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WO2005080327A1 - Insecticidal and nematicidal difluoroalkene derivatives - Google Patents

Insecticidal and nematicidal difluoroalkene derivatives Download PDF

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Publication number
WO2005080327A1
WO2005080327A1 PCT/US2005/005581 US2005005581W WO2005080327A1 WO 2005080327 A1 WO2005080327 A1 WO 2005080327A1 US 2005005581 W US2005005581 W US 2005005581W WO 2005080327 A1 WO2005080327 A1 WO 2005080327A1
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WIPO (PCT)
Prior art keywords
compound
alkyl
optionally substituted
formula
cycloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2005/005581
Other languages
French (fr)
Inventor
Alvin Donald Crews, Jr.
Martin James Currie
Wonpyo Hong
George Philip Lahm
Stephen Frederick Mccann
Ying Song
Thomas Martin Stevenson
Ming Xu
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to EP05713929A priority Critical patent/EP1716112A1/en
Priority to BRPI0507217-4A priority patent/BRPI0507217A/en
Priority to JP2006554291A priority patent/JP2007524694A/en
Publication of WO2005080327A1 publication Critical patent/WO2005080327A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/30—Isothioureas
    • C07C335/32—Isothioureas having sulfur atoms of isothiourea groups bound to acyclic carbon 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
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    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/52—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
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    • C07C255/00—Carboxylic acid nitriles
    • C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C255/64—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to oxygen atoms
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    • C07C333/10—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups being part of any of the groups, X being a hetero atom, Y being any atom, e.g., N-acyl-thiocarbamates
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    • C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C335/18—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms
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    • C07C335/20—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
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    • C07C335/42—Sulfonylthioureas; Sulfonylisothioureas

Definitions

  • This invention relates to certain fluorobutenyl compounds, their N-oxides, salts and compositions suitable for agronomic and nonagronomic uses, including those uses listed below, and methods of their use for controlling invertebrate pests in both agronomic and nonagronomic environments.
  • 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.
  • invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food, 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 which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • WO 94/06777 discloses difluorobutenyl pyrimidines of Formula iii as nematocides, insecticides, acaricides, or fungicides
  • Q is Q-l or Q-2;
  • Q-l Q-2 Y is H, F, CI or CH 3 ;
  • A is C ⁇ , C r C 6 alkyl, OR l , SR la , ⁇ R la R 2a or CONR lb R 2 b;
  • Z is O, S or NR 3 ;
  • W is N or CR 4 ;
  • J 1 and I 2 are C r C 6 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C ⁇ -C alkoxy, C2-Cg alkoxycarbonyl or C2-Cg alkylcarbonyl, each optionally substituted with one G and each optionally substituted with one or more R 5 ; or J 1 and J 2 are G, NO 2 , CN, OH, NR 6 R 7 , CONR 6 R 7 , OCONR 6 R7, C ⁇ C 4 al
  • J 1 is other than CN or NO 2 .
  • This invention also provides a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I, an N-oxide or an agronomic or nonagronomic suitable salt thereof; and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said composition optionally further comprising an effective amount of at least one additional biologically active compound or agent.
  • 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, its N-oxide or an agronomically or nonagronomically suitable salt thereof, or with a biologically effective amount of a composition comprising a compound of Formula I, an N-oxide or an agronomically or nonagronomically suitable salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent, said composition optionally further comprising an effective amount of at least one additional biologically active compound or agent.
  • This invention further provides a spray composition comprising a compound of
  • This invention also provides a bait composition comprising a compound of Formula I, an N-oxide or a suitable salt thereof; one or more food materials; optionally an attractant; and optionally a humectant.
  • This invention further provides 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.
  • compositions, 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. 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).
  • 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.
  • 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, z-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.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • 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”, “dialkylamino”, and the like, are defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • the term “cycloalkylamino” includes the cycloalkyl groups linked through a nitrogen atom such as cyclopentylamino and cyclohexylamino.
  • alkylcarbonyl examples include CH 3 C(O), CH 3 CH 2 CH 2 C(O) and (CH 3 ) 2 CHC(O).
  • heterocyclic ring denotes a fully aromatic heterocyclic ring in which at least one ring atom is not carbon and which comprises 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring includes no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs (where aromatic indicates that the H ⁇ ckel rule is satisfied).
  • aromatic polycyclic ring system denotes polycyclic ring system comprising carbocycles and heterocycles in which at least one ring of the polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied for the ring system).
  • aromatic heterobicyclic ring system denotes a bicyclic ring which contains at least one heteroatom and in which at least one ring of the bicyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied).
  • the heteroaromatic rings or heterobicyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • 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 can be partially or fully substituted with halogen atoms which can be the same or different.
  • haloalkyl examples include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 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 CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 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 .
  • C j -C j The total number of carbon atoms in a substituent group is indicated by the "C j -C j " prefix where i and j are numbers from 1 to 8.
  • C ⁇ -C 4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 4 cycloalkylalkyl designates cyclopropylmethyl
  • C5 cycloalkylalkyl designates, for example, cyclopropylethyl or cyclobutylmethyl
  • C ⁇ cycloalkylalkyl designates the various ring size of a cycloalkyl group substituted with an alkyl group containing a total of six carbon atoms, examples including cyclopentylmethyl, 1- cyclobutylethyl, 2-cyclobutylethyl and 2-cyclopropylpropyl.
  • tertiary amines can form N-oxides.
  • Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and -chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane.
  • MCPBA peracetic and -chloroperbenzoic acid
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethydioxirane.
  • stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer can be more active and/or can 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.
  • the present invention comprises compounds selected from Formula I, N-oxides, and agronomically or nonagronomically salts thereof.
  • the compounds of the invention can be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • Agronomically and nonagronomically suitable 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.
  • Agronomically and nonagronomically suitable salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine or triethylamine) or inorganic bases (e.g., ammonia, hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound includes an acidic group such as a carboxyhc acid or phenol.
  • organic bases e.g., pyridine or triethylamine
  • inorganic bases e.g., ammonia, hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • R 10 groups refers to groups that are unsubstituted or have at least one non- hydrogen substituent that does not extinguish the activity for controlling invertebrate pests possessed by the unsubstituted analog.
  • a group substituted with one or more substituents means that one or more of the hydrogen on that group can be replaced by a substituent. Therefore, as the number of hydrogens of a ' group is limited, the possible number of substituents is limited.
  • phenyl optionally substituted with one or more R 8 is the ring illustrated as U-l in Exhibit 1, wherein R v is H or R 8 and r is an integer from 1 to 5.
  • An example of a naphthyl group optionally substituted with 1 to 5 R 8 is illustrated as U-85 in Exhibit 1, wherein R v is H or R 8 and r is an integer from 1 to 5.
  • Examples of 5- or 6-membered heteroaromatic rings optionally substituted with R 8 include the rings U-2 through U-53 illustrated in Exhibit 1 wherein R v is H or R 8 and r is an integer from 1 to 5 limited by the number of hydrogens on the rings.
  • Examples of aromatic 8-, 9- or 10-membered fused heterobicyclic ring systems optionally substituted with 1 to 5 R 8 include U-54 through U-84 illustrated in Exhibit 1, since the number of replaceable hydrogens is greater than 5, wherein R v is H or R 8 , and the number of R 8 is limited by the definition of r, and r is an integer from 1 to 5.
  • R v groups are shown in the structures U-l through U-85, 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 8 .
  • U groups can only be substituted with less than 4 R v groups (e.g. U-14, U-15, U-l 8 through U-21 and U-32 through U-34 can only be substituted with one R v ).
  • R v groups e.g. U-14, U-15, U-l 8 through U-21 and U-32 through U-34 can only be substituted with one R v ).
  • (R v ) r can be attached to any available carbon atom of the U group.
  • the U group can be attached to the remainder of
  • Embodiments of the present invention include: Embodiment 1. A compound of Formula I wherein Q is Q-l. Embodiment 2. A compound of Formula I wherein Q is Q-2. Embodiment 3. A compound of Formula I wherein J 1 is C ⁇ -C ⁇ alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C -C 4 alkoxy, C 2 -C 6 alkoxycarbonyl or C 2 -Cg alkylcarbonyl, each optionally substituted with one G and each optionally substituted with one or more R 5 ; or Embodiment 4.
  • Embodiment 5. A compound of Formula I wherein J 1 is G, NO 2 , CN, OH, NR 6 R 7 , CONR6R 7 , C r C 4 alkylsulfonyl, C(O)G or S(O) 2 G.
  • Embodiment 6 A compound of Formula I wherein J 1 is CN, NO 2 , OH, C ⁇ -C 4 alkoxy, or phenyl optionally substituted with 1 to 5 R 8 ; Embodiment 6a.
  • Embodiment 6 wherein J 1 is CN, NO 2 , OH or C r C 4 alkoxy.
  • Embodiment 6b A compound of Embodiment 6 wherein J 1 is phenyl optionally substituted with 1 to 5 R 8 .
  • Embodiment 7. A compound of Embodiment 6 wherein J 1 is CN.
  • Embodiment 8. A compound of Embodiment 6 wherein J 1 is NO2.
  • Embodiment 9 A compound of Embodiment 5 wherein J 1 is G or C(O)G.
  • Embodiment 10 A compound of Embodiment 9 wherein J 1 is a phenyl ring or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with 1 to 5 R 8 .
  • Embodiment 11 A compound of Embodiment 10 wherein J 1 is pyridinyl optionally substituted with 1 to 4 R 8 .
  • Embodiment 12 A compound of Formula I wherein J 2 is Ci-Cg alkyl or phenyl optionally substituted with 1 to 5 R 8 .
  • Embodiment 13 A compound of Embodiment 12 wherein J 2 is C ⁇ -Cg alkyl.
  • Embodiment 14 A compound of Formula I wherein I 2 is G, CONR 6 R 7 , C1-C4 alkylsulfonyl, C(O)G or S(O) 2 G.
  • Embodiment 15 A compound of Embodiment 14 wherein J 2 is phenyl or pyridinyl, each optionally substituted with 1 to 4 R 8 .
  • Embodiment 16 A compound of Formula I wherein Y is H or F.
  • Embodiment 17 A compound of Embodiment 16 wherein Y is H.
  • Embodiment 18. A compound of Embodiment 16 wherein Y is F.
  • Embodiment 18a A compound of Formula I wherein Y is H or CH 3 .
  • Embodiment 19 A compound of Formula I wherein A is CN, C j -Cg alkyl, OR la , SR la or NR la R 2a .
  • Embodiment 20 A compound of Embodiment 19 wherein A is CN, Ci-Cg alkyl, OR la or NR la R 2a .
  • Embodiment 21 A compound of Embodiment 20 wherein A is CN.
  • Embodiment 22 A compound of Embodiment 20 wherein A is C ⁇ -Cg alkyl.
  • Embodiment 23 A compound of Embodiment 19 wherein A is OR la , SR la or NR la R 2a .
  • Embodiment 24 A compound of Embodiment 23 wherein A is OR la .
  • Embodiment 25 A compound of Embodiment 23 wherein A is SR la .
  • Embodiment 26 A compound of Embodiment 23 wherein A is NR la R 2a .
  • Embodiment 27 A compound of Formula I wherein Z is S or NR 3 .
  • Embodiment 28 A compound of Embodiment 27 wherein Z is S.
  • Embodiment 29 A compound of Embodiment 27 wherein Z is NR 3 .
  • Embodiment 30 A compound of Formula I wherein W is N or CH.
  • Embodiment 31 A compound of Embodiment 30 wherein W is N.
  • Embodiment 32 A compound of Embodiment 30 wherein W is CH.
  • Embodiment 33 A compound of Formula I wherein R la is H; or C r C 6 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl or C 4 -C 8 cycloalkylalkyl, each optionally substituted with halogen or C2-C 4 alkoxycarbonyl.
  • Embodiment 34 A compound of Embodiment 33 wherein R la is H; or Ci-Cg alkyl, C2 ⁇ Cg alkenyl or C 3 -Cg alkynyl, each optionally substituted with one to three halogen.
  • Embodiment 35 A compound of Formula I wherein R la is H; or Ci-Cg alkyl, C2 ⁇ Cg alkenyl or C 3 -Cg alkynyl, each optionally substituted with one to three halogen.
  • a compound of Embodiment 34 wherein R la is H, C C alkyl, C 3 - C 4 alkenyl or C 3 -C 4 alkynyl.
  • Embodiment 35a A compound of Embodiment 34 wherein R la is H or Ci-Cg alkyl.
  • Embodiment 35b A compound of Embodiment 34 wherein R la is C j -Cg alkyl.
  • Embodiment 36 A compound of Formula I wherein R 2a is H; or C1-C5 alkyl, C 2 -C6 alkenyl, C 3 -Cg alkynyl, C 3 -C 7 cycloalkyl or C 4 -C 8 cycloalkylalkyl, each optionally substituted with halogen or C2-C alkoxycarbonyl.
  • Embodiment 37 A compound of Embodiment 36 wherein R 2a is H; or C1 -Cg alkyl, C2-C alkenyl or C 3 -C6 alkynyl, each optionally substituted with one to three halogen.
  • Embodiment 38 A compound of Formula I wherein R 2a is H; or C1-C5 alkyl, C 2 -C6 alkenyl, C 3 -Cg alkynyl, C 3 -C 7 cycloalkyl or C 4 -C 8 cycloalkylalkyl, each optionally substituted
  • a compound of Embodiment 37 wherein R 2a is H, C ⁇ -C 4 alkyl, C 3 - C 4 alkenyl or C 3 -C 4 alkynyl.
  • Embodiment 39. A compound of Embodiment 37 wherein R 2a is H or C j -Cg alkyl.
  • Embodiment 40. A compound of Formula I wherein R la and R 2a are taken together with the nitrogen to which they are attached to form a ring including 2 to 5 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, and said ring optionally substituted with 1 to 2 R 5 .
  • Embodiment 41. A compound of Formula I wherein R 3 is H or C ⁇ -C6 alkyl.
  • Embodiment 42. A compound of Embodiment 41 wherein R 3 is H.
  • Embodiment 43 A compound of Formula I wherein R 5 is halogen, C 1 -C 4 alkyl, C ⁇ - C 4 alkoxy, CN, NO 2 , CF 3 or OCF 3 .
  • Embodiment 44 A compound of Formula I wherein R 8 is halogen, C ⁇ -C 4 alkyl, C - C 4 alkoxy, CN, NO 2 , CF 3 or OCF 3 .
  • Embodiment 45. A compound of Formula I wherein R 10 is H, C ⁇ -Cg alkyl, C1 -Cg alkylthio, CONR 12 R 13 , CN or phenyl optionally substituted with 1 to 5 R 11 .
  • Embodiment 45a A compound of Formula I wherein R 5 is halogen, C 1 -C 4 alkyl, C ⁇ - C 4 alkoxy, CN, NO 2 , CF 3 or OCF 3 .
  • a compound of Formula I wherein R 10 is H, C ⁇ -Cg alkyl, Ci-Cg alkylthio, CONR 12 R 13 or phenyl optionally substituted with 1 to 5 R 11 .
  • Embodiment 46 A compound of Formula I wherein n is 1, 3 or 5.
  • Embodiment 47 A compound of Embodiment 46 wherein n is 1 or 3.
  • Embodiment 48 A compound of Embodiment 47 wherein n is 1.
  • Embodiment 49. A compound of Formula I wherein when J 1 is C(O)G, then G is other than optionally substituted 3-pyridinyl.
  • Embodiment 50 is
  • Embodiment 51. A compound of Formula I wherein when I 2 is phenyl substituted with R 8 , then R 8 is other than fluoroalkoxy.
  • Embodiment 52. A compound of Formula I wherein when J 2 is phenyl substituted with R 8 , then R 8 is other than haloalkoxy.
  • Embodiment 53. A compound of Formula I wherein when J 2 is phenyl substituted with R 8 , then R 8 is other than haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl.
  • Embodiment 54 A compound of Formula I wherein when Z is NH, W is N, and A is SR la , then I 1 is other than phenyl substituted at the 2 and 6 positions and optionally at other positions.
  • Embodiment 55 A compound of Formula I wherein when Z is NH, W is N, and A is SR la , then I 1 is other than optionally substituted phenyl.
  • Embodiment 56 A compound of Formula I wherein when Z is NR 3 , W is N or CH, J 1 is CN or NO 2 , then A is other than NR la R 2a . Combinations of Embodiments 1-56 are illustrated by: Embodiment A.
  • Embodiment B Embodiment B.
  • Embodiment C Embodiment C.
  • J 1 is G, NO 2 , CN, OH, NR 6 R 7 , CONR 6 R 7 , C r C 4 alkylsulfonyl, C(O)G or S(O) 2 G.
  • A is OR la , SR la or NR la R 2a ;
  • W is N or CH;
  • R la and R 2a are each independently H, C r C 6 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl or C 4 -Cg cycloalkylalkyl, each optionally substituted with one to three halogen;
  • R la and R 2a can be taken together with the nitrogen to which they are attached to form a ring including 2 to 5 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, and said ring can be optionally substituted with 1 to 2 R 5 ;
  • R 3 is H or C r C 4 alkyl;
  • R 5 and R 8 are each independently halogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 alkoxy, CN, NO 2 ,
  • Embodiment E A compound of Formula I wherein Q is Q-l; Y is H; Z is S; W is N; A is NR la R 2a ; J 1 is phenyl optionally substituted with 1 to 5 R 8 ; R la and R 2a are each independently H or C ⁇ -Cg alkyl; and n is 1 or 3.
  • Embodiment F A compound of Formula I wherein Q is Q-l; Y is H; Z is S; W is N; A is NR la R 2a ; J 1 is phenyl optionally substituted with 1 to 5 R 8 ; R la and R 2a are each independently H or C ⁇ -Cg alkyl; and n is 1 or 3.
  • Embodiment F A compound of Formula I wherein Q is Q-l; Y is H; Z is S; W is N; A is NR la R 2a ; J 1 is phenyl optionally substituted with 1 to 5 R 8 ; R la and R 2a are each independently H or C ⁇ -Cg
  • Q is Q-2; Y is H; J 2 is Ci-Cg alkyl or phenyl optionally substituted with 1 to 5 R 8 ; R 10 is H, C r C 6 alkyl, C r C 6 thioalkyl, CONR 12 R 13 or phenyl optionally substituted with 1 to 5 R 11 ; and n is 1 or 3.
