WO2013158422A1 - Composés hétérocycliques pour la lutte contre des animaux nuisibles invertébrés - Google Patents

Composés hétérocycliques pour la lutte contre des animaux nuisibles invertébrés Download PDF

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Publication number
WO2013158422A1
WO2013158422A1 PCT/US2013/035873 US2013035873W WO2013158422A1 WO 2013158422 A1 WO2013158422 A1 WO 2013158422A1 US 2013035873 W US2013035873 W US 2013035873W WO 2013158422 A1 WO2013158422 A1 WO 2013158422A1
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phenyl
compound
alkyl
independently selected
alkoxy
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PCT/US2013/035873
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English (en)
Inventor
Ming Xu
Stephen Frederick Mccann
Ramakrishnan VALLINAYAGAM
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E. I. Du Pont De Nemours And Company
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Publication of WO2013158422A1 publication Critical patent/WO2013158422A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings

Definitions

  • This invention relates to certain substituted pyridine compounds, their N-oxides, salts and their compositions suitable for agronomic, nonagronomic and animal health uses, methods of their use for controlling invertebrate pests such as arthropods in both agronomic and nonagronomic environments, and for treatment of parasite infections in animals or infestations in the general environment.
  • invertebrate pests The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer.
  • the control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public 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 invention is directed to compounds of Formula 1 (including all stereoisomers), N- oxides, and salts thereof, and compositions containing them and their use for controlling invertebrate pests:
  • L is a group selected from
  • A is N or CR 3 ;
  • Q is N, CH or CR 6 ;
  • R l a and R lb are each independently selected from hydrogen, halogen and C1-C2 alkyl;
  • R 2 and R 5 are each independently selected from hydrogen and fluorine
  • R 3 and R 4 are each independently selected from hydrogen, halogen, cyano, amino, nitro, SF 5 , -CHO, -Cg alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -Cg haloalkyl, C 2 -C6 haloalkenyl, C2 ⁇ Cg haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, Cz Cg cycloalkylalkyl, C3-C6 cycloalkenyl, C2 ⁇ Cg alkoxyalkyl, C2 ⁇ Cg alkylthioalkyl, C2 ⁇ Cg alkylcarbonyl, C2 ⁇ Cg
  • haloalkylcarbonyl C2 ⁇ Cg alkoxycarbonyl, C2 ⁇ Cg alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C2 ⁇ Cg cyanoalkyl, C ⁇ -Cg alkoxy, C ⁇ -Cg haloalkoxy, C2- Cg alkoxyalkoxy, C ⁇ -Cg alkylthio, C ⁇ -Cg haloalkylthio, C ⁇ -Cg alkylsulfinyl, C ⁇ -Cg haloalkylsulfinyl, C ⁇ -Cg alkylsulfonyl, C ⁇ -Cg haloalkylsulfonyl, C3-C9 trialkylsilyl, C ⁇ -Cg alkylamino, C2 ⁇ Cg dialkylamino, C2 ⁇ Cg haloalkylamino, C2 ⁇ Cg halodialkylamino and C2 ⁇ Cg alkyl
  • R 7 is hydrogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C2-C3
  • alkylcarbonyl C2-C3 alkoxycarbonyl or C3-C6 cycloalkyl
  • R 10 is independently hydrogen, cyano, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C3-C8
  • cycloalkyl C3-C8 halocycloalkyl, C ⁇ -Cg alkoxy, C ⁇ -Cg haloalkoxy, C ⁇ -Cg alkylamino, C2 ⁇ Cg dialkylamino, C ⁇ -Cg haloalkylamino or phenyl;
  • Q 1 is phenyl or naphthalenyl optionally substituted with up to 3 substituents
  • halogen independently selected from halogen, cyano, C1-C2 alkyl, -C2 haloalkyl, C - C2 alkoxy and C1-C2 haloalkoxy; or a 5- to 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, and optionally substituted with up to 3 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy on carbon atom ring members and cyano, C1-C2 alkyl and C1-C2 alkoxy on nitrogen atom ring members; or a 3- to 7-membered nonaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to
  • n 0, 1 or 2;
  • n 0, 1, 2, 3, 4 or 5;
  • This invention is also directed to such compounds of Formula 1 (including all stereoisomers), N-oxides, and salts thereof, and compositions containing them and their use for controlling invertebrate pests.
  • This invention 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 invention also provides a composition for controlling an invertebrate pest comprising a compound of Formula 1, an N-oxide, or a salt thereof, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition further comprising at least one additional biologically active compound or agent.
  • This invention provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1, an N-oxide, or a salt thereof (e.g., as a composition described herein).
  • This invention also relates to such method wherein the invertebrate pest or its environment is contacted with a composition comprising a biologically effective amount of a compound of Formula 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 invention 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 invention 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 invention 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 invention also provides a method for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of Formula 1, an N-oxide, or a salt thereof (e.g., as a composition described herein). This invention also relates to the treated seed.
