisting of Q-I, Q-2 and Q-3;
Figure imgf000003_0002
Q-I Q-2 Q-3 R1 is X-Z-O-R11;
X is O, S or NR12;
Z is C2-C4 haloalkylene or C2-C4 haloalkenylene; each R2 is independently H, C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl;
R3 is H; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, cyano, nitro, hydroxy, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl, C1-C4 alkylamino, C2-Cg dialkylamino and C3-C6 cycloalkylamino; R4 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, OH, C1-C4 alkoxy, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, (C1-C4 alkyl)(C3-C6 cycloalkyl)amino, C2-C6 alkoxycarbonyl or C2-C6 alkylcarbonyl; R5 is H; G1; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, or C3-C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, G1, cyano, nitro, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C3-C6 trialkylsilyl and G2; or R5 is hydroxy, C1-C4 alkoxy, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-Cg alkoxycarbonyl or C2-C6 alkylcarbonyl; or R4 and R5 are taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring is optionally substituted with 1 to 4 substituents selected from the group consisting of C1-C2 alkyl, halogen, cyano, nitro and C1-C2 alkoxy;
R6 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, CO2H, CONH2, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkyl sulf in yl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg di alkyl aminocarbonyl or C3-C6 trialkylsilyl;
R7 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, CO2H, CONH2, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl; or
R7 is phenyl, benzyl or phenoxy, each optionally substituted with one or more substituents selected from the group consisting of C1-C4 alkyl, C2-C4 alkenyl,
C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, Q1-C7 (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl and C3-Cg dialkylaminocarbonyl; each G* is independently a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(=O), S(O) and S(O)2 and optionally substituted with 1 to 4 substituents independently selected from R10; each G2 is independently a phenyl ring, a phenoxy ring, a 5-membered heteroaromatic ring or a 6-membered heteroaromatic ring, each ring optionally substituted with 1 to 3 substituents independently selected from R^; each R9 is independently Cj-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, Cj- C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, Cj-C4 alkoxy, Cj-C4 haloalkoxy, Cj-C4 alkylthio, Cj-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3-
Cg cycloalkylamino, (Cj-C4 alkyl)(C3-C6 cycloalkyl)amino, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl; each R10 is independently Cj-C2 alkyl, halogen, cyano, nitro or Cj-C2 alkoxy; R11 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C2-C8 alkoxyalkyl, C2-C8 haloalkoxyalkyl, C2-C8 alkoxyhaloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl or C2-C8 haloalkoxyhaloalkyl; R12 is H or C1-C4 alkyl; W is N or CR2;
V is N or CR13;
Y is N or CR14;
R13 and R14 are independently H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, CO2H, CONH2, hydroxy, Cj-C4 alkoxy,
Cj-C4 haloalkoxy, Cj-C4 alkylthio, Cj-C4 alkylsulfinyl, Cj-C4 alkylsulfonyl, Cj-C4 haloalkylthio, Cj-C4 haloalkylsulfinyl or Cj-C4 haloalkyl sulfonyl; L is a direct bond; or a linking chain of one to three members selected from carbon, nitrogen, oxygen, sulfur, C(=E), S(O) and S(O)2, provided that no more than two members are selected from C(=E), S(O) and S(O)2, said linking chain optionally substituted with one to three substituents independently selected from R15; each R15 is independently H, Cj-C4 alkyl, Cj-C4 haloalkyl, halogen, cyano, COOH, Cj-C4 alkoxy, Cj-C4 haloalkoxy, C2-C6 alkoxycarbonyl or C2-C6 alkoxycarbonylalkyl; or a phenyl ring or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R1^; each R16 is independently Cj-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, Cj-C4 alkylthio, Cj-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl,
C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, (Cj-C4 alkyl)(C3-C6 cycloalkyl)amino, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl; E is CH2, O, S or NR17;
R17 is H; G3; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or phenyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, G3, cyano, nitro, hydroxy, Cj-C4 alkoxy, Cj-C4 haloalkoxy, CpC4 alkylthio, C1-C4 alkylsulfinyl, Cj-C4 alkylsulfonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C3-C6 trialkylsilyl and G4; or R17 is hydroxy, Cj-C4 alkoxy, Cj-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl or C2-C6 alkylcarbonyl; each G3 is independently a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(=O), S(O) and S(O)2 and optionally substituted with 1 to 4 substituents independently selected from R19; each G4 is independently a phenyl ring, a phenoxy ring, a 5-membered heteroaromatic ring or a 6-membered heteroaromatic ring, each ring optionally substituted with 1 to 3 substituents independently selected from R 1^; each R18 is independently Cj-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, Cj-
C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, Cj-C4 alkoxy, Cj-C4 haloalkoxy, Cj-C4 alkylthio, Cj-C4 alkylsulfinyl, Cj-C4 alkylsulfonyl, Cj-C4 alkylamino, C2-Cg dialkylamino, C3- C6 cycloalkylamino, C4-C7 (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3- C6 trialkylsilyl; each R19 is independently Cj-C2 alkyl, halogen, cyano, nitro or Cj-C2 alkoxy; and n is 1, 2, 3 or 4.
This invention also provides a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I 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.
This invention further provides a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I or the composition described above and a propellant. This invention also provides a bait composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I or the composition described above, one or more food materials, optionally an attractant, and optionally a humectant. This invention further provides a trap 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 permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula I (e.g., as a composition described herein). This invention also relates to such method wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula I 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. DETAILS OF THE INVENTION
As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, a mixture, process, method, article, or apparatus 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, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: 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. Therefore "a" or "an" should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular. For example, a composition of the present invention comprises a biologically effective amount of "a" compound of Formula I which should be read that the composition includes one or at least one compound of Formula I.
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, /-propyl, or the different butyl, pentyl or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkylene" denotes a straight-chain or branched alkanediyl. Examples of "alkylene" include CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3) and the different butylene isomers. "Alkenylene" denotes a straight-chain or branched alkenediyl containing one olefinic bond. Examples of "alkenylene" include CH=CH, CH2CH=CH, CH=C(CH3) and the different butenylene isomers. "Alkynylene" denotes a straight-chain or branched alkynediyl containing one triple bond. Examples of "alkynylene" include C≡C, CH2C≡C, C≡CCH2 and the different butynylene isomers. "Alkoxy" includes, for example, methoxy, ethoxy, ra-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. "Alkoxyalkoxy" denotes alkoxy substitution on alkoxy. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(O)-, CH3CH2S(O)-, CH3CH2CH2S(O)-, (CH3)2CHS(O> and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2-, CH3CH2S(O)2-, CH3CH2CH2S(O)2-, (CH3)2CHS(O)2-, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkylamino", "dialkylamino", and the like, are defined analogously to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "cycloalkylamino" includes the same groups linked through a nitrogen atom such as cyclopentylamino and cyclohexylamino. The term "alkylcycloalkylamino" denotes a branched or straight-chain alkyl group and another cycloalkyl group both bonded to a nitrogen atom such as methylcyclopentylamino and ethylcyclohexylamino.
The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F3C-, ClCH2-, CF3CH2- and CF3CCl2-. The terms "haloalkenyl", "haloalkynyl", "haloalkylene", "haloalkenylene", "halocycloalkyl", "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (Cl)2C=CHCH2-and CF3CH2CH=CHCH2-. Examples of "haloalkynyl" include HC≡CCHCl-, CF3C≡C-, CC13C≡C- and FCH2C≡CCH2-. Examples of "haloalkoxy" include CF3O-, CCl3CH2O-, HCF2CH2CH2O- and CF3CH2O-. Examples of "haloalkylthio" include CCl3S-, CF3S-, CCl3CH2S- and ClCH2CH2CH2S-. Examples of "haloalkylsulfinyl" include CF3S(O)-, CCl3S(O)-, CF3CH2S(O)- and CF3CF2S(O)-. Examples of "haloalkylsulfonyl" include CF3S(O)2-, CCl3S(O)2-, CF3CH2S(O)2- and CF3CF2S(O)2-.
"Haloalkoxyalkyl" denotes haloalkoxy substitution on an alkyl moiety. Examples of
"haloalkoxyalkyl" include CF3OCH2-, CCl3CH2OCH2CH2-, HCF2CH2CH2O(CH3)CH- and CF3CH2OCH2CH2-, and other straight-chain or branched haloalkyl moieties bonded to a straight-chain or branched alkyl groups. The terms "haloalkoxyhaloalkyl",
"alkoxyhaloalkyl", and the like, are defined analogously to the term "haloalkoxyalkyl".
"Alkylcarbonyl" denotes a straight-chain or branched alkyl moieties bonded to a C(=0) moiety. Examples of "alkylcarbonyl" include CH3C(=0)-, CH3CH2CH2C(=O)- and (CH3)2CHC(=O)-. Examples of "alkoxycarbonyl" include CH30C(=0)-, CH3CH2OC(=O)-, CH3CH2CH2OC(=O)-, (CH3)2CHOC(=O)- and the different butoxy- or pentoxycarbonyl isomers. Examples of "alkylaminocarbonyl" include CH3NHC(=0)-, CH3CH2NHC(=O)-, CH3CH2CH2NHC(=O)-, (CH3)2CHNHC(=O)- and the different butylamino- or pentylaminocarbonyl isomers. Examples of "dialkylaminocarbonyl" include (CH3)2NC(=O)-, (CH3CH2)2NC(=O)-, CH3CH2(CH3)NC(=O)-, (CH3)2CHN(CH3)C(=O)- and CH3CH2CH2(CH3)NC(=O)-.