  • Embodiment G Embodiment G.
  • Q is Q-2; Y is F; J 2 is C j -Cg alkyl or phenyl optionally substituted with 1 to 5 R 8 ; R 10 is H, C r C 6 alkyl, C r C 6 alkylthio, CONRl 2 Rl 3 or phenyl optionally substituted with 1 to 5 R 11 ; and n is 1 or 3.
  • 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 1-17.
  • the definitions of J 1 , J 2 , R la , R 2a , R 3 , n, Q, Q-l and Q-2 in the compounds of Formulae Ia-Ij and Formulae 2-25 below are as defined above in the Summary of the Invention.
  • Compounds of Formulae Ia-Ij are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-Ij are as defined above for Formula I.
  • Compounds of Formula I can be prepared by the general methods of reacting functionalized 1,1-difluoroalkenes 2 with substituted intermediates of Formula 3 as outlined in Scheme 1.
  • the substituent Xa represents organic functional group suitable in well established coupling reactions involving nucleophilic substitution.
  • Qa contains a nucleophilic group such as sulfur, nitrogen or oxygen.
  • Qa contains a leaving group such as halogen, alkoxy, alkylthio and the like.
  • Compounds of Formula la can be prepared by the reaction of thioureas of Formula 4 with fluorobutenyl derivatives of Formula 5 wherein X is halogen (e.g., CI, Br, I), OS(O) 2 CH 3 (methanesulfonate), OS(O) 2 CF 3 , OS(O) 2 Ph-/?-CH 3 (p-toluenesulfonate) and the like as outlined in Scheme 2.
  • X is halogen (e.g., CI, Br, I), OS(O) 2 CH 3 (methanesulfonate), OS(O) 2 CF 3 , OS(O) 2 Ph-/?-CH 3 (p-toluenesulfonate) and the like as outlined in Scheme 2.
  • Suitable bases for the reaction include inorganic bases, such as alkali or alkaline earth metal (such as lithium, sodium, potassium, cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides, and organic bases, such as triethylamine, N,N-diisopropylethylamine and l,8-diazabicyclo[5.4.0]undec-7-ene.
  • inorganic bases such as alkali or alkaline earth metal (such as lithium, sodium, potassium, cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides
  • organic bases such as triethylamine, N,N-diisopropylethylamine and l,8-diazabicyclo[5.4.0]undec-7-ene.
  • Preferred bases are potassium carbonate and potassium hydroxide.
  • a wide variety of solvents are suitable for the reaction, including, for example but are not limited to, NN-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water, as well as mixtures of these solvents.
  • This reaction can be conducted between about 0 to about 120 °C, and preferably between about 0 and 30 °C. Further procedural details for the method of Scheme 2 can be found in Examples 1 and 2.
  • Difluoroalkenyl compounds of Formula 5 are known in the art. For literature procedures to prepare compounds of Formula 5 see PCT Patent Publications WO 94/6777,
  • Thioureas of Formula 4 are well known in the literature and can be readily prepared by the reaction of isothiocyanates of Formula 6 with mono- and dialkylamines of Formula 7 as shown in Scheme 3.
  • the compounds of Formula 6 are either known compounds or can be prepared from amines and thiophosgene.
  • the reaction can be run in a variety of suitable solvents such as acetone, acetonitrile, tetrahydrofuran and dichloromethane.
  • suitable solvents such as acetone, acetonitrile, tetrahydrofuran and dichloromethane.
  • X is a nucleophilic reaction leaving group such as halogen (e.g., CI, Br, I), OS(O) 2 CH 3
  • Oximes of Formula 9 are well known in the literature. As shown in Scheme 5, many of these can be readily prepared by the reaction of aldehydes or ketones of Formula 10, where R 10 and J 2 are, for example, H, alkyl or aryl groups, with hydroxylamine hydrochloride in a suitable solvent such as ethanol, water or dioxane at temperatures ranging from room temperature to the reflux temperature of the solvent A base is needed to liberate hydroxylamine from its salt. Suitable bases for the reaction include, but are not limited to, sodium hydroxide, sodium bicarbonate or sodium carbonate.
  • compounds of Formula Ic can be prepared by the reaction of compounds of Formula 11 with difluoroalkenyl compounds of Formula 5 in the presence of a base.
  • Typical J 1 values for compounds of Formula Ic include phenyl, 5- or 6-membered heteroaromatic ring, CN, alkylcarbonyl and alkoxycarbonyl.
  • X is a leaving group as defined in Scheme 4.
  • Suitable bases for the reaction include inorganic bases, such as alkali or alkali earth metal (such as lithium, sodium, potassium, cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides, and organic bases, such as triethylamine, N,N-diisopropylethylamine and 1,8-diazabicyclo- [5.4.0]undec-7-ene.
  • inorganic bases such as alkali or alkali earth metal (such as lithium, sodium, potassium, cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides
  • organic bases such as triethylamine, N,N-diisopropylethylamine and 1,8-diazabicyclo- [5.4.0]undec-7-ene.
  • Preferred bases are potassium carbonate and potassium hydroxide.
  • Preformed salts of compounds of Formula 11 can also be used in lieu of using a base.
  • a wide variety of solvents can be suitable for the reaction, which include, for example, but are not limited to NN-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of the suitable solvents.
  • This reaction can be conducted between about 0 to about 120 °C, and preferably between about 0 and 30 °C.
  • A is OR la orSR la 11 Ic
  • compounds of Formula Id can be prepared by the reaction of compounds of Formula 12 with an alkylating agent of Formula 13 in the presence of a base.
  • X is a leaving group as defined in Scheme 4 for Formula 5.
  • Suitable bases for the reaction include inorganic bases and organic bases as described above for Scheme 6.
  • Preferred bases are potassium carbonate and potassium hydroxide.
  • Preformed salts of compounds of Formula 12 can also be used in lieu of using a base.
  • a wide variety of solvents can be suitable for the reaction, which include but are not limited to N,N-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of these solvents.
  • This reaction can be conducted between about 0 to about 120 °C. Additional details for this reaction can be found in Example 5.
  • compounds of Formula 11 can be prepared by the reaction of amines of Formula 14 with a compound of Formula 15 in the presence of base.
  • L is halogen (e.g., CI, Br, I), sulfonate (e.g. OS(O) 2 CH 3 (methanesulfonate), OS(O) 2 CF 3 , OS(O) 2 Ph-p-CH 3 (p-toluenesulfonate)), or azole (e.g. imidazoie, 3,5-dimethylpyrazole, benzimidazole, benzotriazole, indazole, pyrazole, and 1,2,4-triazole).
  • halogen e.g., CI, Br, I
  • sulfonate e.g. OS(O) 2 CH 3 (methanesulfonate)
  • OS(O) 2 CF 3 OS(O) 2 Ph-p-CH 3 (p-toluenesulfonate)
  • Suitable bases for the reaction include inorganic bases and organic bases as described above.
  • Preferred bases are amine bases such as triethylamine and N,N- diisopropylethylamine.
  • a wide variety of solvents can be suitable for this reaction, which include but are not limited to N,N-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of these solvents. This reaction can be conducted between about 0 to about 120 °C.
  • dithiocarbamates of Formula Ila can be prepared by the reaction of carbon disulfide with amines of Formula 14 followed by reaction with an alkylating agent of Formula 13.
  • Suitable bases for the reaction include inorganic bases and organic bases as described above for the reaction shown in Scheme 2.
  • Preferred bases are potassium carbonate, cesium carbonate, potassium hydroxide and sodium hydroxide.
  • dithiocarbamates of Formula 12 can be prepared by reacting compounds of Formula 16 with an amine of Formula 14 and a suitable base.
  • L is defined above as in compounds of Formula 15.
  • Preferred bases are amine bases such as triethylamine and N,N-diisopropylethylamine.
  • solvents can be suitable for this reaction, which include but are not limited to N,N-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of the suitable solvents. This reaction can be conducted between about 0 to about 120 °C.
  • dithiocarbamates of Formula 12 can also be prepared by the reaction of carbon disulfide with an amine of Formula 14 followed by reaction with a difluoroalkenyl compound of Formula 5.
  • bases are potassium carbonate, cesium carbonate, potassium hydroxide and sodium hydroxide.
  • solvents can be suitable for this reaction, which include but are not limited to NN-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of the suitable solvents.
  • dithiocarbonylazoles of Formula 17 can be prepared by the reaction of carbon disulfide with an azole followed by reaction with difluoroalkenyl compounds of Formula 5.
  • Suitable azoles include, for example, but are not limited to imidazoie, 3,5-dimethylpyrazole, benzimidazole, benzotriazole, indazole, pyrazole, 1,2,4-triazole and N-alkylimidazolium.
  • Intermediates of Formula lib can be synthesized by the reaction of isothiocyanates of Formula 18 with alcohols of Formula 19 as shown in Scheme 13.
  • the reaction can be carried out in a wide variety of solvents and temperatures. If the compounds of Formula 18 and 19 are liquids, a solvent may not be needed. Preferred solvents include tetrahydrofuran, N,N-dimethylformamide, dichloromethane, acetone or acetonitrile, and optimum temperatures range from room temperature to the reflux temperature of the solvent.
  • Intermediates of Formula lib can be converted to compounds of Formula Ie, a subset of the compounds of Formula I, by the method described previously in Scheme 6.
  • an isothiocyanate of Formula 18 can be reacted with an alcohol of Formula 20 to produce an intermediate of Formula 21.
  • Compounds of Formula 21 can then be transformed to compounds of Formula If by methods outlined in Scheme 7.
  • the reaction of alcohols of Formula 20 with isothiocyanates may be carried out in a wide variety of solvents and temperatures. It may also be carried out without the need for solvent.
  • Preferred solvents include tetrahydrofuran, dimethylformamide, dichloromethane, acetone or acetonitrile with optimum temperatures ranging from room temperature to the reflux temperature of the solvent.
  • the alcohols of Formula 20 are known compounds.
  • Compounds of Formula 23 can be made as shown in Scheme 15 by the reaction of an amine of Formula 22 with an isothiocyanate of Formula 18.
  • the reaction of amines of Formula 22 with isothiocyanates can be carried out in a wide variety of solvents and temperatures. If the compounds of Formula 18 and 23 are liquids, a solvent may not be needed. Preferred solvents include tetrahydrofuran, N,N-dimethylformamide, dichloromethane, acetone or acetonitrile, and optimum temperatures range from room temperature to the reflux temperature of the solvent.
  • Compounds of Formula 23 can be further transformed to compounds of Formula Ig by reaction with an alkyl halide of Formula 13 as outlined in Scheme 15.
  • the amines of Formula 22 are known compounds.
  • Compounds of Formula 24 can be made as shown in Scheme 16 by the reaction of KC ⁇ with an isothiocyanate of Formula 18. The reaction can be carried out in a variety of solvents and temperatures. Compounds of Formula 24 can be further transformed to compounds of Formula Ih by reaction with a difluoroalkenyl halide of Formula 5 as outlined in Scheme 6. Further details on the procedures for preparation of compounds of Formula Ih are provided in Example 11.
  • Scheme 16
  • Step A Preparation of 4,4-Difluoro-3-butenyl-N , -(2-fluorophenyl)-NN-dimethylcarbamimidothioate
  • Step A Preparation of 3-(2-Fluorophenyl)-l,l-dimethylthiourea
  • acetonitrile To a 100 mL single-necked flask equipped with a magnetic stirrer and nitrogen inlet was charged 30 mL of acetonitrile and 2.0 g (0.013 mol) of 2-fluorophenyl isothiocyanate followed by 13.0 mL (0.026 mol) of 2 M dimethylamine in THF. The mixture was stirred at 25 °C for 18 h.
  • Step B Preparation of 4,4-Difluoro-3-butenyl-N , -(2-fluorophenyl)-NN-dimethyl- carbamimidothioate
  • acetone i.e. the product of Step A
  • 3-(2-fluorophenyl)-l,l-dimethyl- thiourea i.e. the product of Step A.
  • the resulting mixture was treated with 1.75 mL (0.0087 mol) of 4-bromo-l,l-difluoro-l-butene followed by 1.2 g (0.0087 mol) of potassium carbonate.
  • Step A Preparation of 4,4-Difluoro-3-butenyl N-(2,4-difluorophenyl)-N , -methylcarbamimidothioate
  • Step A Preparation of l-(2,4-Difluorophenyl -3-methylthiourea
  • acetonitrile a 100 mL single-necked flask equipped with a magnetic stirrer and nitrogen inlet was charged 30 mL of acetonitrile and 4.0 g (0.024 mol) of 2,4-difluorophenyl isothiocyanate followed by 3.8 g (0.048 mol) of 40 wt% methylamine in ethanol.
  • the mixture was stirred at 25 °C for 18 h.
  • Step B Preparation of 4,4-Difluoro-3-butenyl N-f ⁇ -difluorophenylVN'-methyl- carbamimidothioate
  • a 100 mL single-necked flask equipped with a magnetic stirrer and nitrogen inlet was charged 30 mL of acetone and 0.75 g (0.004 mol) of l-(2,4-difluorophenyl)-3-methyl- thiourea (i.e. the product of Step A).
  • the resulting mixture was treated with 0.95 g (0.0056 mol) of 4-bromo-l,l-difluoro-l-butene followed by 0.773 g (0.005 mol) of potassium carbonate.
  • Step B Preparation of Bis(4,4-difluoro-3-butenyl) cyanocarbonimidodithioate A mixture of dipotassium cyanodithioimidocarbonate (3.0 g, 15.5 mmol) and 4-bromo- 1,1-difluoro-but-l-ene (7.9 g, 46.2 mmol) in methyl sulfoxide (20 mL) was stirred at 40 °C overnight.
  • Step B Preparation of S-(4,4-Difluoro-3-butenyl) O-ethyl (ethoxycarbonyl carbonimido- thioate To a mixture of 47.00 g (265.54 mmol) of diethyl thioimidodicarbonate (i.e.
  • Formulation/Utilitv Compounds of this invention will generally be used as a formulation or composition with a carrier suitable for agronomic or 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 ingredient, 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 are 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 In ⁇ redient 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.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-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, N,N-dimethylformamide, dimethyl sulfoxide, N-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 include materials l ⁇ iown as formulation aids like antifoams, film formers and dyes and are well l ⁇ iown to those skilled in the art.
  • Antifoams can include water dispersible liquids comprising polyorganosiloxanes like 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 like 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, 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.
  • 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.
  • Example B Granule Compound C5 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 Compound Dl 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Example D Extruded Pellet Compound Dl 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Example D Extruded Pellet Compound Dl 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite
  • Emulsifiable Concentrate Compound E10 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% , isophorone ⁇ 70.0%.
  • Example E Microemulsion Compound E41 5.0% triacetine 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%
  • Compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and non- agronomic invertebrate pests.
  • 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 flatworms (Platyhelminthes), including tapeworms (Cestoda) and flukes (Trematoda); thorny-headed worms (Acanthocephala); and roundworms (Nematoda), including whipworms (Enoplida), free-living worms (Rhabdita), hookworms and lungworms (Strongylida), intestinal roundworms (Ascarida), pinworms (Oxyurida), filarial nematodes (Spirurida), and plant parasitic nematodes (Tylenchida and Dorylaimida).
  • Flatworms such as flatworms (Platyhelminthes), including tapeworms (Cestoda) and flukes (Trematoda); thorny-headed worms (Acanthocephala); and roundworms (Nematoda), including whipworms
  • agronomic refers to the production of field crops such as for food and fiber and includes the growth of cereal crops (e.g., wheat, oats, barley, rye, rice, maize), soybeans, vegetable crops (e.g., lettuce, cabbage, tomatoes, beans), potatoes, sweet potatoes, grapes, cotton, and tree fruits (e.g., pome fruits, stone fruits and citrus fruits).
  • cereal crops e.g., wheat, oats, barley, rye, rice, maize
  • soybeans vegetable crops (e.g., lettuce, cabbage, tomatoes, beans), potatoes, sweet potatoes, grapes, cotton, and tree fruits (e.g., pome fruits, stone fruits and citrus fruits).
  • nonagronomic refers to other horticultural crops (e.g., forest, greenhouse, nursery or ornamental plants not grown in a field), turf (commercial, golf, residential, recreational, etc.), wood products, public health (human) and animal health, domestic and commercial structure, household, and stored product applications or pests.
  • turf commercial, golf, residential, recreational, etc.
  • wood products wood products
  • public health (human) and animal health domestic and commercial structure, household, and stored product applications or pests.
  • protection from damage or injury caused by invertebrate pests
  • 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 (Forficula 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).
  • spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectus mactans Fabricius)
  • centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus).
  • Compounds of the present invention also have activity on parasitic helminths of the phylum Platyhelminthes (flatworms), including the classes Cestoda (tapeworms) and Trematoda (flukes); the phylum Acanthocephala (thorny-headed worms), including the classes Archiacanthocephala and Palaeacanthocephala; and the phylum Nematoda (roundworms), including the classes Adenophorea (Aphasmidae) and Secementea (Phasmidae).
  • flatworms including the classes Cestoda (tapeworms) and Trematoda (flukes); the phylum Acanthocephala (thorny-headed worms), including the classes Archiacanthocephala and Palaeacanthocephala; and the phylum Nematoda (roundworms), including the classes Adenophorea (Aphasmidae) and Secementea (Phas
  • Compounds of the present invention also have activity on economically important members of the orders Enoplida, Dorylaimida, Rhabditida, Strongylida, Ascaridida, Oxyurida, Spirurida, Tylenchida, Aphelenchida, Diplogasterida, Rhabdiasidaand Camallanida, such as, but not limited to, economically important agricultural. pests (e.g.,
  • flukes, tapeworms and roundworms such as Strangylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis in dogs, Anoplocephala perfoliata in horses and Fasciola hepatica in ruminants , etc . ) .