  • This invention further provides a composition for protecting an animal from an invertebrate parasitic pest comprising a parasiticidally effective amount of a compound of Formula 1, an N-oxide, or a salt thereof, and at least one carrier.
  • This invention further provides a method for treating, preventing, inhibiting and/or killing ecto and/or endoparasites comprising administering to and/or on an 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 invention also relates to such method wherein a parasiticidally effective amount of a compound of Formula 1, an N-oxide, or a salt thereof, (e.g., as a composition described herein) is administered to an environment (e.g., a stall or blanket) in which an animal resides.
  • compositions comprising, “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.
  • invertebrate pest includes arthropods, gastropods, nematodes and helminths of economic importance as pests.
  • 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.
  • 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
  • tapeworms phylum Platyhelminthes, class
  • 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 corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye, rice, maize), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (berries, cherries) and other specialty crops (e.g., canola, sunflower, olives).
  • wheat e.g., wheat, oats, barley, rye, rice, maize
  • leafy vegetables e.g., lettuce, cabbage, and other cole crops
  • fruiting vegetables e.g., tomatoes, pepper, eggplant, crucifers and cucurbits
  • potatoes e.g., sweet potatoes, grapes, cotton, tree fruits (e.g.
  • nonagronomic refers to other than field crops, such as horticultural crops
  • 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
  • animal health e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife
  • 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 invention, 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 invention typically in the form of a composition formulated for veterinary use, to the animal to be protected.
  • parasiticidal i.e. biologically effective
  • 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.
  • Such effects on the pest include necrosis, death, retarded growth, diminished mobility or lessened ability to remain on or in the host animal, reduced feeding and inhibition of reproduction.
  • These effects on invertebrate parasite pests provide control (including prevention, reduction or elimination) of parasitic infestation or infection of the animal.
  • alkyl used either alone or in compound words such as “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • the term “cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • Cycloalkenyl includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1,4-cyclohexadienyl.
  • cycloalkoxy denotes cycloalkyl attached to and linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
  • Alkylcycloalkylalkyl denotes an alkyl group substituted with alkylcycloalkyl. Examples of “alkylcycloalkylalkyl” include 1-, 2-, 3- or 4-methyl or -ethyl cyclohexylmethyl.
  • 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 ⁇ , ⁇ -bicyclopropyl-l-yl, l,l'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4- cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as ⁇ , ⁇ -bicyclohexyl-l-yl), and the different cis- and trans-cycloalkylcycloalkyl isomers, (such as (li?,25)-l,l'-bicyclopropyl-2- yl and (li?,2i?)-l,l'-bicyclopropyl-2-yl).
  • cyclopropylcyclopropyl such as ⁇ , ⁇ -bicyclopropyl-l-yl, l,l'-bicyclopropyl-2-yl
  • Cycloalkylamino denotes an NH radical substituted with cycloalkyl.
  • Examples of “cycloalkylamino” include cyclopropylamino and cyclohexylamino.
  • the term “cycloalkylaminoalkyl” denotes cycloalkylamino substitution on an alkyl group.
  • Examples of “cycloalkylaminoalkyl” include cyclopropylaminomethyl, cyclopentylaminoethyl, and other cycloalkylamino moieties bonded to straight-chain or branched alkyl groups.
  • 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. Further, 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. Examples of “haloalkyl” or “alkyl substituted with halogen” include CF 3 , CH 2 C1, CH 2 CF 3 and CC1 2 CF 3 .
  • haloalkenyl is defined analogously to the term “haloalkyl”.
  • haloalkynyl include HC ⁇ CCHC1, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 0, CC1 3 CH 2 0, HCF 2 CH 2 CH 2 0 and CF 3 CH 2 0.
  • haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • haloalkylamino examples include CF 3 (CH 3 )CHNH, (CF 3 ) 2 CHNH and CH 2 C1CH 2 NH.
  • halocycloalkyl examples include 2-chlorocyclopropyl, 2-fluorocyclobutyl, 3-bromocyclopentyl and 4-chlorocyclohexyl.
  • halodialkyl either alone or in compound words such as “halodialkylamino" means at least one of the two alkyl groups is substituted with at least one halogen atom, and independently each halogenated alkyl group may be partially or fully substituted with halogen atoms which may be the same or different.
  • halodialkylamino include (BrCH 2 CH 2 ) 2 N and BrCH 2 CH 2 (ClCH 2 CH 2 )N.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl include CH 2 OCH 3 , CH 2 CH 2 OCH 3 , CH 2 OCH 2 CH 3 , CH 2 OCH 2 CH 2 CH 2 CH 3 and CH 2 CH 2 OCH 2 CH 3 .
  • alkynyloxy includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC ⁇ CCH 2 0, CH 3 C ⁇ CCH 2 0 and CH 3 C ⁇ CCH 2 CH 2 0.