"Trialkylsilyl" includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom such as trimethylsilyl, triethylsilyl and t-butyl-dimethylsilyl. The total number of carbon atoms in a substituent group is indicated by the "Cj-C;" prefix where i and j are numbers from 1 to j. For example, Cj -C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C2 alkylaminoalkyl designates CH3NHCH2-; C3 alkylaminoalkyl designates, for example, CH3(CH3NH)CH-, CH3NHCH2CH2- or CH3CH2NHCH2-; and C4 alkylaminoalkyl designates the various isomers of an alkyl group substituted with an alkylamino group containing a total of four carbon atoms, examples including CH3CH2CH2NHCH2- and CH3CH2NHCH2CH2-. The terms "phenylcarbonyl", "benzylcarbonyl", and the like, are defined analogously to the term "alkylcarbonyl". "Alkylcarbonylalkyl" denotes alkylcarbonyl substitution on an alkyl moiety. Examples of "alkylcarbonylalkyl" include CH3C(=O)CH2CH2- and (CH3)2CHC(=O)CH2(CH3)CH-. The terms "alkoxycarbonyl-alkyl", "alkylaminocarbonylalkyl", and the like, are defined analogously to the term "alkylcarbonylalkyl".
The total number of carbon atoms in a substituent group is indicated by the "Cj-C;" prefix where i and j are numbers from 2 to 8. For example, Ci-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C2 alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2. When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents, e.g., (R2)n, n is 1, 2, 3 or 4.
When a group contains a substituent which can be hydrogen, for example R2 or R^, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being un substituted.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.
The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.
The term "aromatic ring system" denotes fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied for the ring system). The term "aromatic carbocyclyl" includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied). The term "nonaromatic carbocyclyl" denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the Hϋckel rule is not satisfied by any of the rings in the ring system. The term "aromatic heterocyclyl" includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied). The term "nonaromatic heterocyclyl" denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Hϋckel rule is not satisfied by any of the rings in the ring system. The heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. The term "optionally substituted" in connection with aromatic ring groups refers to groups that are unsubstituted or have at least one non-hydrogen substituent. Commonly, the number of optional substituents (when present) ranges from one to four.
As noted above, G1 (or G3) is a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(=O), S(O) and S(O)2 and optionally substituted with 1 to 4 substituents independently selected from R10 (or R*9). Examples of 5- or 6-membered nonaromatic carbocyclic or heterocyclic rings optionally substituted with R10 (or R1^) include those illustrated as G-I through G-35 in Exhibit 1. Note that the attachment point on these G groups is illustrated as floating, the G group can be attached to the remainder of Formula I through any available carbon or nitrogen of the G group by replacement of a hydrogen atom. The optional substituents R1^ (or R1^) can be attached to any carbon or nitrogen by replacement of a hydrogen atom (said substituents are not illustrated in Exhibit 1 since they are optional substituents). Note that when G comprises a ring selected from G-24 through G-31, G-34 and G-35, Q2 may be selected from O, S, NH or substituted N. Exhibit 1
Figure imgf000012_0001
G-I G-2 G-3 G-4 G-5
Figure imgf000012_0002
G-6 G-7 G-8 G-9 G-IO
Figure imgf000012_0003
G-I l G-12 G-13 G- 14 G-15
Figure imgf000012_0004
G-16 G-17 G-18 G-19 G-20
G-21 G-22 G-23 G-24 G-25
Figure imgf000012_0006
G-26 G-27 G-28 G-29 G-30
Figure imgf000012_0007
G-31 G-32 G-33 G-34 G-35
As noted above, G2 (or G4) is a phenyl ring, a phenoxy ring, a 5-membered heteroaromatic ring or a 6-membered heteroaromatic ring, each ring optionally substituted with 1 to 3 substituents independently selected from R9 (or R18). An example of phenyl optionally substituted with R9 (or R18) is the ring illustrated as U-I in Exhibit 2, wherein Rv is R9 (or R18) and r is an integer from 1 to 3. Examples of 5- or 6-membered heteroaromatic rings optionally substituted with R9 (or R18) include the rings U-2 through U-53 illustrated in Exhibit 2 wherein Rv is R9 (or R18) and r is an integer from 1 to 3.
Although Rv groups are shown in the structures U-I through U-53, it is noted that they do not need to be present since they are optional substituents. Note that when Rv is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or Rv. Note that some U groups can only be substituted with less than 3 Rv groups (e.g. U-16 through U-21, U-32 through U-34 and U-40 can only be substituted with one Rv). Note that when the attachment point between (Rv)r and the U group is illustrated as floating, (Rv)r can be attached to any available carbon atom of the U group. Note that when the attachment point on the U group is illustrated as floating, the U group can be attached to the remainder of Formula I through any available carbon of the U group by replacement of a hydrogen atom.
Exhibit 2
Figure imgf000013_0001
U-6 U-7 U-8 U-9 U-10
Figure imgf000013_0002
U-16 U- 17 U-18 U-19 U-20
Figure imgf000014_0001
U-27 U-28 U-29 U-30 U-31
Figure imgf000014_0002
U-32 U-33 U-34 U-35 U-36 U-37
Figure imgf000014_0003
Embodiments of the present invention include:
Embodiment 1. A compound of Formula I wherein R11 is C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-Cg cycloalkyl, C2-C4 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C4 alkoxyhaloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-Cg halocycloalkyl or C2-C4 haloalkoxyhaloalkyl.
Embodiment 2. A compound of Embodiment 1 wherein R11 is C1-C4 alkyl or C1-C4 haloalkyl. Embodiment 3. A compound of Embodiment 2 wherein R11 is methyl, ethyl, CH2CF3,
CF3, CF2CF3, CF2CF2Br, CF2CF2CF3 or CF(CF3)2. Embodiment 4. A compound of Embodiment 3 wherein R1Ms CF3.
Embodiment 5. A compound of Formula I wherein X is O. Embodiment 6. A compound of Formula I wherein Z is C2 haloalkylene. Embodiment 7. A compound of Embodiment 6 wherein R1 is -X-CF2CHFO-R11. Embodiment 8. A compound of Embodiment 7 wherein R1 is -OCF2CHFO-R11. Embodiment 9. A compound of Embodiment 8 wherein R1 is -OCF2CHFOCF3.
Embodiment 10. A compound of Formula I wherein W is N, CH, CF, CCl, CBr or CL Embodiment 11. A compound of Embodiment 10 wherein W is N, CH, CF or CCl. Embodiment 12. A compound of Formula I wherein each R2 is independently H, C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, or C1-C4 haloalkoxy; and n is 1, 2 or 3.
Embodiment 13. A compound of Embodiment 12 wherein each R2 is independently H,
Cl, F or Br; and n is 1 or 2.
Embodiment 14. A compound of Formula I wherein R3 is H or C1-C4 alkyl. Embodiment 15. A compound of Embodiment 14 wherein R3 is H. Embodiment 16. A compound of Formula I wherein R^ is H or C1-C4 alkyl.
Embodiment 17. A compound of Embodiment 16 wherein R4 is H. Embodiment 18. A compound of Formula I wherein R5 is H; or C1-Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl or C3-Cg cycloalkyl, each optionally substituted with one or more substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, OCH3 and S(O)pCH3; and p is 0, 1, or 2.
Embodiment 19. A compound of Embodiment 18 wherein R5 is H, methyl, ethyl, i- propyl or t-butyl.
Embodiment 20. A compound of Formula I wherein R^ is H, C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl.
Embodiment 21. A compound of Embodiment 20 wherein R^ is CH3, CF3, OCHF2, S(O)qCF3, S(O)qCHF2, cyano or halogen; and q is 0, 1, or 2. Embodiment 22. A compound of Embodiment 21 wherein R6 is F, Cl, Br, I, CH3 or
CF3.
Embodiment 23. A compound of Embodiment 22 wherein R6 is Cl or CH3. Embodiment 24. A compound of Formula I wherein R7 is H, Cj-Cg alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl,
C2-C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl or C3-Cg dialkylaminoc arbon yl . Embodiment 25. A compound of Embodiment 24 wherein R7 is H, F, Cl, Br, I, cyano or
CF3.
Embodiment 26. A compound of Embodiment 25 wherein R7 is Cl, Br or cyano. Embodiment 27. A compound of Embodiment 26 wherein R7 is Cl or cyano.
Embodiment 28. A compound of Formula I wherein R13 is H, CH3, halogen or cyano. Embodiment 29. A compound of Formula I wherein V is CR13. Embodiment 30. A compound of Embodiment 29 wherein V is CH. Embodiment 31. A compound of Formula I wherein R14 is H, CH3, halogen or cyano. Embodiment 32. A compound of Formula I wherein Y is CR14.
Embodiment 33. A compound of Embodiment 32 wherein Y is CH, CF, CCl or CBr. Embodiment 34. A compound of Embodiment 33 wherein Y is CH. Embodiment 35. A compound of Formula I wherein L is a linking chain of one to three carbon atoms, optionally substituted with one to three substituents independently selected from R15.
Embodiment 36. A compound of Formula I wherein each R15 is independently H, C1-C4 alkyl or C1-C4 haloalkyl.
Embodiment 37. A compound of Formula I wherein L is C(=E) and E is oxygen. Embodiment 38. A compound of Formula I wherein L is CH2, CH2CH2 or C=O. Embodiment 39. A compound of Embodiment 38 wherein L is CH2.
Embodiment 40. A compound of Formula I wherein Q is Q-2 or Q-3. Embodiment 41. A compound of Formula I wherein Q is Q-I or Q-3. Embodiment 42. A compound of Formula I wherein Q is Q-I or Q-2. Embodiment 43. A compound of Formula I wherein Q is Q-I. Embodiment 44. A compound of Formula I wherein Q is Q-2.
Embodiment 45. A compound of Formula I wherein Q is Q-3.