  • Compounds of the invention show particularly high activity against pests in 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), Hyalopter
  • Root gall nematodes of the genus Meloidogyne such as Meloidogyne acronea (sorghum root-knot nematode), Meloid ⁇ gnye arenaria (peanut root-knot nematode), Meloidogyne brevicauda (tea root-knot nematode), Meloidogyne chitwoodi (Columbia root-knot nematode), Meloidogyne exigua (Brazilian root-knot nematode), Meloidogyne graminicola (rice root-knot nematode), Meloidogyne hapla (Northern root-knot nematode), Meloidogyne incognita (Southern root-knot nematode), Meloidogyne incognita (Southern root-knot nematode), Meloidogyne
  • 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 agricultural utility.
  • the present invention also pertains to a composition
  • a composition comprising a biologically effective amount of a compound of Formula I, an N- oxide thereof, or an agronomic or nonagronomic suitable salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent or a liquid diluent, said composition optionally further comprising at least one additional biologically active compound or agent.
  • insecticides such as 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
  • penconazole pencycuron, picobenzamid, picoxystrobin, probenazole, prochloraz, propamocarb, propiconazole, proquinazid, prothioconazole, pyraclostrobin, pyrimethanil, pyrifenox, pyroquilon, quinoxyfen, silthiofam, simeconazole, sipconazole, spiroxamine, sulfur, tebuconazole, tetraconazole, tiadinil, thiabendazole, thifluzamide, thiophanate- methyl, thiram, tolylfluanid, triadimefon, triadimenol, triarimol, tricyclazole, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, validamycin, vinclozolin and zoxamide; nematocides such as aldicarb, oxamy
  • Aizawai and Bacillus thuringiensis ssp. Kurstaki entomopathogenic baculovirus (e.g., nucleopolyhedro virus ( ⁇ PNs), granulosis virus (GNs)), entomopathogenic fungi (e.g., green muscardine fungus) and Bacillus thuringiensis encapsulated delta-endotoxin.
  • ⁇ PNs nucleopolyhedro virus
  • GNs granulosis virus
  • entomopathogenic fungi e.g., green muscardine fungus
  • Bacillus thuringiensis encapsulated delta-endotoxin encapsulated delta-endotoxin.
  • 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).
  • insecticides and acaricides for mixing with compounds of this invention include pyrethroids such as cypermethrin, cyhalothrin, cyfluthrin, beta-cyfluthrin, esfenvalerate, fenvalerate and tralomethrin; carbamates such as fenothicarb, methomyl, oxamyl and thiodicarb; neonicotinoids such as acetamiprid, clothianidin, imidacloprid, thiamethoxam, 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; insectici
  • Preferred biological agents for mixing with compounds of this invention include Bacillus thuringiensis and Bacillus thuringiensis encapsulated 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 py
  • 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 spectmm of control but a different mode of action.
  • a plant protection compound e.g., protein
  • a biologically effective amount of a compound of this 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 one or more of the compounds of this invention, in an 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.
  • the present invention further comprises a method for the control of invertebrates in agronomic and/or nonagronomic applications, comprising contacting the invertebrates or their 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 with a composition comprising at least one such compound and an effective amount of at least one additional biologically active compound or agent.
  • 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.
  • Compounds can also be effective by topical application of a composition comprising a compound of this invention 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, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • the compounds of this invention may also be impregnated into materials for fabricating invertebrate control devices (e.g. insect netting).
  • a compound 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) an active ingredient, namely a compound of Formula I, an N-oxide, or agronomic or nonagronomic suitable 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 ingredient; about 40-99% food material and/or attractant; and optionally about 0.05-10% humectants; can be 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.
  • 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 an invertebrate pest including individually or in combinations 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 in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • a preferred method of application involves spraying a water dispersion or refined oil solution of the compounds.
  • Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide can 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 compound or composition of the present invention and a propellant.
  • propellants include, but are not limited to, methane, ethane, propane, iospropane, butane, isobutane, butene, pentane, iospentane, neopentane, pentene, hydrofluorocarbons, chlorofluoroacarbons, dimethyl ether, and mixtures of the foregoing.
  • a spray composition used to control an invertebrate pest
  • an invertebrate pest including individually or in combinations mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like.
  • 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.
  • a ⁇ H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (bs)-broad singlet, (br d)-broad doublet, (br q)-broad quartet, (br t)-broad triplet, (bm)-broad multiplet.
  • 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 SUI2 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. Test compounds were sprayed at 250 ppm and 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 °C and 70% relative humidity. Plant feeding damage was then visually assessed based on foliage consumed.
  • test unit For evaluating control of corn planthopper (Peregrinus maidis) through contact and/or systemic means, the test unit consisted of a small open container with a 3-4 day old corn (maize) plant (spike) inside. White sand was added to the top of the soil prior to application. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. After spraying, the test units were allowed to dry for 1 hour before they were post-infested with 10-20 corn planthoppers (18- to 20-day old nymphs) by sprinkling them onto the sand with a salt shaker. A black, screened cap was placed on the top of the cylinder.
  • test units were held for 6 days in a growth chamber at 19-21 °C and 50-70% relative humidity. Each test unit was then visually assessed for insect mortality. Of the compounds tested, the following resulted in at least 80% mortality: Al, A2, A5, A7, A8, A9, A10, A12, A13, A14, A15, A18, A20, A21, A23, A28, A29, A31, A34, A43, A45, A46, Bl, B3, B4, B5, B6, B8, CI, Dl, D3, El, E3, E4, E18, E23, E27, E29, E75, E77, E79, E80, E81, E82, F17, F20, F24, F25, F32, F36, F40, F58, F59, F78, F79, G7, G8, Gil, G13, G14, G15, G16, G17, G18, G21, G22, G23, G26, G42, J3, J6.
  • test unit For evaluating control of green peach aphid (Myzus persicae) through contact and/or systemic means, the test unit consisted of a small open container with a 12-15-day-old radish plant inside. This was pre-infested by placing on a leaf of the test plant 30-40 aphids on a piece of leaf excised from a culture plant (cut-leaf method). The larvae moved onto the test plant as the leaf piece desiccated. After pre-infestation, the soil of the test unit was covered with a layer of sand. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A.
  • 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 19-21 °C and 50- 70% relative humidity. Each test unit was then visually assessed for insect mortality.
  • test unit For evaluating control of the Root Knot Nematode (Meloidogyne incognita) through contact and/or systemic means, the test unit consisted of a small open container with a 7-9 day old tomato plant inside. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. After spraying, the test units were allowed to dry for 1 hour and then about 250 juvenile stages 2 (J2) larvae were pipetted into the soil and then a black, screened cap was placed on top. The test units were held for 6 days at 25 °C and 65-70% relative humidity. Each test unit was then visually assessed for root damage.
  • J2 juvenile stages 2
  • 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 5-6 day old Longio bean plant (primary leaves emerged) inside. White sand was added to the top of the soil and one of the primary leaves was excised prior to application. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. 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 19-21 °C and 50-70% relative humidity.
  • test unit was then visually assessed for insect mortality. Of the compounds tested, the following resulted in at least 80% mortality: A8, AlO, A15, A16, A28, A31, A43, CI, Dl, E10, E18, E19, E27, E29, F29, F36, F58, F59, F64, G7, Gil, G13, G14, G20, G23, G24.
  • TEST F For evaluating control of cotton melon aphid (Aphis gossypii) through contact and/or systemic means, the test unit consisted of a small open container with a 6-7-day-old cotton plant inside.
  • Test compounds were formulated and sprayed at 250 ppm as described for Test A.
  • test units were maintained in a growth chamber and then visually assessed for insect mortality Of the compounds tested, the following resulted in at least 80% mortality: A2, A8, A9, A12, A14, A15, A21, A28, A31, A42, A43, A45, A47, B5, CI, Dl, D2, D3, D4, D5.
  • TEST G For evaluating control of the Western Flower Thrip (Frankliniella occidentalis) through contact and or systemic means, the test unit consisted of a small open container with a 5-7 day old Longio Bean plant inside. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A.
  • test units were allowed to dry for 1 hour and then 22-27 adult thrips were added to the unit and then a black, screened cap was placed on top. The test units were held for 7 days at 25 °C and 45-55% relative humidity.
  • the following provided excellent levels of plant protection (20% or less feeding damage): Al, A2, A5, A7, A8, AlO, All, A12, A14, A15, A16, A18, A23, A25, A28, A29, A31, A34, A36, A38, A42, A43, A45, A46, A47, B7, CI, C2, C4, C5, Dl, D2, D3, D4, D5, E18, E23, E27, E29, E31, E51, E52, E71, E72, E75, E77, E78, E79, E82, F5, F13, F16, F18, F31, F32, F33, F34, F35, F36, F40, F58, F
  • test unit For evaluating control of adult two-spotted spider mite (Tetranychus urticae) through contact and or systemic means, the test unit consisted of a small open container with a 7-day- old Soliel bean plant inside. The test plant was pre-infested by placing cut leaves bearing 25- 50 adult two-spotted spider mites on the test plant leaves. Overhead fluorescent lights were used to induce migration of the mites from the cut leaves to the underside of the leaves of the test plants, which occurred over the course of 18 hr. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. 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 °C and 50-70% relative humidity. Each test unit was then visually assessed for adult mite mortality. Of the compounds tested, the following resulted in at least 80% mortality: A2, A3, A4,

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Abstract

Disclosed are compounds of Formula I, and their N-oxides and suitable salts thereof, which are useful for controlling invertebrate pests. I wherein Q is Q-1 or Q-2; Y is H, F, Cl or CH3; A is CN, C1-C6 alkyl, ORla, SRla, NRlaR2a or CONR1bR2b; Z is O, S or NR3; W is N or CR4; and J1, J2, Rla, R2a, R1b, R2b, R3, R4, R10 and n are as defined in the disclosure. Also disclosed are methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula I, an N-oxide thereof or a suitable salt of the compound (e.g., as a composition described herein). This invention also pertains to a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I, an N-oxide thereof or a suitable salt of the compound and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent.

Description

TNSECTICIDAL AND NEMATICID AL DIFLUOROALKENE DERIVATIVES BACKGROUND OF THE INVENTION This invention relates to certain fluorobutenyl compounds, their N-oxides, salts and compositions suitable for agronomic and nonagronomic uses, including those uses listed below, and methods of their use for controlling invertebrate pests in both agronomic and nonagronomic environments. 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, 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 which are more effective, less costly, less toxic, environmentally safer or have different modes of action. US 3,510,503 discloses trifluorobutenyl thioureas of Formula i as herbicides or nematocides X II CF2=CFCH2CH2S C— R i wherein, ter alia, X is phenylimino, chlorophenylimino, or Cj-Cg alkylimino; and R is CrCio alkylamino, C2-C20 dialkylamino, or alkylthio. PCT Patent Publication WO 88/00183 discloses trifluorobutenyl thiocarbonic acid esters of Formula ii which exhibit nematicidal and anthelmintic activity X II CF2=CFCH2CH2S C— ■ Y ii wherein, inter alia, X is ΝR1 or S; Y is SR or ΝR2R3; R is alkyl or haloalkyl; R1 is alkyl or cyano; R2 is H or alkyl; and R3 is phenyl or pyridinyl. WO 94/06777 discloses difluorobutenyl pyrimidines of Formula iii as nematocides, insecticides, acaricides, or fungicides
Figure imgf000002_0001
iii wherein, ter alia, R2, R3and R4 are each independently H, halogen, alkyl, optionally substituted aryl. SUMMARY OF THE INVENTION This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides thereof, agronomically or nonagronomically suitable salts thereof, agricultural and nonagricultural compositions containing them, and their use for controlling invertebrate pests:
Figure imgf000003_0001
wherein Q is Q-l or Q-2;
Figure imgf000003_0002
Q-l Q-2 Y is H, F, CI or CH3; A is CΝ, CrC6 alkyl, ORl , SRla, ΝRlaR2a or CONRlbR2b; Z is O, S or NR3; W is N or CR4; J1 and I2 are CrC6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl, C4-C8 cycloalkylalkyl, Cι-C alkoxy, C2-Cg alkoxycarbonyl or C2-Cg alkylcarbonyl, each optionally substituted with one G and each optionally substituted with one or more R5; or J1 and J2 are G, NO2, CN, OH, NR6R7, CONR6R7, OCONR6R7, CΓC4 alkylsulfonyl, C(O)G or S(O)2G; each G is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9-, or 10-membered fused heterobicyclic ring system, each ring or ring system optionally substituted with 1 to 5 R8; Rla and Rlb are H; G; CN; or CrC6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl or C4-Cg cycloalkylalkyl, each optionally substituted with one or more substituents selected from the group consisting of G, halogen, CN, NO2, CrC4 alkoxy, CrC4 alkylthio, CrC4 alkylsulfinyl, Cι-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl, C1-C4 alkylamino, C2~Cg dialkylamino and C3-Cg cycloalkylamino; R2a and R2b are H; or CrC6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl or C4-Cg cycloalkylalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, CrC4 alkoxy, C1-C4 alkylthio, Cι-C alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl, Ci~C4 alkylamino, C2-C8 dialkylamino and C3-C6 cycloalkylamino; or Rla and R2a or Rlb and R2b are taken together with the nitrogen to which they are attached to form a ring including 2 to 5 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring optionally substituted with 1 to 2 R5; R3 is H, CrC6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl or C4-C8 cycloalkylalkyl; R4 is H, CrC4 alkyl or CN; or R4 is a phenyl ring optionally substituted with 1 to 5 R8; each R5 is independently halogen, CN, NO2, Cι -Cg alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-Cg cycloalkyl, Cj-Cg haloalkyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, C3-Cg halocycloalkyl, C^-C alkoxy, Cι-C4 haloalkoxy, Cι~C alkylthio, Cι-C4 alkylsulfinyl, C1-C alkylsulfonyl, C1-C4 haloalkylmio, C1-C4 haloalkylsulfinyl, Cι~C4 haloalkylsulfonyl, Cι-C4 alkylamino, C2-Cg dialkylamino, C3-Cg cycloalkylamino, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl; R6 and R7 are each independently H; or Cι-C6 alkyl, C3-C6 alkenyl, C3-Cg alkynyl, C -Cg cycloalkyl, C2-Cg alkylcarbonyl or C2-C5 alkoxycarbonyl, each optionally substituted with halogen; or R6 and R7 can be taken together with the nitrogen to which they are attached to form a ring which includes 2 to 5 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring optionally substituted with halogen; each R8 is independently halogen, CN, NO2, Cι-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, CrC6 haloalkyl, C2-Cg haloalkenyl, C2-C6 haloalkynyl, C3-Cg halocycloalkyl, C1-C4 alkoxy, Cι -C haloalkoxy, Cι-C4 alkylthio, Cι-C4 alkylsulfinyl, CrC4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkylcarbonyl or C2-C6 alkoxycarbonyl; or each R8 is independently a phenoxy ring or a phenyl ring, each ring optionally substituted with 1 to 5 R5; R10 is H; or CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl or C4-C8 cycloalkylalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, C1-C4 alkoxy, C1-C4 alkylthio, C1-C alkylsulfinyl, Cι-C alkylsulfonyl, C2-C4 alkoxycarbonyl, CrC4 alkylamino, C2-C8 dialkylamino and C3-C6 cycloalkylamino; or R10 is CrC6 alkylthio, CN, CO2R12, CONR12Rl3 or phenyl optionally substituted with 1 to 5 R11; each R11 is independently halogen, CN, NO2, Cι-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, Cι-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, Cj-C4 alkoxy, C1-C haloalkoxy, CrC4 alkylthio, Cι-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C haloalkylthio, CrC haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3-Cg cycloalkylamino, C2-C alkylcarbonyl, or C2-C5 alkoxycarbonyl; R12 and R13 are each independently H or Cj-C6 alkyl; and n is 1, 3 or 5; provided that (1) when Y is F, Z is S, n is 1, A is SRla, NRlaR2a and W is N, then I1 is other than alkyl, G, CN or cycloalkyl; (2) J1 is other than 3-(4-trifluoromethyl)pyridinylcarbonyl or an N-oxide thereof; (3) when R10 is H, methyl, ethyl, phenyl or 4-fluorophenyl, and J2 is phenyl substituted with R8, then R8 is other than 2-fluoroethoxy; '(4) 'when Z is ΝH, W is Ν, and A is SRla, then J1. is other than phenyl substituted at the 2 and the 6 positions with alkyl or cycloalkyl; and (5) when Z is ΝR3, W is Ν or CH, A is ΝRlaR2a, and Rla or R2a is H or alkyl, then J1 is other than CN or NO2. This invention also provides a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I, an N-oxide or an agronomic or nonagronomic suitable salt thereof; and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said composition optionally further comprising an effective amount of at least one additional biologically active compound or agent. 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, its N-oxide or an agronomically or nonagronomically suitable salt thereof, or with a biologically effective amount of a composition comprising a compound of Formula I, an N-oxide or an agronomically or nonagronomically suitable salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent, said composition optionally further comprising an effective amount of at least one additional biologically active compound or agent. This invention further provides a spray composition comprising a compound of
Formula I, an N-oxide, or an agronomically or nonagronomically suitable salt thereof or the composition described above; and a propellant. This invention also provides a bait composition comprising a compound of Formula I, an N-oxide or a suitable salt thereof; one or more food materials; optionally an attractant; and optionally a humectant. This invention further provides 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. 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, z-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. "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "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. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. The term "cycloalkylamino" includes the cycloalkyl groups linked through a nitrogen atom such as cyclopentylamino and cyclohexylamino. Examples of "alkylcarbonyl" include CH3C(O), CH3CH2CH2C(O) and (CH3)2CHC(O). Examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. The term "heteroaromatic ring" denotes a fully aromatic heterocyclic ring in which at least one ring atom is not carbon and which comprises 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring includes no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs (where aromatic indicates that the Hϋckel rule is satisfied). The term "aromatic polycyclic ring system" denotes polycyclic ring system comprising carbocycles and heterocycles in which at least one ring of the polycyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied for the ring system). The term "aromatic heterobicyclic ring system" denotes a bicyclic ring which contains at least one heteroatom and in which at least one ring of the bicyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied). The heteroaromatic rings or heterobicyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. 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 can be partially or fully substituted with halogen atoms which can be the same or different. Examples of "haloalkyl" include F3C, C1CH2, CF3CH2 and CF3CC12. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)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 CC13S, CF3S, CC13CH2S and C1CH2CH2CH2S. 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. The total number of carbon atoms in a substituent group is indicated by the "Cj-Cj" prefix where i and j are numbers from 1 to 8. For example, Cι-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C4 cycloalkylalkyl designates cyclopropylmethyl; C5 cycloalkylalkyl designates, for example, cyclopropylethyl or cyclobutylmethyl; and Cζ, cycloalkylalkyl designates the various ring size of a cycloalkyl group substituted with an alkyl group containing a total of six carbon atoms, examples including cyclopentylmethyl, 1- cyclobutylethyl, 2-cyclobutylethyl and 2-cyclopropylpropyl. In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. When a group contains a substituent which can be hydrogen, for example R3 or R4, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. 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 well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and -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. N. 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. 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 can be more active and/or can 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 agronomically or nonagronomically salts thereof. The compounds of the invention can be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. Agronomically and nonagronomically suitable 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. Agronomically and nonagronomically suitable salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine or triethylamine) or inorganic bases (e.g., ammonia, hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound includes an acidic group such as a carboxyhc acid or phenol. The term "optionally substituted" in connection with J1, J2, G, Rla, Rlb, R2a, R2b, R4, R6, R7, R8, R10 groups refers to groups that are unsubstituted or have at least one non- hydrogen substituent that does not extinguish the activity for controlling invertebrate pests possessed by the unsubstituted analog. A group substituted with one or more substituents means that one or more of the hydrogen on that group can be replaced by a substituent. Therefore, as the number of hydrogens of a' group is limited, the possible number of substituents is limited. An example of phenyl optionally substituted with one or more R8 is the ring illustrated as U-l in Exhibit 1, wherein Rv is H or R8 and r is an integer from 1 to 5. An example of a naphthyl group optionally substituted with 1 to 5 R8 is illustrated as U-85 in Exhibit 1, wherein Rv is H or R8 and r is an integer from 1 to 5. Examples of 5- or 6-membered heteroaromatic rings optionally substituted with R8 include the rings U-2 through U-53 illustrated in Exhibit 1 wherein Rv is H or R8 and r is an integer from 1 to 5 limited by the number of hydrogens on the rings. Examples of aromatic 8-, 9- or 10-membered fused heterobicyclic ring systems optionally substituted with 1 to 5 R8 include U-54 through U-84 illustrated in Exhibit 1, since the number of replaceable hydrogens is greater than 5, wherein Rv is H or R8 , and the number of R8 is limited by the definition of r, and r is an integer from 1 to 5. Although Rv groups are shown in the structures U-l through U-85, 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 R8. Note that some U groups can only be substituted with less than 4 Rv groups (e.g. U-14, U-15, U-l 8 through U-21 and U-32 through U-34 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 1 4
Figure imgf000010_0001
U-ll U-12 U-13 U-14 U-15
Figure imgf000010_0002
Figure imgf000011_0001
U-43 U-44 U-45 U-46 U-47
Figure imgf000011_0002
U-48 U-49 U-50 U-51 U-52
Figure imgf000011_0003
Figure imgf000012_0001
N(Rv)r "N (Rv)r *N N(RV): U-69 U-70 U-71 U-72
Figure imgf000012_0002
Figure imgf000012_0003
Embodiments of the present invention include: Embodiment 1. A compound of Formula I wherein Q is Q-l. Embodiment 2. A compound of Formula I wherein Q is Q-2. Embodiment 3. A compound of Formula I wherein J1 is C^-C^ alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl, C4-C8 cycloalkylalkyl, C -C4 alkoxy, C2-C6 alkoxycarbonyl or C2-Cg alkylcarbonyl, each optionally substituted with one G and each optionally substituted with one or more R5; or Embodiment 4. A compound of Embodiment 3 wherein J1 is Cχ-C4 alkoxy or C2~C4 alkoxycarbonyl, each optionally substituted with one or more R5. Embodiment 5. A compound of Formula I wherein J1 is G, NO2, CN, OH, NR6R7, CONR6R7, CrC4 alkylsulfonyl, C(O)G or S(O)2G. Embodiment 6. A compound of Formula I wherein J1 is CN, NO2, OH, Cι-C4 alkoxy, or phenyl optionally substituted with 1 to 5 R8; Embodiment 6a. A compound of Embodiment 6 wherein J1 is CN, NO2, OH or Cr C4 alkoxy. Embodiment 6b. A compound of Embodiment 6 wherein J1 is phenyl optionally substituted with 1 to 5 R8. Embodiment 7. A compound of Embodiment 6 wherein J1 is CN. Embodiment 8. A compound of Embodiment 6 wherein J1 is NO2.
