Classifications

• • 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.
• 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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• 2005
  • 2005-08-17 BR BRPI0515221-6A patent/BRPI0515221A/pt not_active Application Discontinuation
  • 2005-08-17 WO PCT/US2005/029639 patent/WO2006023783A1/en not_active Application Discontinuation
  • 2005-08-17 AU AU2005277228A patent/AU2005277228A1/en not_active Abandoned
  • 2005-08-17 JP JP2007528063A patent/JP2008510721A/ja active Pending
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