Combinations of Embodiments 1-45 are illustrated by: Embodiment A. A compound of Formula I wherein W is N, CH, CF, CCl, CBr or CI; each R2 is independently H, C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano, nitro,
CpC4 alkoxy, or Cj-C4 haloalkoxy; n is 1, 2 or 3; R3 is H or C1-C4 alkyl;
R4 is H or C1-C4 alkyl;
R5 is H; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl, each optionally substituted with one or more substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, OCH3 and S(COpCH3; p is O, 1, or 2;
R6 is CH3, CF3, OCHF2, S(O)pCF3, S(O)pCHF2, cyano or halogen; R7 is H, F, Cl, Br, I, cyano or CF3;
Y is CR13; R13 is H, CH3, halogen or cyano; Y is CR14; and
R14 is H, CH3, halogen or cyano. Embodiment B. A compound of Embodiment A wherein
X is O;
Z is C2 haloalkylene; and R11 is C1-C4 alkyl or C1-C4 haloalkyl.
Embodiment C. A compound of Embodiment B wherein
Q is Q-I;
W is N, CCl, CF or CH;
R2 is H, Cl, F or Br; n is 1 or 2;
R3 and R4 are H;
R5 is H, methyl, ethyl, /-propyl or t-butyl;
R6 is F, Cl, Br, I, CH3 or CF3;
R7 is Cl, Br or cyano; V is CH; and
Y is CH, CF, CCl or CBr.
Embodiment D. A compound of Embodiment C wherein
R1 is -OCF2CHF-O-R11; and
R11 is methyl, ethyl, CH2CF3, CF3, CF2CF3, CF2CF2Br, CF2CF2CF3 or CF(CF3)2.
Embodiment E. A compound of Embodiment D wherein
R1 is -OCF2CHFOCF3;
Y is CH; R6 is Cl or CH3; and R7 is Cl or CN. Embodiment F. A compound of Embodiment B wherein
Q is Q-2; W is N, CCl, CF or CH;
R2 is H, Cl, F or Br; n is 1 or 2; R3 and R4 are H;
R5 is H, methyl, ethyl, /-propyl or t-butyl; R6 is F, Cl, Br, I, CH3 or CF3;
R7 is Cl, Br or cyano;
Y is CH;
Y is CH, CF, CCl or CBr; and L is CH2, CH2CH2 or C=O. Embodiment G. A compound of Embodiment F wherein
R1 is -OCF2CHF-O-R11; and R11 is methyl, ethyl, CH2CF3, CF3, CF2CF3, CF2CF2Br, CF2CF2CF3 or
CF(CF3)2.
Embodiment H. A compound of Embodiment G wherein R1 is -OCF2CHFOCF3;
Y is CH;
R6 is Cl or CH3; and
R7 is Cl or CN.
Embodiment I. A compound of Embodiment B wherein Q is Q-3;
W is N, CCl, CF or CH;
R2 is H, Cl, F or Br; n is 1 or 2;
R3 and R4 are H; R5 is H, methyl, ethyl, /-propyl or t-butyl;
R6 is F, Cl, Br, I, CH3 or CF3;
R7 is Cl, Br or cyano;
Y is CH; and
Y is CH, CF, CCl or CBr. Embodiment J. A compound of Embodiment I wherein
R1 is -OCF2CHF-O-R11; and
R11 is methyl, ethyl, CH2CF3, CF3, CF2CF3, CF2CF2Br, CF2CF2CF3 or CF(CF3)2. Embodiment K. A compound of Embodiment J wherein R1 is -OCF2CHFOCF3. Y is CH;
R6 is Cl or CH3; and R7 is Cl or cyano.
Of note are compounds selected from the group consisting of: l-(3-chloro-2-pyridinyl)-iV-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]- 3-[l,l,2-trifluoro-2-(trifluoromethoxy)ethoxy]-lH-pyrazole-5-carboxamide; l-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl- 6-[[(l-methylethyl)amino]carbonyl]phenyl]-3-[l,l,2-trifluoro-
2-(trifluoromethoxy)ethoxy]-lH-pyrazole-5-carboxamide; iV-[2-(aminocarbonyl)-4-cyano-6-methylphenyl]-l-(3-chloro-2-pyridinyl)- 3-[l,l,2-trifluoro-2-(trifluoromethoxy)ethoxy]-lH-pyrazole-5-carboxamide; and l-(3-chloro-2-pyridinyl)-N-[4-cyano-2-[(ethylamino)carbonyl]-6-methylphenyl]- 3-[l,l,2-trifluoro-2-(trifluoromethoxy)ethoxy]-lH-pyrazole-5-carboxamide.
Also noteworthy as embodiments of the present invention are compositions for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding Embodiments, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent. Embodiments of the 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 of any of the preceding Embodiments (e.g., as a composition described herein). Embodiments of the invention also include a composition comprising a compound of any of the preceding Embodiments, in the form of a soil drench liquid formulation. Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the soil with a liquid composition as a soil drench comprising a biologically effective amount of a compound of any of the preceding Embodiments. Embodiments of the invention also include a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of 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 of 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 permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
Compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-11. The definitions of Y, V, W, X, Z, n, R1, R2, R3, R4, R5, R6 and R7 in the compounds of Formulae 1-15 below are as defined above in the Summary of the Invention unless indicated otherwise.
Compounds of Formula I, where Q is Q-I, can be prepared by the reaction of benzoxazinones of Formula 2 with amines of Formula 3 as outlined in Scheme 1. Scheme 1
is Q-I
Figure imgf000020_0001
This reaction can be run neat or in a variety of suitable solvents including tetrahydrofuran, diethyl ether, dichloromethane or chloroform with optimum temperatures ranging from room temperature to the reflux temperature of the solvent. The general reaction of benzoxazinones with amines to produce anthranilamides is well documented in the chemical literature. For a review of benzoxazinone chemistry see Jakobsen et al., Biorganic and Medicinal Chemistry 2000, 8, 2095-2103 and references cited within. See also G. M. Coppola, J. Heterocyclic Chemistry 1999, 36, 563-588. Benzoxazinones of Formula 2 can be prepared by a variety of methods. Three methods that are especially useful are detailed in Schemes 2-4. In Scheme 2, a benzoxazinone of Formula 2 is prepared directly by coupling of a carboxylic acid of Formula 4 with an anthranilic acid of Formula 5. Scheme 2
Figure imgf000021_0001
3. Et3N
4. MeSO2Cl
This involves sequential addition of methanesulfonyl chloride in the presence of a tertiary amine such as triethylamine to a pyrazolecarboxylic acid of Formula 4, followed by the addition of the anthranilic acid of Formula 5, followed by a second addition of triethylamine and methanesulfonyl chloride. This method generally affords good yields of the benzoxazinone.
Scheme 3 depicts an alternate preparation for benzoxazinones of Formula 2 involving coupling of an acid chloride of Formula 7 with an isatoic anhydride of Formula 6 to provide the Formula 2 benzoxazinone directly. Solvents such as pyridine or pyridine/acetonitrile are suitable for this reaction. The acid chlorides of Formula 7 are available from the corresponding acids of Formula 4 by known methods such as chlorination with thionyl chloride or oxalyl chloride.
Scheme 3
Figure imgf000021_0002
In Scheme 4, the benzoxazinone of Formula 2 is prepared directly via coupling of a carboxylic acid of Formula 4 with an anthranilic acid of Formula 5. This involves sequential addition of a pyridine base such as 3-picoline to a mixture of the pyrazolecarboxylic acid of Formula 4 and the anthranilic acid of Formula 5, followed by addition of methanesulfonyl chloride. This method affords very good yields of the benzoxazinone and is illustrated with greater detail in Example 1. Scheme 4
Figure imgf000022_0001
Anthranilic acids of Formula 5 are available commercially or by a variety of known methods. As shown in Scheme 5, anthranilic acids of Formula 5b containing an R7 substituent of chloro, bromo or iodo can be prepared by direct halogenation of an unsubstituted anthranilic acid of Formula 5a with Λf-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or iV-iodosuccinimide (NIS) respectively in solvents such as N,iV-dimethylformamide. The anthranilic acids of Formula 5b represent intermediates for a preferred set of compounds of Formula I.
Scheme 5
Figure imgf000022_0002
Cyanoanthranilic acids of Formula 5c can be prepared from haloanthranilic acids of Formula 5b as outlined in Scheme 6. Reaction of a haloanthranilic acid of Formula 5b (wherein R7 is bromo or iodo) with a metal cyanide (e.g., cuprous cyanide, zinc cyanide, or potassium cyanide), optionally with or without a suitable palladium catalyst (e.g., tetrakis(triphenylphosphine)palladium(0) or dichlorobis(triphenylphosphine) palladium(II)) and optionally with or without a metal halide (e.g., cuprous iodide, zinc iodide, or potassium iodide) in a suitable solvent such as acetonitrile, N,N-dimethylformamide or N- methylpyrrolidinone, optionally at temperatures ranging from room temperature to the reflux temperature of the solvent, affords compounds of Formula 5c. The suitable solvent can also be tetrahydrofuran or dioxane when palladium catalyst is used in the coupling reaction. The anthranilic acids of Formula 5c also represent intermediates for a preferred set of compounds of Formula I. Scheme 6
metal cyanide
Pd catalyst (optional) metal hydride (optional)
Figure imgf000023_0001
Figure imgf000023_0002
Anthranilic acids of Formula 5, where one or both of Y and Z are selected from N, are available by a variety of known methods; see e.g., PCT Patent Publication WO 2002/070483.
Preparation of isatoic anhydrides of Formula 6 wherein Y and V are CH can be achieved from isatins of Formula 9 as outlined in Scheme 7. Isatins of Formula 9 are available from aniline derivatives of Formula 8 following literature procedures such as F. D. Popp, Adv. Heterocycl. Chem. 1975, 18, 1-58 and J. F. M. Da Silva et al., Journal of the Brazilian Chemical Society 2001, 12(3), 273-324. Oxidation of isatin 9 with hydrogen peroxide generally affords good yields of the corresponding isatoic anhydride 6 (G. Reissenweber and D. Mangold, Angew. Chem. Int. Ed. Engl. 1980, 19, 222-223). Isatoic anhydrides are also available from the anthranilic acids 5 via many known procedures involving reaction of 5 with phosgene or a phosgene equivalent.