Embodiment 9. A compound of Embodiment 5 wherein J1 is G or C(O)G. Embodiment 10. A compound of Embodiment 9 wherein J1 is a phenyl ring or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with 1 to 5 R8. Embodiment 11. A compound of Embodiment 10 wherein J1 is pyridinyl optionally substituted with 1 to 4 R8.
Embodiment 12. A compound of Formula I wherein J2 is Ci-Cg alkyl or phenyl optionally substituted with 1 to 5 R8. Embodiment 13. A compound of Embodiment 12 wherein J2 is C^-Cg alkyl. Embodiment 14. A compound of Formula I wherein I2 is G, CONR6R7, C1-C4 alkylsulfonyl, C(O)G or S(O)2G.
Embodiment 15. A compound of Embodiment 14 wherein J2 is phenyl or pyridinyl, each optionally substituted with 1 to 4 R8. Embodiment 16. A compound of Formula I wherein Y is H or F. Embodiment 17. A compound of Embodiment 16 wherein Y is H. Embodiment 18. A compound of Embodiment 16 wherein Y is F.
Embodiment 18a. A compound of Formula I wherein Y is H or CH3. Embodiment 19. A compound of Formula I wherein A is CN, Cj-Cg alkyl, ORla, SRla or NRlaR2a. Embodiment 20. A compound of Embodiment 19 wherein A is CN, Ci-Cg alkyl, ORla or NRlaR2a.
Embodiment 21. A compound of Embodiment 20 wherein A is CN. Embodiment 22. A compound of Embodiment 20 wherein A is C^-Cg alkyl. Embodiment 23. A compound of Embodiment 19 wherein A is ORla, SRla or NRlaR2a. Embodiment 24. A compound of Embodiment 23 wherein A is ORla.
Embodiment 25. A compound of Embodiment 23 wherein A is SRla. Embodiment 26. A compound of Embodiment 23 wherein A is NRlaR2a. Embodiment 27. A compound of Formula I wherein Z is S or NR3. Embodiment 28. A compound of Embodiment 27 wherein Z is S. Embodiment 29. A compound of Embodiment 27 wherein Z is NR3. Embodiment 30. A compound of Formula I wherein W is N or CH. Embodiment 31. A compound of Embodiment 30 wherein W is N. Embodiment 32. A compound of Embodiment 30 wherein W is CH.
Embodiment 33. A compound of Formula I wherein Rla is H; or CrC6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl or C4-C8 cycloalkylalkyl, each optionally substituted with halogen or C2-C4 alkoxycarbonyl. Embodiment 34. A compound of Embodiment 33 wherein Rla is H; or Ci-Cg alkyl, C2~Cg alkenyl or C3-Cg alkynyl, each optionally substituted with one to three halogen. Embodiment 35. A compound of Embodiment 34 wherein Rla is H, C C alkyl, C3- C4 alkenyl or C3-C4 alkynyl. Embodiment 35a. A compound of Embodiment 34 wherein Rla is H or Ci-Cg alkyl. Embodiment 35b. A compound of Embodiment 34 wherein Rla is Cj-Cg alkyl.
Embodiment 36. A compound of Formula I wherein R2a is H; or C1-C5 alkyl, C2-C6 alkenyl, C3-Cg alkynyl, C3-C7 cycloalkyl or C4-C8 cycloalkylalkyl, each optionally substituted with halogen or C2-C alkoxycarbonyl. Embodiment 37. A compound of Embodiment 36 wherein R2a is H; or C1 -Cg alkyl, C2-C alkenyl or C3-C6 alkynyl, each optionally substituted with one to three halogen. Embodiment 38. A compound of Embodiment 37 wherein R2a is H, Cχ-C4 alkyl, C3- C4 alkenyl or C3-C4 alkynyl. Embodiment 39. A compound of Embodiment 37 wherein R2a is H or Cj-Cg alkyl. Embodiment 40. A compound of Formula I wherein Rla and R2a are taken together with the nitrogen to which they are attached to form a ring including 2 to 5 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, and said ring optionally substituted with 1 to 2 R5. Embodiment 41. A compound of Formula I wherein R3 is H or Cχ-C6 alkyl. Embodiment 42. A compound of Embodiment 41 wherein R3 is H.
Embodiment 43. A compound of Formula I wherein R5 is halogen, C1-C4 alkyl, C^- C4 alkoxy, CN, NO2, CF3 or OCF3. Embodiment 44. A compound of Formula I wherein R8 is halogen, Cι-C4 alkyl, C - C4 alkoxy, CN, NO2, CF3 or OCF3. Embodiment 45. A compound of Formula I wherein R10 is H, Cι -Cg alkyl, C1 -Cg alkylthio, CONR12R13, CN or phenyl optionally substituted with 1 to 5 R11. Embodiment 45a. A compound of Formula I wherein R10 is H, C^-Cg alkyl, Ci-Cg alkylthio, CONR12R13 or phenyl optionally substituted with 1 to 5 R11. Embodiment 46. A compound of Formula I wherein n is 1, 3 or 5. Embodiment 47. A compound of Embodiment 46 wherein n is 1 or 3. Embodiment 48. A compound of Embodiment 47 wherein n is 1. Embodiment 49. A compound of Formula I wherein when J1 is C(O)G, then G is other than optionally substituted 3-pyridinyl. Embodiment 50. A compound of Formula I wherein when J1 is C(O)G, then G is other than optionally substituted pyridinyl. Embodiment 51. A compound of Formula I wherein when I2 is phenyl substituted with R8, then R8 is other than fluoroalkoxy. Embodiment 52. A compound of Formula I wherein when J2 is phenyl substituted with R8, then R8 is other than haloalkoxy. Embodiment 53. A compound of Formula I wherein when J2 is phenyl substituted with R8, then R8 is other than haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl. Embodiment 54. A compound of Formula I wherein when Z is NH, W is N, and A is SRla, then I1 is other than phenyl substituted at the 2 and 6 positions and optionally at other positions. Embodiment 55. A compound of Formula I wherein when Z is NH, W is N, and A is SRla, then I1 is other than optionally substituted phenyl. Embodiment 56. A compound of Formula I wherein when Z is NR3, W is N or CH, J1 is CN or NO2, then A is other than NRlaR2a. Combinations of Embodiments 1-56 are illustrated by: Embodiment A. A compound of Formula I wherein Q is Q-l; J1 is G; or CrC6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl, C4- Cg cycloalkylalkyl, C -C4 alkoxy, C2-Cg alkoxycarbonyl or C2-C,5 alkylcarbonyl, each optionally substituted with one G and each optionally substituted with one or more R5. Embodiment B. A compound of Embodiment A wherein Y is H orF; A is CN, CrC6 alkyl, ORla or NRlaR2a; Z is S; W is N; Rla and R2a are each independently H, CrC4 alkyl, C3-C4 alkenyl, C3-C4 alkynyl; and R5 and R8 are each independently halogen, Ci -C4 alkyl, Cχ-C4 alkoxy, CN, NO2, CF3 or OCF3. Embodiment C. A compound of Formula I wherein Q is Q-l; J1 is G, NO2, CN, OH, NR6R7, CONR6R7, CrC4 alkylsulfonyl, C(O)G or S(O)2G. Embodiment D. A compound of Embodiment C wherein Y is H or F; A is ORla, SRla or NRlaR2a; W is N or CH; Rla and R2a are each independently H, CrC6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl or C4-Cg cycloalkylalkyl, each optionally substituted with one to three halogen; Rla and R2a can be taken together with the nitrogen to which they are attached to form a ring including 2 to 5 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, and said ring can be optionally substituted with 1 to 2 R5; R3 is H or CrC4 alkyl; R5 and R8 are each independently halogen, Cχ-C4 alkyl, Cχ-C4 alkoxy, CN, NO2, CF3 or OCF3; and n is 1 or 3. Embodiment E. A compound of Formula I wherein Q is Q-l; Y is H; Z is S; W is N; A is NRlaR2a; J1 is phenyl optionally substituted with 1 to 5 R8; Rla and R2a are each independently H or C^-Cg alkyl; and n is 1 or 3. Embodiment F. A compound of Formula I wherein Q is Q-2; Y is H; J2 is Ci-Cg alkyl or phenyl optionally substituted with 1 to 5 R8; R10 is H, CrC6 alkyl, CrC6 thioalkyl, CONR12R13 or phenyl optionally substituted with 1 to 5 R11; and n is 1 or 3. Embodiment G. A compound of Formula I wherein Q is Q-2; Y is F; J2 is Cj-Cg alkyl or phenyl optionally substituted with 1 to 5 R8; R10 is H, CrC6 alkyl, CrC6 alkylthio, CONRl2Rl3 or phenyl optionally substituted with 1 to 5 R11; and n is 1 or 3. Embodiment H. A compound of Formula I wherein Q is Q-l; Y is H; Z is S; A is SRla; W is N; J1 is CN, NO2, OH, CrC4 alkoxy, or phenyl optionally substituted with 1 to 5 RS; Rla is CrC6 alkyl; and n is 1 or 3. Embodiment I. A compound of Formula I wherein Q is Q-l; Y is H or CH3; Z is S; A is ORl or SRla; W is N; and J1 is CN. 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 1-17. The definitions of J1, J2, Rla, R2a, R3, n, Q, Q-l and Q-2 in the compounds of Formulae Ia-Ij and Formulae 2-25 below are as defined above in the Summary of the Invention. Compounds of Formulae Ia-Ij are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-Ij are as defined above for Formula I. Compounds of Formula I can be prepared by the general methods of reacting functionalized 1,1-difluoroalkenes 2 with substituted intermediates of Formula 3 as outlined in Scheme 1. The substituent Xa represents organic functional group suitable in well established coupling reactions involving nucleophilic substitution. For reactions where Xa is a leaving group such as CI, Br or I then Qa contains a nucleophilic group such as sulfur, nitrogen or oxygen. In the reverse sense if Xa contains a nucleophilic group such as sulfur, nitrogen or oxygen then Qa contains a leaving group such as halogen, alkoxy, alkylthio and the like. These reactions employ a wide assortment of bases, solvents and conditions. The following schemes are intended to provide examples of the varied procedures useful for the preparation of compounds of Formula I. Scheme 1
Figure imgf000018_0001
Compounds of Formula la can be prepared by the reaction of thioureas of Formula 4 with fluorobutenyl derivatives of Formula 5 wherein X is halogen (e.g., CI, Br, I), OS(O)2CH3 (methanesulfonate), OS(O)2CF3, OS(O)2Ph-/?-CH3 (p-toluenesulfonate) and the like as outlined in Scheme 2. Suitable bases for the reaction include inorganic bases, such as alkali or alkaline earth metal (such as lithium, sodium, potassium, cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides, and organic bases, such as triethylamine, N,N-diisopropylethylamine and l,8-diazabicyclo[5.4.0]undec-7-ene. Preferred bases are potassium carbonate and potassium hydroxide. A wide variety of solvents are suitable for the reaction, including, for example but are not limited to, NN-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water, as well as mixtures of these solvents. This reaction can be conducted between about 0 to about 120 °C, and preferably between about 0 and 30 °C. Further procedural details for the method of Scheme 2 can be found in Examples 1 and 2. Difluoroalkenyl compounds of Formula 5 are known in the art. For literature procedures to prepare compounds of Formula 5 see PCT Patent Publications WO 94/6777,
WO 95/4727, WO 97/09292, and especially WO 99/52874. For other references related to the difluoroalkenyl compounds see J. Am. Chem. Soc. 1983, 195, 4634-4639; J. Org. Chem. 1991, 56, 1037-1041; and J. Chem. Soc. Perkin 2, 1998, 219-231. Scheme 2
Figure imgf000019_0001
4 la
Thioureas of Formula 4 are well known in the literature and can be readily prepared by the reaction of isothiocyanates of Formula 6 with mono- and dialkylamines of Formula 7 as shown in Scheme 3. The compounds of Formula 6 are either known compounds or can be prepared from amines and thiophosgene. The reaction can be run in a variety of suitable solvents such as acetone, acetonitrile, tetrahydrofuran and dichloromethane. The synthesis methods of Schemes 2 and 3 are illustrated with greater detail in Examples 1 and 2. Scheme 3
Figure imgf000019_0002
6 7 4 As outlined in Scheme 4, compounds of Formula lb (Formula I where Q is Q-2) can be prepared by the reaction of oximes of Formula 9 with fluorobutenyl compounds of Formula
5, X is a nucleophilic reaction leaving group such as halogen (e.g., CI, Br, I), OS(O)2CH3
(methanesulfonate), OS(O)2CF3, OS(O)2Ph-/?-CH3 (p-toluenesulfonate), and the like. The reactions can be conducted in a variety of solvents such as tetrahydrofuran, N,N- dimethylformamide, dichloromethane, acetone or acetonitrile with optimum temperatures ranging from room temperature to the reflux temperature of the solvent. Suitable bases for this reaction include potassium carbonate, sodium carbonate, sodium hydride and potassium tert-butoxide. The method of Scheme 4 is illustrated in Examples 3 and 4. Scheme 4
Figure imgf000020_0001
Oximes of Formula 9 are well known in the literature. As shown in Scheme 5, many of these can be readily prepared by the reaction of aldehydes or ketones of Formula 10, where R10 and J2 are, for example, H, alkyl or aryl groups, with hydroxylamine hydrochloride in a suitable solvent such as ethanol, water or dioxane at temperatures ranging from room temperature to the reflux temperature of the solvent A base is needed to liberate hydroxylamine from its salt. Suitable bases for the reaction include, but are not limited to, sodium hydroxide, sodium bicarbonate or sodium carbonate. Scheme 5
Figure imgf000020_0002
10 9 As shown in Scheme 6, compounds of Formula Ic can be prepared by the reaction of compounds of Formula 11 with difluoroalkenyl compounds of Formula 5 in the presence of a base. Typical J1 values for compounds of Formula Ic include phenyl, 5- or 6-membered heteroaromatic ring, CN, alkylcarbonyl and alkoxycarbonyl. In the difluoroalkenyl compounds of Formula 5, X is a leaving group as defined in Scheme 4. Suitable bases for the reaction include inorganic bases, such as alkali or alkali earth metal (such as lithium, sodium, potassium, cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides, and organic bases, such as triethylamine, N,N-diisopropylethylamine and 1,8-diazabicyclo- [5.4.0]undec-7-ene. Preferred bases are potassium carbonate and potassium hydroxide. Preformed salts of compounds of Formula 11 can also be used in lieu of using a base. A wide variety of solvents can be suitable for the reaction, which include, for example, but are not limited to NN-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of the suitable solvents. This reaction can be conducted between about 0 to about 120 °C, and preferably between about 0 and 30 °C. Scheme 6
A
Figure imgf000021_0001
is ORla orSRla 11 Ic As shown in Scheme 7, compounds of Formula Id can be prepared by the reaction of compounds of Formula 12 with an alkylating agent of Formula 13 in the presence of a base. In the alkylating agent of Formula 13, X is a leaving group as defined in Scheme 4 for Formula 5. Suitable bases for the reaction include inorganic bases and organic bases as described above for Scheme 6. Preferred bases are potassium carbonate and potassium hydroxide. Preformed salts of compounds of Formula 12 can also be used in lieu of using a base. A wide variety of solvents can be suitable for the reaction, which include but are not limited to N,N-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of these solvents. This reaction can be conducted between about 0 to about 120 °C. Additional details for this reaction can be found in Example 5. Scheme 7
Figure imgf000021_0002
As shown in Scheme 8, compounds of Formula 11 can be prepared by the reaction of amines of Formula 14 with a compound of Formula 15 in the presence of base. In the compounds of Formula 15, L is halogen (e.g., CI, Br, I), sulfonate (e.g. OS(O)2CH3 (methanesulfonate), OS(O)2CF3, OS(O)2Ph-p-CH3 (p-toluenesulfonate)), or azole (e.g. imidazoie, 3,5-dimethylpyrazole, benzimidazole, benzotriazole, indazole, pyrazole, and 1,2,4-triazole). Suitable bases for the reaction include inorganic bases and organic bases as described above. Preferred bases are amine bases such as triethylamine and N,N- diisopropylethylamine. A wide variety of solvents can be suitable for this reaction, which include but are not limited to N,N-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of these solvents. This reaction can be conducted between about 0 to about 120 °C.