  • alkylthio includes straight-chain or branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfmyl includes both enantiomers of an alkylsulfinyl group.
  • Alkylamino denotes an NH radical substituted with straight-chain or branched alkyl.
  • alkylamino examples include NHCH 2 CH 3 , NHCH 2 CH 2 CH 3 , and NHCH 2 CH(CH 3 ) 2 .
  • Dialkylamino denotes an N radical substituted independently with two straight-chain or branched alkyl groups. Examples of “dialkylamino” include N(CH 3 ) 2 , N(CH 3 CH 2 CH 2 ) 2 and N(CH 3 )CH 2 CH 3 .
  • Halodialkylamino denotes one straight-chain or branched alkyl moiety and one straight-chain or branched haloalkyl moiety bonded to an N radical, or two independent straight-chain or branched haloalkyl moieties bonded to an N radical, wherein "haloalkyl” is as defined above.
  • Examples of “halodialkylamino” include N(CH 2 CH 3 )(CH 2 CH 2 C1) and N(CF 2 CF 3 ) 2 .
  • An example of haloalkylcarbonylamino is NHC(0)CF 3 and an example of haloalkylcarbonyl(alkyl)amino is N(CH 3 )C(0)CF 3 .
  • Alkylcarbonyl denotes a straight-chain or branched alkyl moiety bonded to a C(O) moiety.
  • alkylcarbonyl include C(0)CH 3 , C(0)CH 2 CH 2 CH 3 and C(0)CH(CH 3 ) 2 .
  • haloalkylcarbonyl include C(0)CF 3 , C(0)CC1 3 , C(0)CH 2 CF 3 and C(0)CF 2 CF 3 .
  • Alkoxycarbonyl denotes a straight-chain or branched alkyl moiety bonded to a C0 2 moiety.
  • Examples of “alkoxycarbonyl” include C(0)OCH 3 , C(0)OCH 2 CH 3 , C(0)OCH 2 CH 2 CH 3 and C(0)OCH(CH 3 ) 2 .
  • Alkylaminocarbonyl denotes a straight-chain or branched alkyl moiety bonded to a C(0)NH moiety.
  • the chemical abbreviations C(0)NH, and C(0)N as used herein represent an amide moiety (i.e. an aminocarbonyl group).
  • alkylaminocarbonyl include C(0)NHCH 3 , C(0)NHCH 2 CH 2 CH 3 and C(0)NHCH(CH 3 ) 2 .
  • Dialkylaminocarbonyl denotes two independent straight-chain or branched alkyl moieties bonded to a C(0)N moiety.
  • dialkylaminocarbonyl include C(0)N(CH 3 ) 2 and C(0)N(CH 3 )(CH 2 CH 3 ).
  • 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.
  • C1-C4 alkyl designates methyl through butyl
  • C 2 alkoxyalkyl designates CH 2 OCH 3
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 2 CH 2 OCH 3 or CH 2 OCH 2 CH 3
  • 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 2 OCH 2 CH 2 CH 3 and CH 2 CH 2 OCH 2 CH 3 .
  • a group contains a substituent which can be hydrogen, for example R 2 , then when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
  • R 2 When a variable group is shown to be optionally attached to a position, for example (R 6 ) n in Formula 1 wherein n may be 0, then hydrogen can be at the position even if not recited in the variable group definition.
  • hydrogen atoms are attached to take up any free valency.
  • ring or “ring system” as a component of Formula 1 is carbocyclic or heterocyclic.
  • ring system denotes two or more connected rings.
  • bicyclic ring system denotes a ring system consisting of two rings sharing two or more common atoms.
  • a ring or a bicyclic ring system can be part of an extended ring system containing more than two rings wherein substituents on the ring or bicyclic ring system are taken together to form the additional rings, which may be in bicyclic relationships with other rings in the extended ring system.
  • aromatic indicates that each of the ring atoms is essentially in the same plane and has a / ⁇ -orbital perpendicular to the ring plane, and that (4n + 2) ⁇ electrons, where n is a positive integer, are associated with the ring or ring system to comply with Huckel's rule.
  • Partially saturated and “partially unsaturated” with reference to a ring or ring system means that the ring or ring system contains at least one double bond but the ring or ring system is not aromatic.
  • a ring system is aromatic if at least one component ring is aromatic.
  • carbocyclic ring denotes a ring wherein the atoms forming the ring backbone are selected only from carbon. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated carbocyclic ring satisfies Huckel's rule, then said ring is also called an "aromatic ring". "Saturated carbocyclic ring” refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
  • heterocyclic ring or “heterocycle” denotes a ring wherein at least one of the atoms forming the ring backbone is other than carbon. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring.
  • saturated heterocyclic ring refers to a heterocyclic ring containing only single bonds between ring members.