Scheme 7
Figure imgf000023_0003
° 9 6a
Where Y and V are CH
Pyrazole acids 4a represent a preferred set of pyrazole acids for the synthesis of compounds of Formula I. Their preparation involves reaction of a 5-hydroxypyrazole of Formula 10 with a substituted trifluoroethylene 11 in the presence of a base such as sodium hydroxide or potassium hydroxide in polar solvents such as dimethylsulfoxide, N,N- dimethylformamide or N-methylpyrrolidinone. Cosolvents such as toluene, tetrahydrofuran, dioxane and the like may be used. The reaction is generally conducted in the range of 0 0C to room temperature. This method affords very good yields of the pyrazole ester of Formula 12. The pyrazole ester of Formula 12 is converted to the acid of Formula 4a by conventional hydrolytic methods and is illustrated with greater detail in Example 1.
Scheme 8
Figure imgf000024_0001
10 12 4a The preparation of 5-hydroxypyrazole 10 is depicted in Scheme 9. For a leading reference see PCT Patent Publication WO 2004/046129. Reaction of aryl hydrazine 13 with diethylmaleate affords the 5-hydroxypyrazoline 14. Oxidation of 14 with a variety of oxidizing reagents including hydrogen peroxide, manganese dioxide and most preferably potassium persulfate affords the 5-hydroxypyrazole 10. This method is described with greater detail in Example 1.
Scheme 9
Figure imgf000024_0002
13 14 10
Compounds of Formula I, where Q is Q-2, can be prepared by reaction of Formula 14 intermediates with acid chlorides of Formula 7 as shown in Scheme 10. The reaction can be run neat or in a variety of suitable solvents including tetrahydrofuran, toluene, methylene chloride or chloroform with optimum temperatures ranging from room temperature to the reflux temperature of the solvent. Typical bases include amines such as triethylamine and pyridine, carbonates such as potassium and sodium carbonate and hydrides such as potassium and sodium hydride. For examples of this type and for the preparation of intermediates of Formula 15 see PCT Patent Publication WO 2003/062226. Scheme 10
Wherein Q is Q-2
Figure imgf000025_0001
Compounds of Formula I, where Q is Q-3, can be prepared directly by treatment of Formula I compounds, where Q is Q-I, with dehydrating reagents such as phosphoryl chloride, thionyl chloride and oxalyl chloride. The reaction can be run neat or in solvents such as dichloromethane, dichloroethane, chloroform, benzene, toluene, xylene, tetrahydrofuran, dioxane and chlorobenzene at temperatures ranging from 0 0C to the reflux temperature of the solvent. For examples of this type of reaction see PCT Patent Publication WO 2003/032731.
Scheme 11
Figure imgf000025_0002
I Q is Q-3
Q is Q-I; R3 and R4 is H
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I. One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. 1H NMR spectra are reported in ppm downfield from tetramethylsilane; "s" means singlet, "d" means doublet, "t" means triplet, "q" means quartet, "m" means multiplet, "dd" means doublet of doublets, "dt" means doublet of triplets, and "br s" means broad singlet.
EXAMPLE 1
Preparation of l-(3-chloro-2-pyridinyl)-N-r4-cyano-2-methyl- 6-r(methylamino')carbonyl1phenyll-3-riJ,2-trifluoro-2-(trifluoromethoxy')ethoxyl- lH-pyrazole-5-carboxamide Step A: Preparation of ethyl 2-(3-chloro-2-pyridinyl)-5-oxo-
3 -p yrazoli dinecarbox yl ate
A 2-L four-necked flask equipped with a mechanical stirrer, thermometer, addition funnel, reflux condenser, and nitrogen inlet was charged with absolute ethanol (250 mL) and an ethanolic solution of sodium ethoxide (21%, 19O mL, 0.504 mol). The mixture was heated to reflux at about 83 0C. It was then charged with 3-chloro-2-hydrazinopyridine (68.0 g, 0.474 mol). The mixture was re-heated to reflux over a period of 5 minutes. The yellow slurry was then treated dropwise with diethyl maleate (88.0 mL, 0.544 mol) over a period of 5 minutes. The reflux rate increased markedly during the addition. By the end of the addition all of the starting material had dissolved. The resulting orange-red solution was held at reflux for 10 minutes. After being cooled to 65 0C, the reaction mixture was treated with glacial acetic acid (50.0 mL, 0.873 mol). A precipitate formed. The mixture was diluted with water (650 mL), causing the precipitate to dissolve. The orange solution was cooled in an ice bath. Product began to precipitate at 28 0C. The slurry was held at about 2 0C for 2 hours. The product was isolated by filtration, washed with aqueous ethanol (40%,
3 x 50 mL), then air-dried on the filter for about 1 hour. The title product compound was obtained as a highly crystalline, light orange solid (70.3 g, 55% yield). No significant impurities were observed by ^H NMR. 1H NMR (Me2SO-J6) δ 10.18 (s, IH), 8.27 (d, IH), 7.92 (d, IH), 7.20 (dd, IH), 4.84 (d, IH), 4.20 (q, 2H), 2.91 (dd, IH), 2.35 (d, IH), 1.22 (t, 3H).
Step B: Preparation of ethyl 2-(3-chloro-2-pyridinyl)-2,5-dihvdro-5-oxo-lH-pyrazole-
3-carboxylate
To a suspension of ethyl l-(3-chloro-2-pyridinyl)-3-pyrazolidinone-5-carboxylate (27 g, 100 mmol) stirred in dry acetonitrile (200 mL) was added sulfuric acid (20 g, 200 mmol) in one portion. The reaction mixture thinned to form a pale green, nearly clear solution before thickening again to form a pale yellow suspension. Potassium persulfate (33 g, 120 mmol) was added in one portion, and then the reaction mixture was heated at gentle reflux for 3.5 hours. After cooling using an ice bath, a precipitate of white solid was removed by filtration and discarded. Concentration of the acetonitrile mother liquor and then dilution with water (400 mL) was followed by extraction three times with diethyl ether (700 mL total). The diethyl ether phase was concentrated to a reduced volume (75 mL) to precipitate an off-white solid (3.75 g), which was collected by filtration. The ether mother liquor was further concentrated to yield a second crop of an off-white precipitate (4.2 g) which was collected by filtration. Further precipitation of an off-white solid (4.5 g) from the aqueous phase yielded a combined total of 12.45 g of the title compound. IH NMR (Me2SO-J6) δ 10.6 (s, IH), 8.5 (d, IH), 8.19 (d, IH), 7.6 (t, IH), 6.34 (s, IH), 4.11 (q, 2H), 1.06 (t, 3H). Step C: Preparation of ethyl l-(3-chloro-2-pyridinyl)-3-Fl,l,2-trifluoro- 2-(trifluoromethoxy)ethoxyl-lH-pyrazole-5-carboxylate
To a solution of the pyrazole ester from Step B (1.0 g, 3.7 mmol) in 1:1 methanol/dimethyl sulfoxide (20 mL) was added potassium hydroxide (42 mg, 0.7 mmol). The mixture was stirred at room temperature for 5 minutes and then cooled to 0 0C. Trifluoromethyl trifluorovinyl ether (approx 1.0 mL) was then added dropwise and the reaction was allowed to warm to room temperature and stirred overnight. The mixture was then diluted with water and extracted into diethyl ether (2 X 75 mL). The organic extracts were dried over magnesium sulfate, and concentrated. Chromatography of the crude product on silica gel using a hexane/ethyl acetate gradient of 9:1 to 7:3 as eluent afforded 1.44 g of the title compound as an oil. 1H NMR (CDCl3) δ 8.50 (d, IH), 7.92 (d, IH), 7.45 (dd, IH), 6.81 (s, IH), 5.9-6-1 (dt, IH), 4.23 (q, 2H), 1.23 (t, 3H).
Step D: Preparation of l-(3-chloro-2-pyridinyl)-3-ri.l,2-trifluoro-
2-(trifluoromethoxy)ethoxyl- lH-pyrazole-5-carboxylic acid To a stirred solution of the pyrazole ester from Step C (1.26 g, 2.9 mmol) in methanol (15 mL) was added an aqueous solution of sodium hydroxide (131 mg, 3.2 mmol) in water (5 mL), and the reaction mixture was stirred at room temperature for 30 minutes. A solution of 1 N HCl was then added and the reaction mixture was extracted with ethyl acetate (2 X 100 mL). The ethyl acetate extracts were dried over magnesium sulfate and concentrated to give the title compound.
1H NMR (CDCl3) δ 8.50 (d, IH), 7.91 (d, IH), 7.47 (dd, IH), 6.87 (s, IH), 5.9-6.1 (dt, IH). Step E: Preparation of 2-amino-5-iodo-3-methylbenzoic acid
To a solution of 2-amino-3-methylbenzoic acid (Aldrich, 5 g, 33 mmol) in iV,N-dimethylformamide (30 mL) was added N-iodosuccinimide (7.8 g, 34.7 mmol), and the reaction mixture was heated in a 75 0C oil bath overnight. After removal of the oil bath, the reaction mixture was then slowly poured into ice-water (100 mL) to precipitate a light grey solid. The solid was filtered and washed four times with water and then placed in a vacuum oven at 70 °C to dry overnight. The desired intermediate was isolated as a light grey solid (8.8 g).
1H NMR (Me2SO-J6) δ 7.86 (d,lH), 7.44 (d,lH), 2.08 (s,3H).