Scheme 8
Figure imgf000022_0001
14 15 11
As shown in Scheme 9, dithiocarbamates of Formula Ila can be prepared by the reaction of carbon disulfide with amines of Formula 14 followed by reaction with an alkylating agent of Formula 13. For a review of dithiocarbamate chemistry see Angewdndte Chem., Int. Ed., 1967, 6, 281-293. Suitable bases for the reaction include inorganic bases and organic bases as described above for the reaction shown in Scheme 2. Preferred bases are potassium carbonate, cesium carbonate, potassium hydroxide and sodium hydroxide. A wide variety of solvents are suitable for this reaction, which include but are not limited to N,N-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of these solvents. This reaction is conducted between about 0 to about 120 °C. Scheme 9
Figure imgf000022_0002
14 Ila As shown in Scheme 10, dithiocarbamates of Formula 12 can be prepared by reacting compounds of Formula 16 with an amine of Formula 14 and a suitable base. In the compounds of Formula 16, L is defined above as in compounds of Formula 15. Preferred bases are amine bases such as triethylamine and N,N-diisopropylethylamine. A wide variety of solvents can be suitable for this reaction, which include but are not limited to N,N-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of the suitable solvents. This reaction can be conducted between about 0 to about 120 °C.
Figure imgf000023_0001
As shown in Scheme 11, dithiocarbamates of Formula 12 can also be prepared by the reaction of carbon disulfide with an amine of Formula 14 followed by reaction with a difluoroalkenyl compound of Formula 5. For a review of dithiocarbamates chemistry see Angewandte Chem., Int. Ed., 1967, 6, 281-293. Preferred bases are potassium carbonate, cesium carbonate, potassium hydroxide and sodium hydroxide. A wide variety of solvents can be suitable for this reaction, which include but are not limited to NN-dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, acetone, alcohols and water as well as mixtures of the suitable solvents. This reaction can be conducted between about 0 to about 120 °C. For leading references to prepare dithiocarbamates of Formula 12 see, Tetrahedron Lett, 2001, 42, 2055-2058, and Tetrahedron, 2002, 58, 3329- 3347. '_ Scheme 11
Figure imgf000023_0002
As shown in Scheme 12, dithiocarbonylazoles of Formula 17 (Formula 16 where L is an azole) can be prepared by the reaction of carbon disulfide with an azole followed by reaction with difluoroalkenyl compounds of Formula 5. Suitable azoles include, for example, but are not limited to imidazoie, 3,5-dimethylpyrazole, benzimidazole, benzotriazole, indazole, pyrazole, 1,2,4-triazole and N-alkylimidazolium. For leading references to prepare dithiocarbonylazoles see, Tetrahedron, 2000, ■56', 629-637, J. Org. Chem., 1978, 43, 337-339, and the references cited therein. Scheme 12
Figure imgf000024_0001
5 17 Intermediates of Formula lib can be synthesized by the reaction of isothiocyanates of Formula 18 with alcohols of Formula 19 as shown in Scheme 13. The reaction can be carried out in a wide variety of solvents and temperatures. If the compounds of Formula 18 and 19 are liquids, a solvent may not be needed. Preferred solvents include tetrahydrofuran, N,N-dimethylformamide, dichloromethane, acetone or acetonitrile, and optimum temperatures range from room temperature to the reflux temperature of the solvent. Intermediates of Formula lib can be converted to compounds of Formula Ie, a subset of the compounds of Formula I, by the method described previously in Scheme 6. Scheme 13
Figure imgf000024_0002
18 lib Ie As shown in Scheme 14, an isothiocyanate of Formula 18 can be reacted with an alcohol of Formula 20 to produce an intermediate of Formula 21. Compounds of Formula 21 can then be transformed to compounds of Formula If by methods outlined in Scheme 7. The reaction of alcohols of Formula 20 with isothiocyanates may be carried out in a wide variety of solvents and temperatures. It may also be carried out without the need for solvent. Preferred solvents include tetrahydrofuran, dimethylformamide, dichloromethane, acetone or acetonitrile with optimum temperatures ranging from room temperature to the reflux temperature of the solvent. The alcohols of Formula 20 are known compounds. Scheme 14
Figure imgf000024_0003
Compounds of Formula 23 can be made as shown in Scheme 15 by the reaction of an amine of Formula 22 with an isothiocyanate of Formula 18. The reaction of amines of Formula 22 with isothiocyanates can be carried out in a wide variety of solvents and temperatures. If the compounds of Formula 18 and 23 are liquids, a solvent may not be needed. Preferred solvents include tetrahydrofuran, N,N-dimethylformamide, dichloromethane, acetone or acetonitrile, and optimum temperatures range from room temperature to the reflux temperature of the solvent. Compounds of Formula 23 can be further transformed to compounds of Formula Ig by reaction with an alkyl halide of Formula 13 as outlined in Scheme 15. The amines of Formula 22 are known compounds. Scheme 15
Figure imgf000025_0001
Compounds of Formula 24 can be made as shown in Scheme 16 by the reaction of KCΝ with an isothiocyanate of Formula 18. The reaction can be carried out in a variety of solvents and temperatures. Compounds of Formula 24 can be further transformed to compounds of Formula Ih by reaction with a difluoroalkenyl halide of Formula 5 as outlined in Scheme 6. Further details on the procedures for preparation of compounds of Formula Ih are provided in Example 11. Scheme 16
Figure imgf000025_0002
A useful procedure for the preparation of compounds of Formula Ii and Ij is shown in
Scheme 17. Compound Ii is prepared in a two step synthesis involving the reaction of a compound of Formula 14 with carbon disulfide in the presence of base followed by the addition of two equivalents of the difluoroalkenyl compound 5 to give the compound of Formula Ii. Selective displacement with one equivalent of either an amine or alcohol (Formula 25) affords the compound of Formula Ij. Examples 6, 9 and 10 provide further details for this method. Scheme 17
Figure imgf000026_0001
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 materials and methods described herein and the following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. 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. *H 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, bs means broad singlet, bt means broad triplet, and bm means broad multiplet. EXAMPLE 1
Preparation of 4,4-Difluoro-3-butenyl-N,-(2-fluorophenyl)-NN-dimethylcarbamimidothioate Step A: Preparation of 3-(2-Fluorophenyl)-l,l-dimethylthiourea To a 100 mL single-necked flask equipped with a magnetic stirrer and nitrogen inlet was charged 30 mL of acetonitrile and 2.0 g (0.013 mol) of 2-fluorophenyl isothiocyanate followed by 13.0 mL (0.026 mol) of 2 M dimethylamine in THF. The mixture was stirred at 25 °C for 18 h. The resulting mixture was concentrated in vacuo to a yellow solid, which was slurried in diethyl ether (150 mL). The solid was collected by filtration and air dried to afford (2.3 g, 89% yield) the title compound as a pale yellow solid. IH ΝMR (DMSO- 6) δ 8.89 (s, IH), 7.20 (m, 4H), 3.28 (s, 6H).
Step B: Preparation of 4,4-Difluoro-3-butenyl-N,-(2-fluorophenyl)-NN-dimethyl- carbamimidothioate To a 100 mL single-necked flask equipped with a magnetic stirrer and nitrogen inlet was charged 30 mL of acetone and 1.15 g (0.0058 mol) of 3-(2-fluorophenyl)-l,l-dimethyl- thiourea (i.e. the product of Step A). The resulting mixture was treated with 1.75 mL (0.0087 mol) of 4-bromo-l,l-difluoro-l-butene followed by 1.2 g (0.0087 mol) of potassium carbonate. The mixture was stirred at 25 °C for 18 h. The resulting mixture was filtered and concentrated. The residue was chromatographed- on silica gel using ethyl acetate/hexanes as eluent to give the title compound (0.594 g, 36% yield), a compound of the present invention, as a yellow oil.
IH ΝMR (CDC13) δ 7.0 (bm, 4H), 4.0 (dt, IH), 3.1 (s, 6H), 5 (bt, 2H), 2.12 (m, 2H). EXAMPLE 2
Preparation of 4,4-Difluoro-3-butenyl N-(2,4-difluorophenyl)-N,-methylcarbamimidothioate Step A: Preparation of l-(2,4-Difluorophenyl -3-methylthiourea To a 100 mL single-necked flask equipped with a magnetic stirrer and nitrogen inlet was charged 30 mL of acetonitrile and 4.0 g (0.024 mol) of 2,4-difluorophenyl isothiocyanate followed by 3.8 g (0.048 mol) of 40 wt% methylamine in ethanol. The mixture was stirred at 25 °C for 18 h. The resulting mixture was concentrated in vacuo to a yellow solid, which was slurried in diethyl ether (150 mL). The solid was collected by filtration and air dried to afford (3.7 g, 76% yield) of the title compound as a pale yellow solid. iH ΝMR (DMSO- 6) δ 9.23 (bs, IH), 7.76 (bs, IH), 7.51 (bs, IH), 7.30 (m, IH), 7.08 (m, IH), 2.90 (d, 3H).
Step B: Preparation of 4,4-Difluoro-3-butenyl N-fΣ^-difluorophenylVN'-methyl- carbamimidothioate To a 100 mL single-necked flask equipped with a magnetic stirrer and nitrogen inlet was charged 30 mL of acetone and 0.75 g (0.004 mol) of l-(2,4-difluorophenyl)-3-methyl- thiourea (i.e. the product of Step A). The resulting mixture was treated with 0.95 g (0.0056 mol) of 4-bromo-l,l-difluoro-l-butene followed by 0.773 g (0.005 mol) of potassium carbonate. The mixture was stirred at 25 °C for 18 h. The resulting mixture was filtered and concentrated. The residue was chromatographed on silica gel using ethyl acetate/hexanes as eluent to give the title compound (0.255 g, 22% yield), a compound of the present invention, as yellow oil.
!H NMR (CDC13) δ 6.84 (m, 3H), 4.72 (bs, IH), 4.17 (dt, IH), 2.95 (s, 3H), 2.77 (bm, 2H), 2.29 (bs, 2H). EXAMPLE 3 Preparation of l-(2,4-DichlorophenvDethanone O-(4,4-difluoro-3-butenyl oxime To a 100 mL single-necked flask equipped with a magnetic stirrer and nitrogen inlet was charged 30 mL of acetone and 0.5 g (0.0024 mol) of l-(2,4-dichlorophenyl)ethanone oxime followed by 0.55 g (0.0037 mol) of potassium carbonate and 0.628 g (0.0037 mol) of 4-bromo-l,l-difluoro-l-butene. After stirring at 25°C for 18 h, the mixture was filtered and concentrated to afford the title compound (0.129 g, 18% yield), a compound of the present invention, as an amber liquid. lR NMR (CDC13) δ 7.4 (m, IH), 7.24 (d, 2H), 4.24 (dt, IH), 4.17 (t, 2H)„ 2.39 (m, 2H) 2.19 (s, 3H). EXAMPLE 4 Preparation of Methyl N-r(4,4-difluoro-3-butenyl oxy1-2-(dimethylamino)-2-oxoethanimido- thioate To a 100 mL single-necked flask equipped with a magnetic stirrer and nitrogen inlet was charged 30 mL of acetone and 1.0 g (0.006 mol) of methyl 2-dimethylamino-N- hydroxy-2-oxoethanimidothionate followed by 1.66 g (0.012 mol) of potassium carbonate and 2.05 g (0.012 mol) of 4-bromo-l,l-difluoro-l-butene. After stirring at 25°C for 18 h, the mixture was concentrated. The residue was chromatographed on silica gel using ethyl acetate/hexanes as eluent to give the title compound (0.05 g, 3.3% yield), a compound of the present invention, as an amber liquid.
!H ΝMR (CDC13) δ 4.23 (dt, IH), 4.15 (t, 2H), 3.07(d, 6H), 2.36 (m, 2H), 2.27 (s, 3H). EXAMPLE 5
Preparation of 4,4-Difluoro-3-butenyl methyl cyanocarbonimidodithioate To a solution of cyanimidodithiocarbonic acid monomethylester mono potassium salt
(0.5 g) in N,N-dimethylformamide (5 mL) was added 4-bromo-l,l-difluorobutene (0.5 g) and the mixture was stirred at 23 °C for 20 hours. The reaction mixture was partitioned between 20 mL of water and ethyl acetate (2 x 50 mL). The combined organic layers were washed with water (4 x 20 mL), dried over magnesium sulfate and concentrated. The residue was chromatographed on silica gel using ethyl acetate/hexanes (gradient 1:9 to 1:1) as eluent to give the title compound (220 mg), a compound of the present invention, as yellow oil. !H NMR (C C13) δ 2.43 (2H), 2.66 (3H), 3.2 (2H), 4.2 (IH). EXAMPLE 6
Preparation of Bis(4.4-difluoro-3-butenyl) r3-chloro-5-(trifluoromethyl -2-pyridinyll carbonimidodithioate To a solution of 2-amino-3-chloro-5-trifluoromethylpyridine (688 mg, 3.50 mmol), cesium carbonate (1.1 g, 5.26 mmol), and tetrabutylammonium iodide (648 mg, 1.75 mmol) in anhydrous NN-dimethylformamide (5 mL) were added carbon disulfide (316 μL, 5.26 mmol) and 4-bromo-l,l-difluorobutene (300 mg, 1.75 mmol) sequentially at 0 °C. The reaction mixture was allowed to warm to room temperature and stirred for 5 hours. Then the reaction mixture was partitioned between water (3 x 30 mL) and ethyl acetate (30 mL). The organic layer was dried over magnesium sulfate and concentrated. The residue was chromatographed on silica gel using ethyl acetate/hexanes as eluent to give the title compound (120 mg), a compound. of the present invention, as a pale yellow oil. IH ΝMR (CDCI3) δ 8.57 (s, IH), 7.94 (s, IH), 4.25 (m, 2H); 3.2 (t, 4H), 2.45 (m, 4H). EXAMPLE 7 Preparation of Bis(4,4-difluoro-3-butenyl) cyanocarbonimidodithioate Step A: Preparation of dipotassium cvanodithioimidocarbonate To a stirred solution of cyanamide (21.2 g, 0.50 mol) and carbon disulfide (42 g, 0.55 mol) cooled with an ice-salt bath was added an alcohol solution of potassium hydroxide (56.2 g, 1.00 mol, in 180 mL of 95% ethanol) dropwise over 2.5 h. The reaction temperature was maintained below 10 °C. Upon completion of the addition, the reaction mixture was allowed to warm to room temperature and stirred overnight. The insoluble solid was removed by filtration, rinsed with 95% ethanol, and dried under vacuum to provide the dipotassium cyanodithioimidocarbonate (72 g, 0.37 mol) in 75% yield. Step B: Preparation of Bis(4,4-difluoro-3-butenyl) cyanocarbonimidodithioate A mixture of dipotassium cyanodithioimidocarbonate (3.0 g, 15.5 mmol) and 4-bromo- 1,1-difluoro-but-l-ene (7.9 g, 46.2 mmol) in methyl sulfoxide (20 mL) was stirred at 40 °C overnight. Then the reaction mixture was cooled to room temperature and partitioned between ethyl ether and water. The combined organic layers were washed with brine, dried (Νa2SO4) and concentrated. The residue was chromatographed to afford the title compound (4.0 g, 13.4 mmol, 87% yield), a compound of the present invention, as a pale yellow oil. IH NMR (CDCI3): 4.24 (dt, 2H), 3.23 (t, 4H), 2.44 (q, 4H). EXAMPLE 8 Preparation of S-(4.4-Difluoro-3-butenyl O-ethyl (ethoxycarbonv carbonimidothioate Step A: Preparation of Diethyl thioimidodicarbonate To 2.00 g (15.27 mmol) of ethoxycarbonyl isothiocyanate was added 20 mL of ethanol. The resulting solution was heated at 80 °C overnight. Removal of volatile organics in vacuo afforded 2.7 g of the title compound, mp 43-45 °C.