  • Partially saturated heterocyclic ring refers a heterocyclic ring containing at least one double bond but which is not aromatic.
  • heteroheteroaromatic ring denotes a fully unsaturated aromatic ring in which at least one atom forming the ring backbone is not carbon.
  • heteroaromatic ring typically contains no more than 4 nitrogens, no more than 1 oxygen and no more than 1 sulfur. Unless otherwise indicated, heteroaromatic rings can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • heteroaromatic bicyclic ring system denotes a ring system consisting of two fused rings, in which at least one of the two rings is a heteroaromatic ring as defined above.
  • radical e.g., a 5- to 6-membered heteroaromatic ring in the definition of R 6
  • the radical may be unsubstituted or substituted with a number of substituents ranging up to the high number stated (e.g., "3"), and the attached substituents are independently selected from the substituents listed.
  • a substituent e.g., Q 1
  • a substituent is a ring or ring system
  • it can be attached to the remainder of Formula 1 through any available ring member, unless otherwise described.
  • the ring members selected from up to 2 O, up to 2 S and up to 4 N are optional, because the number of heteroatom ring members may be zero.
  • the ring or ring system is carbocyclic.
  • the ring or ring system is heterocyclic.
  • the nitrogen atom ring members may be oxidized as N-oxides, because compounds relating to Formula 1 also include N-oxide derivatives.
  • unsubstituted in connection with a group such as a ring or ring system means the group does not have any substituents other than its one or more attachments to the remainder of Formula 1.
  • optionally substituted means that the number of substituents can be zero. Unless otherwise indicated, optionally substituted groups may be substituted with as many optional substituents as can be accommodated by replacing a hydrogen atom with a non-hydrogen substituent on any available carbon or nitrogen atom. Commonly, the number of optional substituents (when present) ranges from 1 to 3.
  • the number of optional substituents may be restricted by an expressed limitation.
  • the phrase "optionally substituted with up to 3 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy on carbon atom ring members and cyano, C1-C2 alkyl and C1-C2 alkoxy on nitrogen atom ring members” means that 0, 1, 2 or 3 substituents can be present (if the number of potential connection points allows).
  • a range specified for the number of substituents exceeds the number of positions available for substituents on a ring, the actual higher end of the range is recognized to be the number of available positions.
  • the number of optional substituents is not restricted by an expressed limitation (e.g., the phrases "optionally substituted with halogen” or “unsubstituted or substituted with at least one substituent independently selected from”), it is understood to mean that the number of optional substituents can range from 0 up to the number of positions available.
  • substituents such as halogen can be present at every available position (for example, the C2F5 substituent is a C2 alkyl group substituted with the maximum number of 5 fluorine atoms)
  • practical factors such as cost and synthetic accessibility can limit the number of occurences of other substituents.
  • These limitations are part of the general synthetic knowledge known to those skilled in the art.
  • the number of optional substituents is up to 3 (i.e. 0, 1, 2 or 3) if accommodated by the number of available positions.
  • substituents such as R 6 can be (among others) a 5- or 6-membered heteroaromatic ring optionally substituted with up to 3 substituents selected from a group of substituents as defined in the Summary of Invention.
  • Examples of a 5- or 6-membered heteroaromatic ring optionally substituted with 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 of the Invention for R 6 (halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy on carbon atom ring members and cyano, C1-C2 alkyl and C1-C2 alkoxy on nitrogen atom ring members) and r is an integer from 0 to 3, limited by the number of available positions on each U group.
  • U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42 and U-43 have only one available position, for these U groups 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 .
  • R 6 is a 3- to 7-membered saturated or unsaturated non-aromatic heterocyclic ring optionally substituted with up to 3 substituents selected from the group of substituents as defined in the Summary of Invention for R 6
  • one or two carbon ring members of the heterocycle can optionally be in the oxidized form of a carbonyl moiety.
  • Examples of a 3- to 7-membered saturated or non-aromatic unsaturated heterocyclic ring include the rings G-1 through G-40 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.
  • R 6 comprises a ring selected from G-33 through G-40
  • G 2 is selected from O, S or 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 of Invention for R 6 (i.e. halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy on carbon atom ring members and cyano, C1-C2 alkyl and C1-C2 alkoxy on nitrogen atom ring members).
  • R v groups are shown in the structures of Exhibits 1 and 2, 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 ring is illustrated as floating, (R v ) r can be attached to any available carbon atom or nitrogen atom of the ring. Note that when the attachment point on the ring is illustrated as floating, the ring can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the ring by replacement of a hydrogen atom.
  • Compounds of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers and atropisomers.
  • 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 invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.
  • two possible enantiomers of Formula 1 are depicted as Formula la and Formula lb involving the chiral center identified with an asterisk (*). Analogously, other chiral centers are possible in other roups, for example in R 4 or R 6 .