Step F: Preparation of 2-amino-5-cvano-3-methylbenzoic acid
A mixture of the product from Step E (17.0 g, 61.3 mmol) and copper cyanide (7.2 g, 78.7 mmol) was heated in Λ^N-dimethylformamide (200 mL) to 140-145 0C for 20 hours. The reaction mixture was then cooled, and most of the dimethylformamide was removed by concentration on a rotary evaporator at reduced pressure. Water (200 mL) was added to the oily solid followed by ethylenediamine (20 mL), and the mixture was stirred vigorously to dissolve most of the solids. Residual solids were removed by filtration, and concentrated hydrochloric acid was then added to the filtrate to adjust the pH to 5. As the pH decreased, some solids precipitated. The resulting mixture was partitioned between ethyl acetate and water. The separated organic solution was dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residual solids were triturated with a mixture of diethyl ether, hexane and ethyl acetate to afford 7.61 g of the title compound as a tan solid. 1H NMR (Me2SO-J6) δ 7.97 (s,lH), 7.50 (s,lH), 7.3-7.5 (br s,lH), 2.12 (s,3H). Step G: Preparation of 2-ri-(3-chloro-2-pyridinyl)-3-riJ,2-trifluoro-
2-(trifluoromethoxy)ethoxyl-lH-pyrazol-5-yl1-8-methyl-4-oxo-4H-3,l-benzoxazine- 6-carbonitrile
A mixture of the carboxylic acid from Step D (0.7 g, 1.73 mmol), the anthranilic acid from Step F (305 mg, 1.73 mmol) and 3-picoline (0.85 mL, 8.63 mmol) in acetonitrile (10 mL) was stirred to form a homogeneous mixture, and the reaction mixture was then cooled to -10 0C. Methanesulfonyl chloride (0.34 mL, 4.3 mmol) in acetonitrile (5 mL) was added dropwise, and the reaction mixture was then allowed to warm to room temperature, and stirred overnight. Water was then added to the reaction mixture, followed by extraction with ethyl acetate. The ethyl acetate extracts were dried over magnesium sulfate, concentrated and chromatographed on silica gel to afford 0.9 g of the title compound.
1H NMR (CDCl3) 6 8.57 (d, IH), 8.31 (s, IH), 8.00 (d, IH), 7.75 (s, IH), 7.50 (dd, IH), 7.10
(s, IH), 5.95-6.15 (dt, IH). Step H: Preparation of l-(3-chloro-2-pyridinyl)-N-r4-cvano-2-methyl-
6-r(methylamino)carbonyllphenyll-3-rU,2-trifluoro-2-(trifluoromethoxy)ethoxy1-lH- pyrazole-5-carboxamide
The product from Step G (125 mg, 0.23 mmol) was dissolved in acetonitrile (10 ml), and methylamine (2.0 M solution in TΗF, 2.0 mL, 4.0 mmol) was added. The resulting solution was stirred for 15 minutes at room temperature. The reaction mixture was concentrated to dryness, and the residue was suspended in hexane and filtered to yield
109 mg of the title product, a compound of the present invention, as a white solid, m.p. 169-
170 0C.
1H NMR (CDCl3) δ 10.6 (br s, IH), 8.45 (d, IH), 7.85 (d, IH), 7.56 (s, 2H), 7.41 (dd, IH), 6.85 (s, IH), 6.32 (br q, IH), 5.95-6.15 (dt, IH), 2.98 (d, 3H), 2.24 (s, 3H).
EXAMPLE 2
Preparation of l-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-
6-rr(l-methylethyl)aminolcarbonyllphenyll-3-riJ,2-trifluoro-2-(trifluoromethoxy)ethoxy1- lH-pyrazole-5-carboxamide
The product from Example 1, Step G (100 mg, 0.18 mmol) was dissolved in acetonitrile (10 ml), and isopropylamine (0.6 mL, 7.1 mmol) was added. The resulting solution was stirred for 20 minutes at room temperature. The reaction mixture was concentrated to dryness, suspended in hexane and filtered to yield 93 mg of the title product, a compound of the present invention, as a white solid, m.p. 184-185 0C.
1H NMR (CDCl3) δ 8.45 (d, IH), 7.85 (d, IH), 7.54 (s, 2H), 7.40 (dd, IH), 6.90 (s, IH),
5.95-6.15 (dt, IH), 6.05 (br d, IH), 4.20 (m, IH), 2.23 (s, 3H), 1.23 (d, 6H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 11 can be prepared. The following abbreviations are used in the Tables which follow: t means tertiary, i means iso, Me means methyl,
Et means ethyl, i-Pr means isopropyl, Bu means butyl, CN means cyano, 2-C1-4-F means 2- chloro-4-fluoro.
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Table 2
Figure imgf000033_0003
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br
Figure imgf000033_0002
CN
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Table 3
Figure imgf000036_0002
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Table 4
Figure imgf000039_0002
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Table 5
Figure imgf000042_0002
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Table 6
Figure imgf000045_0002
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Table 8
Figure imgf000052_0002
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Table 9
Figure imgf000055_0002
R1 is OCF2CFHOCF3
Y V Si Si SZ Y V El Bi SZ
N CH H Me Cl N N H Me Cl
N CH Me Me Cl N N Me Me Cl
N CH Et Me Cl N N Et Me Cl
N CH j-Pr Me Cl N N j-Pr Me Cl
N CH f-Bu Me Cl N N f-Bu Me Cl
N CH H Cl Cl N N H Cl Cl
N CH Me Cl Cl N N Me Cl Cl
N CH Et Cl Cl N N Et Cl Cl
N CH j-Pr Cl Cl N N j-Pr Cl Cl
N CH f-Bu Cl Cl N N f-Bu Cl Cl
N CH H Me Br N N H Me Br
N CH Me Me Br N N Me Me Br
N CH Et Me Br N N Et Me Br
N CH i-Pr Me Br N N j-Pr Me Br
N CH /-Bu Me Br N N f-Bu Me Br
N CH H Cl Br N N H Cl Br
Figure imgf000056_0001
Table 10
Figure imgf000056_0003
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Figure imgf000056_0002
Cl
Figure imgf000057_0001
Figure imgf000058_0001
Table 11
Figure imgf000058_0002
Figure imgf000059_0001
Formulation/Utility
Compounds of this invention can generally be used as a formulation or composition with a carrier suitable for agronomic and nonagronomic uses comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredients, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films (including seed treatment), and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions can be primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
Weight Percent
Active
Ingredient Diluent Surfactant
Water-Dispersible and Water-soluble .001-90 0-99.999 0-15 Granules, Tablets and Powders.
Suspensions, Emulsions, Solutions 1-50 40-99 0-50 (including Emulsifiable Concentrates)
Dusts 1-25 70-99 0-5
Granules and Pellets 0.001-99 5-99.999 0-15
High Strength Compositions 90-99 0-10 0-2
Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New
Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ.
Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, iV,iV-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, glycerol esters, poly- oxyethylene/polyoxypropylene block copolymers, and alkylpolyglycosides where the number of glucose units, referred to as degree of polymerization (D.P.), can range from 1 to 3 and the alkyl units can range from Cg-C^ (see Pure and Applied Chemistry 72, 1255- 1264). Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, iV,N-dimethylformamide, dimethyl sulfoxide, Λf-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, glycerine, triacetine, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4- hydroxy-4-methyl-2-pentanone, acetates and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol. Useful formulations of this invention can also contain materials known as formulation aids including antifoams, film formers and dyes and are well known to those skilled in the art.
Antifoams can include water dispersible liquids comprising polyorganosiloxanes such as Rhodorsil® 416. The film formers can include polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Dyes can include water dispersible liquid colorant compositions such as Pro-lzed® Colorant Red. One skilled in the art will appreciate that this is a non-exhaustive list of formulation aids. Suitable examples of formulation aids include those listed herein and those listed in McCutcheon's 2001, Volume 2: Functional Materials, published by MC Publishing Company and PCT Publication WO 03/024222.
Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can 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 can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; Developments in formulation technology, PJB Publications, Richmond, UK, 2000.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. "Active ingredient" refers to a compound of Formula I. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be constructed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated. Example A
Wettable Powder active ingredient 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
Example B
Granule active ingredient 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example C
Extruded Pellet active ingredient 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
Example D
Emulsifiable Concentrate active ingredient 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%
Example E Microemulsion active ingredient 5.0% triacetine 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%. Example F Seed Treatment active ingredient 20.00% polyvinylpyrrolidone-vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water 65.75%.
Compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and nonagronomic invertebrate pests. Compounds of this invention are also characterized by favorable foliar and or soil-applied systemicity in plants exhibiting translocation to protect foliage and other plant parts not directly contacted with invertebrate pest control compositions comprising the present compounds. (In the context of this disclosure "invertebrate pest control" means inhibition of invertebrate pest development (including mortality) that causes significant reduction in feeding or other injury or damage caused by the pest; related expressions are defined analogously.) As referred to in this disclosure, the term "invertebrate pest" includes arthropods, gastropods and nematodes of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term "gastropod" includes snails, slugs and other Stylommatophora. The term "nematode" includes all of the helminths, such as: roundworms, heartworms, and phytophagous nematodes (Nematoda), flukes (Tematoda), Acanthocephala, and tapeworms (Cestoda). Those skilled in the art will recognize that not all compounds are equally effective against all pests. Compounds of this invention display activity against economically important agronomic and nonagronomic pests. The term "agronomic" refers to the production of field crops such as for food and fiber and includes the growth of corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye, rice, maize), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (berries, cherries) and other specialty crops (e.g., canola, sunflower, olives). The term "nonagronomic" refers to other horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential and commercial structures in urban and industrial settings, turf (commercial, golf, residential, recreational, etc.), wood products, stored product agro-forestry and vegetation management public health (human) and animal health (pets, livestock, poultry) applications. For reasons of invertebrate pest control spectrum and economic importance, protection of agronomic crops from damage or injury caused by invertebrate pests by controlling invertebrate pests are embodiments of the invention.
