WO2022192224A1 - Amides bicycliques pour lutter contre les invertébrés nuisibles - Google Patents

Amides bicycliques pour lutter contre les invertébrés nuisibles Download PDF

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Publication number
WO2022192224A1
WO2022192224A1 PCT/US2022/019301 US2022019301W WO2022192224A1 WO 2022192224 A1 WO2022192224 A1 WO 2022192224A1 US 2022019301 W US2022019301 W US 2022019301W WO 2022192224 A1 WO2022192224 A1 WO 2022192224A1
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alkyl
haloalkyl
cycloalkyl
optionally substituted
halogen
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PCT/US2022/019301
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English (en)
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Andrew Jon DEANGELIS
Zhengao FENG
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Fmc Corporation
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Publication of WO2022192224A1 publication Critical patent/WO2022192224A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
    • C07D307/935—Not further condensed cyclopenta [b] furans or hydrogenated cyclopenta [b] furans
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/002—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing a foodstuff as carrier or diluent, i.e. baits
    • A01N25/006—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing a foodstuff as carrier or diluent, i.e. baits insecticidal
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/08—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing boron
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
    • C07D307/935—Not further condensed cyclopenta [b] furans or hydrogenated cyclopenta [b] furans
    • C07D307/937—Not further condensed cyclopenta [b] furans or hydrogenated cyclopenta [b] furans with hydrocarbon or substituted hydrocarbon radicals directly attached in position 2, e.g. prostacyclins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • invertebrate pests Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity, and thereby result in increased costs to the consumer.
  • the control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action.
  • This disclosure also provides a composition comprising a compound of Formula 1, an N-oxide or a salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • this disclosure also provides a composition for controlling an invertebrate pest comprising a compound of Formula 1, an N-oxide or a salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising at least one additional biologically active compound or agent.
  • This disclosure 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 1, an N-oxide or a salt thereof, (e.g., as a composition described herein).
  • This disclosure also relates to such method wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent.
  • This disclosure also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of any of the aforesaid compositions wherein the environment is a plant.
  • This disclosure also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of any of the aforesaid compositions wherein the environment is an animal.
  • This disclosure also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of any of the aforesaid compositions wherein the environment is a seed.
  • This disclosure also provides a method for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, (e.g., as a composition described herein).
  • This disclosure also relates to the treated seed (i.e. seed contacted with a compound of Formula 1).
  • This disclosure also provides a method for increasing vigor of a crop plant comprising contacting the crop plant, the seed from which the crop plant is grown or the locus (e.g., growth medium) of the crop plant with a biologically effective amount of a compound of Formula 1 (e.g., as a composition described herein).
  • This disclosure further provides a method for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of Formula 1, an N-oxide or a salt thereof, (e.g., as a composition described herein).
  • This disclosure also provides for the use of a compound of Formula 1, an N-oxide or a salt thereof, (e.g., as a composition described herein) in protecting an animal from an invertebrate pest.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains”, “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated.
  • a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
  • the transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith.
  • invertebrate pest includes arthropods, gastropods, nematodes and helminths of economic importance as pests.
  • arthropod includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
  • the term “gastropod” includes snails, slugs and other Stylommatophora.
  • nematode includes members of the phylum Nematoda, such as phytophagous nematodes and helminth nematodes parasitizing animals.
  • helminth includes all of the parasitic worms, such as roundworms (phylum Nematoda), heartworms (phylum Nematoda, class Secernentea), flukes (phylum Platyhelminthes, class Tematoda), acanthocephalans (phylum Acanthocephala), and tapeworms (phylum Platyhelminthes, class Cestoda).
  • invertebrate pest control means inhibition of invertebrate pest development (including mortality, feeding reduction, and/or mating disruption), and related expressions are defined analogously.
  • agronomic refers to the production of field crops such as for food and fiber and includes the growth of maize or corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (e.g., berries and cherries) and other specialty crops (e.g., canola, sunflower and olives).
  • nonagronomic refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
  • horticultural crops e.g., greenhouse, nursery or ornamental plants not grown in a field
  • turf e.g., sod farm, pasture, golf course, lawn, sports field, etc.
  • wood products stored product
  • agro-forestry and vegetation management e.g., public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
  • crop vigor refers to
  • crop yield refers to the return on crop material, in terms of both quantity and quality, obtained after harvesting a crop plant.
  • An “increase in crop yield” refers to an increase in crop yield relative to an untreated control crop plant.
  • biologically effective amount refers to the amount of a biologically active compound (e.g., a compound of Formula 1) sufficient to produce the desired biological effect when applied to (i.e. contacted with) an invertebrate pest to be controlled or its environment, or to a plant, the seed from which the plant is grown, or the locus of the plant (e.g., growth medium) to protect the plant from injury by the invertebrate pest or for other desired effect (e.g., increasing plant vigor).
  • a biologically active compound e.g., a compound of Formula 1
  • Nonagronomic applications include protecting an animal from an invertebrate parasitic pest by administering a parasiticidally effective (i.e. biologically effective) amount of a compound of the disclosure, typically in the form of a composition formulated for veterinary use, to the animal to be protected.
  • a parasiticidally effective (i.e. biologically effective) amount of a compound of the disclosure typically in the form of a composition formulated for veterinary use, to the animal to be protected.
  • parasiticidal i.e. biologically effective
  • Parasiticidal refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest.
  • a wavy line in a structure fragment denotes the attachment point of the fragment to the remainder of the molecule.
  • T-2 the variable T in the structure shown in Table 1
  • the wavy line bisecting the bond in the 6-position of the 2-oxabicyclo[3.1.0]hexane T-2 means that the 2-oxabicyclo[3.1.0]hexane T-2 is attached to the remainder of the Table 1 structure at said 6-position, as shown below.
  • 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, i-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.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkoxyalkoxy denotes alkoxy substitution on another alkoxy moiety.
  • alkoxyalkoxy examples include CH 3 OCH 2 O, CH 3 OCH 2 CH 2 O, CH 3 CH 2 OCH 2 O, CH 3 CH 2 CH 2 OCH 2 O, and CH 3 CH 2 OCH 2 CH 2 O.
  • Alkoxyalkoxyalkyl denotes alkoxyalkoxy substitution on alkyl. Examples of “alkoxyalkoxyalkyl” include CH 3 OCH 2 OCH 2 CH 3 OCH 2 OCH 2 CH 2 and CH 3 CH 2 OCH 2 OCH 2 .
  • 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.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl examples include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 ; “alkylsulfinylalkyl” and “alkylsulfonylalkyl” include the corresponding sulfoxides and sulfones, respectively.
  • Alkylamino includes an NH radical substituted with a straight-chain or branched alkyl group. Examples of “alkylamino” include CH 3 CH 2 NH, CH 3 CH 2 CH 2 NH, and (CH 3 ) 2 CHCH 2 NH.
  • dialkylamino examples include (CH 3 ) 2 N, (CH 3 CH 2 CH 2 ) 2 N and CH 3 CH 2 (CH 3 )N.
  • Alkylaminoalkyl denotes alkylamino substitution on alkyl.
  • alkylaminoalkyl examples include CH 3 NHCH 2 , CH 3 NHCH 2 CH 2 , CH 3 CH 2 NHCH 2 , CH 3 CH 2 CH 2 CH 2 NHCH 2 and CH 3 CH 2 NHCH 2 CH 2 .
  • dialkylaminoalkyl examples include (CH 3 ) 2 NCH 2 , (CH 3 CH 2 CH 2 ) 2 NCH 2 CH 2 and CH 3 CH 2 (CH 3 )NCH 2 .
  • alkoxycarbonylalkyl denotes alkoxycarbonyl substitution on alkyl.
  • alkylaminocarbonylalkyl denotes a straight-chain or branched alkylaminocarbonyl attached to alkyl.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • the term “cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to a straight-chain or branched alkyl group.
  • alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, i-propylcyclobutyl, methylcyclopentyl and methylcyclohexyl.
  • Alkylcycloalkylalkyl denotes an alkyl group substituted with alkylcycloalkyl. Examples of “alkylcycloalkylalkyl” include methylcyclohexylmethyl and ethylcycloproylmethyl.
  • Cycloalkenyl includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- or 1,4-cyclohexadienyl.
  • cycloalkylcycloalkyl denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members.
  • cycloalkylcycloalkyl examples include cyclopropylcyclopropyl (such as 1,1'-bicyclopropyl-1-yl, 1,1'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4-cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as 1,1'-bicyclohexyl-1-yl), and the different cis- and trans- cycloalkylcycloalkyl isomers, (such as (1R,2S)-1,1'-bicyclopropyl-2-yl and (1R,2R)-1,1'-bicyclopropyl-2-yl).
  • cyclopropylcyclopropyl such as 1,1'-bicyclopropyl-1-yl, 1,1'-bicyclopropyl-2-yl
  • cyclohexylcyclopentyl such as 4-cyclopent
  • cycloalkoxy denotes cycloalkyl attached to and linked through an oxygen atom including, for example, cyclopentyloxy and cyclohexyloxy.
  • cycloalkoxyalkyl denotes cycloalkoxy substitution on an alkyl moiety. Examples of “cycloalkoxyalkyl” include cyclopropyloxymethyl, cyclopentyloxyethyl, and other cycloalkoxy groups bonded to a straight-chain or branched alkyl moiety.
  • cycloalkylaminoalkyl denotes cycloalkylamino substitution on an alkyl group.
  • cycloalkylaminoalkyl examples include cyclopropylaminomethyl, cyclopentylaminoethyl, and other cycloalkylamino moieties bonded to a straight-chain or branched alkyl group.
  • Trialkylsilyl includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl and tert-butyldimethylsilyl.
  • halogen either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine.
  • alkyl when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl or “alkyl substituted with halogen” include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • halocycloalkyl halocycloalkyl
  • haloalkoxy haloalkylthio
  • haloalkylsulfinyl haloalkylsulfonyl
  • haloalkenyl haloalkynyl
  • haloalkoxyalkoxy are defined analogously to the term “haloalkyl”.
  • examples of “halocycloalkyl” include 2-chlorocyclopropyl, 2-fluorocyclobutyl, 3-bromocyclopentyl and 4-chorocyclohexyl.
  • haloalkoxy include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CCl 3 S, CF 3 S, CCl 3 CH 2 S and ClCH 2 CH 2 CH 2 S.
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CCl 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxyalkoxy examples include CF 3 OCH 2 O, ClCH 2 CH 2 OCH 2 CH 2 O, Cl 3 CCH 2 OCH 2 O as well as branched alkyl derivatives.
  • “CHO” means formyl.
  • the total number of carbon atoms in a substituent group is indicated by the “C i –C j ” prefix where i and j are numbers from 1 to 15.
  • C 1 –C 4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2 -
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 )-, CH 3 OCH 2 CH 2 - or CH 3 CH 2 OCH 2 -
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 - and CH 3 CH 2 OCH 2 CH 2 -.
  • variable group When a variable group is shown to be optionally attached to a position, for example (R v ) r in Exhibit 1 wherein r may be 0, then hydrogen may be at the position even if not recited in the definition of the variable group.
  • hydrogen atoms When one or more positions on a group are said to be “not substituted” or “unsubstituted”, then hydrogen atoms are attached to take up any free valency.
  • the number of optional substituents may be restricted by an expressed limitation. For example, the phrase “optionally substituted with up to 5 substituents independently selected from R JC ” means that 0, 1, 2, 3, 4 or 5 substituents can be present (if the number of potential connection points allows).
  • bicyclic ring system denotes a ring system consisting of two rings sharing one or more common atoms.
  • a “bicyclic ring system” can be “ortho-fused”, “bridged bicyclic” or “spirobicyclic”. In an “ortho-fused bicyclic ring system” the common atoms are adjacent, and therefore the rings share two adjacent atoms and a bond connecting them.
  • a “bridged bicyclic ring system” is formed by bonding a segment of one or more atoms to nonadjacent ring members of a ring.
  • a “spirobicyclic ring system” is formed by bonding a segment of two or more atoms to the same ring member of a ring.
  • fused heterobicyclic ring system denotes a fused bicyclic ring system in which at least one ring atom is not carbon.
  • carrier denote a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon.
  • heterocyclic ring denotes a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen, sulfur or boron.
  • a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens, no more than 2 sulfurs and no more than 1 boron.
  • a carbocyclic ring or heterocyclic ring can be a saturated or unsaturated ring.
  • “Saturated” refers to a ring having a backbone consisting of atoms linked to one another by single bonds; unless otherwise specified, the remaining atom valences are occupied by hydrogen atoms. Unless otherwise stated, an “unsaturated ring” may be partially unsaturated or fully unsaturated.
  • partially unsaturated ring denotes a ring comprising at least one ring member bonded to an adjacent ring member through a double bond and which conceptually potentially accommodates a number of non-cumulated double bonds between adjacent ring members (i.e. in its fully unsaturated counterpart form) greater than the number of double bonds present (i.e. in its partially unsaturated form).