  • enantiomeric excess which is defined as (2 ⁇ -1) ⁇ 100 %, where x is the mole fraction of the dominant enantiomer in the mixture (e.g., an ee of 20 % corresponds to a 60:40 ratio of enantiomers).
  • compositions of this invention have at least a 50 % enantiomeric excess; more preferably at least a 75 % enantiomeric excess; still more preferably at least a 90 % enantiomeric excess; and the most preferably at least a 94 % enantiomeric excess of the more active isomer.
  • enantiomerically pure embodiments of the more active isomer are enantiomerically pure embodiments of the more active isomer.
  • Compounds of Formula 1 can comprise additional chiral centers.
  • substituents and other molecular constituents such as R 4 may themselves contain chiral centers.
  • This invention comprises racemic mixtures as well as enriched and essentially pure stereoconfigurations at these additional chiral centers.
  • 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.
  • 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.
  • 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
  • salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms.
  • 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.
  • salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides, and salts thereof.
  • Embodiments of the present invention as described in the Summary of the Invention include those described below.
  • Formula 1 includes stereoisomers, N-oxides, and salts thereof, and reference to "a compound of Formula 1" includes the definitions of substituents specified in the Summary of the Invention unless further defined in the Embodiments.
  • Embodiment 1 A compound of Formula 1 wherein L is L-l, L-2, L-3, L-4 or L-5.
  • Embodiment la A compound of Embodiment 1 wherein L is L-l, L-2 or L-3.
  • Embodiment lb A compound of Embodiment la wherein L is L-l or L-2.
  • Embodiment lc A compound of Formula 1 wherein L is O, S(0) m or NR 7 provided that A is CR 3 and both R 3 and R 4 are other than hydrogen.
  • Embodiment 2 A compound of Formula 1 or any one of Embodiments 1 through lc wherein A is N.
  • Embodiment 2a A compound of Formula 1 or any one of Embodiments 1 through lc wherein A is CR 3 .
  • Embodiment 3 A compound of Formula 1 or any one of Embodiments 1 through 2a either alone or in combination, wherein Q is N.
  • Embodiment 3 a A compound of Formula 1 or any one of Embodiments 1 through 2a either alone or in combination, wherein Q is CH or CR 6 .
  • Embodiment 3b A compound Embodiment 3a wherein Q is CH.
  • Embodiment 3c A compound of Embodiment 3a wherein Q is CR 6 .
  • Embodiment 4 A compound of Formula 1 or any one of Embodiments 1 through 3 c either alone or in combination, wherein R la and R 1 ⁇ are each independently selected from hydrogen, fluorine, chlorine and C1-C2 alkyl.
  • Embodiment 4a A compound of Embodiment 4 wherein R la and R 1 ⁇ are each
  • Embodiment 4b A compound of Embodiment 4a wherein R la and R 1 ⁇ are each
  • Embodiment 4c A compound of Embodiment 4b wherein at least one of R la or R 1 ⁇ is fluorine.
  • Embodiment 4d A compound of Embodiment 4b wherein R la and R 1 ⁇ are each
  • Embodiment 5 A compound of Formula 1 or any one of Embodiments 1 through 4d, either alone or in combination, wherein at least one of R 2 and R 5 is fluorine.
  • Embodiment 5 a A compound of Formula 1 or any one of Embodiments 1 through 4d, either alone or in combination, wherein R 2 and R 5 are each hydrogen.
  • R 3 and R 4 are each independently selected from hydrogen, halogen, cyano, amino, nitro, SF 5 , -CHO, C ⁇ -Cg alkyl, C2-C6 alkenyl, C2 ⁇ Cg alkynyl, C ⁇ -Cg haloalkyl, C2 ⁇ Cg haloalkenyl, C2 ⁇ Cg haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C3-C6 cycloalkenyl, C2 ⁇ Cg alkoxyalkyl, C2 ⁇ Cg alkylthioalkyl, C2 ⁇ Cg alkylcarbonyl, C2 ⁇ Cg haloalkylcarbonyl, C2 ⁇ Cg
  • Embodiment 6a A compound of Embodiment 6 wherein R 3 and R 4 are each
  • Embodiment 6b A compound of Embodiment 6a wherein R 3 and R 4 are each
  • Embodiment 6c A compound of Embodiment 6b wherein R 3 and R 4 are each
  • Embodiment 6d A compound of Embodiment 6c wherein R 3 and R 4 are each
  • Embodiment 6e A compound of Embodiments 6 through 6d wherein R 3 and R 4 are other than hydrogen.