1H NMR (CDC13): δ 1.30 (t, 3H), 1.43 (t, 3H), 4.23 (q, 2H), 4.61 (q, 2H), 8.16 (bs, IH). Step B: Preparation of S-(4,4-Difluoro-3-butenyl) O-ethyl (ethoxycarbonyl carbonimido- thioate To a mixture of 47.00 g (265.54 mmol) of diethyl thioimidodicarbonate (i.e. the product of Step A) and 54.38 g (394.03 mmol) of potassium carbonate in 850 mL of acetone was added 49.95 g (292.09 mmol) of 4-bromo-l,l-difluorobut-l-ene. The resulting mixture was stirred at room temperature for around 3 days. The reaction mixture was filtered through Celite® (diatomaceous filter aid), washed with minimal acetone, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica using an automated collector and a gradient of hexanes to 90:10 hexanes: ethyl acetate. The resulting material was triturated with 100 mL of hexanes, cooled to -78 °C, and filtered to give 52.0 g of the title compound, mp 37-39 °C, a compound of the present invention. 1H NMR (CDCI3): δ 1.31-1.40 (m, 6H); 2.36 (m, 2H); 2.95 (t, 2H); 4.17-4.30 (m, 3H); 4.42 (q, 2H). EXAMPLE 9
Preparation of S-(4,4-Difluoro-3-butenyl') O-methyl cyanocarbonimidothioate To a stirred mixture of bis(4,4-difluoro-3-butenyl) cyanocarbonimidodithioate (i.e. the product of Example 7, 286 mg, 0.96 mmol) and MeOH (192 mg, 4.5 mmol) in acetonitrile (3 mL) was added a trace amount of sodium. After stirring at room temperature for 4.5 h, the reaction mixture was concentrated and the residue was purified by column chromatography to afford S-(4,4-difluoro-3-butenyl) O-methyl cyanocarbonimidothioate (17 mg, 0.083 mmol, 9% yield), a compound of the present invention, as a pale yellow oil. 1H NMR (CDCI3): 4.23 (dt, IH), 4.04 (s, 3H), 3.09 (t, 2H), 2.39 (q, 2H). EXAMPLE 10
Preparation of 4,4-Difluoro-3-butenyl N'-cyano-N.N-dimethylcarbamimidothioate A mixture of bis(4,4-difluoro-3-butenyl) cyanocarbonimidodithioate (i.e. the product of Example 7, 102 mg, 0.34 mmol) and dimethylamine (0.34 mL, 0.68 mmol, 2.0 M in THF) in acetonitrile (2 mL) was stirred at room temperature for 0.5 h. The reaction mixture was concentrated, and the residue was purified by column chromatography to afford 4,4-difluoro- 3-butenyl N'-cyano-NN-dimethylcarbamimidothioate (61 mg, 0.28 mmol, 81% yield), a compound of the present invention, as a pale yellow oil. IH ΝMR (CDC13): 4.25 (dt, IH), 3.41 (t, 2H), 3.26 (s, 6H), 2.41 (q, 2H). EXAMPLE 11 Preparation of 4,4-Difluoro-3-butenyl phenylcarbonocyanidimidothioate A mixture of 1-cyanothioformanalide (373 mg, 2.3 mmol), 1,1-difluoro-l-butenyl- bromide (314 μL, 2.8 mmol) and potassium carbonate (981 mg , 7.0 mmol) in 3 mL of acetonitrile was heated at 85 °C for 2 h. The reaction mixture was then filtered and concentrated in vacuo. The crude product was purified by chromatography on silica gel using ethyl acetate/hexanes (1:9 mixture) as eluent to give 326 mg of the title product, a compound of the present invention, as light yellow oil.
IH ΝMR (CDCI3): 7.40 (m, 2H), 7.27 (m, IH), 7.06 (m, 2H), 4.23 (m, IH), 3.25 (t, 2H), 2.45 (m, 2H). By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 8 can be prepared. The following abbreviations are used in the Tables which follow: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, z-Pr means isopropyl, Bu means butyl, Hex means hexyl, Ph means phenyl, SMe means methylthio, SO2Me means methylsulfonyl, SO2Et means ethylsulfonyl, SO2Ph means phenylsulfonyl, CΝ means cyano, ΝO2 means nitro, and 2-C1-4-F means 2-chloro-4-fluoro, and other substituent abbreviations are defined analogously. Table 1
Figure imgf000031_0001
Figure imgf000032_0001
-
Figure imgf000033_0001
Table 2
Figure imgf000033_0002
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Table 4
Figure imgf000039_0002
ll Rla n X Y ii Rla a Y
Me Me 1 s H Me Me 3 S H
Et Me 1 s H Et Me 3 S H i-Pr Me 1 s H i-Pr Me 3 S H
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Table 5
-
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Tat le 6
Figure imgf000047_0002
ii A Z n Y ii A Z n Y C02Me SMe S 1 H C02Me SMe S 1 F C02Me SEt s 1 H C02Me SEt S 1 F C02Me S-n-Pr s 1 H C02Me S-n-Pr S 1 F
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Tabl.3 7
Figure imgf000066_0002
ii A n Y ii A j 1 Y Ph CN H Ph CN F 2-Cl-Ph CN H 2-Cl-Ph CN F 2-F-Ph CN H 2-F-Ph CN F 2-Me-Ph CN H 2-Me-Ph CN F 2-OMe-Ph CN H 2-OMe-Ph CN F 2-SMe-Ph CN H 2-SMe-Ph CN F 2-CF3 -Ph CN H 2-CF3-Ph CN F
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Table ;8
Figure imgf000078_0002
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Formulation/Utilitv Compounds of this invention will generally be used as a formulation or composition with a carrier suitable for agronomic or 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 ingredient, 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 are 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 Inεredient 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 include 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, N,N-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, N,N-dimethylformamide, dimethyl sulfoxide, N-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 include materials lαiown as formulation aids like antifoams, film formers and dyes and are well lαiown to those skilled in the art. Antifoams can include water dispersible liquids comprising polyorganosiloxanes like 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 like 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. Compound numbers refer to compounds in Index Tables A-J. Example A Wettable Powder Compound Al 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%. Example B Granule Compound C5 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 Compound Dl 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 Compound E10 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% , isophorone ι 70.0%. Example E Microemulsion Compound E41 5.0% triacetine 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0% Example F Seed Treatment Compound G23 20.0% polyvinylpyrrolidone-vinyl acetate copolymer 5.0% montan acid wax 5.0% calcium ligninsulfonate 1.0% polyoxyethylene/polyoxypropylene block copolymers 1.0% stearyl alcohol (POE 20) 2.0% polyorganosilane 0.2% 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 non- agronomic invertebrate pests. (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 flatworms (Platyhelminthes), including tapeworms (Cestoda) and flukes (Trematoda); thorny-headed worms (Acanthocephala); and roundworms (Nematoda), including whipworms (Enoplida), free-living worms (Rhabdita), hookworms and lungworms (Strongylida), intestinal roundworms (Ascarida), pinworms (Oxyurida), filarial nematodes (Spirurida), and plant parasitic nematodes (Tylenchida and Dorylaimida). 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 cereal crops (e.g., wheat, oats, barley, rye, rice, maize), soybeans, vegetable crops (e.g., lettuce, cabbage, tomatoes, beans), potatoes, sweet potatoes, grapes, cotton, and tree fruits (e.g., pome fruits, stone fruits and citrus fruits). The term "nonagronomic" refers to other horticultural crops (e.g., forest, greenhouse, nursery or ornamental plants not grown in a field), turf (commercial, golf, residential, recreational, etc.), wood products, public health (human) and animal health, domestic and commercial structure, household, and stored product applications or pests. For reason of invertebrate pest control spectrum and economic importance, protection (from damage or injury caused by invertebrate pests) of agronomic crops of cotton, maize, soybeans, rice, vegetable crops, potato, sweet potato, grapes and tree fruit by controlling invertebrate pests are preferred 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 Hϋbner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworm (Herpetogramma 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 orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella germanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)); 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 com 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 (Forficula 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 (Dennacentor 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, E. 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 (Iridomynnex humilis Mayr), crazy ant (Paratrechina longicomis Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Forster), odorous house ant (Tapinoma sessile Say)), bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.; Cephus spp.); insect pests of the order Isoptera including the eastern subterranean termite (Reticulitennes flavipes Kollar), western subterranean termite (Reticulitennes 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 (Thennobia domestica Packard); insect pests of the order Mallophaga and including the head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus 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 parasitic helminths of the phylum Platyhelminthes (flatworms), including the classes Cestoda (tapeworms) and Trematoda (flukes); the phylum Acanthocephala (thorny-headed worms), including the classes Archiacanthocephala and Palaeacanthocephala; and the phylum Nematoda (roundworms), including the classes Adenophorea (Aphasmidae) and Secementea (Phasmidae). Compounds of the present invention also have activity on economically important members of the orders Enoplida, Dorylaimida, Rhabditida, Strongylida, Ascaridida, Oxyurida, Spirurida, Tylenchida, Aphelenchida, Diplogasterida, Rhabdiasidaand Camallanida, such as, but not limited to, economically important agricultural. pests (e.g. root knot .nematodes in the genus Meloidogyne, cyst nematodes in the genus Heterόdera, lesion nematodes in the genus Pratylenchus, stem nematodes in the genus Ditylenchus, seed and leaf nematodes in the genus Aphelenchoides, and sting nematodes in the genus Xiphinema); and animal and human health pests (e.g. flukes, tapeworms and roundworms, such as Strangylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis in dogs, Anoplocephala perfoliata in horses and Fasciola hepatica in ruminants , etc . ) . Compounds of the invention show particularly high activity against pests in 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 (com 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 (com planthopper), Sogatella furcifera Horvath (white-backed planthopper), Sogato' des orizicola Muir (rice delphacid), Typhlocyba pomaria McAtee white apple leafhopper, Erythroneoura spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); leery a 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 the present invention show particularly high activity against nematode pests of the orders Tylenchida and Dorylaimida including: root gall nematodes of the genus Meloidogyne, such as Meloidogyne acronea (sorghum root-knot nematode), Meloidόgnye arenaria (peanut root-knot nematode), Meloidogyne brevicauda (tea root-knot nematode), Meloidogyne chitwoodi (Columbia root-knot nematode), Meloidogyne exigua (Brazilian root-knot nematode), Meloidogyne graminicola (rice root-knot nematode), Meloidogyne hapla (Northern root-knot nematode), Meloidogyne incognita (Southern root-knot nematode), Meloidogyne incognita acrita (cotton root-knot nematode), Meloidogyne indica (citrus root-knot nematode), Meloidogyne javanica (Javanese root-knot nematode) and Meloidogyne mali (apple root-knot nematode); cyst nematodes of the genus Heterodera, such as Heterodera amygdali (almond cyst nematode), Heterodera avenae (cereal cyst nematode), Heterodera carotae (carrot cyst nematode), Heterodera cruciferae (Brassica root eelworm), Heterodera elachista (Japanese cyst nematode), Heterodera fici (fig cyst nematode), Heterodera glycines (soybean cyst nematode), Heterodera goettingiana (pea cyst nematode), Heterodera oryzae (rice cyst nematode), Heterodera sacchari (sugar cane cyst nematode), Heterodera schachtii (sugar beet cyst nematode) and Heterodera zeae (com cyst nematode); cyst nematodes of the genus Globodera, such as Globodera mali (apple cyst nematode), Globodera pallida (potato cyst nematode), Globodera rostochiensis (golden nematode) and Globodera tabacum (tobacco cyst nematode); lesion nematodes of the genus Pratylenchus, such as Pratylenchus brachyurus (Godfrey's root-lesion nematode), Pratylenchus coffeae (banana meadow nematode), Pratylenchus musicola (banana nematode), Pratylenchus penetrans (Cobb's meadow nematode), Pratylenchus pratensis (De Man's root-lesion nematode), Pratylenchus scribneri (Scribner's lesion nematode), Pratylenchus thornei (Thome's root-lesion nematode), Pratylenchus vulnus (walnut root-lesion nematode) and Pratylenchus zeae (com root-lesion nematode); stem nematodes of the genus Ditylenchus, such as Ditylenchus angustus (rice stem nematode), Ditylenchus destructor (potato tuber nematode), Ditylenchus dipsaci (beet stem nematode) and Ditylenchus myceliophagus (mushroom spawn nematode); sting or dagger nematodes of the genus Xiphinema, such as Xiphinema americanum (American dagger nematode), Xiphinema chambersi (Chamber's dagger nematode), Xiphinema diversicaudatum (European dagger nematode), Xiphinema index (California dagger nematode) and Xiphinema radicicola (Pacific dagger nematode); seed and leaf nematodes of the genus Aphelenchoides, such as Aphelenchoides besseyi (rice white-tip nematode), Aphelenchoides composticola (mushroom nematode), Aphelenchoides fragariae (strawberry nematode), Aphelenchoides oryzae (rice nematode) and Aphelenchoides ritzemabosi (chrysanthemum nematode). 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 agricultural utility. Thus the present invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I, an N- oxide thereof, or an agronomic or nonagronomic suitable salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent or a liquid diluent, said composition optionally further comprising at least one additional biologically active compound or agent. Examples of such biologically active compounds or agents with which compounds of this invention can be formulated are: insecticides such as 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-chalothrin, 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, S1812 (Nalent) spinosad, spiromesifen (BSΝ 2060), sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap- sodium, tolfenpyrad, tralomethrin, trichlorfon and triflumuron; fungicides such as acibenzolar, S-methyl, azoxystrobin, benalazy-M, benthiavalicarb, benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), boscalid, bromuconazole, buthiobate, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, clotrimazole, copper oxychloride, copper salts, cymoxanil, cyazofamid, cyflufenamid, cyproconazole, cyprodinil, diclocymet, diclomezine, dicloran, difenoconazole, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dodine, edifenphos, epoxiconazole, ethaboxam, famoxadone, fenarimol, fenbuconazole, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, fluazinam, fludioxonil, flumorph, fluoxastrobin, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, furametapyr, guazatine, hexaconazole, hymexazol, imazalil, imibenconazole, iminoctadine, ipconazole, iprobenfos, iprodione, iprovalicarb, isoconazole, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mepanapyrim, mepronil, metalaxyl, metconazole, metominostrobin/fenominostrobin, metrafenone, miconazole, myclobutanil, neo-asozin (ferric methanearsonate), nuarimol, oryzastrobin, oxadixyl, oxpoconazole. penconazole, pencycuron, picobenzamid, picoxystrobin, probenazole, prochloraz, propamocarb, propiconazole, proquinazid, prothioconazole, pyraclostrobin, pyrimethanil, pyrifenox, pyroquilon, quinoxyfen, silthiofam, simeconazole, sipconazole, spiroxamine, sulfur, tebuconazole, tetraconazole, tiadinil, thiabendazole, thifluzamide, thiophanate- methyl, thiram, tolylfluanid, triadimefon, triadimenol, triarimol, tricyclazole, trifloxystrobin, triflumizole, triforine, triticonazole, uniconazole, validamycin, vinclozolin and zoxamide; 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 entomopathogenic bacteria (e.g., Bacillus thuringiensis ssp. Aizawai and Bacillus thuringiensis ssp. Kurstaki), entomopathogenic baculovirus (e.g., nucleopolyhedro virus (ΝPNs), granulosis virus (GNs)), entomopathogenic fungi (e.g., green muscardine fungus) and Bacillus thuringiensis encapsulated delta-endotoxin. 