  • heterocyclic rings and ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • aromatic indicates that each of the ring atoms of a fully unsaturated ring are essentially in the same plane and have a p-orbital perpendicular to the ring plane, and that (4n + 2) ⁇ electrons, where n is a positive integer, are associated with the ring to comply with Hückel’s rule.
  • aromatic ring system denotes a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic. When a fully unsaturated carbocyclic ring satisfies Hückel’s rule, then said ring is also called an “aromatic ring” or “aromatic carbocyclic ring”.
  • aromatic carbocyclic ring system denotes a carbocyclic ring system in which at least one ring of the ring system is aromatic.
  • aromatic heterocyclic ring system denotes a heterocyclic ring system in which at least one ring of the ring system is aromatic.
  • nonaromatic ring system denotes a carbocyclic or heterocyclic ring system that may be fully saturated, as well as partially or fully unsaturated, provided that none of the rings in the ring system are aromatic.
  • nonaromatic carbocyclic ring system denotes a carbocyclic ring in which no ring in the ring system is aromatic.
  • nonaromatic heterocyclic ring system denotes a heterocyclic ring system in which no ring in the ring system is aromatic.
  • optionally substituted in connection with the heterocyclic rings refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated.
  • an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other.
  • J When J is a 5- or 6-membered nitrogen-containing heteroaromatic ring, it may be attached to the remainder of Formula 1 though any available carbon or nitrogen ring atom, unless otherwise described.
  • J can be (among others) phenyl optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary.
  • phenyl optionally substituted with one to five substituents is the ring illustrated as U-1 in Exhibit 1, wherein R v is R JC as defined in the Summary for J and r is an integer from 0 to 5.
  • J can be (among others) 5- or 6-membered heteroaromatic ring, which may be saturated or unsaturated, optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary.
  • Examples of a 5- or 6-membered unsaturated aromatic heterocyclic ring optionally substituted with from one or more substituents include the rings U-2 through U-61 illustrated in Exhibit 1 wherein R v is any substituent as defined in the Summary for J (i.e.
  • R JC or R JN is an integer from 0 to 4, limited by the number of available positions on each U group.
  • r is limited to the integers 0 or 1, and r being 0 means that the U group is unsubstituted, and a hydrogen is present at the position indicated by (R v ) r .
  • J is a 5- or 6-membered saturated or unsaturated non-aromatic heterocyclic ring optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary for R JC
  • one or two carbon ring members of the heterocycle can optionally be in the oxidized form of a carbonyl moiety.
  • Examples of a 5- or 6-membered saturated or non-aromatic unsaturated heterocyclic ring include the rings G-1 through G-35 as illustrated in Exhibit 2. Note that when the attachment point on the G group is illustrated as floating, the G group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the G group by replacement of a hydrogen atom.
  • the optional substituents corresponding to R v can be attached to any available carbon or nitrogen by replacing a hydrogen atom.
  • r is typically an integer from 0 to 4, limited by the number of available positions on each G group.
  • J comprises a ring selected from G-28 through G-35
  • G 2 is selected from O, S or N.
  • G 2 is N, the nitrogen atom can complete its valence by substitution with either H or the substituents corresponding to R v as defined in the Summary for J (i.e. R JC or R JN ).
  • J can be (among others) an 8-, 9- or 10-membered bicyclic ring system optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary (i.e. R JC or R JN ).
  • 8-, 9- or 10-membered ortho-fused bicyclic ring system optionally substituted with from one or more substituents include the rings U-81 through U-124 illustrated in Exhibit 3 wherein R v is any substituent as defined in the Summary for J (i.e. R JC or R JN ), and r is typically an integer from 0 to 4.
  • Exhibit 3 U -109 U-110 U-111 U-112
  • R v groups are shown in the structures U-1 through U-124, it is noted that they do not need to be present since they are optional substituents. Note that when R v is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or R v . Note that when the attachment point between (R v ) r and the U group is illustrated as floating, (R v ) r can be attached to any available carbon atom or nitrogen 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 1 through any available carbon or nitrogen of the U group by replacement of a hydrogen atom.
  • U groups can only be substituted with less than 4 R v groups (e.g., U-2 through U-5, U-7 through U-48, and U-52 through U-61).
  • R v groups e.g., U-2 through U-5, U-7 through U-48, and U-52 through U-61).
  • a wide variety of synthetic methods are known in the art to enable preparation of aromatic and nonaromatic heterocyclic rings and ring systems; for extensive reviews see the eight-volume set of Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1984 and the twelve-volume set of Comprehensive Heterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.
  • Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species.
  • One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to 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 compounds of the disclosure may be present as a mixture of stereoisomers or individual stereoisomers.
  • four possible stereoisomers of Formula 1 are depicted as Formula 1 i , 1 ii , 1 iii , and Formula 1 iv , involving the three cyclopropane chiral centers identified with asterisks (*). Analogously, other chiral centers are possible at, for example, R 1 .
  • Molecular depictions drawn herein follow standard conventions for depicting stereochemistry.
  • bonds rising from the plane of the drawing and towards the viewer are denoted by solid wedges wherein the broad end of the wedge is attached to the atom rising from the plane of the drawing towards the viewer. Bonds going below the plane of the drawing and away from the viewer are denoted by dashed wedges wherein the broad end of the wedge is attached to the atom further away from the viewer.
  • the compounds of the disclosure can exist as stereoisomers due to the possible chiral carbon atoms present in Formula 1.
  • this disclosure comprises the individual stereoisomers of the compounds of Formula 1, as well as mixtures of stereoisomers of the compounds of Formula 1.
  • This disclosure comprises racemic mixtures of equal amounts of the enantiomers of Formulae 1 i and 1 ii .
  • this disclosure includes mixtures that are enriched in the Formula 1 i enantiomer compared to the racemic mixture of Formulae 1 i and 1 ii .
  • This disclosure also comprises the essentially pure enantiomer of Formula 1 i .
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 i and Formula 1 ii , wherein the ratio of 1 i to 1 ii is at least 75:25 (a 50% enantiomeric excess of 1 i ).
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 i and Formula 1 ii , wherein the ratio of 1 i to 1 ii is at least 90:10 (an 80% enantiomeric excess of 1 i ).
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 i and Formula 1 ii , wherein the ratio of 1 i to 1 ii is at least 95:5 (a 90% enantiomeric excess of 1 i ).
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 i and Formula 1 ii , wherein the ratio of 1 i to 1 ii is at least 98:2 (a 96% enantiomeric excess of 1 i ).
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 i and Formula 1 ii , wherein the ratio of 1 i to 1 ii is at least 99:1 (a 98% enantiomeric excess of 1 i ).
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 i and Formula 1 ii , wherein the ratio of 1 i to 1 ii is essentially 100:0.
  • An embodiment of this disclosure comprises the compounds of Formula 1 i .
  • this disclosure includes mixtures that are enriched in the Formula 1 ii enantiomer compared to the racemic mixture of Formulae 1 ii and 1 i .
  • This disclosure also comprises the essentially pure enantiomer of Formula 1 ii .
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 ii and Formula 1 i , wherein the ratio of 1 ii to 1 i is at least 75:25 (a 50% enantiomeric excess of 1 ii ).
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 ii and Formula 1 i , wherein the ratio of 1 ii to 1 i is at least 90:10 (an 80% enantiomeric excess of 1 ii ).
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 ii and Formula 1 i , wherein the ratio of 1 ii to 1 i is at least 95:5 (a 90% enantiomeric excess of 1 ii ).
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 ii and Formula 1 i , wherein the ratio of 1 ii to 1 i is at least 98:2 (a 96% enantiomeric excess of 1 ii ).
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 ii and Formula 1 i , wherein the ratio of 1 ii to 1 i is at least 99:1 (a 98% enantiomeric excess of 1 ii ).
  • An embodiment of this disclosure comprises mixtures of stereoisomers of the compounds of Formula 1 ii and Formula 1 i , wherein the ratio of 1 ii to 1 i is essentially 100:0.
  • An embodiment of this disclosure comprises the compounds of Formula 1 ii .
  • Compounds of Formula 1 can comprise additional chiral centers. For example, substituents and other molecular constituents such as Y may themselves contain chiral centers.
  • This disclosure comprises racemic mixtures as well as enriched and essentially pure stereoconfigurations at these additional chiral centers.
  • This disclosure comprises mixtures of conformational isomers.
  • this disclosure includes compounds that are enriched in one conformer relative to others.
  • This disclosure comprises all stereoisomers, conformational isomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides.
  • nitrogen-containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and 3-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane
  • the salts of the compounds of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium.
  • the present disclosure comprises compounds selected from Formula 1, N-oxides and suitable salts thereof.
  • Compounds selected from Formula 1, stereoisomers, tautomers, N-oxides, and salts thereof typically exist in more than one form, and Formula 1 thus includes all crystalline and non-crystalline forms of the compounds that Formula 1 represents.
  • Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types).
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • a polymorph of a compound represented by Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1.
  • Preparation and isolation of a particular polymorph of a compound represented by Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.
  • Compounds of this disclosure may exist as one or more crystalline polymorphs. This disclosure comprises both individual polymorphs and mixtures of polymorphs, including mixtures enriched in one polymorph relative to others. For a comprehensive discussion of polymorphism see R.
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 alkylsulfonyl or C 1 -C 4 haloalkylsulfonyl.
  • Embodiment 1a Embodiment 1a.
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen, halogen, cyano, C 1 -C 3 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 haloalkylthio, C 1 -C 2 alkylsulfinyl, C 1 -C 2 haloalkylsulfinyl, C 1 -C 2 alkylsulfonyl or C 1 -C 2 haloalkylsulfonyl.
  • Embodiment 1b Embodiment 1b.
  • Embodiment 2. A compound of Formula 1 or any of the preceding Embodiments wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen, halogen or methyl.
  • Embodiment 3a A compound of Formula 1 or any of the preceding Embodiments wherein R 5 , R 6 and R 7 are each independently hydrogen, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 alkylsulfonyl or C 1 -C 4 haloalkylsulfonyl.
  • Embodiment 3a A compound of Formula 1 or any one of Embodiments 1 through 2a wherein R 5 , R 6 and R 7 are each independently hydrogen, halogen, cyano, C 1 -C 3 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 haloalkylthio, C 1 -C 2 alkylsulfinyl, C 1 -C 2 haloalkylsulfinyl, C 1 -C 2 alkylsulfonyl, C 1 -C 2 haloalkylsulfonyl or Q 1 .
  • Embodiment 3b A compound of Embodiment 3a or 3a1 wherein R 5 , R 6 and R 7 are each independently hydrogen, halogen, cyano, C 1 -C 3 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 haloalkylthio, C 1 -C 2 alkylsulfinyl, C 1 -C 2 haloalkylsulfinyl, C 1 -C 2 alkylsulfonyl or C 1 -C 2 haloalkylsulfonyl.
  • Embodiment 3c A compound of Embodiment 3a wherein R 5 , R 6 and R 7 are each independently hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.
  • Embodiment 3d A compound of Embodiment 3c wherein R 5 , R 6 and R 7 are each independently hydrogen, halogen, methyl, ethyl, isopropyl or C 1 -C 2 haloalkyl.
  • Embodiment 3e A compound of Formula 1 or any of the preceding Embodiments wherein R 5 , R 6 and R 7 are each independently hydrogen, halogen or methyl.
  • Embodiment 3f A compound of Formula 1 or any of the preceding Embodiments wherein R 5 , R 6 and R 7 are each independently hydrogen, halogen or methyl.
  • Embodiment 4a A compound of Formula 1 or any of the preceding Embodiments wherein Q 1 is a 6- to 10-membered carbocyclic ring or ring system, each ring or ring system optionally substituted with one or more substituents independently selected from halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 alkylsulfonyl and C 1 -C 4 haloalkylsulfonyl.
  • Embodiment 4b A compound of Embodiment 4a wherein Q 1 is a 6- to 8-membered aromatic carbocyclic ring, each ring optionally substituted with one or more substituents independently selected from halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 alkylsulfonyl and C 1 -C 4 haloalkylsulfonyl.
  • Q 1 is a 6- to 8-membered aromatic carbocyclic ring, each ring optionally substituted with one or more substituents independently selected from halogen, cyano, C 1
  • Embodiment 4c A compound of Formula 1 or any one of Embodiments 1 through 3f wherein Q 1 is a 6- to 14-membered carbocyclic ring or ring system, each ring or ring system optionally substituted with one or more substituents independently selected from halogen, cyano, C 1 -C 4 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy.
  • Q 1 is a 6- to 14-membered carbocyclic ring or ring system, each ring or ring system optionally substituted with one or more substituents independently selected from halogen, cyano, C 1 -C 4 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy.
  • Q 1 is a 6- to 14-membered carbocyclic ring or ring system, each ring or ring
  • Q 1 is a 6- to 10-membered carbocyclic ring or ring system, each ring or ring system optionally substituted with one or more substituents independently selected from halogen, cyano, C 1 -C 4 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy.