Agronomic or nonagronomic pests include larvae of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., fall armyworm (Spodoptera fugiperda J. E. Smith), beet armyworm {Spodoptera exigua Hϋbner), black cutworm (Agrotis ipsilon Hufnagel), cabbage looper (Trichoplusia ni Hϋbner), tobacco budworm {Heliothis virescens Fabricius)); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hubner), navel orangeworm (Amyelois transitella Walker), corn root webworm {Crambus caliginosellus Clemens), sod webworm (Herpelo gramma licarsisalis Walker)); leafrollers, budworms, seed worms, and fruit worms in the family Tortricidae (e.g., codling moth {Cydia pomonella Linnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruit moth (Grapholita molesta Busck)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus)); nymphs and adults of the order Blattodea including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta oήentalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach {Blattella germanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach {Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)); foliar feeding larvae and adults of the order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil {Sitophilus oryzae Linnaeus)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers in the family Chrysomelidae (e.g., Colorado potato beetle {Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera virgifera LeConte)); chafers and other beetles from the family Scaribaeidae (e.g., Japanese beetle (Popillia japonica Newman) and European chafer (Rhizotrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae. In addition, agronomic and nonagronomic pests include: adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forfϊcula auricularia Linnaeus), black earwig (Chelisoches mono Fabricius)); adults and nymphs of the orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, planthoppers from the families Fulgoroidae and Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, cinch bugs (e.g., Blissus spp.) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae. Also included are adults and larvae of the order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdanieli McGregor)); flat mites in the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodicidae, grain mites in the family Glycyphagidae, ticks in the order Ixodidae (e.g., deer tick (Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma americanum Linnaeus)) and scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; adults and immatures of the order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), bush locust (Zonocerus spp.), house cricket (Acheta domesticus Linnaeus), mole crickets (Gryllotalpa spp.)); adults and immatures of the order Diptera including leafminers, midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids, and other Nematocera; adults and immatures of the order Thysanoptera including onion thrips (Thrips tabaci Lindeman), flower thrips (Frankliniella spp.), and other foliar feeding thrips; insect pests of the order Hymenoptera including ants (e.g., red carpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechina longicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Fδrster), odorous house ant (Tapinoma sessile Say), bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodipήon spp.; Cephas spp.); insect pests of the order Isoptera including the eastern subterranean termite {Reticulitermes flavipes Kollar), western subterranean termite {Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite {Incisitermes immigrans Snyder) and other termites of economic importance; insect pests of the order Thysanura such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the order Mallophaga and including the head louse {Pediculus humanus capitis De Geer), body louse {Pediculus humanus Linnaeus), chicken body louse {Menacanthus stramineus Nitszch), dog biting louse {Trichodectes canis De Geer), fluff louse {Goniocotes gallinae De Geer), sheep body louse {Bovicola ovis Schrank), short-nosed cattle louse {Haematopinus eurysternus Nitzsch), long-nosed cattle louse {Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the oriental rat flea {Xenopsylla cheopis Rothschild), cat flea {Ctenocephalides felis Bouche), dog flea {Ctenocephalides canis Curtis), hen flea {Ceratophyllus gallinae Schrank), sticktight flea {Echidnophaga gallinacea Westwood), human flea {Pulex irritans Linnaeus) and other fleas afflicting mammals and birds. Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider {Loxosceles reclusa Gertsch & Mulaik) and the black widow spider {Latrodectus mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede {Scutigera coleoptrata Linnaeus). Compounds of the present invention also have activity on members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e. all economically important flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).
Compounds of the invention show particularly high activity against pests in the order Lepidoptera (e.g., Alabama argillacea Hϋbner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hϋbner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis & Schiffermϋller (grape berry moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hϋbner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hϋbner (cabbage looper) and Tuta absoluta Meyrick (tomato leafminer)). Compounds of the invention also have commercially significant activity on members from the order Homoptera including: Acyrthisiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis erysimi Kaltenbach (turnip aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosipum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid), and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp. (adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citrus whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris (potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestes quadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler (green leafhopper), Nephotettix nigropictus Stal (rice leafhopper), Nilaparvata lugens Stal (brown planthopper), Peregrinus maidis Ashmead (corn planthopper), Sogatella furcifera Horvath (white-backed planthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAtee white apple leafhopper, Erythroneoura spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla). Compounds of this invention also have activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp. (complex of seed bugs), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper). Other insect orders controlled by compounds of the invention include Thysanoptera (e.g., Frankliniella occidentalis Pergande (western flower thrip), Scirthothrips citri Moulton (citrus thrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaci Lindeman (onion thrip); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius).
Of note is use of compounds of this invention for controlling silverleaf whitefly (Bemisia argentifoliϊ). Of note is use of compounds of this invention for controlling western flower thrip {Frankliniella occidentalis). Of note is use of compounds of this invention for controlling potato leafhopper (Empoasca fabae). Of note is use of compounds of this invention for controlling corn planthopper {Peregrinus maidis). Of note is use of compounds of this invention for controlling cotton melon aphid (Aphis gossypii). Of note is use of compounds of this invention for controlling green peach aphid (Myzus persicae).
One or more compounds of this invention can also be mixed with one or more "other" biologically active compounds or agents where "other" biologically active compounds or agents do not include compounds of Formula I. Such "other" biologically active compounds or agents include insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators such as rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agronomic and nonagronomic utility. Thus the present invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I and an effective amount of at least one additional biologically active compound or agent and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. Examples of such biologically active compounds or agents with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, binfenazate, buprofezin, carbofuran, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothicarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flucythrinate, tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, fonophos, halofenozide, hexaflumuron, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, methoxyfenozide, nithiazin, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, pymetrozine, pyridalyl, pyriproxyfen, rotenone, spinosad, spiromesifin (BSN 2060), sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, trichlorfon and triflumuron; fungicides such as acibenzolar, azoxystrobin, benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, (1S)-3,5-dichloro-yV-(3-chloro-l-ethyl-l-methyl-2-oxopropyl)-4-methylbenzamide (RH 7281), diclocymet (S-2900), diclomezine, dicloran, difenoconazole, (5)-3,5-dihydro-5-methyl- 2-(methylthio)-5-phenyl-3-(phenylamino)-4H-imidazol-4-one (RP 407213), dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dodine, edifenphos, epoxiconazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramid (SZX0722), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, fluazinam, fludioxonil, flumetover (RPA 403397), flumorf/flumorlin (SYP-L190), fluoxastrobin (ΗEC 5725), fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, furametapyr (S-82658), hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mepronil, metalaxyl, metconazole, metominostrobin/fenominostrobin (SSF-126), metrafenone (AC375839), myclobutanil, neo-asozin (ferric methanearsonate), nicobifen (BAS 510), orysastrobin, oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propamocarb, propiconazole, proquinazid (DPX-KQ926), prothioconazole (JAU 6476), pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon, quinoxyfen, spiroxamine, sulfur, tebuconazole, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, triadimefon, triadimenol, tricyclazole, trifloxystrobin, triticonazole, validamycin and vinclozolin; nematocides such as aldicarb, oxamyl and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus thuringiensis including ssp. aizawai and kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi. Compounds of this invention and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin). The effect of the exogenously applied invertebrate pest control compounds of this invention may be synergistic with the expressed toxin proteins.
A general reference for these agricultural protectants is The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003.
One embodiment of insecticides and acaricides for mixing with compounds of this invention include pyrethroids such as acetamiprid, cypermethrin, cyhalothrin, cyfluthrin, beta-cyfluthrin, esfenvalerate, fenvalerate and tralomethrin; carbamates such as fenothicarb, methomyl, oxamyl and thiodicarb; neonicotinoids such as clothianidin, imidacloprid and thiacloprid; neuronal sodium channel blockers such as indoxacarb; insecticidal macrocyclic lactones such as spinosad, abamectin, avermectin and emamectin; γ-aminobutyric acid (GABA) antagonists such as endosulfan, ethiprole and fipronil; insecticidal ureas such as flufenoxuron and triflumuron; juvenile hormone mimics such as diofenolan and pyriproxyfen; pymetrozine; and amitraz. One embodiment of biological agents for mixing with compounds of this invention include Bacillus thuringiensis and Bacillus thuringiensis delta endotoxin as well as naturally occurring and genetically modified viral insecticides including members of the family Baculoviridae as well as entomophagous fungi.
Another embodiment of mixtures include a mixture of a compound of this invention with cyhalothrin; a mixture of a compound of this invention with beta-cyfluthrin; a mixture of a compound of this invention with esfenvalerate; a mixture of a compound of this invention with methomyl; a mixture of a compound of this invention with imidacloprid; a mixture of a compound of this invention with thiacloprid; a mixture of a compound of this invention with indoxacarb; a mixture of a compound of this invention with abamectin; a mixture of a compound of this invention with endosulfan; a mixture of a compound of this invention with ethiprole; a mixture of a compound of this invention with fipronil; a mixture of a compound of this invention with flufenoxuron; a mixture of a compound of this invention with pyriproxyfen; a mixture of a compound of this invention with pymetrozine; a mixture of a compound of this invention with amitraz; a mixture of a compound of this invention with Bacillus thuringiensis and a mixture of a compound of this invention with Bacillus thuringiensis delta endotoxin.
In certain instances, combinations with other invertebrate pest control compounds or agents having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management. Thus, compositions of the present invention can further comprise a biologically effective amount of at least one additional invertebrate pest control compound or agent having a similar spectrum of control but a different mode of action. Contacting a plant genetically modified to express a plant protection compound (e.g., protein) or the locus of the plant with a biologically effective amount of a compound of invention can also provide a broader spectrum of plant protection and be advantageous for resistance management.
Invertebrate pests are controlled in agronomic and nonagronomic applications by applying a composition comprising a compound of this invention, in a biologically effective amount, to the environment of the pests, including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Agronomic applications include protecting a field crop from invertebrate pests typically by applying a composition or a mixture of the invention to the seed of the crop before the planting, to the foliage, stems, flowers and/or fruit of crop plants, or to the soil or other growth medium before or after the crop is planted. Nonagronomic applications refer to invertebrate pest control in the areas other than fields of crop plants. Nonagronomic applications include control of invertebrate pests in stored grains, beans and other foodstuffs, and in textiles such as clothing and carpets. Nonagronomic applications also include invertebrate pest control in ornamental plants, forests, in yards, along roadsides and railroad rights of way, and on turf such as lawns, golf courses and pastures. Nonagronomic applications also include invertebrate pest control in houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo or other animals. Nonagronomic applications also include the control of pests such as termites that can damage wood or other structural materials used in buildings. Nonagronomic applications also include protecting human and animal health by controlling invertebrate pests that are parasitic or transmit infectious diseases. Such pests include, for example, chiggers, ticks, lice and fleas.