  • Embodiment 7 A compound of Formula 1 or any one of Embodiments 1 through 6e, either alone or in combination, wherein each R 6 is independently halogen, hydroxy, amino, cyano, nitro, SF 5 , C ⁇ -Cg alkyl, C2 ⁇ Cg alkenyl, C2 ⁇ Cg alkynyl, C3 ⁇ Cg cycloalkyl, C4-C10 cycloalkylalkyl, C4-C10 alkylcycloalkyl, C5-C10 alkylcycloalkylalkyl, Cg-C ⁇ cycloalkylcycloalkyl, C ⁇ -Cg haloalkyl, C2 ⁇ Cg haloalkenyl, C2 ⁇ Cg haloalkynyl, C3 ⁇ Cg halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alky
  • haloalkylsulfonyl C1-C4 alkylamino, C2 ⁇ Cg dialkylamino, C3 ⁇ Cg
  • alkylcarbonyl C2 ⁇ Cg alkoxycarbonyl, C2 ⁇ Cg alkylcarbonyloxy, C2 ⁇ Cg alkylcarbonylthio, C2 ⁇ Cg alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, C3-C6 haloalkylcarbonylamino, C3-C6 haloalkylcarbonyl(alkyl)amino or C3-C6 trialkylsilyl; or phenyl.
  • Embodiment 7a A compound of Embodiment 7 wherein R 6 is halogen, hydroxy,
  • alkylcycloalkylalkyl Cg-C ⁇ cycloalkylcycloalkyl, C ⁇ -Cg haloalkyl, C2 ⁇ Cg haloalkenyl, C2 ⁇ Cg haloalkynyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2 ⁇ Cg dialkylamino, C3-C6 cycloalkylamino, C2-C4 alkoxyalkyl, C1-C4 hydroxyalkyl, C2-C
  • Embodiment 7b A compound of Embodiment 7a wherein each R 6 is independently halogen, SF 5 , C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy,
  • Embodiment 7c A compound of Embodiment 7b wherein each R 6 is independently halogen, SF 5 , C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy -C4 alkylthio or C!-C 4 haloalkylthio.
  • Embodiment 7d A compound of Embodiment 7c wherein each R 6 is independently halogen, SF 5 , ieri-butyl, CF 3 , OCF 3 , CF 2 CF 3 , CF(CF 3 ) 2 or SCF 3 .
  • Embodiment 8 A compound of Formula 1 or any one of Embodiments 1 through 7d, either alone or in combination, wherein n is 0, 1 or 2.
  • Embodiment 8a A compound of Embodiment 8 wherein n is 0 or 1.
  • Embodiment 8b A compound of Embodiment 8 wherein n is 1.
  • Embodiment 9 A compound of Formula 1 or any one of Embodiments 1 through 8b, either alone or in combination, wherein R 7 is hydrogen or C1-C3 alkyl.
  • Embodiment 10 A compound of Formula 1 or any one of Embodiments 1 through 9, either alone or in combination, wherein Q 1 is phenyl optionally substituted with up to 3 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy; or a 5- to 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, and optionally substituted with up to 3 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy on carbon atom ring members and cyano, C1-C2 alkyl and C1-C2 alkoxy on nitrogen atom ring members
  • Embodiment 10a A compound of Embodiment 10 wherein Q 1 is phenyl optionally substituted with up to 3 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy.
  • Embodiment 10b A compound of Embodiment 10 wherein Q 1 is phenyl optionally substituted with up to 3 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy.
  • Embodiment 10b A compound of Embodiment 10 wherein Q 1 is phenyl optionally substituted with up to 3 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C
  • Embodiment lOd A compound of Embodiment 10c wherein Q 1 is pyrazole, imidazole,
  • Embodiment lOe A compound of Embodiment lOd wherein Q 1 is pyrazole.
  • Embodiments of this invention including Embodiments 1-1 Oe 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 invention including Embodiments 1-1 Oe above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.
  • Embodiment A A compound of Formula 1 wherein
  • L is L-l, L-2, L-3, L-4 or L-5;
  • A is CR 3 ;
  • R la and R 1 ⁇ are each independently selected from hydrogen, fluorine and methyl
  • R 2 and R 5 are each hydrogen
  • R 3 and R 4 are each independently selected from hydrogen, halogen, C ⁇ -Cg alkyl, C ⁇ -C ⁇ haloalkyl, C ⁇ -C ⁇ alkoxy, C ⁇ -C ⁇ haloalkoxy, C ⁇ -C ⁇ alkylthio, C ⁇ -Cg alkylsulfmyl and C ⁇ -Cg alkylsulfonyl; or Q 1 ;
  • Q is CH or CR 6 ;
  • each R 6 is independently halogen, SF 5 , C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfmyl, Cj- C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C 3 -C6 trialkylsilyl.
  • Embodiment Al A compound of Formula 1 wherein
  • L is O, S(0) m or NR 7 ;
  • A is CR 3 ;
  • R 2 and R 5 are each hydrogen
  • R 3 and R 4 are each independently selected from halogen, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C ⁇ -Cg alkoxy, C ⁇ -Cg haloalkoxy, C ⁇ -Cg alkylthio, C ⁇ -Cg alkylsulfmyl and C ⁇ -Cg alkylsulfonyl; or Q 1 ;
  • Q is CH or CR 6 ;
  • each R 6 is independently halogen, SF 5 , C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C ⁇ -
  • R 7 is hydrogen or C1-C 3 alkyl.