  • Embodiment 5a A compound of Formula 1 or any one of Embodiments 1 through 4e wherein W is O.
  • Embodiment 5b. A compound of Formula 1 or any one of Embodiments 1 through 4e wherein W is S.
  • Embodiment 6a A compound of Formula 1 or any one of Embodiments 1 through 4e wherein W is S.
  • Embodiment 6c wherein Y is hydrogen, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 6 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 6 cycloalkyl.
  • Embodiment 6f A compound of Formula 1 or any of the preceding Embodiments wherein Y is hydrogen or C 1 -C 6 alkyl.
  • Embodiment 6g A compound of Embodiment 6f wherein Y is hydrogen or C 1 -C 4 alkyl.
  • Embodiment 6h
  • Embodiment 6g wherein Y is hydrogen, methyl, ethyl or isopropyl.
  • Embodiment 6i A compound of Embodiment 6h wherein Y is hydrogen or methyl.
  • Embodiment 6j A compound of Embodiment 6i wherein Y is hydrogen.
  • Embodiment 7a A compound of Embodiment 6g wherein Y is hydrogen, methyl, ethyl or isopropyl.
  • Embodiment 6i A compound of Embodiment 6h wherein Y is hydrogen or methyl.
  • Embodiment 6j A compound of Embodiment 6i wherein Y is hydrogen.
  • Embodiment 7a A compound of Embodiment 6g wherein Y is hydrogen, methyl, ethyl or isopropyl.
  • Embodiment 6i A compound of Embodiment 6h wherein Y is hydrogen or methyl.
  • Embodiment 6j A compound of Embodiment 6i wherein
  • R 8 , R 9 and R 10 are each independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 2 -C 7 alkoxyalkyl or C 4 -C 7 cycloalkylalkyl; or phenyl optionally substituted by R 13 .
  • Embodiment 7b Embodiment 7b.
  • Embodiment 8a is
  • R 11 is hydrogen, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 2 -C 7 alkoxyalkyl C 4 -C 7 cycloalkylalkyl, C 2 -C 4 alkylthioalkyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, C 2 -C 4 alkylsulfinylalkyl, C 2 -C 4 alkylsulfonylalkyl, C 2 -C 4 -C 4
  • Embodiment 8b A compound of Embodiment 8a wherein R 11 is hydrogen, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 2 -C 7 alkoxyalkyl C 4 -C 7 cycloalkylalkyl, C 2 -C 4 alkylthioalkyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, C 2 -C 4 alkylsulfinylalkyl, C 2 -C 4 alkylsulfonylalkyl, C 2 -C
  • Embodiment 8c A compound of Embodiment 8b wherein R 11 is hydrogen, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 2 -C 7 alkoxyalkyl C 4 -C 7 cycloalkylalkyl, C 2 -C 4 alkylthioalkyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, C 2 -C 4 alkylsulfinylalkyl or C 2 -C 4 alkylsulfonylalkyl.
  • Embodiment 8d A compound of Embodiment 8c wherein R 11 is hydrogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 2 -C 7 alkoxyalkyl or C 4 -C 7 cycloalkylalkyl.
  • Embodiment 8e A compound of Embodiment 8c wherein R 11 is hydrogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 halo
  • Embodiment 8d wherein R 11 is hydrogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl or C 4 -C 7 cycloalkylalkyl.
  • Embodiment 8f A compound of Embodiment 8e wherein R 11 is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl or C 4 -C 7 cycloalkylalkyl.
  • Embodiment 8g
  • a compound of Embodiment 8f wherein R 11 is C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl or C 4 -C 7 cycloalkylalkyl.
  • Embodiment 9a A compound of Formula 1 or any of the preceding Embodiments wherein R 12 is hydrogen, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 2 -C 7 alkoxyalkyl C 4 -C 7 cycloalkylalkyl, C 2 -C 4 alkylthioalkyl, C 1 -C 4 alkylsulfonyl, C
  • Embodiment 9b A compound of Embodiment 9a wherein R 12 is hydrogen, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 2 -C 7 alkoxyalkyl C 4 -C 7 cycloalkylalkyl, C 2 -C 4 alkylthioalkyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, C 2 -C 4 alkylsulfinylalkyl, C 2 -C 4 alkylsulfonylalkyl, C 2 -C
  • Embodiment 9c A compound of Embodiment 9b wherein R 12 is hydrogen, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 4 -C 7 cycloalkylalkyl, C 1 -C 4 alkylsulfonyl, C 2 -C 4 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • R 12 is hydrogen, C 1 -C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 4 -C 7 cycloalkylalkyl, C 1 -C 4 alkylsulfonyl, C 2 -C 4 alkylcarbonyl or C 2 -
  • Embodiment 9c wherein R 12 is hydrogen, C 1 -C 4 alkyl, C 2 -C 4 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • Embodiment 9e A compound of Embodiment 9c wherein R 12 is C 1 -C 4 alkyl, C 2 -C 4 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • Embodiment 9f A compound of Embodiment 9c wherein R 12 is hydrogen, C 2 -C 4 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • Embodiment 10a A compound of Embodiment 9c wherein R 12 is hydrogen, C 1 -C 4 alkyl, C 2 -C 4 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • Embodiment 10b Embodiment 10b.
  • R 11 and R 12 are taken together with the nitrogen to which they are attached to form a 3- to 6-membered ring containing ring members selected from carbon atoms and up to two additional atoms independently selected from nitrogen, sulfur and oxygen, said ring optionally substituted with 1 to 2 substituents independently selected from halogen, C 1 -C 2 alkyl and C 1 -C 2 haloalkyl.
  • Embodiment 11a A compound of Formula 1 or any of the preceding Embodiments wherein R 13 is halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy.
  • Embodiment 11b A compound of Embodiment 11a wherein R 13 is halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl.
  • Embodiment 11c A compound of Embodiment 11b wherein R 13 is halogen.
  • Embodiment 12a A compound of Embodiment 11a wherein R 13 is halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl.
  • Embodiment 12c A compound of Embodiment 12a wherein J is phenyl, each ring optionally substituted with up to 4 substituents independently selected from R JC ; or a 5- or 6-membered heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 3 heteroatoms independently selected
  • a compound of Formula 1 or any of the preceding Embodiments wherein J is selected from U-1 through U-61 as shown in Exhibit 1 wherein up to 1 carbon ring member is optionally selected from C( O); and when R v is attached to a carbon ring member, said R v is selected from R JC , and when R v is attached to a nitrogen ring member, said R v is selected from R JN ; and r is 0, 1, 2, 3 or 4.
  • Embodiment 12d A compound of Embodiment 12c wherein J is selected from U-2 through U-61.
  • a compound of Embodiment 12c wherein J is selected from U-49 through U-61.
  • Embodiment 12e A compound of Embodiment 12c wherein J is selected from U-1, U-2, U-4, U-26, U-28, U-37, U-38, U-39, U-49, U-50, U-51, U-53 or U-56.
  • Embodiment 12f A compound of Formula 1 or any of the preceding Embodiments wherein J is selected from U-1, U-2, U-4, U-26, U-37, U-38, U-39, U-49, U-50 or U-51.
  • Embodiment 12g A compound of Embodiment 12g.
  • Embodiment 12h A compound of Embodiment 12g wherein J is U-1.
  • Embodiment 12i A compound of Embodiment 12g wherein J is U-26.
  • Embodiment 12j A compound of Embodiment 12g wherein J is U-50.
  • a compound of Formula 1 or any one of Embodiments 1 through 12a wherein J is selected from U-81 through U-124 as shown in Exhibit 3 wherein up to 1 carbon ring member is optionally selected from C( O); and when R v is attached to a carbon ring member, said R v is selected from R JC , and when R v is attached to a nitrogen ring member, said R v is selected from R JN ; and r is 0, 1, 2, 3 or 4.
  • Embodiment 13a A compound of Embodiment 13 wherein J is selected from U-90 through U-96, U-105, U-110 or U-117 through U-124.
  • Embodiment 13b A compound of Embodiment 13 wherein J is U-105.
  • Embodiment 13c A compound of Embodiment 13 wherein J is selected from U-91, U-94, U-95, U-96, U-110, U-117, U-118 or U-124.
  • Embodiment 13d A compound of Embodiment 13 wherein J is selected from U-91.
  • Embodiment 14a A compound of Formula 1 or any of the preceding Embodiments wherein r is 1 or 2.
  • Embodiment 14b. A compound of Embodiment 14a wherein r is 1.
  • Embodiment 14c A compound of Embodiment 14a wherein r is 2.
  • Embodiment 14d A compound of Formula 1 or any one of Embodiments 1 through 13d wherein r is 3. Embodiment 14d.
  • Embodiment 15a A compound of Formula 1 or any one of Embodiments 1 through 13d wherein r is 4.
  • Embodiment 15d Embodiment 15d.
  • Embodiment 16d Embodiment 16d.
  • Embodiment 17 A compound of Formula 1 or any of the preceding Embodiments wherein each R JB is independently hydroxy or C 1 -C 6 alkoxy.
  • Embodiment 18a is independently hydroxy or C 1 -C 6 alkoxy.
  • each R 14 is independently C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, C 1 -C 6 haloalkyl or C 3 -C 7 halocycloalkyl.
  • Embodiment 18a A compound of Embodiment 18a wherein each R 14 is independently C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl or C 3 -C 6 halocycloalkyl.
  • Embodiment 18a2 A compound of Formula 1 or any of the preceding Embodiments wherein each R 14 is independently C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, C 1 -C 6 haloalkyl or C 3 -C 7 halocycloalkyl.
  • each R 14 is independently C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl or C 1 -C 4 haloalkyl.
  • Embodiment 18b A compound of Formula 1 or any of the preceding Embodiments wherein each R 15 is independently C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, C 1 -C 6 haloalkyl or C 3 -C 6 halocycloalkyl.
  • Embodiment 18b 1.
  • each R 15 is independently C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl or C 3 -C 6 halocycloalkyl.
  • Embodiment 18b2. A compound of Embodiment 18b1 wherein each R 15 is independently C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl or C 1 -C 4 haloalkyl.
  • Embodiment 18c A compound of Formula 1 or any of the preceding Embodiments wherein each R 16 is independently C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl or C 1 -C 6 haloalkyl.
  • Embodiment 18c A compound of Embodiment 18c wherein each R 16 is independently C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl or C 3 -C 6 halocycloalkyl.
  • Embodiment 18c2. A compound of Embodiment 18c1 wherein each R 16 is independently C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl or C 1 -C 4 haloalkyl.
  • Embodiment 18d A compound of Formula 1 or any one of the preceding Embodiments wherein Z is O.
  • Embodiment 19a A compound of Formula 1 or any one of Embodiments 1 through 18c2 wherein Z is S.
  • Embodiment 19a A compound of Formula 1 or any one of Embodiments 1 through 18c2 wherein Z is S.
  • Embodiment 19a A compound of Formula 1 or any of the preceding Embodiments wherein each R 17 is independently hydrogen, hydroxy, OR 22 ,
  • Embodiment 19c Embodiment 19c.
  • Embodiment 19d A compound of Embodiment 19c wherein each R 17 is independently hydrogen; or C 1 -C 4 alkyl or C 3 -C 5 cycloalkyl, each optionally substituted with 1 to 3 substituents independently selected from R x .
  • Embodiment 19e Embodiment 19e.
  • each R 17 is independently C 1 -C 4 alkyl or C 3 -C 5 cycloalkyl, each optionally substituted with 1 to 3 substituents independently selected from R x .
  • Embodiment 20 A compound of Formula 1 or any of the preceding Embodiments wherein each R 18 is independently hydrogen or Q 2 ; or C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl, each optionally substituted by R x .
  • Embodiment 20a is
  • each R 18 is independently hydrogen; or C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl, each optionally substituted with 1 to 3 substituents independently selected from R x .
  • Embodiment 20b A compound of Embodiment 20a wherein each R 18 is independently hydrogen, C 1 -C 4 alkyl, C 3 -C 5 cycloalkyl, C 2 -C 5 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • Embodiment 20c Embodiment 20
  • Embodiment 20d. A compound of Embodiment 20c wherein R 18 is hydrogen.
  • Embodiment 22b A compound of Embodiment 22 wherein each R x is independently halogen, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C
  • Embodiment 22c is independently hal
  • Embodiment 22d A compound of Embodiment 22c wherein each R x is independently halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.
  • each R 19 is independently OR 22 or NHR 32 .
  • Embodiment 24 A compound of Formula 1 or any of the preceding Embodiments wherein each R 20 is independently hydrogen; or C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl, each optionally substituted with 1 to 3 R x .
  • Embodiment 25 A compound of Formula 1 or any of the preceding Embodiments wherein each R 21 is independently amino, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl or phenyl.
  • Embodiment 26 A compound of Formula 1 or any of the preceding Embodiments wherein each R 19 is independently OR 22 or NHR 32 .
  • Embodiment 24 A compound of Formula 1 or any of the preceding Embodiments wherein each R 20 is independently hydrogen; or C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl, each optionally substituted with 1 to
  • each R 22 is independently C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl or Q 2 .