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. General references for these agricultural protectants include The Pesticide Manual, 12th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2000, and The BioPestcide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 1998. One embodiment of insecticides and acaricides for mixing with compounds of this invention include pyrethroids such as cypermethrin, cyhalothrin, cyfluthrin, beta-cyfluthrin, esfenvalerate, fenvalerate and tralomethrin; carbamates such as fenothicarb, methomyl, oxamyl and thiodicarb; neonicotinoids such as acetamiprid, clothianidin, imidacloprid, thiamethoxam, 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. Preferred biological agents for mixing with compounds of this invention include Bacillus thuringiensis and Bacillus thuringiensis encapsulated 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 aiz wai or Bacillus thuringiensis kurstaki, and a mixture of a compound of this invention with Bacillus thuringiensis encapsulated 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 spectmm 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 this 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 one or more of the compounds of this invention, in an 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. Thus, the present invention further comprises a method for the control of invertebrates in agronomic and/or nonagronomic applications, comprising contacting the invertebrates or their 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 with a composition comprising at least one such compound and an effective amount of at least one additional biologically active compound or agent. Examples of suitable compositions comprising a compound of the invention and an effective amount of at least one additional biologically active compound or agent include granular compositions wherein the additional biologically active compound is present on the same granule as the compound of the invention or on granules separate from those of the compound of this 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. Compounds can also be effective by topical application of a composition comprising a compound of this invention 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, eartags, boluses, foggers, fumigants, aerosols, dusts and many others. The compounds of this invention may also be impregnated into materials for fabricating invertebrate control devices (e.g. insect netting). A compound 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) an active ingredient, namely a compound of Formula I, an N-oxide, or agronomic or nonagronomic suitable 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 ingredient; about 40-99% food material and/or attractant; and optionally about 0.05-10% humectants; can be 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 an invertebrate pest including individually or in combinations 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 in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide can 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 compound or composition of the present invention and a propellant. Representative propellants include, but are not limited to, methane, ethane, propane, iospropane, butane, isobutane, butene, pentane, iospentane, neopentane, pentene, hydrofluorocarbons, chlorofluoroacarbons, 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 an invertebrate pest including individually or in combinations mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like. 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 ingredient per hectare can be sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg/hectare can be sufficient or as much as 8 kg/hectare can be required. For nonagronomic applications, effective use rates can range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter can be sufficient or as much as 150 mg/square meter can 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 TESTS demonstrate the control efficacy of compounds of this invention on specific pests. "Control efficacy" represents inhibition of arthropod 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 Tables A-K for compound descriptions. The following abbreviations are used in the Index Tables which follow: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, -Pr means isopropyl, c-pentyl means cyclopentyl, Bu means butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, CN and NC both mean cyano, PhSO2 means phenylsulfonyl and NO2 means nitro. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared. INDEX TABLE A
Figure imgf000099_0001
Compd. ] No. ll Rla g2a Y NMR Al (Ex. 1) 2-F-Ph Me Me H * A2 (Ex. 2) 2,4-di-F-Ph Me H H * A3 2-pyridyl Me Me H * 4,6-di-ethoxy-2-[l,3,5]- A4 Me Me H * triazine 4,6-di-methyl-2- A5 Me Me H * pyrimidine 4,6-di-methyl-2- A6 Et Et H * pyrimidine A7 2,6-di-F-Ph Et Et H * A8 2,6-di-F-Ph Me Me H * A9 2-N02-Ph Me Me H * A10 2,6-di-i-Pr-Ph H t-Bu H * All 2,6-di-i-Pr-Ph Me Me H =!• A12 2,4-di-Cl-Ph Me Me H * A13 2,6-di-Cl-Ph Me Me H * Compd. No. ii Rla R2a Y NMR A14 3,4-di-Cl-Ph Me Me H * A15 4-SCHF2-Ph Me Me H * A16 2-i-Pr-4-Br-Ph Me Me H * A17 2-i-Pr-6-Br-Ph Me Me H * A18 Ph Me Me H * A19 2-i-Pr-6-(2,5-di-Cl-Ph)-Ph Me Me H * A20 3-N02-Ph Me Me H * A21 4-N02-Ph Me Me H * A23 4-Cl-Ph Me Me H *
Figure imgf000100_0001
A28 4-CN-Ph Me Me H * A29 2,4-di-F-Ph Me Me H * A31 4-F-Ph Me Me H * A34 2-Cl-Ph Me Me H * A36 2-OCHF2-Ph Me H H * A38 2-Me-Ph H Me ' H * A42 4-OMe-Ph H Me H * A43 3-Cl-Ph Me Me H * A45 3-N02-Ph Me Me H * A46 3-OMe-Ph Me Me H * A47 2-Me-4-N02-Ph Me Me H *
* See Index Table K for *H NMR data. INDEX TABLE B
Figure imgf000100_0002
Compd. No. U Y NMR Bl 2-pyrimidine CH2 H * B2 4,6-di-methyl-2-pyrimidine CH2 H * B3 2,6-di-F-Ph CH2 H * B4 2,6-di-F-Ph 0 H * B5 2-N02-Ph 0 H * B6 4,6-di-methyl-2-pyrimidine 0 H * B7 2,6-di-i-Pr-Ph 0 H * B8 2,6-di-Cl-Ph 0 H * Comϋd. No. ii U Y NMR B9 4,5-di-Cl-Ph 0 -H * BIO 4-SCHF2 0 H * Bl l 2-Br-6-i-Pr-Ph 0 H * B12 2-i-Pr-4-Br-Ph 0 H *
* See Index Table K for *H NMR data. INDEX TABLE C
Figure imgf000101_0001
Compd. No. fl RlO Y NMR Cl (Ex 3) 2,4-di-Cl-Ph H H * C2 2,6-di-Cl-Ph H H * C3 Ph CN F * C4 Ph CN H * C5 (Ex 4) (CH3)2NC(=0) SMe H * C6 2-Cl,6-F-Ph H H * C7 Ph Me H * C8 CH2CH2CH=CF2 CONMe2 H *
* See Index Table K for lH NMR data. INDEX TABLE D
Figure imgf000101_0002
Compd. No. ii Rla Y 2 . NMR Dl CN CH2CH2CH=CF2 H * D2 (Ex. 5) CN Me H ] * D3 2,6-di-F-Ph CH2CH2CH=CF2 H ] * D4 (Ex. 6) 3-Cl-5-CF3-Pyridin-2 -yl CH2CH2CH=CF2 H ] * D5 Pyrimidin-2-yl CH2CH2CH=CF2 H ] *
* See Index Table K for *H NMR data. INDEX TABLE E
Figure imgf000102_0001
ii Rla R2a Y 1 a NMR No. El 2-Cl-5-thiazolyl-CH2 Me Me H [ * E2 3-pyridinyl-CH2 3-pyridinyl-CH2 H H I * E3 2,6-di-F-benzoyl Me Me H I * E4 4-CF3-3-pyridinyl-C(0) Me Me H E5 2-F-Ph Me Me F ^ * E6 4-Cl-Ph Me Me F * E7 4-CF3-Ph Me Me F * E8 4-CN-Ph Me Me F * E9 2,4-di-F-Ph Me Me F * E10 4-F-Ph Me Me . F * Ell 2-Cl-Ph Me Me F * E12 CHF20-Ph Me H F * E13 2,4-di-F-Ph Me H F * E14 2-CH3-Ph Me H F ] * E15 4-CH30-Ph Me H F ] * E16 2,4-di-Cl-Ph Me H F ] * E17 2-CH3-4-N02-Ph Me Me F ] * E18 Ph Me Me H ] * E19 Ph Me Me F ] * E20 3-Cl-Ph Me Me F ] * E21 3-N02-Ph Me Me F ] * E22 3-CH30-Ph Me Me F ] *
' E23 3-pyridinyl Me Me H ] * E24 3-pyridinyl Me Me F 1 * E25 1-naphthalenyl Me Me H ] * E26 1-naphthalenyl Me Me F 1 * E27 3,4-di-Cl-Ph Me Me H ] * E28 3,4-di-Cl-Ph Me Me F ] * E29 3-CN-Ph Me Me H 1 * E30 3-CN-Ph Me Me F 1 * ompd.
Figure imgf000103_0001
E31 2-F-Ph Me H H * E32 c-pentyl Me Me H * E33 2,1 ,3-benzothiadiazol-5-yl Me Me H * E34 2, 1 ,3-benzothiadiazol-5-yl Me Me F * E35 2,3-dihydro- 1 ,4-benzodioxin-6-yl Me Me H * E36 2,3-dihydro- 1 ,4-benzodioxin-6-y 1 Me Me F * E37 2-(CH3OC(0))-3-thienyl Me Me H * E38 2-(CH3OC(0))-3-thienyl Me Me F * E39 2-F-Ph H H H * E40 CN (CH3)2CHCH2 H H * E41 CN Me Me H *
(Ex. 10) E42 CN c-propyl H H * E43 CN (E/Z) 2-F-Ph-CH2 H H * E44 CN fCH2CH2CH(CH3)CH2CH2J H * E45 CN t-butyl H H * E46 CN τCH2CH2CH2CH2 - H * E47 CN Me Et H ] * E48 CN i-Pr H H ] * E49 CN XCH2CH20CH2CH2} H ] * E50 CN f H2CH2CH2CH2CH2T H ] * E51 CN Et H H 1 * E52 CN Me H H ] * E53 CN Me Me F ] * E54 CN τCH2CH2CH(CH3)CH2CH2} F ] * E55 CN i-Bu H F ] * E56 CN 2-F-Ph-CH2 H F 1 * E57 Ph CN H H 1 * E58 4-CH30-Ph CN H H ] * E59 2-F-Ph CN H H ] * E60 2,4-di-F-Ph CN H H 1 * E61 2-Cl-Ph CN H H 1 * E62 2,6-di-Cl-Ph CN H H ] * E63 4-Cl-Ph CN H H 1 * E64 CN Et (Et)2NCH2CH2 H ] * E65 CN Me (CH3)2NCH2CH2 H ] * Compd. ll Rla R2a Y a NMR No. E66 CN fCH2CH2N(CH3)CH2CH2} H 1 * E67 CN (CH3)2NCH2CH2 PhCH2 H 1 * E68 CN (CH3)2N(CH2)3 (CH3)2N(CH2)3 H 1 * E69 CN KS)-CH(C02-t-Bu)CH2CH2CH2} H 1 * E70 CN (MeO)2CHCH(CH3) H H 1 * E71 CH3S(0)2 Me Et H 1 * E72 CH3S(0)2 Et H H 1 * E73 PhS02 Et H H 1 * E74 PhS02 Me Et H 1 * E75 CH3OC(0) Me Et H 1 * E76 CH3OC(0) Et H H 1 * E77 CH3CH2OC(0) Et H H 1 * E78 CH3CH2OC(0) Me Et H 1 * E79 2-Ph-6-i-Pr-Ph t-Bu H H 1 * E80 benzoyl Me Me H 1 * E81 ■ c-pentyl Me Me H 1 * E82 c-hexyl Me Me H 1 * E83 PhCH2 Me Me H 1 * E84 3,4-diF-Ph Me Me F 3 * E85 CN Me Et H 3 * E86 CN Me Me H 3 * E87 CN Me H H 3 *
* See Index Table K for H NMR data. INDEX TABLE F
Figure imgf000104_0001
Compd. No. il Rla Y n NMR Fl CN Me F * F2 (CH3)2N Me H * F3 c-propyl Me H F4 CH2=CHCH2 Me H * F5 PhCH2 Me H * F6 c-propyl CH2=CHCH2 H Compd. No. ii Rla Y 3 a NMR F7 c-propyl Et H [ * F8 i-Pr Me H ! * F9 (CH3)2CHCH2 Me H * F10 CH3CH2 Me H * Fl l c-propyl-CH2 Me H * F12 CN PhCH2 H * F13 CN CH2=CHCH2 H * F14 Ph Me F * F15 2-F-Ph Me H * F16 Ph Me H * F17 CN Et H * F18 CN c-pentyl H * F19 CN CH3OC(0)CH2CH2 H * F20 CN (CH3)2C=CHCH2 H * F21 CN NC-CH2 H ] * F22 CN c-Bu-CH2 H * F23 CN CH3CH2OC(0)CH2 H * F24 CN i-Pr H * F25 CN c-propyl-CH2 H ] * F26 CN 4-N02-PhCH2 H ] * F27 CN 2,6-di-F-PhCH2 H ] * F28 CN CH3OC(0)C(CH3)2 H 1 * F29 CH3C(0) Me H 1 * F30 (CH3)2N i-Pr H ] * F31 CN 3-F-Ph H 1 * F32 CN Ph H ] * F33 CN 2-CH3-Ph H ] * F34 CN 2,6-di-Cl-Ph H 1 * F35 CN 2-benzoxazolyl H ] * F36 CN 2-benzothiazolyl H 1 * F37 CF2=CHCH2CH2 Me H 1 * F38 CF2=CHCH2CH2 CH2=CHCH2 H ] * F39 benzoyl Me H 1 * F40 CH3CH2C(0) Me H ] * F41 PhS02 Me H 1 * F42 PhS02 Et H 1 * F43 PhS02 NC-CH2 H 1 * Compd. No. ii Rla Y 11 NMR F44 PhS02 CH30C(0)CH2 H * F45 PhS02 PhCH2 H * F46 PhS02 CF2=CHCH2CH2 H * F47 CH3S(0)2 PhCH2 H * F48 CH3S(0)2 Me H * F49 CH3S(0)2 i-Pr H * F50 CH3S(0)2 NC-CH2 H * F51 CH3S(0)2 CH30C(0)CH2 H * F52 CH3S(0)2 CF2=CHCH2CH2 H * F53 PhS02 i-Pr H 1 * F54 PhS02 c-hexyl H * F55 CH3CH20C(0) PhCH2 H * F56 CH3OC(0) Et H * F57 CH3OC(0) PhCH2 H ] * F58 CH3OC(0) CF2=CHCH2CH2 H ] * F59 CH3CH2OC(0) CF2=CHCH2CH2 H ] * F60 CH3OC(0) i-Pr. . H J * F61 CH3OC(0) CH3OC(0)CH2 H ] * F62 CH3CH2OC(0) Me H ] * F63 CH3CH20C(0) CH3CH2 H 1 * F64 CH3CH2OC(0) i-Pr H ] * F65 (CH3C(0))2N Me H ] * F66 CH3C(0)NH Me H 1 * F67 Me Me H ] * F68 NH2 Me H \ * F69 CF2=CHCH2CH2NH Me H 1 * F70 CF2=CHCH2CH2N(CH3) Me H 1 * F71 CF2=CHCH2CH2N(C(0)OCH) Me H 1 * F72 CF2=CHCH2CH2N(C(0)OCH2CH3) Me H ] * F73 CH3NH Me H 1 * F74 2-F-benzoyl-NH Me H 1 * F75 CH3OC(0)NH Me H 1 * F76 CH3CH2OC(0)NH Me H 1 * F77 CN CF2=CH(CH2)4- H 2 * F78 CN CH2=CHCH2- H 2 * F79 CH3C(0) Me H 2 * F80 NH2 Me H 2 * * See Index Table K for *H NMR data. TNDEX TABLE G
Figure imgf000107_0001
Compd. No. ii A a Y NMR Gl OMe CONMe2 1 L H * G2 OH CONMe2 1 [ H * G3 OCONEt CONMe2 1 L H * G4 OCONEt CONMe2 ] I H * G5 Ph Me 1 L H * G6 2,6-diF-Ph Me ] I H * G7 (Ex. 11) Ph CN 1 [ H * G8 3-CF3-Ph CN ] I H * G9 2-F-Ph CN ] I H * G10 2-F-Ph Me 1 H * Gi l Ph CN 1 L H * G12 Me CN 1 L H * G13 4-Cl-Ph CN 1 L H * G14 4-CF3-Ph CN 1 I H * G15 2,6-diF-Ph CN 1 L H * G16 4-CN-Ph CN 1 L H * G17 4-F-Ph CN 1 L H * G18 4-OCF3-Ph CN 1 L H * G19 «-Pr CN 1 L H * G20 2-Cl-Ph CN 1 L H * G21 3-pyridinyl CN L H * G22 4-SCHF2-Ph CN L H * G23 (Ex. 8) C02Et OEt I H mp 37-39°C G24 C02Et OMe L H * G25 C02Et O-i-Pr L H * G26 (Ex.9) CN OMe L H * G27 C02Me OEt L H * G28 CN OMe L F * G29 CN OEt L F * G30 CN OEt L H * G31 COPh OMe L H * Compd. No. ii A n Y NMR G32 COPh OEt H * G33 COPh O-i-Pr H * G34 COPh O-w-Pr H * G35 COPh OCH2Ph H * G36 CO-2,6-diF-Ph OEt H * G37 COPh OEt H * G38 2,6-diF-Ph O-i-Pr H * G39 2,6-diF-Ph OMe H * G40 2,6-diF-Ph OEt H * G41 C02Et OEt F * G42 COMe OEt H * G43 COMe OEt 3 H * G44 CO Et OEt 3 H *
* See Index Table K for T-H NMR data. INDEX TABLEH
Figure imgf000108_0001
Compd. No. ii A n Y NMR HI CN SMe 1 H * H3 CN OMe 1 H * H5 CN OPh 1 H * H6 CN SEt 1 H * See Index Table K for *H NMR data. INDEX TABLE I
Figure imgf000108_0002
Compd. No. ii Rla n Y NMR 11 C02Et Me H * 12 C02Et Et H * 13 C02Et n-Bu(2-Me) H * 14 C02Et i-Pr H * 15 C02Et CH2-c-Pr H * Compd. No. ii Rla n Y NMR 16 C02Et c-pentyl H * 17 C02Et CH2CH20(C=0)Me H * 18 C02Et CH2CH2C00Me H * 19 C02Et CH2CH2NEt2 H * 110 C02Et (CH2)4C1 H * Index Table K for *H NMR data. INDEX TABLE J
Figure imgf000109_0001
Compd. No. ii El A Z ] ι Y NMR JI CN CN SCH2CH2CF=CF2 S F * J2 CN CN SCH2CH2CH=CF2 s H * J3 CN H SCH2CH2CH=CF2 s H * J4 CN 4-F-Ph SCH2CH2CH=CF2 s H * J5 CN Ph SCH2CH2CH=CF2 s . H * J6 N02 H SCH2CH2CH=CF2 s H * J7 N02 H SCH2CH2CH=CF2 s H * J8 N02 H SCH2CH2CH=CF2 s H * J9 N02 H 1-pyrrolidine s H * J10 N02 H SMe NH H *
See Index Table K for H NMR data. INDEX TABLE K
Figure imgf000109_0002
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
a ^H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (bs)-broad singlet, (br d)-broad doublet, (br q)-broad quartet, (br t)-broad triplet, (bm)-broad multiplet. BIOLOGICAL EXAMPLES OF THE INVENTION TEST A For evaluating control of diamondback moth (Plutella xylostella) the test unit consisted of a small open container with a 12-14-day-old radish plant inside. This was pre-infested with neonate larvae mixed into dry corncob grits that had been sifted through a Standard Testing Sieve No. 30 and retained on a No. 40 sieve. The ratio of larvae to grits was adjusted such that the amount administered to each test unit by a "bazooka" sample transfer device contained 50-80 larvae. 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 SUI2 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. Test compounds were sprayed at 250 ppm and 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 °C and 70% relative humidity. Plant feeding damage was then visually assessed based on foliage consumed.