Therefore, the present invention further comprises a method for controlling an invertebrate pest in agronomic and/or nonagronomic applications, comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the compounds of the invention, or with a composition comprising at least one such compound or a composition comprising at least one such compound and 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 granule as the compound of the invention or on granules separate from those of the compound of the invention.
One embodiment of a method of contact is by spraying. Alternatively, a granular composition comprising a compound of the invention can be applied to the plant foliage or the soil. Compounds of this invention can also be effectively delivered through plant uptake by contacting the plant with a composition comprising a compound of this invention applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants. Of note is a composition 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 soil environment of the invertebrate pest with a biologically effective amount of a compound of the present invention. Of further note are compounds of this invention also effective by topical application to the locus of infestation. Other methods of contact include application of a compound or a composition of the invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols, dusts and many others. The compounds of this invention can also be impregnated into materials for fabricating invertebrate control devices (e.g. insect netting).
The compounds of this invention can be incorporated into a bait composition that is consumed by an invertebrate pest or used within a device such as a trap, bait station, and the like. Such a bait composition can be in the form of granules which comprise (a) active ingredients, namely a biologically effective amount of a compound of Formula I, an N- oxide, or salt thereof; (b) one or more food materials; optionally (c) an attractant, and optionally (d) one or more humectants. Of note are granules or bait compositions which comprise between about 0.001-5% active ingredients, about 40-99% food material and/or attractant; and optionally about 0.05-10% humectants, which are effective in controlling soil invertebrate pests at very low application rates, particularly at doses of active ingredient that are lethal by ingestion rather than by direct contact. Some food materials can function both as a food source and an attractant. Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids. Examples of attractants are odorants and flavorants, such as fruit or plant extracts, perfume, or other animal or plant component, pheromones or other agents known to attract a target invertebrate pest. Examples of humectants, i.e. moisture retaining agents, are glycols and other polyols, glycerine and sorbitol. Of note is a bait composition (and a method utilizing such a bait composition) used to control at least one invertebrate pest selected from the group consisting of ants, termites and cockroaches. A device for controlling an invertebrate pest can comprise the present bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest. The compounds of this invention can be applied without other adjuvants, but most often application will be of a formulation comprising one or more active ingredients with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. One method of application involves spraying a water dispersion or refined oil solution of a compound of the present invention. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy. For nonagronomic uses such sprays can be applied from spray containers such as a can, a bottle or other container, either by means of a pump or by releasing it from a pressurized container, e.g., a pressurized aerosol spray can. Such spray compositions can take various forms, for example, sprays, mists, foams, fumes or fog. Such spray compositions thus can further comprise propellants, foaming agents, etc. as the case may be. Of note is a spray composition comprising a biologically effective amount of a compound or a composition of the present invention and a carrier. One embodiment of such a spray composition comprises a biologically effective amount of a compound or a composition of the present invention and a propellant. Representative propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing. Of note is a spray composition (and a method utilizing such a spray composition dispensed from a spray container) used to control at least one invertebrate pest selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like, including individually or in combinations. The rate of application required for effective control (i.e. "biologically effective amount") will depend on such factors as the species of invertebrate to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredients per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg/hectare may be sufficient or as much as 8 kg/hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required. One skilled in the art can easily determine the biologically effective amount necessary for the desired level of invertebrate pest control.
The following TEST demonstrates the control efficacy of compounds of this invention on specific pests. "Control efficacy" represents inhibition of invertebrate pest development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Table A for compound descriptions. The following abbreviations are used in the Index Tables which follow: i is iso, Me is methyl, Pr is propyl, z'-Pr is isopropyl, and CN is cyano. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared. INDEX TABLE A
Figure imgf000074_0001
Compound Ri E! ≠ sZ W m.D. (0C)
1(Ex. 1) OCF2CFHOCF3 Me Me CN N 169-170
2(Ex. 2) OCF2CFHOCF3 j-Pr Me CN N 184-185
3 OCF2CFHOCF3 H Me CN N 151-152
4 OCF2CFHOCF3 Et Me CN N 187-188
5 OCF2CFHOCF3 Me Me Cl N 170-171
6 OCF2CFHOCF3 / Pr Me Cl N 201-202
7 OCF2CFHOCF3 H Me Cl N 98-99
8 OCF2CFHOCF3 Me Me CN CH 144-145
9 OCF2CFHOCF3 j-Pr Me CN CH 154-155
10 OCF2CFHOCF3 H Me CN CH 112-114
11 OCF2CFHOCF3 Me Me Cl CH 171-172
12 OCF2CFHOCF3 j-Pr Me Cl CH 210-211
13 OCF2CFHOCF3 H Me Cl CH 105-107
14 OCF2CFHOCF3 Et Me CN CH 189-190
BIOLOGICAL EXAMPLES OF THE INVENTION
TEST A
For evaluating control of fall armyworm (Spodoptera frugiperda) the test unit consisted of a small open container with a 4-5-day-old corn (maize) plant inside. This was pre-infested (using a core sampler) with 10-15 1-day-old larvae on a piece of insect diet.
Test compounds were formulated using a solution containing 10% acetone, 90% water and 300 ppm X-77™ Spreader Lo-Foam Formula non-ionic surfactant containing alkylarylpolyoxyethylene, free fatty acids, glycols and isopropanol (Loveland Industries, Inc. Greeley, Colorado, USA). The formulated compounds were applied in 1 mL of liquid through a SUJ2 atomizer nozzle with 1/8 JJ custom body (Spraying Systems Co. Wheaton, Illinois, USA) positioned 1.27 cm (0.5 inches) above the top of each test unit. All experimental compounds in these tests were sprayed at 10 ppm replicated three times. After spraying of the formulated test compound, each test unit was allowed to dry for 1 hour and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 25 0C and 70% relative humidity. Each test unit was then visually assessed for insect mortality.
Of the compounds tested, the following resulted in at least 80% mortality: 2, 5, 6, 7, 9, 11, 12, 13 and 14.
TEST B For evaluating control of potato leafhopper {Empoasca fabae Harris) through contact and/or systemic means, the test unit consisted of a small open container with a 3-4 day old corn plant. White sand was added to the top of the soil prior to application and misted with water to form a sand crust.
Test compounds were formulated as described for Test A and sprayed at 50 ppm and replicated three times. After spraying, the test units were allowed to dry for 1 hour before they were post-infested with 5 potato leafhoppers (18 to 21 day old adults). A black, screened cap was placed on the top of the cylinder. The test units were held for 6 days in a growth chamber at 20 °C and 70% relative humidity. Each test unit was then visually assessed for insect mortality. Of the compounds tested, the following resulted in at least 80% mortality: 3 and 7.

Claims

What is claimed is: 1. A compound of Formula I, an TV-oxide, or a salt thereof,
Figure imgf000076_0001
I wherein
Q is selected from the group consisting of Q-I, Q-2 and Q-3;
Figure imgf000076_0002
Q-I Q-2 Q-3
R1 is X-Z-O-R11;
X is O, S or NR12;
Z is C2-C4 haloalkylene or C2-C4 haloalkenylene; each R2 is independently H, Cj-C4 alkyl, Cj-C4 haloalkyl, halogen, cyano, nitro, Cj-C4 alkoxy, C1-C4 haloalkoxy, Ci-C4 alkylthio, Cj-C4 alkylsulfinyl, Cj-C4 alkylsulfonyl, Cj-C4 haloalkylthio, Cj-C4 haloalkylsulfinyl or Cj-C4 haloalkylsulfonyl;
R3 is H; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, cyano, nitro, hydroxy, Cj-C4 alkoxy, C1-C4 alkylthio, Cj-C4 alkylsulfinyl, Cj-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl, C1-C4 alkylamino, C2-Cg dialkylamino and C3-C6 cycloalkylamino;
R4 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, OH, C1-C4 alkoxy, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, (C1-C4 alkyl)(C3-C6 cycloalkyl)amino, C2-C6 alkoxycarbonyl or C2-C6 alkylcarbonyl; R5 is H; G1; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, or C3-C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, G1, cyano, nitro, hydroxy, C1-C4 alkoxy, Q-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C3-C6 trialkylsilyl and G2; or
R5 is hydroxy, C1-C4 alkoxy, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl or C2-C6 alkylcarbonyl; or R4 and R^ are taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring is optionally substituted with 1 to 4 substituents selected from the group consisting of C1-C2 alkyl, halogen, cyano, nitro and C1-C2 alkoxy;
R6 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, CO2H, CONH2, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, CpC4 alkylthio, C^-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl;
R7 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, CO2H, CONH2, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C^-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl; or
R7 is phenyl, benzyl or phenoxy, each optionally substituted with one or more substituents selected from the group consisting of C1-C4 alkyl, C2-C4 alkenyl,
C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C4-C7 (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl and C3-Cg dialkylaminocarbonyl; each G1 is independently a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(=O), S(O) and S(O)2 and optionally substituted with 1 to 4 substituents independently selected from R10; each G2 is independently a phenyl ring, a phenoxy ring, a 5-membered heteroaromatic ring or a 6-membered heteroaromatic ring, each ring optionally substituted with 1 to 3 substituents independently selected from R9; each R9 is independently C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl,
C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, CJ-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, (C1-C4 alkyl)(C3-C6 cycloalkyl)amino, C2-C4 alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl; each R10 is independently C1-C2 alkyl, halogen, cyano, nitro or C1-C2 alkoxy;
R11 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C2-C8 alkoxyalkyl, C2-Cg haloalkoxyalkyl, C2-Cg alkoxyhaloalkyl, C1-C6 haloalkyl,
C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl or C2-C8 haloalkoxyhaloalkyl; R12 is H or C1-C4 alkyl; W is N or CR2; V is N or CR13;
Y is N or CR14;
R13 and R14 are independently H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, CO2H, CONH2, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl,
C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; L is a direct bond; or a linking chain of one to three members selected from carbon, nitrogen, oxygen, sulfur, C(=E), S(O) and S(O)2, provided that no more than two members are selected from C(=E), S(O) and S(O)2, said linking chain optionally substituted with one to three substituents independently selected from
RlS; each R15 is independently H, C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano, COOH, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C6 alkoxycarbonyl or C2-C6 alkoxycarbonylalkyl; or a phenyl ring or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from R1(>; each R16 is independently C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, (C1-C4 alkyl)(C3-C6 cycloalkyl)amino, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl;
E is CH2, O, S or NR17;
R17 is H; G3; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl phenyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, G2, cyano, nitro, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C3-C6 trialkylsilyl and G4; or R17 is hydroxy, C1-C4 alkoxy, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkoxycarbonyl or C2-C6 alkylcarbonyl; each G3 is independently a 5- or 6-membered nonaromatic carbocyclic or heterocyclic ring, optionally including one or two ring members selected from the group consisting of C(=O), S(O) and S(O)2 and optionally substituted with 1 to 4 substituents independently selected from R19; each G4 is independently a phenyl ring, a phenoxy ring, a 5-membered heteroaromatic ring or a 6-membered heteroaromatic ring, each ring optionally substituted with 1 to 3 substituents independently selected from R^; each R18 is independently C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl,
C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, Q4-C7 (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl,
C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl or C3-C6 trialkylsilyl; each Rl9 js independently C1-C2 alkyl, halogen, cyano, nitro or C1-C2 alkoxy; and n is 1, 2, 3 or 4. 2. The compound of Claim 1 wherein
W is N, CH, CF, CCl, CBr or CI; each R2 is independently H, C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano, nitro,
C1-C4 alkoxy, or C1-C4 haloalkoxy; n is 1,
2 or 3; R3 is H or C1-C4 alkyl;
R4 is H or C1-C4 alkyl;
R5 is H; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl, each optionally substituted with one or more substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, OCH3 and
S(COpCH3; p is 0, 1, or 2;
R6 is CH3, CF3, OCHF2, S(O)pCF3, S(O)pCHF2, cyano or halogen; R7 is H, F, Cl, Br, I, cyano or CF3;
Y is CR13; R13 is H, CH3, halogen or cyano;
Y is CR14; and R14 is H, CH3, halogen or cyano.