  • Embodiment 26a A compound of Embodiment 26 wherein each R 22 is independently C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl or C 1 -C 4 haloalkyl.
  • Embodiment 26b A compound of Embodiment 26a wherein each R 22 is independently C 1 -C 4 alkyl.
  • Embodiment 27 is
  • each R 23 is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 4 -C 7 cycloalkylalkyl or C 4 -C 7 halocycloalkylalkyl.
  • Embodiment 27a A compound of Embodiment 27 wherein each R 23 is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl.
  • Embodiment 27b A compound of Embodiment 27 wherein each R 23 is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl.
  • each R 23 is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 3 -C 6 cycloalkyl.
  • Embodiment 28 A compound of Formula 1 or any of the preceding Embodiments wherein each R 24 is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl.
  • Embodiment 29 is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl.
  • Embodiment 30 A compound of Formula 1 or any of the preceding Embodiments wherein each R 26 is independently hydrogen or C 1 -C 6 alkyl.
  • Embodiment 31 A compound of Formula 1 or any of the preceding Embodiments wherein each R 26 is independently hydrogen or C 1 -C 6 alkyl.
  • Embodiment 32 is
  • each R 27 is independently C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.
  • Embodiment 33 A compound of Formula 1 or any of the preceding Embodiments wherein each R 28 is independently C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.
  • each R 29 is independently hydrogen or C 1 -C 4 alkyl.
  • Embodiment 35 A compound of Formula 1 or any of the preceding Embodiments wherein each Q 2 is independently phenyl, optionally substituted with one or more substituents independently selected from the group consisting of halogen, cyano, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy; or a 5- or 6-membered heterocyclic aromatic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from one oxygen atom, one sulfur atom, and up to 2 nitrogen atoms, each ring optionally substituted with one or more substituents independently selected from the group consisting of halogen, cyano, C 1 -C 4 alkyl, C 3 -C 6 cycloal
  • Embodiment 35a A compound of Formula 1 or any of the preceding Embodiments wherein each Q 2 is independently phenyl, optionally substituted with one or more substituents independently selected from the group consisting of halogen, cyano, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy.
  • Embodiment 36a A compound of Formula 1 or any of the preceding Embodiments wherein n is 0.
  • Embodiment 36b A compound of Formula 1 or any one of Embodiments 1 through 35 wherein n is 1 or 2.
  • Embodiment 36c A compound of Formula 1 or any one of Embodiments 1 through 35 wherein n is 1 or 2.
  • Embodiment 36b wherein n is 1.
  • Embodiment 36d A compound of Embodiment 36b wherein n is 2.
  • Embodiment 37a A compound of Formula 1 or any of the preceding Embodiments wherein u is 0.
  • Embodiment 37b A compound of Formula 1 or any one of Embodiments 1 through 36d wherein u is 1.
  • Embodiment S1. A compound of any one of Embodiments 1-37b wherein the compound of Formula 1 is a compound of Formula 1 i .
  • Embodiment S2. A compound of any one of Embodiments 1-37b wherein the compound of Formula 1 is a compound of Formula 1 ii .
  • Embodiment S3c A composition of Embodiment S3 wherein the ratio of the compound of Formula 1 i to the compound of Formula 1 ii is greater than 99:1.
  • Embodiment S4a. A composition of Embodiment S4 wherein the ratio of the compound of Formula 1 ii to the compound of Formula 1 i is greater than 80:20.
  • Embodiment S4b. A composition of Embodiment S4 wherein the ratio of the compound of Formula 1 ii to the compound of Formula 1 i is greater than 90:10.
  • Embodiment S4c A composition of Embodiment S4 wherein the ratio of the compound of Formula 1 ii to the compound of Formula 1 i is greater than 99:1.
  • a compound of any one of Embodiments 1-37b wherein the compound of Formula 1 is a compound of Formula 1 iii .
  • Embodiment S6 A compound of any one of Embodiments 1-37b wherein the compound of Formula 1 is a compound of Formula 1 iv .
  • Embodiments of this disclosure including Embodiments 1-S6 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1.
  • embodiments of this disclosure including Embodiments 1-S6 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present disclosure.
  • Embodiment A A compound of Formula 1 wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 alkylsulfonyl or C 1 -C 4 haloalkylsulfonyl; R 5 , R 6 and R 7 are each independently hydrogen, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -
  • Embodiment H An insecticidal composition
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl or Q 1 ;
  • R 5 , R 6 and R 7 are each independently hydrogen, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 halo
  • Embodiment I An insecticidal composition of Embodiment H wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; R 5 , R 6 and R 7 are each independently hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl; and W is O.
  • Embodiment J An insecticidal composition of Embodiment I wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each hydrogen.
  • Embodiment K An insecticidal composition of Embodiment I wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each hydrogen.
  • An insecticidal composition of Embodiment H wherein the compound of Formula 8a is (1R,5R,6R)-2-oxabicyclo[3.1.0]hexane-6-carboxamide.
  • Embodiment L An insecticidal composition of Embodiment H wherein the compound of Formula 8a is (1S,5S,6S)-2-oxabicyclo[3.1.0]hexane-6-carboxamide.
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of: (1S,5S,6S)-N-[2-[(methylamino)carbonyl]phenyl]-2-oxabicyclo- [3.1.0]hexane-6-carboxamide; (1R,5R,6R)-N-[2-[(methylamino)carbonyl]phenyl]-2-oxabicyclo- [3.1.0]hexane-6-carboxamide; rel-(1R,5R,6R)-N-[2-[(methylamino)carbonyl]phenyl]-2-oxabicyclo[3.1.0]- hexane-6-carboxamide; (1R,5R,6R)-N-phenyl-2-oxabicyclo[3.1.0]hexane-6-carboxamide; (1S,5S,6S)-N-phenyl-2-oxabicyclo[3.1.0]hexane-6-carboxamide; rel-(1R,5R,
  • compounds of this disclosure are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and nonagronomic invertebrate pests.
  • protection of agronomic crops from damage or injury caused by invertebrate pests by controlling invertebrate pests are embodiments of the disclosure.
  • Compounds of this disclosure because of their favorable translocation properties or systemicity in plants also protect foliar or other plant parts which are not directly contacted with a compound of Formula 1 or a composition comprising the compound.
  • compositions comprising a compound of any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said compositions optionally further comprising at least one additional biologically active compound or agent.
  • compositions for controlling an invertebrate pest comprising a compound of any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said compositions optionally further comprising at least one additional biologically active compound or agent.
  • Embodiments of the disclosure 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 disclosure 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 disclosure 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 disclosure 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 disclosure 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 disclosure 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.
  • Embodiments of the disclosure also include methods for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of any of the preceding Embodiments.
  • Embodiments of the disclosure also include methods for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of any of the preceding Embodiments.
  • Embodiments of the disclosure also include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, (e.g., as a composition described herein), provided that the methods are not methods of medical treatment of a human or animal body by therapy.
  • This disclosure also relates to such methods wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent, provided that the methods are not methods of medical treatment of a human or animal body by therapy.
  • Embodiments of this disclosure also include use of an unmanned aerial vehicle (UAV) for the dispersion of the compositions disclosed herein over a planted area.
  • the planted area is a crop-containing area.
  • the crop is selected from a monocot or dicot. In some embodiments, the crop is selected form rice, corn, barley, soybean, wheat, vegetable, tobacco, tea tree, fruit tree and sugar cane.
  • the compositions disclosed herein are formulated for spraying at an ultra-low volume. Products applied by drones may use water or oil as the spray carrier. Typical spray volume (including product) used for drone applications globally is 5.0 liters/ha – 100 liters/ha (approximately 0.5-10 gpa). This includes the range of ultra-low spray volume (ULV) to low spray volume (LV). Although not common there may be situations where even lower spray volumes could be used as low as 1.0 liter/ha (0.1 gpa).
  • the compounds of Formula 1 can be prepared by one or more of the following methods and variations as described in Schemes 1–10.
  • the definitions of substituents in the compounds of Formulae 1–11 below are as defined above in the Summary unless otherwise noted.
  • Compounds of Formulae 1a are subsets of the compounds of Formula 1.
  • Formula 8a is a subset of Formula 8; Substituents for each subset formula are as defined for its parent formula unless otherwise noted.
  • Ambient or room temperature is defined as about 20–25 °C.
  • compounds of Formula 1 can be prepared by reacting an acid of Formula 2 with amines of Formula 3 in the presence of a coupling reagent.
  • Useful coupling reagents include, for example, dicyclohexyl carbodiimide, 1-(3-dimethylaminopropyl)-3- ethylcarbodiimide (EDC) and carbonyl diimidazole.
  • Further coupling reagents useful in this method include O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluoro- phosphate (HATU), propylphosphonic anhydride (T3P), O-(7-azabenzotriazol-1-yl)- N,N,N',N'-tetramethyluranium tetrafluoroborate (TATU) and 2-(1H-benzotriazol-1-yl)- 1,1,3,3-tetramethyluronium hexafluorophosphate (HBTU).
  • HATU O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluoro- phosphate
  • T3P propylphosphonic anhydride
  • TATU O-(7-azabenzotriazol-1-yl)- N,N,N',
  • These coupling reagents are generally used in the presence of a base such as triethylamine, pyridine, 4-(dimethylamino)pyridine or N,N-diisopropylethylamine.
  • a base such as triethylamine, pyridine, 4-(dimethylamino)pyridine or N,N-diisopropylethylamine.
  • Typical reaction conditions include an anhydrous aprotic solvent such as ethyl acetate, dichloromethane, tetrahydrofuran or N,N-dimethylformamide, and a reaction temperature between room temperature and 80 °C.
  • Step C illustrates the method of Scheme 1.
  • Amines of Formula 3 are commercially available or can be prepared by methods well established in the art.
  • Scheme 1 Alternatively, as shown in Scheme 2, compounds of Formula 1 can be prepared by reacting an acid chloride of Formula 4 with an amine of Formula 3 in the presence of an acid scavenger.
  • Typical acid scavengers include amine bases such as triethylamine, N,N-diisopropylethylamine and pyridine.
  • Other scavengers include hydroxides such as sodium hydroxide and potassium hydroxide, or carbonates such as sodium carbonate and potassium carbonate.
  • Typical reaction conditions include an organic solvent such as ethyl acetate, dichloromethane, tetrahydrofuran or N,N-dimethylformamide, and a reaction temperature between room temperature and 80 °C.
  • nantioenriched compounds of Formulae 1 i and 1 ii can be obtained from a racemic mixture of compounds of Formulae 1 i and 1 ii through the utilization of well-known chiral chromatography separation methods.
  • Enantioenriched compounds of Formulae and 1 iv can also be obtained from a racemic mixture of compounds of Formulae and 1 iv using these well-known chiral chromatography separation methods.
  • Step D illustrates the method of chiral separation.
  • acid chlorides of Formula 4 wherein W is O are easily prepared from carboxylic acids of Formula 2 by numerous well-known methods.
  • Example 1 illustrates the method of Scheme 4.
  • compounds of Formula 5 can be prepared by the cyclopropanation of an olefin of Formula 6 with a diazoester of Formula 7 in the presence of a transition metal catalyst such as Rh 2 OAc 4 (i.e. rhodium(II) acetate dimer), Rh 2 oct 4 (i.e. rhodium(II) octanoate dimer), Rh 2 esp 2 (i.e. bis[rhodium( ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethyl-1,3- benzenedipropionic acid)]) or copper(II) sulfate.
  • the reaction can be carried out without solvent other than the compounds of Formulae 6 and 7.
  • reaction is conducted in a liquid phase with a solvent such as methylene chloride, hexanes, or toluene, and a reaction temperature between -78 and 110 °C.
  • a solvent such as methylene chloride, hexanes, or toluene
  • reaction temperature between -78 and 110 °C.
  • compounds of Formula 1 can also be prepared by a transition- metal-catalyzed cross coupling of a compound of Formula 8 with a compound of Formula 9 wherein Lg is a leaving group such as halide (e.g., Cl, Br, I) or sulfonate (e.g., mesylate, triflate, p-toluenesulfonate), and the like.
  • Lg is a leaving group such as halide (e.g., Cl, Br, I) or sulfonate (e.g., mesylate, triflate, p-toluenesulfonate), and the like.
  • Reactions of this type are typically carried out using a palladium catalyst such as palladium(II) acetate with a phosphine ligand such as t-BuBrettPhos (i.e., 2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-bi- phenyl), or a copper catalyst such as copper (I) iodide with a diamine ligand such as trans- N,N′-dimethylcyclohexane-1,2-diamine.
  • a palladium catalyst such as palladium(II) acetate with a phosphine ligand such as t-BuBrettPhos (i.e., 2-(di-tert-butylphosphino)-2′,4′,6′-triisopropyl-3,6-dimethoxy-1,1′-bi
  • compounds of Formula 1 can be prepared from an amide of Formula 8 by reacting with a compound of Formula 9 wherein Lg is a leaving group such as a halide (e.g., Cl, Br, I) in the presence of a base such as sodium hydride or in the presence of a dilute acid such as hydrochloric acid.