Of the compounds tested the following provided very good to excellent levels of plant protection (20% or less feeding damage): Al, A2, A8, A15, A16, A23, A25, A28, A29, A31, A34, A36, A38, A42, A43, A45, A46, A47, CI, C2, C4, Dl, D2, D3, D4, D5, E4, E18, E19, E20, E23, E27, E29, E47, E76, F5, F13, F31, F33, F36, F39, F58, F59, F61, F78, F79, G7, G8, G9, Gil, G14, G17, G18, G20, G22, G23, G26, G27, G31, G32, G33, G34, G36, G44, H3, H6, II, 12, 13, 14, 15, J2, J3, J5, J7, J8, J10. TEST B For evaluating control of corn planthopper (Peregrinus maidis) through contact and/or systemic means, the test unit consisted of a small open container with a 3-4 day old corn (maize) plant (spike) inside. White sand was added to the top of the soil prior to application. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. After spraying, the test units were allowed to dry for 1 hour before they were post-infested with 10-20 corn planthoppers (18- to 20-day old nymphs) by sprinkling them onto the sand with a salt shaker. 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 19-21 °C and 50-70% relative humidity. Each test unit was then visually assessed for insect mortality. Of the compounds tested, the following resulted in at least 80% mortality: Al, A2, A5, A7, A8, A9, A10, A12, A13, A14, A15, A18, A20, A21, A23, A28, A29, A31, A34, A43, A45, A46, Bl, B3, B4, B5, B6, B8, CI, Dl, D3, El, E3, E4, E18, E23, E27, E29, E75, E77, E79, E80, E81, E82, F17, F20, F24, F25, F32, F36, F40, F58, F59, F78, F79, G7, G8, Gil, G13, G14, G15, G16, G17, G18, G21, G22, G23, G26, G42, J3, J6. TEST C For evaluating control of green peach aphid (Myzus persicae) through contact and/or systemic means, the test unit consisted of a small open container with a 12-15-day-old radish plant inside. This was pre-infested by placing on a leaf of the test plant 30-40 aphids on a piece of leaf excised from a culture plant (cut-leaf method). The larvae moved onto the test plant as the leaf piece desiccated. After pre-infestation, the soil of the test unit was covered with a layer of sand. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. 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 19-21 °C and 50- 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: Al, A2, A3, A4, A5, A6, A8, A9, A12, A14, A15, A18, A20, A21, A23, A25, A28, A29, A31, A34, A36, A38, A42, A43, A45, A47, Bl, B4, B5, B6, B9, CI, Dl, D2, D3, D4, D5, El, E2, E3, E18, E23, E27, E29, E37, E40, E41, E42, E45, E47, E48, E49, E51, E52, E57, E58, E59, E60, E61, E63, E64, E65, E66, E67, E69, E71, E72, E73, E74, E75, E77, E78, E80, E85, E86, E87, F4, F5, F6, Fll, F12, F13, F16, F17, F18, F19, F20, F21, F22, F23, F25, F26, F27, F28, F29, F31, F32, F33, F34, F39, F40, F41, F42, F43, F44, F46, F47, F58, F58, F60, F61, F62, F64, F65, F66, F67, F77, F78, F79, G7, G8, G9, Gil, G13, G14, G15, G16, G17, G18, G20, G21, G22, G23, G24, G25, G26, G27, G30, G31, G32, G33, G34, G35, G36, G42, G43, G44, HI, H6, II, 12, 13, 14, 15, 16, 17, 19, 110, J2, J3, J5, J6, J7, J8, J9, J10. TEST D For evaluating control of the Root Knot Nematode (Meloidogyne incognita) through contact and/or systemic means, the test unit consisted of a small open container with a 7-9 day old tomato plant inside. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. After spraying, the test units were allowed to dry for 1 hour and then about 250 juvenile stages 2 (J2) larvae were pipetted into the soil and then a black, screened cap was placed on top. The test units were held for 6 days at 25 °C and 65-70% relative humidity. Each test unit was then visually assessed for root damage. Of the compounds tested, the following provided excellent levels of plant protection (80% or more reduction in root galling): Al, A2, A3, A4, A5, A6, A7, A8, A9, AlO, A12, A13, A14, A15, A16, A18, A19, A21, A23, A25, A28, A29, A31, A34, A36, A38, A42, A43, A45, A46, A47, Bl, B2, B4, B5, B6, B9, B10, C3, C5, C8, Dl, D2, D3, D4, D5, E3, E4, E6, E10, E12, E13, E15, E16, E17, E18, E19, E20, E21, E22, E23, E27, E28, E29, E30, E31, E33, E37, E39, E40, E41, E42, E43, E44, E45, E46, E47, E48, E49, E50, E51, E52, E57, E61, E63, E64, E65, E66, E69, E70, E72, E74, E75, E77, E79, E80, E82, E83, E86, Fl, F3, F4, F5, F12, F13, F14, F16, F17, F18, F19, F20, F20, F21, F22, F23, F24, F25, F26, F27, F28, F29, F31, F32, F33, F34, F39, F40, F41, F42, F43, F44, F46, F47, F58, F59, F60, F61, F62, F64, F65, F66, F77, F78, F79, Gl, G2, G3, G4, G6, G7, G8, G9, Gil, G13, G14, G15, G20, G21, G22, G23, G24, G25, G26, G27, G28, G30, G31, G32, G33, G34, G35, G36, G43, G44, HI, II, 12, 13, 14, 15, 16, 17, 18, 19, 110, JI, J2, J3, J6, J7, J8, J9, J10. TEST E 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 5-6 day old Longio bean plant (primary leaves emerged) inside. White sand was added to the top of the soil and one of the primary leaves was excised prior to application. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. 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 19-21 °C and 50-70% relative humidity. Each test unit was then visually assessed for insect mortality. Of the compounds tested, the following resulted in at least 80% mortality: A8, AlO, A15, A16, A28, A31, A43, CI, Dl, E10, E18, E19, E27, E29, F29, F36, F58, F59, F64, G7, Gil, G13, G14, G20, G23, G24. TEST F For evaluating control of cotton melon aphid (Aphis gossypii) through contact and/or systemic means, the test unit consisted of a small open container with a 6-7-day-old cotton plant inside. This was pre-infested with 30^40 insects on a piece of leaf according to the cut-leaf method described for Test C, and the soil of the test unit was covered with a layer of sand. Test compounds were formulated and sprayed at 250 ppm as described for Test A.
The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually assessed for insect mortality Of the compounds tested, the following resulted in at least 80% mortality: A2, A8, A9, A12, A14, A15, A21, A28, A31, A42, A43, A45, A47, B5, CI, Dl, D2, D3, D4, D5. TEST G For evaluating control of the Western Flower Thrip (Frankliniella occidentalis) through contact and or systemic means, the test unit consisted of a small open container with a 5-7 day old Longio Bean plant inside. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. After spraying, the test units were allowed to dry for 1 hour and then 22-27 adult thrips were added to the unit and then a black, screened cap was placed on top. The test units were held for 7 days at 25 °C and 45-55% relative humidity. Of the compounds tested, the following provided excellent levels of plant protection (20% or less feeding damage): Al, A2, A5, A7, A8, AlO, All, A12, A14, A15, A16, A18, A23, A25, A28, A29, A31, A34, A36, A38, A42, A43, A45, A46, A47, B7, CI, C2, C4, C5, Dl, D2, D3, D4, D5, E18, E23, E27, E29, E31, E51, E52, E71, E72, E75, E77, E78, E79, E82, F5, F13, F16, F18, F31, F32, F33, F34, F35, F36, F40, F58, F59, F61, F66, Gl, G8, G9, G13, G14, G16, G21, G22, G27, G28, G30, G32, G33, G34, G35, G36, G38, G39, G40, G42, H3, H5, H6, II, 13, J2, J6, J7, J8. TEST H For evaluating control of adult two-spotted spider mite (Tetranychus urticae) through contact and or systemic means, the test unit consisted of a small open container with a 7-day- old Soliel bean plant inside. The test plant was pre-infested by placing cut leaves bearing 25- 50 adult two-spotted spider mites on the test plant leaves. Overhead fluorescent lights were used to induce migration of the mites from the cut leaves to the underside of the leaves of the test plants, which occurred over the course of 18 hr. Test compounds were formulated and sprayed at 250 ppm and replicated three times as described for Test A. 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 °C and 50-70% relative humidity. Each test unit was then visually assessed for adult mite mortality. Of the compounds tested, the following resulted in at least 80% mortality: A2, A3, A4,
A5, A7, A8, A9, A12, A13, A14, A15, A16, A17, A18, A20, A21, B4, B5, B6, B10, El, E2, E3, E4, E79, E80, E83, G23, G28.

Claims

CLAIMS What is claimed is: 1. A compound of Formula I, an N-oxide thereof or an agronomically or nonagronomically suitable salt thereof,
Figure imgf000124_0001
wherein Q is Q-l or Q-2;
Figure imgf000124_0002
Q-l Q-2 Y is H, F, Cl or CH3; A is CN, CrC6 alkyl, ORla, SRla, NRlaR2a or CONRlbR2b; Z is O, S or NR3; W is N or CR4; J1 and J2 are Cι-C6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl, C4-C8 cycloalkylalkyl, Cι-C4 alkoxy, C2-C5 alkoxycarbonyl or C2-C6 alkylcarbonyl, each optionally substituted with one G and each optionally substituted with one or more R5; or J1 and J2 are G, NO2, CN, OH, NR6R7, CONR6R7, OCONR6R7, CrC4 alkylsulfonyl, C(O)G or S(O)2G; each G is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9-, or 10-membered fused heterobicyclic ring system, each ring or ring system optionally substituted with 1 to 5 R8; Rla and ib are H; G; CN; or CrC6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl or C -C§ cycloalkylalkyl, each optionally substituted with one or more substituents selected from the group consisting of G, halogen, CN, NO2, CrC4 alkoxy, CrC4 alkylthio, CrC4 alkylsulfinyl, CrC4 alkylsulfonyl, C2-C4 alkoxycarbonyl, Cι-C alkylamino, C2-C8 dialkylamino and C3-C6 cycloalkylamino; R2a and R2b are H; or C1-C6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl or C4-C8 cycloalkylalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, C1 -C alkoxy, Cj-C alkylthio, CrC alkylsulfinyl, Cι-C alkylsulfonyl, C2-C4 alkoxycarbonyl, CrC4 alkylamino, C2-C8 dialkylamino and C3-C6 cycloalkylamino; or Rla and R2a or Rlb and R2b are taken together with the nitrogen to which they are attached to form a ring including 2 to 5 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring optionally substituted with 1 to 2 R5; R3 is H, CrC6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl or C4-C8 cycloalkylalkyl; R4 is H, CrC4 alkyl or CN; or R4 is a phenyl ring optionally substituted with 1 to 5 R8; each R5 is independently halogen, CN, NO2, Ci -C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-Cg cycloalkyl, C^Cg haloalkyl, C2-C6 haloalkenyl, C2-Cg haloalkynyl, C3-Cg halocycloalkyl, C1-C4 alkoxy, CrC4 haloalkoxy, CrC alkylthio, C1-C4 alkylsulfinyl, C1-C alkylsulfonyl, CrC4 haloalkylthio, CrC haloalkylsulfinyl, Cι-C4 haloalkylsulfonyl, CrC alkylamino, C2-C8 dialkylamino, C3-C5 cycloalkylamino, C2-Cg alkylcarbonyl or C2-C alkoxycarbonyl; R6 and R7 are each independently H; or CrC6 alkyl, C -C6 alkenyl, C3-C6 alkynyl, C3-C6 cycloalkyl, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl, each optionally substituted with halogen; or R6 and R7 can be taken together with the nitrogen to which they are attached to form a ring which includes 2 to 5 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring optionally substituted with halogen; each R8 is independently halogen, CN, NO2, CrC6 alkyl, C2-Cg alkenyl, C2-C6 alkynyl, C3-Cg cycloalkyl, Cι-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, Cι-C4 alkoxy, Cι-C4 haloalkoxy, Cι-C alkylthio, C1-C4 alkylsulfinyl, C!-C4 alkylsulfonyl, Cι~C4 haloalkylthio, Cj-C4 haloalkylsulfinyl, Cj-C4 haloalkylsulfonyl, Cι-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl, or each R8 is independently a phenoxy ring or a phenyl ring, each ring optionally substituted with 1 to 5 R5; R10 is H; or CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl or C4-C8 cycloalkylalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, Cι-C alkoxy, C C4 alkylthio, Cι-C4 alkylsulfinyl, CrC4 alkylsulfonyl, C2-C alkoxycarbonyl, Ci-C alkylamino, C2-C8 dialkylamino and C3~C6 cycloalkylamino; or R10 is CrC6 alkylthio, CN, CO2R12, CONR12R13 or phenyl optionally substituted with 1 to 5 R11; each R11 is independently halogen, CN, NO2, CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, Cι-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C!-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C}^ haloalkylthio, C1-C4 haloalkylsulfinyl, Cι-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-Cg alkylcarbonyl, or C2-Cg alkoxycarbonyl; R12 and R13 are each independently H or Cι-C6 alkyl; and n is 1, 3 or 5; provided that (1) when Y is F, Z is S, n is 1, A is SRla, NRlaR2 and W is N, then J1 is other than alkyl, G, CN or cycloalkyl; (2) J1 is other than 3-(4-trifluoromethyl)pyridinylcarbonyl or an N-oxide thereof; (3) when R10 is H, methyl, ethyl, phenyl or 4-fluorophenyl, and J2 is phenyl substituted with R8, then R8 is other than 2-fluoroethoxy; (4) when Z is ΝH, W is Ν, and A is SRla, then J1 is other than phenyl substituted at the 2 and the 6 positions with alkyl or cycloalkyl; and (5) when Z is ΝR3, W is Ν or CH, A is ΝRlaR2 , and Rla or R2a is H or alkyl, then J1 is other than CN or NO2.
2. A compound of Claim 1 wherein Q is Q-l; and J1 is G; or Ci-Cg alkyl, C2-Cg alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl, C4-C8 cycloalkylalkyl, Cj-C4 alkoxy, C2-Cg alkoxycarbonyl or C2-C6 alkylcarbonyl, each optionally substituted with one or more R5.
3. A compound of Claim 2 wherein Y is H or F; A is CN, CrC6 alkyl, ORla or NRlaR2 ; Z is S; W is N; Rl and R2a are each independently H, CrC4 alkyl, C3-C4 alkenyl, C3-C4 alkynyl; and R5 and R8 are each independently halogen, C1 -C alkyl, CJ- J. alkoxy, CN, NO2, CF3 or OCF3.
4. A compound of Claim 1 wherein Q is Q-l; and J1 is G, NO2, CN, OH, NR^R7, CONR6R7, CrC4 alkylsulfonyl, C(O)G or S(O)2G.
5. A compound of Claim 4 wherein Y is H or F; A is ORla, SR a or NRlaR2a; W is N or CH; Rla and R2a are each independently H, CrC6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C3-C7 cycloalkyl or C4-C8 cycloalkylalkyl, each optionally substituted with one to three halogen; Ria and R2a can be taken together with the nitrogen to which they are attached to form a ring including 2 to 5 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, and said ring can be optionally substituted with 1 to 2 R5; R3 is H or CrC4 alkyl; R5 and R8 are each independently halogen, C1-C4 alkyl, C1-C4 alkoxy, CN, NO2, CF3 or OCF3; and n is 1 or 3.
6. A compound of Claim 1 wherein Q is Q-l; Y is H; Z is S; Wr is N; A is NRiaR2a; Jl is phenyl optionally substituted with 1 to 5 R5; Ria and R2a are each independently H or C1 -Cg alkyl; and n is 1 or 3.
7. A compound of Claim 1 wherein Q is Q-2; Y is H; J2 is C1 -C6 alkyl or phenyl optionally substituted with 1 to 5 R5; Rl° is H, CrC6 alkyl, CrC6 alkylthio, CONR12Rl3 or phenyl optionally substituted with 1 to 5 R11; and n is 1 or 3.
8. A compound of Claim 1 wherein Q is Q-2; Y is F; J2 is C1 -Cg alkyl or phenyl optionally substituted with 1 to 5 R5; Rl° is H, CrC6 alkyl, CrC6 alkylthio, CONR12Rl3 or phenyl optionally substituted with 1 to 5 Rl 1 ; and n is 1 or 3.
9. A compound of Claim 1 wherein Q is Q-l; Y is H; Z is S; A is SRla; W is N; J1 is CN, NO2, OH, CrC4 alkoxy, or phenyl optionally substituted with 1 to 5 R5; Ria is CrC6 alkyl; and n is 1 or 3.
10. A compound of Claim 1 wherein Q is Q-l; Y is H or CH3; Z is S; A is ORla or SRia; W is N; and J1 is CN.
11. 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 an effective amount of at least one additional biologically active compound or agent.
12. The composition of Claim 11 wherein the at least one additional biologically active compound or agent is selected from an insecticides of the group consisting of a pyrethroid, a carbamate, a neonicotinoid, a neuronal sodium channel blocker, an insecticidal macrocyclic lactone, a γ-aminobutyric acid (GAB A) antagonist, an insecticidal urea, a juvenile hormone mimic, a member of Bacillus thuringiensis, a
Bacillus thuringiensis delta endotoxin, and a naturally occurring or a genetically modified viral insecticide.
13. The composition of Claim 11 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-chalothrin, 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, S1812 (Nalent) spinosad, spiromesifen (BSΝ 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 encapsulated delta-endotoxin, baculovirus, entomopathogenic bacteria, entomopathogenic virus and entomopathogenic fungi.
14. The composition of Claim 11 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 encapsulated delta-endotoxin and entomophagous fungi.
15. 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.
16. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a composition of Claim 11.
17. The method of Claim 15 or Claim 16 wherein the invertebrate pest is a cockroach, an ant or a termite which is contacted by the compound by consuming a bait composition comprising the compound.
18. The method of Claim 15 or Claim 16 wherein the invertebrate pest is 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 which is contacted by a spray composition comprising the compound dispensed from a spray container.
19. A spray composition, comprising:
(a) a compound of Claim 1; and
(b) a propellant.
20. A bait composition, comprising:
(a) a compound of Claim 1;
(b) one or more food materials;
(c) optionally an attractant; and (d) optionally a humectant.
21. A 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.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
US3510503A (en) * 1968-05-27 1970-05-05 Wayne C Jaeschke Trifluorobutenylthiocarbamates and thiocarbonates
WO1988000183A1 (en) * 1986-06-30 1988-01-14 Fmc Corporation S-trifluorobutenyl derivatives and pesticidal uses
WO1994006777A1 (en) * 1992-09-16 1994-03-31 Zeneca Limited Heterocyclic compounds wiht parasitical activity

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3510503A (en) * 1968-05-27 1970-05-05 Wayne C Jaeschke Trifluorobutenylthiocarbamates and thiocarbonates
WO1988000183A1 (en) * 1986-06-30 1988-01-14 Fmc Corporation S-trifluorobutenyl derivatives and pesticidal uses
WO1994006777A1 (en) * 1992-09-16 1994-03-31 Zeneca Limited Heterocyclic compounds wiht parasitical activity

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