  • Embodiment B A compound of Embodiment A wherein
  • L is L-l or L-2;
  • R la and R lb are each independently selected from hydrogen and fluorine; Q is CH;
  • n 0, 1 or 2;
  • R 6 is independently halogen, SF 5 , C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy C1-C4 alkylthio or C1-C4 haloalkylthio.
  • Embodiment B 1. A compound of Embodiment Al wherein
  • n 0, 1 or 2;
  • R 6 is independently halogen, SF 5 , C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, -C4 alkoxy, C1-C4 haloalkoxy C1-C4 alkylthio or C1-C4 haloalkylthio.
  • Embodiment C A compound of Embodiment B wherein
  • R 3 and R 4 are each independently selected from hydrogen, fluoro, chloro, methoxy, methylthio, methylsulfmyl, methylsulfonyl and pyrazole; and each R 6 is independently halogen, SF 5 , tert-butyl, CF 3 , OCF 3 , CF 2 CF 3 ,
  • Embodiment CI A compound of Embodiment Bl wherein
  • R 3 and R 4 are each independently selected from fluoro, chloro, methoxy, methylthio, methylsulfmyl, methylsulfonyl and pyrazole; and each R 6 is independently halogen, SF 5 , tert-butyl, CF 3 , OCF 3 , CF 2 CF 3 ,
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of:
  • compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and nonagronomic invertebrate pests.
  • 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 (i.e. in a biologically effective amount) 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 (i.e. in a biologically effective amount).
  • Embodiments of the invention also include a composition for protecting an animal comprising a compound (i.e. in a parasiticidally effective amount) of any of the preceding Embodiments, either alone or in combination, and a carrier.
  • Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of any of the preceding Embodiments, either alone or in combination, (e.g., as a composition described herein).
  • a method for protecting an animal comprising administering to the animal a parasiticidally effective amount of a compound of any of the preceding Embodiments, either alone or in combination, (e.g., as a composition described herein).
  • Embodiments of the invention also include a composition comprising a compound of any of the preceding Embodiments, either alone or in combination, in the form of a soil drench liquid formulation.
  • Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the soil with a liquid composition as a soil drench comprising a biologically effective amount of a compound of any of the preceding Embodiments, either alone or in combination.
  • Embodiments of the invention also include a spray composition for controlling an invertebrate pest comprising a compound (i.e. in a biologically effective amount) of any of the preceding Embodiments, either alone or in combination, and a propellant.
  • Embodiments of the invention further include a bait composition for controlling an invertebrate pest comprising a compound (i.e. in a biologically effective amount) of any of the preceding Embodiments, either alone or in combination, one or more food materials, optionally an attractant, and optionally a humectant.
  • Embodiments of the invention also include a device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
  • Embodiments of the invention also include a method 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, either alone or in combination, (e.g., as a composition described herein).
  • Embodiments of the invention also include methods for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of any of the preceding Embodiments, either alone or in combination.
  • Embodiments of the invention also include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1, an N-oxide, or a salt thereof, (e.g., as a composition described herein), provided that the methods are not methods of medical treatment of a human or animal body by therapy.
  • Embodiments of the invention also include any of the preceding embodiments, either alone or in combination, wherein the invertebrate pest is an arthropod.
  • Embodiments of the invention also include any of the preceding embodiments, either alone or in combination, wherein the arthropod is selected from the group consisting of insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
  • Embodiments of the invention also include any of the preceding embodiments, either alone or in combination, wherein the arthropod is an insect.
  • Embodiments of the invention also include any of the preceding embodiments, either alone or in combination, wherein the invertebrate pest is a gastropod.
  • Embodiments of the invention also include any of the preceding embodiments, either alone or in combination, wherein the gastropod is selected from the group consisting of snails, slugs and other Stylommatophora.
  • Embodiments of the invention also include any of the preceding embodiments, either alone or in combination, wherein the invertebrate pest is a nematode.
  • Embodiments of the invention also include any of the preceding embodiments, either alone or in combination, wherein the nematode is selected from phytophagous nematodes.
  • Embodiments of the invention also include any of the preceding embodiments, either alone or in combination, wherein the invertebrate pest is a helminth.
  • Embodiments of the invention also include any of the preceding embodiments, either alone or in combination, wherein the helminth is selected from the group consisting of roundworms, heartworms, flukes, acanthocephalans and tapeworms.
  • This invention 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.
  • compounds of Formula la can be prepared by treatment of the corresponding olefin compounds of Formula lb (compounds of Formula 1 wherein L is L-3) with Me3SI/t-BuOK or CH2l2 ZnEt3 in various solvents, such as diethyl ether, tetrahydrofuran or dichloromethane.