  • Reactions of this type are typically carried out in a solvent such as dimethyl sulfoxide, N,N-dimethylformamide, or tert-butanol, at a temperature ranging from about room temperature to the reflux temperature of the reaction mixture (see, for example, US 2003119829A1).
  • ammonia can be substituted for the compound of Formula 3 in the reactions of Schemes 1 and 2 to yield amides of Formula 8a (i.e. Formula 8 wherein Y is H).
  • An acid chloride of Formula 4 can also be generated in situ from a compound of Formula 2 with thionyl chloride prior to the addition of ammonia optionally in the presence a base, such as triethylamine or N,N-diisopropylethylamine.
  • a base such as triethylamine or N,N-diisopropylethylamine.
  • Formula 1 wherein W is O can be prepared by rhodium- catalyzed oxidative amidation of alcohols of Formula 10 with amines of Formula 3, as shown in Scheme 9.
  • This reaction is typically carried out in the presence of a catalyst such as Rh(COD) 2 BF 4 (i.e., bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate), a ligand such as 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (i.e., Xantphos) or 1,4-bis(diphenyl- phosphino)butane (i.e., DPPB), a hydrogen acceptor such as trifluoroacetophenone, and a base such as cesium acetate or cesium carbonate.
  • a catalyst such as Rh(COD) 2 BF 4 (i.e., bis(1,5-cyclooctadiene)rhodium
  • compounds of Formula 1a can be prepared by coupling alcohols of Formula 10 with amines of Formula 3 in the presence of a catalyst such as RuHClCO(AsPh 3 ) 3 (i.e., carbonylchlorohydrotris(triphenylarsine) ruthenium(II)) with a suitable thiocarboxamide ligand such as 2-pyridinecarbothioamide.
  • a catalyst such as RuHClCO(AsPh 3 ) 3 (i.e., carbonylchlorohydrotris(triphenylarsine) ruthenium(II)
  • a suitable thiocarboxamide ligand such as 2-pyridinecarbothioamide.
  • reaction is typically conducted under aerobic conditions in an organic solvent such as ethanol at a temperature ranging from about room temperature to the reflux temperature of the solvent (see, for example, Organometallics, 2014, 33, 4269).
  • organic solvent such as ethanol
  • compounds of Formula 1a i.e. Formula 1 wherein W is O
  • Scheme 9 compounds of Formula 1a (i.e. Formula 1 wherein W is O) can also be prepared by rhodium-catalyzed oxidative amidation of aldehydes of Formula 11 with amines of Formula 3.
  • Scheme 9 10 1a 11 Alcohols of Formula 10 and aldehydes of Formula 11, as shown in Scheme 10, can be prepared from esters of Formula 5 according to general methods known to one skilled in the art.
  • a suitable amount of reducing agent such as diisobutylaluminum hydride, in an aprotic solvent such as dichloromethane or tetrahydrofuran, at a suitable temperature results in the transformation of a compounds of Formula 5 to compounds of Formulae 10 and 11.
  • Schemes 1 through 10 illustrate methods to prepare compounds of Formula 1 having a variety of substituents.
  • Compounds of Formula 1 having substituents other than those particularly noted for Schemes 1 through 10 can be prepared by general methods known in the art of synthetic organic chemistry, including methods analogous to those described for Schemes 1 to 10. It is recognized by one skilled in the art that various functional groups can be converted into others to provide different compounds of Formula 1.
  • Compounds of Formula 1, or intermediates for their preparation may contain aromatic nitro groups, which can be reduced to amino groups, and then converted via reactions well-known in the art (e.g., Sandmeyer reaction) to various halides.
  • aromatic amines anilines
  • diazonium salts phenols
  • aromatic halides such as bromides or iodides prepared via the Sandmeyer reaction can react with alcohols under copper-catalyzed conditions, such as the Ullmann reaction or known modifications thereof, to provide compounds of Formula 1 that contain alkoxy substituents.
  • halogen groups such as fluorine or chlorine
  • alcohols under basic conditions to provide compounds of Formula 1 containing the corresponding alkoxy substituents.
  • reaction mixture was stirred for 20 min, concentrated under reduced pressure and purified by silica gel column chromatography (eluting with a gradient of 0 to 15% ethyl acetate in hexanes) to yield a 3:1 mixture of diastereomers as a colorless liquid (4.24 g) containing the title compound as the major diastereomer.
  • Step D Preparation of (1R,5R,6R)-N-(3-methylphenyl)-2-oxabicyclo[3.1.0]hexane-6- carboxamide and (1S,5S,6S)-N-(3-methylphenyl)-2-oxabicyclo[3.1.0]hexane- 6-carboxamide.
  • the enantiomers of rel-(1R,5R,6R)-N-(3-methylphenyl)-2-oxabicyclo[3.1.0]hexane-6- carboxamide i.e.
  • Example 1 Step B the product of Example 1 Step B) (100 mg, 0.78 mmol) and O-(7-azabenzotriazol-1-yl)- N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU) (326 mg, 0.86 mmol) in DMF (0.5 mL) was added 2-amino-N-methyl-benzamide (114 ⁇ L, 0.86 mmol) followed by N,N- diisopropylethylamine (0.34 mL, 1.95 mmol). The reaction mixture was stirred at room temperature overnight.
  • HATU O-(7-azabenzotriazol-1-yl)- N,N,N',N'-tetramethyluronium hexafluorophosphate
  • reaction mixture was diluted with ethyl acetate, washed with brine, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure and purified by silica gel column chromatography (eluting with a gradient of 10 to 70% ethyl acetate in hexanes) to yield the title compound, a compound of the present invention, as a solid (86 mg).
  • Step C Preparation of rel-(1R,5R,6R)-N-(5-fluoro-2-methoxyphenyl)-2- oxabicyclo[3.1.0]hexane-6-carboxamide (Compound 222).
  • Example 5 Step B the product of Example 5 Step B) (75 mg, 0.59 mmol), 4-chloro-2-iodo-N-methylbenzamide (145 mg, 0.49 mmol), potassium phosphate tribasic (0.21 g, 0.98 mmol), and copper(I) iodide (4.7 mg, 0.025 mmol) under a dry nitrogen atmosphere was added (trans)-N,N′-dimethyl- 1,2-cyclohexanediamine (7.0 mg, 0.049 mmol) followed by N,N-dimethylformamide (0.49 mL) and stirred at 50 °C for 40 h.
  • reaction mixture was diluted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure and concentrated under reduced pressure and purified by silica gel column chromatography (eluting with a gradient of 30 to 80% ethyl acetate in hexanes) to yield the title compound, a compound of the present invention, as a solid (56 mg).
  • EXAMPLE 7 Chiral Preparation of a single enantiomer of rel-(1R,5R,6R)-[1,3-dioxoisoindol-2-yl 2- oxabicyclo[3.1.0]hexane-6-carboxylate].
  • Step A Preparation of [(p-cymene)Ru((S)-Pheox)(MeCN)]PF 6 .
  • Step B Chiral Preparation of a single enantiomer of rel-(1R,5R,6R)-[1,3- dioxoisoindol-2-yl 2-oxabicyclo[3.1.0]hexane-6-carboxylate].
  • a solution of 2,3-dihydrofuran (0.758.6 g, 10.822 mmol, 5.0 eq) in toluene (20 mL) at 0 °C was sparged with nitrogen for 10 min, followed by the addition of [(p-cymene)Ru((S)- Pheox)(MeCN)]PF 6 (i.e. the product of Example 7 Step A) (28 mg, 0.043 mmol).
  • 1,3- dioxoisoindol-2-yl 2-diazoacetate (see Angew. Chem. Int. Ed.2019, 58, 5930 for preparation) (0.5 g, 2.2 mmol) in toluene (8 mL) was added over a period of 50 min at 0 °C, stirred 5 h. The resultant mixture was concentrated under reduced pressure and purified by silica gel column chromatography (eluting with a gradient of 15% ethyl acetate in petroleum ether) to yield an enantiomer of the title compound as a solid (0.20 g) with 62% enantiomeric excess.
  • T has the following meaning as defined in Exhibit 4. Of note for values of T is where T is selected from T-2 and T-3. T is T-1 and Y is H.
  • the present disclosure also includes Tables 2 through 10, each of which is constructed the same as Table 1 above, except that the row heading in Table 1 (i.e. “T is T-1 and Y is H”) is replaced with the respective row headings shown below.
  • Table 11 moieties listed with a dash on each end (i.e., -CH 2 CH 2 CH 2 CH 2 -) denote a ring wherein R 17 and R 18 are taken together with the nitrogen to which they are attached to form a ring with said moiety.
  • T is T-1
  • R JC-A is H
  • R JC-B is H
  • R JC-C is H
  • R JC-D is H
  • Y is H.
  • the present disclosure also includes Tables 12 through 60, each of which is constructed the same as Table 11 above, except that the row heading in Table 11 (i.e. “T is T-1, R JC-A is H, R JC-B is H, R JC-C is H, R JC-D is H and Y is H. ”) is replaced with the respective row headings shown below.
  • the present disclosure also includes Tables 62 through 145, each of which is constructed the same as Table 61 above, except that the row heading in Table 61 (i.e. “T is T-1, R JC-A is H, R JC-B is H, R JC-C is H and Y is H. ”) is replaced with the respective row headings shown below.
  • the present disclosure also includes Tables 147 through 155, each of which is constructed the same as Table 146 above, except that the row heading in Table 146 (i.e. “T is T-1 and Y is H”) is replaced with the respective row headings shown below.
  • Table 156 is constructed the same as Table 146 except that the structure in Table 146 is replaced with the structure above for Table 156.
  • Table 157 through Table 165 Table 157 is constructed the same as Table 147 except that the structure in Table 147 is replaced with the structure above for Table 157.
  • Tables 158 through 165 are constructed in the same fashion as Tables 148 through D-155.
  • Table 176 is constructed the same as Table 166 except that the structure in Table 166 is replaced with the structure above for Table 176.
  • Table 177 through Table 185 Table 177 is constructed the same as Table 167 except that the structure in Table 167 is replaced with the structure above for Table 177.
  • Tables 178 through 185 are constructed in the same fashion as Tables 168 through 175.
  • Table 186 is constructed the same as Table 166 except that the structure in Table 166 is replaced with the structure above for Table 186.
  • Table 187 through Table 195 Table 187 is constructed the same as Table 167 except that the structure in Table 167 is replaced with the structure above for Table 187.
  • Tables 188 through 195 are constructed in the same fashion as Tables 168 through 175.
  • the present disclosure also includes Tables 197 through 205, each of which is constructed the same as Table 196 above, except that the row heading in Table 196 (i.e.
  • T is T-1 and Y is H
  • Formulation/Utility A compound of this disclosure will generally be used as an invertebrate pest control active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier.
  • 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 both liquid and solid compositions.
  • Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil in water emulsions, flowable concentrates and/or suspoemulsions) and the like, which optionally can be thickened into gels.
  • aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil in water emulsion, flowable concentrate and suspoemulsion.
  • the general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
  • the general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film- forming solutions or flowable suspensions are particularly useful for seed treatment.
  • 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.
  • An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation.
  • High-strength compositions are primarily used as intermediates for further formulation.
  • Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare.
  • Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting.
  • Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic uptake.
  • 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.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
  • Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates (e.g., triethylphosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone,
  • Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C 6 –C 22 ), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof.
  • plant seed and fruit oils e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel
  • animal-sourced fats e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil
  • Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation.
  • Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
  • the solid and liquid compositions of the present disclosure often include one or more surfactants. When added to a liquid, surfactants (also known as “surface-active agents”) generally modify, most often reduce, the surface tension of the liquid.
  • surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
  • surfactants can be classified as nonionic, anionic or cationic.
  • Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide
  • Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of e
  • Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
  • amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amine
  • Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon’s Emulsifiers and Detergents, annual American and International Editions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
  • compositions of this disclosure may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants).
  • formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes.
  • Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes.
  • formulation auxiliaries and additives include those listed in McCutcheon’s Volume 2: Functional Materials, annual International and North American editions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
  • the compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent.
  • Solutions including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 ⁇ m can be wet milled using media mills to obtain particles with average diameters below 3 ⁇ m. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S.3,060,084) or further processed by spray drying to form water-dispersible granules.
  • Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill).
  • 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.
  • T. S. Woods “The Formulator’s Toolbox – Product Forms for Modern Agriculture” in Pesticide Chemistry and Bioscience, The Food–Environment Challenge, T. Brooks and T. R.
  • insects include, for example, invertebrates feeding on foliage (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or animal blood or tissues, and thereby causing injury or damage to, for example, growing or stored agronomic crops, forests, greenhouse crops, ornamentals, nursery crops, stored foodstuffs or fiber products, or houses or other structures or their contents, or being harmful to animal health or public health.