3. The compound of Claim 2 wherein
X is O; Z is C2 haloalkylene; and
R11 is C1-C4 alkyl or C1-C4 haloalkyl.
4. The compound of Claim 3 wherein
Q is Q-I;
W is N, CCl, CF or CH; R2 is H, Cl, F or Br; n is 1 or 2;
R3 and R4 are H;
R5 is H, methyl, ethyl, /-propyl or f-butyl;
R6 is F, Cl, Br, I, CH3 or CF3; R7 is Cl, Br or cyano;
Y is CH; and
Y is CH, CF, CCl or CBr.
5. The compound of Claim 4 wherein
R1 is -OCF2CHF-O-R11; and R11 is methyl, ethyl, CH2CF3, CF3, CF2CF3, CF2CF2Br, CF2CF2CF3 or
CF(CF3)2.
6. The compound of Claim 5 wherein
R1 is -OCF2CHFOCF3;
Y is CH; R6 is Cl or CH3; and
R7 is Cl or cyano.
7. The compound of Claim 3 wherein
Q is Q-2;
W is N, CCl, CF or CH; R2 is H, Cl, F or Br; n is 1 or 2; R3 and R4 are H; R5 is H, methyl, ethyl, /-propyl or f-butyl; R6 is F, Br, I, CH3 or CF3; R7 is Cl, Br or cyano;
Y is CH;
Y is CH, CF, CCl or CBr; and L is CH2, CH2CH2 or C=O.
8. The compound of Claim 7 wherein R1 is -OCF2CHF-O-R11; and R11 is methyl, ethyl, CH2CF3, CF3, CF2CF3, CF2CF2Br, CF2CF2CF3 or
CF(CF3)2.
9. The compound of Claim 8 wherein
R1 is -OCF2CHFOCF3;
Y is CH;
R6 is Cl or CH3; and
R7 is Cl or cyano.
10. The compound of Claim 3 wherein
Q is Q-3;
W is N, CCl, CF or CH;
R2 is H, Cl, F or Br; n is 1 or 2; R3 and R4 are H;
R^ is H, methyl, ethyl, /-propyl or t-butyl;
R6 is H, Cl, Br, I, CH3 or CF3;
R7 is Cl, Br or cyano;
Y is CH; and Y is CH, CF, CCl or CBr.
11. The compound of Claim 10 wherein R1 is -OCF2CHF-O-R11; and R11 is methyl, ethyl, CH2CF3, CF3, CF2CF3, CF2CF2Br, CF2CF2CF3 or
CF(CF3)2.
12. The compound of Claim 11 wherein
R1 is -OCF2CHFOCF3.
Y is CH;
R6 is Cl or CH3; and
R7 is Cl or cyano.
13. The compound of Claim 1 that is selected from the group consisting of: l-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-
3-[l,l,2-trifluoro-2-(trifluoromethoxy)ethoxy]-lH-pyrazole-5-carboxamide; l-(3-chloro-2-pyridinyl)-./V-[4-cyano-2-methyl- 6-[[(l-methylethyl)amino]carbonyl]phenyl]-3-[l,l,24rifluoro- 2-(trifluoromethoxy)ethoxy]-lH-pyrazole-5-carboxamide; N-[2-(aminocarbonyl)-4-cyano-6-methylphenyl]-l-(3-chloro-2-pyridinyl)- 3-[l,l,2-trifluoro-2-(trifluoromethoxy)ethoxy]-lH-pyrazole-5-carboxamide; and l-(3-chloro-2-pyridinyl)-N-[4-cyano-2-[(ethylamino)carbonyl]-6-methylphenyl]-
3-[l,l,2-trifluoro-2-(trifluoromethoxy)ethoxy]-lH-pyrazole-5-carboxamide.
14. A composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Claim 1 and at least one additional component selected from the group consisting of 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.
15. The composition of Claim 14 wherein at least one additional biologically active compound or agent is selected from insecticides of the group consisting of pyrethroids, carbamates, neonicotinoids, neuronal sodium channel blockers, insecticidal macrocyclic lactones, γ-aminobutyric acid (GABA) antagonists, insecticidal ureas and juvenile hormone mimics, a member of Bacillus thuήngiensis, a Bacillus thuringiensis delta endotoxin, and a naturally occurring or a genetically modified viral insecticide.
16. The composition of Claim 14 wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acephate, acetamiprid, acetoprole, amidoflumet (S- 1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron, buprofezin, carbofuran, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothicarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flucythrinate, tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, gamma- cyhalothrin, halofenozide, hexaflumuron, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, monocrotophos, methoxyfenozide, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, protrifenbute, pymetrozine, pyridalyl, pyriproxyfen, rotenone, S 1812 (Valent), spinosad, spiromesifen (BSN 2060), sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, trichlorfon, triflumuron, aldicarb, fenamiphos, amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpyroximate, hexythiazox, propargite, pyridaben, tebufenpyrad, Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, entomopathogenic virus and entomopathogenic fungi.
17. The composition of Claim 16 wherein the at least one additional biologically active compound or agent is selected from the group consisting of cypermethrin, cyhalothrin, cyfluthrin and beta-cyfluthrin, esfenvalerate, fenvalerate, tralomethrin, fenothicarb, methomyl, oxamyl, thiodicarb, acetamiprid, clothianidin, imidacloprid, thiamethoxam, thiacloprid, indoxacarb, spinosad, abamectin, avermectin, emamectin, endosulfan, ethiprole, fipronil, flufenoxuron, triflumuron, diofenolan, pyriproxyfen, pymetrozine, amitraz, Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis delta endotoxin and entomophagous fungi.
18. The composition of Claim 14 in the form of a soil drench liquid formulation.
19. A spray composition for controlling an invertebrate pest, comprising:
(a) a biologically effective amount of the compound of Claim 1 or the composition of Claim 14; and
(b) a propellant.
20. A bait composition for controlling an invertebrate pest, comprising: (a) a biologically effective amount of the compound of Claim 1 or the composition of Claim 14;
(b) one or more food materials;
(c) optionally an attractant; and
(d) optionally a humectant.
21. A trap device for controlling an invertebrate pest, comprising:
(a) the bait composition of Claim 20; and
(b) a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
22. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Claim 1.
23. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a composition of Claim 14.
24. The method of Claim 23 wherein the environment is soil and the composition is applied to the soil as a soil drench formulation.
25. A method for controlling a cockroach, an ant or a termite, comprising contacting a cockroach, an ant, or a termite with the bait composition in a trap device of Claim 21.
26. A method for controlling a mosquito, a black fly, a stable, fly, a deer fly, a horse fly, a wasp, a yellow jacket, a hornet, a tick, a spider, an ant, or a gnat, comprising contacting a mosquito, a black fly, a stable, fly, a deer fly, a horse fly, a wasp, a yellow jacket, a hornet, a tick, a spider, an ant, or a gnat with a spray composition of Claim 19 dispensed from a spray container.
PCT/US2005/029639 2004-08-17 2005-08-17 Novel anthranilamides useful for controlling invertebrate pests WO2006023783A1 (en)

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BRPI0515221-6A BRPI0515221A (en) 2004-08-17 2005-08-17 compound, invertebrate plague control composition, spray and bait compositions, trap device, invertebrate plague control methods and control methods
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