  • foliage including leaves, stems, flowers and fruits
  • seeds wood, textile fibers or animal blood or tissues
  • This utility includes protecting crops and other plants (i.e. both agronomic and nonagronomic) that contain genetic material introduced by genetic engineering (i.e. transgenic) or modified by mutagenesis to provide advantageous traits.
  • traits include tolerance to herbicides, resistance to phytophagous pests (e.g., insects, mites, aphids, spiders, nematodes, snails, plant- pathogenic fungi, bacteria and viruses), improved plant growth, increased tolerance of adverse growing conditions such as high or low temperatures, low or high soil moisture, and high salinity, increased flowering or fruiting, greater harvest yields, more rapid maturation, higher quality and/or nutritional value of the harvested product, or improved storage or process properties of the harvested products.
  • phytophagous pests e.g., insects, mites, aphids, spiders, nematodes, snails, plant- pathogenic fungi, bacteria and viruses
  • adverse growing conditions such as high or low temperatures, low or high soil moisture, and high salinity,
  • Transgenic plants can be modified to express multiple traits.
  • traits provided by genetic engineering or mutagenesis include varieties of corn, cotton, soybean and potato expressing an insecticidal Bacillus thuringiensis toxin such as YIELD GARD ® , KNOCKOUT ® , STARLINK ® , BOLLGARD ® , NuCOTN ® and NEWLEAF ® , INVICTA RR2 PRO TM , and herbicide-tolerant varieties of corn, cotton, soybean and rapeseed such as ROUNDUP READY ® , LIBERTY LINK ® , IMI ® , STS ® and CLEARFIELD ® , as well as crops expressing N-acetyltransferase (GAT) to provide resistance to glyphosate herbicide, or crops containing the HRA gene providing resistance to herbicides inhibiting acetolactate synthase (ALS).
  • GAT N-acetyltransferase
  • compositions of this disclosure can also optionally comprise plant nutrients, e.g., a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum.
  • plant nutrients e.g., a fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium, magnesium, iron, copper, boron, manganese, zinc, and molybdenum.
  • compositions comprising at least one fertilizer composition comprising at least one plant nutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium and magnesium.
  • Compositions of the present disclosure which further comprise at least one plant nutrient can be in the form of liquids or solids.
  • solid formulations in the form of granules, small sticks or tablets.
  • Solid formulations comprising a fertilizer composition can be prepared by mixing the compound or composition of the present disclosure with the fertilizer composition together with formulating ingredients and then preparing the formulation by methods such as granulation or extrusion.
  • solid formulations can be prepared by spraying a solution or suspension of a compound or composition of the present disclosure in a volatile solvent onto a previous prepared fertilizer composition in the form of dimensionally stable mixtures, e.g., granules, small sticks or tablets, and then evaporating the solvent.
  • Nonagronomic uses refer to invertebrate pest control in the areas other than fields of crop plants.
  • Nonagronomic uses of the present compounds and compositions include control of invertebrate pests in stored grains, beans and other foodstuffs, and in textiles such as clothing and carpets.
  • Nonagronomic uses of the present compounds and compositions also include invertebrate pest control in ornamental plants, forests, in yards, along roadsides and railroad rights of way, and on turf such as lawns, golf courses and pastures.
  • Nonagronomic uses of the present compounds and compositions also include invertebrate pest control in houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo or other animals.
  • Nonagronomic uses of the present compounds and compositions also include the control of pests such as termites that can damage wood or other structural materials used in buildings.
  • Nonagronomic uses of the present compounds and compositions also include protecting human and animal health by controlling invertebrate pests that are parasitic or transmit infectious diseases.
  • the controlling of animal parasites includes controlling external parasites that are parasitic to the surface of the body of the host animal (e.g., shoulders, armpits, abdomen, inner part of the thighs) and internal parasites that are parasitic to the inside of the body of the host animal (e.g., stomach, intestine, lung, veins, under the skin, lymphatic tissue).
  • External parasitic or disease transmitting pests include, for example, chiggers, ticks, lice, mosquitoes, flies, mites and fleas.
  • Internal parasites include heartworms, hookworms and helminths.
  • Compounds and compositions of the present disclosure are suitable for systemic and/or non-systemic control of infestation or infection by parasites on animals.
  • Compounds and compositions of the present disclosure are particularly suitable for combating external parasitic or disease transmitting pests.
  • Compounds and compositions of the present disclosure are suitable for combating parasites that infest agricultural working animals, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, hens, turkeys, ducks, geese and bees; pet animals and domestic animals such as dogs, cats, pet birds and aquarium fish; as well as so-called experimental animals, such as hamsters, guinea pigs, rats and mice.
  • agronomic or nonagronomic invertebrate pests include eggs, larvae and adults of the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioides Lefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm (Spodoptera frugiperda J.
  • Lepidoptera such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioides Lefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm (Spodoptera frugiperda J.
  • agronomic and nonagronomic pests include: eggs, adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults and nymphs of the order Hemiptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g.
  • Agronomic and nonagronomic pests also include: eggs, larvae, nymphs and adults 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), McD
  • ticks in the family Ixodidae commonly known as hard ticks (e.g., deer tick (Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyomma americanum Linnaeus)) and ticks in the family Argasidae, commonly known as soft ticks (e.g., relapsing fever tick (Ornithodoros turicata), common fowl tick (Argas radiatus)); scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; eggs, adults and immatures of the order Orthoptera including grasshoppers, locus
  • serpentine vegetable leafminer Liriomyza sativae Blanchard
  • midges fruit flies
  • frit flies e.g., Oscinella frit Linnaeus
  • soil maggots e.g., house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, F.
  • femoralis Stein stable flies (e.g., Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium s
  • Hymenoptera including bees (including carpenter bees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.; Cephus spp.); insect pests of the order Isoptera including termites in the Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g., Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen) families, the eastern subterranean termite (Reticulitermes flavipes Kollar), western subterranean termite (Reticulitermes hesperus Banks), Formosan subterranean termite (Coptotermes formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans
  • insect pests of the order Thysanura such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the order Mallophaga and including the head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurysternus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the oriental rat fle
  • 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).
  • invertebrate pests of stored grain include larger grain borer (Prostephanus truncatus), lesser grain borer (Rhyzopertha dominica), rice weevil (Stiophilus oryzae), maize weevil (Stiophilus zeamais), cowpea weevil (Callosobruchus maculatus), red flour beetle (Tribolium castaneum), granary weevil (Stiophilus granarius), Indian meal moth (Plodia interpunctella), Mediterranean flour beetle (Ephestia kuhniella) and flat or rusty grain beetle (Cryptolestis ferrugineus).
  • Compounds of the present disclosure also have activity on members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e.
  • Compounds of this disclosure also have activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Cimex lectularius Linnaeus (bed bug) Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schäffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp.
  • Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius).
  • Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and
  • compounds of this disclosure are also useful for increasing vigor of a crop plant. This method comprises contacting the crop plant (e.g., foliage, flowers, fruit or roots) or the seed from which the crop plant is grown with a compound of Formula 1 in amount sufficient to achieve the desired plant vigor effect (i.e.
  • the compound of Formula 1 is applied in a formulated composition.
  • the compound of Formula 1 is often applied directly to the crop plant or its seed, it can also be applied to the locus of the crop plant, i.e. the environment of the crop plant, particularly the portion of the environment in close enough proximity to allow the compound of Formula 1 to migrate to the crop plant.
  • the locus relevant to this method most commonly comprises the growth medium (i.e. medium providing nutrients to the plant), typically soil in which the plant is grown.
  • Treatment of a crop plant to increase vigor of the crop plant thus comprises contacting the crop plant, the seed from which the crop plant is grown or the locus of the crop plant with a biologically effective amount of a compound of Formula 1.
  • Increased crop vigor can result in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by excellent seed germination, crop emergence and crop stand; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., measured by leaf area index), plant height, number of tillers (e.g., for rice), root mass and overall dry weight of vegetative mass of the crop; (c) improved crop yields, as demonstrated by time to flowering, duration of flowering, number of flowers, total biomass accumulation (i.e. yield quantity) and/or fruit or grain grade marketability of produce (i.e.
  • the compounds of the present disclosure can increase the vigor of treated plants compared to untreated plants by killing or otherwise preventing feeding of phytophagous invertebrate pests in the environment of the plants. In the absence of such control of phytophagous invertebrate pests, the pests reduce plant vigor by consuming plant tissues or sap, or transmiting plant pathogens such as viruses.
  • the compounds of the disclosure may increase plant vigor by modifying metabolism of plants.
  • the vigor of a crop plant will be most significantly increased by treating the plant with a compound of the disclosure if the plant is grown in a nonideal environment, i.e. an environment comprising one or more aspects adverse to the plant achieving the full genetic potential it would exhibit in an ideal environment.
  • a nonideal environment i.e. an environment comprising one or more aspects adverse to the plant achieving the full genetic potential it would exhibit in an ideal environment.
  • the present method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising phytophagous invertebrate pests.
  • the present method for increasing vigor of a crop plant wherein the crop plant is grown in an environment not comprising phytophagous invertebrate pests.
  • the present method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising an amount of moisture less than ideal for supporting growth of the crop plant.
  • the present method for increasing vigor of a crop plant wherein the crop is rice.
  • the present method for increasing vigor of a crop plant wherein the crop is maize (corn).
  • the present method for increasing vigor of a crop plant wherein the crop is soybean.
  • Compounds of this disclosure can also be mixed with one or more other biologically active compounds or agents including insecticides, fungicides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agronomic and nonagronomic utility.
  • insecticides fungicides, nematocides, bactericides, acaricides, herbicides, herbicide safeners
  • growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopath
  • the present disclosure also pertains to a composition
  • a composition comprising a biologically effective amount of a compound of Formula 1, at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, and at least one additional biologically active compound or agent.
  • the other biologically active compounds or agents can be formulated together with the present compounds, including the compounds of Formula 1, to form a premix, or the other biologically active compounds or agents can be formulated separately from the present compounds, including the compounds of Formula 1, and the two formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.
  • insecticides such as abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, acynonapyr, afidopyropen ([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3- [(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b- trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl cyclopropanecarboxylate), amidoflumet, amitraz, avermectin, azadirachtin, azinphos-
  • insecticides such as abamectin, acetamiprid, acrinathrin, acynonapyr, afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, broflanilide, cadusafos, carbaryl, cartap, chlorantraniliprole, chloroprallethrin, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin,
  • One embodiment of biological agents for mixing with compounds of this disclosure include entomopathogenic bacteria such as Bacillus thuringiensis, and the encapsulated delta- endotoxins of Bacillus thuringiensis such as MVP ® and MVPII ® bioinsecticides prepared by the CellCap ® process (CellCap ® , MVP ® and MVPII ® are trademarks of Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi such as green muscardine fungus; and entomopathogenic (both naturally occurring and genetically modified) viruses including baculovirus, nucleopolyhedro virus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus (GV) such as Cydia pomonella granulosis virus (CpGV).
  • NPV nu
  • biological agents for mixing with compounds of this disclosure include one or a combination of (i) a bacterium of the genus Actinomycetes, Agrobacterium, Arthrobacter, Alcaligenes, Aureobacterium, Azobacter, Bacillus, Beijerinckia, Bradyrhizobium, Brevibacillus, Burkholderia, Chromobacterium, Clostridium, Clavibacter, Comamonas, Corynebacterium, Curtobacterium, Enterobacter, Flavobacterium, Gluconobacter, Hydrogenophaga, Klebsiella, Methylobacterium, Paenibacillus, Pasteuria, Photorhabdus, Phyllobacterium, Pseudomonas, Rhizobium, Serratia, Sphingobacterium, Stenotrophomonas, Streptomyces, Variovorax, or Xenorhabdus, for example a bacterium of Bacillus amyloliquef
  • a combination with at least one other invertebrate pest control active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management.
  • a composition of the present disclosure can further comprise a biologically effective amount of at least one additional invertebrate pest control active ingredient having a similar spectrum of control but belonging to a different chemical class or having a different site of action.
  • acetylcholinesterase (AChE) inhibitors such as the carbamates methomyl, oxamyl, thiodicarb, triazamate, and the organophosphates chlorpyrifos
  • GABA-gated chloride channel antagonists such as the cyclodienes dieldrin and endosulfan, and the phenylpyrazoles ethiprole and fipronil
  • sodium channel modulators such as the pyrethroids bifenthrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, deltamethrin, dimefluthrin, esfenvalerate, metofluthrin and profluthrin
  • nicotinic acetylcholinereceptor (nAChR) agonists such as the neonico
  • biologically active compounds or agents with which compounds of this disclosure can be formulated are: fungicides such as acibenzolar-S-methyl, aldimorph, ametoctradin, aminopyrifen, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), benodanil, benomyl, benthiavalicarb (including benthiavalicarb- isopropyl), benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, copper hydroxide, copper oxychloride, copper
  • combinations of a compound of this disclosure with other biologically active (particularly invertebrate pest control) compounds or agents can result in an enhanced effect. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable.
  • enhanced invertebrate pest control occurs at application rates giving agronomically satisfactory levels of invertebrate pest control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load.
  • Compounds of this disclosure and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins). Such an application may provide a broader spectrum of plant protection and be advantageous for resistance management.
  • the exogenously applied invertebrate pest control compounds of this disclosure in combination with the expressed toxin proteins may provide an enhanced effect.
  • General references for these agricultural protectants i.e. insecticides, fungicides, nematocides, acaricides, herbicides and biological agents
  • pesticide Manual 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003
  • the BioPesticide Manual 2 nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.
  • Compounds of this disclosure can be combined or formulated with polynucleotides including, but not limited to, DNA, RNA, and/or chemically modified nucleotides influencing the amount of a particular target through down regulation, interference, suppression or silencing of the genetically derived transcript that render an insecticidal effect.
  • the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1).
  • One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity.
  • Invertebrate pests are controlled in agronomic and nonagronomic applications by applying one or more compounds of this disclosure, typically in the form of a composition, in a biologically effective amount, to the environment of the pests, including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • the present disclosure comprises a method for controlling an invertebrate pest in agronomic and/or nonagronomic applications, comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the compounds of the disclosure, or with a composition comprising at least one such compound or a composition comprising at least one such compound and a biologically effective amount of at least one additional biologically active compound or agent.
  • suitable compositions comprising a compound of the disclosure and a biologically effective amount of at least one additional biologically active compound or agent include granular compositions wherein the additional active compound is present on the same granule as the compound of the disclosure or on granules separate from those of the compound of the disclosure.
  • the compound or composition is typically applied to the seed of the crop before planting, to the foliage (e.g., leaves, stems, flowers, fruits) of crop plants, or to the soil or other growth medium before or after the crop is planted.
  • a method of contact is by spraying.
  • a granular composition comprising a compound of the disclosure can be applied to the plant foliage or the soil.
  • Compounds of this disclosure can also be effectively delivered through plant uptake by contacting the plant with a composition comprising a compound of this disclosure applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants.
  • composition of the present disclosure in the form of a soil drench liquid formulation.
  • a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of the present disclosure or with a composition comprising a biologically effective amount of a compound of the present disclosure.
  • this method wherein the environment is soil and the composition is applied to the soil as a soil drench formulation.
  • compounds of this disclosure are also effective by localized application to the locus of infestation.
  • Other methods of contact include application of a compound or a composition of the disclosure by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • One embodiment of a method of contact is a dimensionally stable fertilizer granule, stick or tablet comprising a compound or composition of the disclosure.
  • the compounds of this disclosure can also be impregnated into materials for fabricating invertebrate control devices (e.g., insect netting).
  • Compounds of the disclosure are useful in treating all plants, plant parts and seeds. Plant and seed varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods.
  • transgenic plants or seeds are those in which a heterologous gene (transgene) has been stably integrated into the plant's or seed’s genome.
  • a transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
  • Genetically modified plant and seed cultivars which can be treated according to the disclosure include those that are resistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold temperature, soil salinity, etc.), or that contain other desirable characteristics.
  • Plants and seeds can be genetically modified to exhibit traits of, for example, herbicide tolerance, insect-resistance, modified oil profiles or drought tolerance.
  • OECD BioTrack Product Database [database online]. Retrieved from The Organisation for Economic Co-operation and Development (OECD) using internet ⁇ https://biotrackproductdatabase.oecd.org/byidentifier.aspx> USDA Animal and Plant Health Inspection Service [database online]. Retrieved from the US Department of Agriculture using the internet ⁇ http://www.aphis.usda.gov> Deliberate Release and Placing on the EU Market of GMOs - GMO Register [database online].
  • tol. is tolerance
  • res. is resistance
  • SU is sulfonylurea
  • ALS is acetolactate synthase
  • HPPD 4- Hydroxyphenylpyruvate Dioxygenase
  • NA is Not Available?
  • Treatment of genetically modified plants and seeds with compounds of the disclosure may result in enhanced effects. For example, reduction in application rates, broadening of the activity spectrum, increased tolerance to biotic/abiotic stresses or enhanced storage stability may be greater than expected from just simple additive effects of the application of compounds of the disclosure on genetically modified plants and seeds.
  • treating a seed means contacting the seed with a biologically effective amount of a compound of this disclosure, which is typically formulated as a composition of the disclosure.
  • This seed treatment protects the seed from invertebrate soil pests and generally can also protect roots and other plant parts in contact with the soil of the seedling developing from the germinating seed.
  • the seed treatment may also provide protection of foliage by translocation of the compound of this disclosure or a second active ingredient within the developing plant. Seed treatments can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate.
  • compositions formulated for seed treatment generally comprise a film former or adhesive agent. Therefore typically a seed coating composition of the present disclosure comprises a biologically effective amount of a compound of Formula 1, an N-oxide or salt thereof, and a film former or adhesive agent.
  • Seed can be coated by spraying a flowable suspension concentrate directly into a tumbling bed of seeds and then drying the seeds.
  • other formulation types such as wetted powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water can be sprayed on the seed. This process is particularly useful for applying film coatings on seeds.
  • Suitable coating machines and processes are available to one skilled in the art. Suitable processes include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994 BCPC Mongraph No.57, and references listed therein.
  • Compounds of Formula 1 and their compositions are particularly useful in seed treatment for crops including, but not limited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats, barley, rye and rice), potatoes, vegetables and oilseed rape.
  • crops including, but not limited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats, barley, rye and rice), potatoes, vegetables and oilseed rape.
  • insecticides with which compounds of Formula 1 can be formulated to provide mixtures useful in seed treatment include abamectin, acetamiprid, acrinathrin, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, carbaryl, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyfluthrin, beta- cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha- cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, end
  • Fungicides with which compounds of Formula 1 can be formulated to provide mixtures useful in seed treatment include amisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, fluazinam, fludioxonil, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam, metconazole, myclobutanil, paclobutrazole, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole, thiophanate-methyl, thiram, trifloxystrobin and triticonazole.
  • Compositions comprising compounds of Formula 1 useful for seed treatment can further comprise bacteria such as Bacillus pumilus (e.g., strain GB34) and Bacillus firmus (e.g., isolate 1582), rhizobia inoculants/extenders, isoflavonoids and lipo-chitooligosaccharides.
  • the treated seed typically comprises a compound of the present disclosure in an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. from about 0.0001 to 1% by weight of the seed before treatment).
  • a flowable suspension formulated for seed treatment typically comprises from about 0.5 to about 70% of the active ingredient, from about 0.5 to about 30% of a film-forming adhesive, from about 0.5 to about 20% of a dispersing agent, from 0 to about 5% of a thickener, from 0 to about 5% of a pigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0 to about 1% of a preservative, and from 0 to about 75% of a volatile liquid diluent.
  • the compounds of this disclosure can be incorporated into a bait composition that is consumed by an invertebrate pest or used within a device such as a trap, bait station, and the like.
  • Such a bait composition can be in the form of granules which comprise (a) active ingredients, namely a biologically effective amount of a compound of Formula 1, an N-oxide, or salt thereof; (b) one or more food materials; optionally (c) an attractant, and optionally (d) one or more humectants.
  • active ingredients namely a biologically effective amount of a compound of Formula 1, an N-oxide, or salt thereof
  • one or more food materials optionally (c) an attractant, and optionally (d) one or more humectants.
  • granules or bait compositions which comprise between about 0.001-5% active ingredients, about 40-99% food material and/or attractant; and optionally about 0.05-10% humectants, which are effective in controlling soil invertebrate pests at very low application rates, particularly at doses of active ingredient that are lethal by ingestion rather than by direct contact.
  • Some food materials can function both as a food source and an attractant.
  • Food materials include carbohydrates, proteins and lipids.
  • food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids.
  • attractants are odorants and flavorants, such as fruit or plant extracts, perfume, or other animal or plant component, pheromones or other agents known to attract a target invertebrate pest.
  • humectants i.e. moisture retaining agents, are glycols and other polyols, glycerine and sorbitol.
  • a bait composition (and a method utilizing such a bait composition) used to control at least one invertebrate pest selected from the group consisting of ants, termites and cockroaches.
  • a device for controlling an invertebrate pest can comprise the present bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
  • the compounds of this disclosure can be applied without other adjuvants, but most often application will be of a formulation comprising one or more active ingredients with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • One method of application involves spraying a water dispersion or refined oil solution of a compound of the present disclosure.
  • Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and piperonyl butoxide often enhance compound efficacy.
  • sprays can be applied from spray containers such as a can, a bottle or other container, either by means of a pump or by releasing it from a pressurized container, e.g., a pressurized aerosol spray can.
  • Such spray compositions can take various forms, for example, sprays, mists, foams, fumes or fog.
  • Such spray compositions thus can further comprise propellants, foaming agents, etc. as the case may be.
  • a spray composition comprising a biologically effective amount of a compound or a composition of the present disclosure and a carrier.
  • a spray composition comprises a biologically effective amount of a compound or a composition of the present disclosure and a propellant.
  • propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing.
  • a spray composition (and a method utilizing such a spray composition dispensed from a spray container) used to control at least one invertebrate pest selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like, including individually or in combinations.
  • One embodiment of the present disclosure relates to a method for controlling invertebrate pests, comprising diluting the pesticidal composition of the present disclosure (a compound of Formula 1 formulated with surfactants, solid diluents and liquid diluents or a formulated mixture of a compound of Formula 1 and at least one other pesticide) with water, and optionally adding an adjuvant to form a diluted composition, and contacting the invertebrate pest or its environment with an effective amount of said diluted composition.
  • a spray composition formed by diluting with water a sufficient concentration of the present pesticidal composition can provide sufficient efficacy for controlling invertebrate pests
  • separately formulated adjuvant products can also be added to spray tank mixtures.
  • Adjuvants are commonly known as “spray adjuvants” or “tank-mix adjuvants”, and include any substance mixed in a spray tank to improve the performance of a pesticide or alter the physical properties of the spray mixture.
  • Adjuvants can be surfactants, emulsifying agents, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners or defoaming agents. Adjuvants are used to enhancing efficacy (e.g., biological availability, adhesion, penetration, uniformity of coverage and durability of protection), or minimizing or eliminating spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization and degradation.
  • adjuvants are selected with regard to the properties of the active ingredient, formulation and target (e.g., crops, insect pests).
  • targets e.g., crops, insect pests.
  • oils including crop oils, crop oil concentrates, vegetable oil concentrates and methylated seed oil concentrates are most commonly used to improve the efficacy of pesticides, possibly by means of promoting more even and uniform spray deposits.
  • spray compositions prepared from the composition of the present disclosure will generally not contain oil-based spray adjuvants.
  • spray compositions prepared from the composition of the present composition can also contain oil- based spray adjuvants, which can potentially further increase control of invertebrate pests, as well as rainfastness.
  • Products identified as “crop oil” typically contain 95 to 98% paraffin or naphtha-based petroleum oil and 1 to 2% of one or more surfactants functioning as emulsifiers.
  • Products identified as “crop oil concentrates” typically consist of 80 to 85% of emulsifiable petroleum- based oil and 15 to 20% of nonionic surfactants.
  • Products correctly identified as “vegetable oil concentrates” typically consist of 80 to 85% of vegetable oil (i.e.
  • Adjuvant performance can be improved by replacing the vegetable oil with methyl esters of fatty acids that are typically derived from vegetable oils.
  • methylated seed oil concentrates include MSO ® Concentrate (UAP-Loveland Products, Inc.) and Premium MSO Methylated Spray Oil (Helena Chemical Company).
  • the amount of adjuvants added to spray mixtures generally does not exceed about 2.5% by volume, and more typically the amount is from about 0.1 to about 1% by volume.
  • the application rates of adjuvants added to spray mixtures are typically between about 1 to 5 L per hectare.
  • spray adjuvants include: Adigor ® (Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons, Silwet ® (Helena Chemical Company) polyalkyleneoxide modified heptamethyltrisiloxane and Assist ® (BASF) 17% surfactant blend in 83% paraffin based mineral oil.
  • Nonagronomic applications include protecting an animal, particularly a vertebrate, more particularly a homeothermic vertebrate (e.g., mammal or bird) and most particularly a mammal, from an invertebrate parasitic pest by administering a parasiticidally effective (i.e.
  • a method for protecting an animal comprising administering to the animal a parasiticidally effective amount of a compound of the disclosure.
  • parasiticidal and “parasiticidally” refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest.
  • invertebrate parasite pests provide control (including prevention, reduction or elimination) of parasitic infestation or infection of the animal.
  • invertebrate parasitic pests controlled by administering a parasiticidally effective amount of a compound of the disclosure to an animal to be protected include ectoparasites (arthropods, acarines, etc) and endoparasites (helminths, e.g., nematodes, trematodes, cestodes, acanthocephalans, etc.).
  • the compounds of this disclosure are effective against ectoparasites including: flies such as Haematobia (Lyperosia) irritans (horn fly), Stomoxys calcitrans (stable fly), Simulium spp. (blackfly), Glossina spp. (tsetse flies), Hydrotaea irritans (head fly), Musca autumnalis (face fly), Musca domestica (house fly), Morellia simplex (sweat fly), Tabanus spp. (horse fly), Hypoderma bovis, Hypoderma lineatum, Lucilia sericata, Lucilia cuprina (green blowfly), Calliphora spp.
  • flies such as Haematobia (Lyperosia) irritans (horn fly), Stomoxys calcitrans (stable fly), Simulium spp. (blackfly), Glossina spp. (tsetse flies), Hydro
  • cyanotis ear mites
  • ticks such as Ixodes spp., Boophilus spp., Rhipicephalus spp., Amblyomma spp., Dermacentor spp., Hyalomma spp. and Haemaphysalis spp.
  • fleas such as Ctenocephalides felis (cat flea) and Ctenocephalides canis (dog flea).
  • Nonagronomic applications in the veterinary sector are by conventional means such as by enteral administration in the form of, for example, tablets, capsules, drinks, drenching preparations, granulates, pastes, boli, feed-through procedures, or suppositories; or by parenteral administration, such as by injection (including intramuscular, subcutaneous, intravenous, intraperitoneal) or implants; by nasal administration; by topical administration, for example, in the form of immersion or dipping, spraying, washing, coating with powder, or application to a small area of the animal, and through articles such as neck collars, ear tags, tail bands, limb bands or halters which comprise compounds or compositions of the present disclosure.
  • a parasiticidal composition comprises a mixture of a compound of Formula 1, an N-oxide or a salt thereof, with one or more pharmaceutically or veterinarily acceptable carriers comprising excipients and auxiliaries selected with regard to the intended route of administration (e.g., oral, topical or parenteral administration such as injection) and in accordance with standard practice.
  • a suitable carrier is selected on the basis of compatibility with the one or more active ingredients in the composition, including such considerations as stability relative to pH and moisture content. Therefore of note is a composition for protecting an animal from an invertebrate parasitic pest comprising a parasitically effective amount of a compound of the disclosure and at least one carrier.
  • a compound of the present disclosure can be formulated in suspension, solution or emulsion in oily or aqueous vehicles, and may contain adjuncts such as suspending, stabilizing and/or dispersing agents.
  • Pharmaceutical compositions for injection include aqueous solutions of water-soluble forms of active ingredients (e.g., a salt of an active compound), preferably in physiologically compatible buffers containing other excipients or auxiliaries as are known in the art of pharmaceutical formulation.
  • a compound of the present disclosure can be formulated with binders/fillers known in the art to be suitable for oral administration compositions, such as sugars (e.g., lactose, sucrose, mannitol, sorbitol), starch (e.g., maize starch, wheat starch, rice starch, potato starch), cellulose and derivatives (e.g., methylcellulose, carboxymethylcellulose, ethylhydroxycellulose), protein derivatives (e.g., zein, gelatin), and synthetic polymers (e.g., polyvinyl alcohol, polyvinylpyrrolidone).
  • sugars e.g., lactose, sucrose, mannitol, sorbitol
  • starch e.g., maize starch, wheat starch, rice starch, potato starch
  • cellulose and derivatives e.g., methylcellulose, carboxymethylcellulose, ethylhydroxycellulose
  • protein derivatives e.g., zein
  • lubricants e.g., magnesium stearate
  • disintegrating agents e.g., cross-linked polyvinylpyrrolidinone, agar, alginic acid
  • dyes or pigments can be added.
  • Pastes and gels often also contain adhesives (e.g., acacia, alginic acid, bentonite, cellulose, xanthan gum, colloidal magnesium aluminum silicate) to aid in keeping the composition in contact with the oral cavity and not being easily ejected.
  • adhesives e.g., acacia, alginic acid, bentonite, cellulose, xanthan gum, colloidal magnesium aluminum silicate
  • the carrier is typically selected from high-performance feed, feed cereals or protein concentrates.
  • Such feed concentrate-containing compositions can, in addition to the parasiticidal active ingredients, comprise additives promoting animal health or growth, improving quality of meat from animals for slaughter or otherwise useful to animal husbandry.
  • additives can include, for example, vitamins, antibiotics, chemotherapeutics, bacteriostats, fungistats, coccidiostats and hormones.
  • Compounds of the present disclosure have been discovered to have favorable pharmacokinetic and pharmacodynamic properties providing systemic availability from oral administration and ingestion. Therefore after ingestion by the animal to be protected, parasiticidally effective concentrations of compounds of the disclosure in the bloodstream protect the treated animal from blood-sucking pests such as fleas, ticks and lice.
  • compositions for protecting an animal from an invertebrate parasite pest in a form for oral administration i.e. comprising, in addition to a parasiticidally effective amount of a compound of the disclosure, one or more carriers selected from binders and fillers suitable for oral administration and feed concentrate carriers).
  • Formulations for topical administration are typically in the form of a powder, cream, suspension, spray, emulsion, foam, paste, aerosol, ointment, salve or gel. More typically a topical formulation is a water-soluble solution, which can be in the form of a concentrate that is diluted before use.
  • Parasiticidal compositions suitable for topical administration typically comprise a compound of the present disclosure and one or more topically suitable carriers.
  • formulations for topical localized administration often comprise at least one organic solvent to facilitate transport of the active ingredient over the skin and/or penetration into the epidermis of the animal.
  • Solvents commonly used as carriers in such formulations include propylene glycol, paraffins, aromatics, esters such as isopropyl myristate, glycol ethers, and alcohols such as ethanol and n-propanol.
  • 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 parasiticidally effective amount is the amount of active ingredient needed to achieve an observable effect diminishing the occurrence or activity of the target invertebrate parasite pest.
  • the parasitically effective dose can vary for the various compounds and compositions of the present disclosure, the desired parasitical effect and duration, the target invertebrate pest species, the animal to be protected, the mode of application and the like, and the amount needed to achieve a particular result can be determined through simple experimentation.
  • the daily dosage of a compound of the present disclosure typically ranges from about 0.01 mg/kg to about 100 mg/kg, more typically from about 0.5 mg/kg to about 100 mg/kg, of animal body weight.
  • dips and sprays typically contain from about 0.5 ppm to about 5000 ppm, more typically from about 1 ppm to about 3000 ppm, of a compound of the present disclosure.
  • the compounds of this disclosure prepared by the methods described herein are shown in Index Tables A–F.
  • Me means methyl
  • OMe means methoxy
  • Et means ethyl
  • i-Pr means iso-propyl
  • i-OPr means iso-propoxy (i.e. -OCH(CH 3 ) 2 )
  • c-Pr means cyclo-propyl
  • t-Bu means tert-butyl
  • Ph means phenyl.
  • MS molecular weight of the highest isotopic abundance positively charged parent ion (M+1) formed by addition of H + (molecular weight of 1) to the molecule having the highest isotopic abundance, or the highest isotopic abundance negatively charged ion (M–1) formed by loss of H + (molecular weight of 1).
  • BIOLOGICAL EXAMPLES Formulation and Spray Methodology for Tests A-G Test compounds were formulated using a solution containing 10% acetone, 90% water and 300 ppm Activator 90 ® non-ionic surfactant (Loveland Products, Loveland, Colorado, USA). The formulated compounds were applied in 1 mL of liquid through an atomized nozzle positioned 1.27 cm (0.5 inches) above the top of each test unit. Test compounds were sprayed at the rates indicated, and each test was replicated three times. Test A For evaluating control of Diamond Back Moth (Plutella xylostella L.) through contact and/or systemic means, each test unit consisted of a small open container with a 10- to 12-day- old mustard plant inside.
  • Test compounds were formulated and sprayed at 250, 50 and 2 ppm with three replications as described above. After spraying, the test units were allowed to dry for 1 hour before they were infested with 30-50 neonate larvae. A black, screened cap was placed on the top of each container. The test units were held for six days in a growth chamber at 24-25 °C and 70% relative humidity. Plant feeding damage was then visually assessed based on foliage consumed, and larvae were assessed for mortality.
  • test unit consisted of a small open container with a 4- to 5-day-old corn (maize) plant inside. This was pre-infested with 10 to 15 one-day-old larvae on a piece of insect diet.
  • Test compounds were formulated and sprayed at 50 and 2 ppm with three replications as described above. After spraying of the formulated test compound, the test units were maintained in a growth chamber for 6 days at 25 °C and 70% relative humidity. Plant feeding damage was then visually assessed based on foliage consumed, and larvae were assessed for mortality.
  • the compounds of Formula 1 tested at 50 ppm the following provided very good to excellent levels of control efficacy (20% or less feeding damage): 27 and 221.
  • Test C For evaluating control of Corn Planthopper (Peregrinus maidis (Ashmead)) through contact and/or systemic means, the test unit consisted of a small open container with a 3- to 4- day-old corn (maize) plant inside. White sand was added to the top of the soil prior to application of the test compound. Test compounds were formulated and sprayed at 250 and 50 ppm with three replications as described above.
  • test units After spraying of the formulated test compound, the test units were allowed to dry for 1 h before they were post-infested with ⁇ 15–20 nymphs (18-to-21-day-old). A black, screened cap was placed on the top of each test unit, and the test units were held for 6 days in a growth chamber at 22 to 24 °C and 50–70% relative humidity. Each test unit was then visually assessed for insect mortality. Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 80% mortality: 1, 4, 15, 70, 78, 81, 83, 147, 178, 213, 214, 221, 228, 231 and 233.
  • Test D For evaluating control of Green Peach Aphid (Myzus persicae (Sulzer)) through contact and/or systemic means, the test unit consisted of a small open container with a 12- to 15-day- old radish plant inside. Prior to compound application, each test unit 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 aphids 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, 50 and 10 ppm with three replications as described above.
  • 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 E For evaluating control of cotton melon aphid (Aphis gossypii (Glover)) through contact and/or systemic means, the test unit consisted of a small open container with a 5-day-old okra plant inside.
  • Test compounds were formulated and sprayed at 250, 50 and 10 ppm with three replications as described above. After spraying, the test units were maintained in a growth chamber for 6 days at 19 °C and 70% relative humidity. Each test unit was then visually assessed for insect mortality.
  • test F For evaluating control of silverleaf whitefly (Bemisia argentifolii (Bellows and Perring)) through contact and/or systemic means, each test unit consisted of a small open container with a 5- to 7-day old soybean plant inside. This was pre-infested by placing test units into cages containing adult whiteflies so that oviposition on the leaves could occur. The adults were removed from the plants with an air-blast nozzle, and the test units were capped. The test units were then stored 2 to 3 days before spraying.
  • Test compounds were formulated and sprayed at 250, 50 and 10 ppm with three replications as described above. After spraying, the test units were maintained in a growth chamber for 12 days at 23 °C and 70% relative humidity. Each test unit was then visually assessed for insect mortality. Of the compounds of Formula 1 tested at 250 ppm, the following resulted in at least 50% mortality: 23, 51, 55, 84, 117, 127, 128, 129, 140, 167, 190, 228, 201, 214 and 117. Of the compounds of Formula 1 tested at 50 ppm, the following resulted in at least 50% mortality: 201, 214 and 117. Of the compounds of Formula 1 tested at 10 ppm, the following resulted in at least 50% mortality: 177.
  • test G For evaluating control of Western Flower Thrips (Frankliniella occidentalis Pergande) through contact and/or systemic means, each test unit consisted of a small open container with a 5- to 7-day-old Soleil bean plant inside. Test compounds were formulated and sprayed at 250ppm with three replications as described above. After spraying, the test units were allowed to dry for 1 hour and then 22 to 27 adult thrips were added to each unit which were then capped with screened lid. The test units were held for 7 days at 25 °C and 45-55% relative humidity. Each test unit was then visually assessed for plant damage and insect mortality. Of the compounds of Formula 1 tested at 250 ppm, the following provided very good to excellent levels of control efficacy (20% or less feeding damage): 142, 178, 181, 182, 195, 223, and 234.

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  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Organic Chemistry (AREA)
  • Insects & Arthropods (AREA)
  • Food Science & Technology (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des composés de formule 1, y compris tous les isomères géométriques et stéréo-isomères, des N-oxydes et des sels de ceux-ci, formule dans laquelle R1, R2, R3, R4, R5, R6, R7, W, J et Y sont tels que définis dans la description. L'invention concerne également des compositions contenant les composés de formule 1 et des procédés pour lutter contre un invertébré nuisible comprenant la mise en contact de l'invertébré nuisible ou de son environnement avec une quantité biologiquement efficace d'un composé ou d'une composition de l'invention.
PCT/US2022/019301 2021-03-09 2022-03-08 Amides bicycliques pour lutter contre les invertébrés nuisibles WO2022192224A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023097341A3 (fr) * 2023-03-20 2023-12-28 Fmc Corporation Esters et amides bicycliques pour lutter contre des nuisibles invertébrés

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023097341A3 (fr) * 2023-03-20 2023-12-28 Fmc Corporation Esters et amides bicycliques pour lutter contre des nuisibles invertébrés

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