  • solvents such as diethyl ether, tetrahydrofuran or dichloromethane.
  • the formation of cyclopropyl derivatives are well known in the literature, for example, see V. J. Cee, et al. WO2009/154775 and B. Lv, et al. Bio. & Med. Chem. Lett. 2009, 19, 6877.
  • the method of Scheme 1 is illustrated by synthesis Example 1, Step E.
  • compounds of Formula lc (compounds of Formula 1 wherein L is L-2) can be prepared by treatment of the corresponding olefin compounds of Formula lb (compounds of Formula 1 wherein L is L-3) with oxidant reagents, such as mCPBA (meto-chloroperbenzoic acid) or methyl(trifluoromethyl)dioxirane in various solvents, such as dichloromethane or acetonitrile/water.
  • oxidant reagents such as mCPBA (meto-chloroperbenzoic acid) or methyl(trifluoromethyl)dioxirane in various solvents, such as dichloromethane or acetonitrile/water.
  • compounds of Formula lb (compounds of Formula 1 wherein L is L-3) can be prepared by elimination of corresponding alcohol compounds of Formula 3 with acids, such as H 2 S0 4 , HC1, HBr, acetic acid or /?-toluenesulfonic acid in solvents like toluene, xylene, acetic acid or water in a temperature range from 50 to 150 °C.
  • acids such as H 2 S0 4 , HC1, HBr, acetic acid or /?-toluenesulfonic acid in solvents like toluene, xylene, acetic acid or water in a temperature range from 50 to 150 °C.
  • This method of olefin synthesis via elimination of water from an alcohol is well known in the art, for example, see Q. Hu, et al. J. Med. Chem. 2010, 53, 5049.
  • the method of Scheme 4 is illustrated by synthesis Example 1, Step D.
  • compounds of Formula 3 can be prepared by reaction of the corresponding carbonyl compounds of Formula 2 with commercially available Grinard reagents or lithium reagents, such as methylmagnesium bromide or methyl lithium in ethereal solvents like diethyl ether or tetrahydrofuran at a temperature range from -78 °C to room temperature.
  • Grinard reagents or lithium reagents such as methylmagnesium bromide or methyl lithium in ethereal solvents like diethyl ether or tetrahydrofuran
  • compounds of Formula 2 can be prepared by oxidation reaction of the corresponding alcohol compounds of Formula 4 with oxidants, such as manganese dioxide or Dess-Martin periodiane in solvents like dichloromethane or chloroform at a temperature range from room temperature to the reflux temperature of the solvent.
  • oxidants such as manganese dioxide or Dess-Martin periodiane in solvents like dichloromethane or chloroform
  • This oxidation reaction is well known in the chemical literature.
  • the method of Scheme 6 is illustrated by synthesis Example 1, Step B.
  • compounds of Formula 4 can be prepared by reaction of nucleophiles generated from compounds of Formula 5 with aldehydes of Formula 6.
  • metal-halogen exchange of compounds of Formula 5 (wherein X is Br or I) with n-butyllithium or z ' -propylmagnesium bromide in ether solvents, such as THF, diethyl ether or dioxanes at temperatures between -100 °C to -40 °C will generate the desired anions.
  • the compounds of Formula 4 can be prepared by trapping those anions with various aldehydes of Formula 6. This method is well known in the chemical literature, see for example, T. Francois, et al. Tetrahedron, 2000, 56, 1349.
  • Compounds of Formula 4 can also be prepared by treating compounds of Formula 5 (wherein X is H) with bases, such as lithium diisopropylamide or 2,2,6,6- tetramethylpiperidinyl magnesium chloride - lithium chloride complex in ether solvents, such as tetrahydrofuran, diethyl ether or dioxanes at temperatures between -100 °C to - 10 °C.
  • bases such as lithium diisopropylamide or 2,2,6,6- tetramethylpiperidinyl magnesium chloride - lithium chloride complex in ether solvents, such as tetrahydrofuran, diethyl ether or dioxanes at temperatures between -100 °C to - 10 °C.
  • ether solvents such as tetrahydrofuran, diethyl ether or dioxanes
  • Compounds of Formula Id (compounds of Formula 1 wherein R la is F) can be prepared using the procedure shown in Scheme 8.
  • Compounds of Formula 7 react with aryllithium reagents of Formula 8 to form products of Formula Id.
  • Aryllithiums of Formula 8 are typically generated in tetrahydrofuran or diethyl ether solvent at a temperature ranging from -78 °C to 0 °C, followed by treatment with a compound of Formula 7 at temperatures ranging from -78 °C to ambient temperatures.
  • the aryllithium reagents of Formula 8 are typically used in stoichiometric excess, typically 1.1 to 3.0 molar equivalents.
  • An example of an analogous reaction may be found in J. Fluorine Chem. 1984, 25, 169-193.
  • the method of Scheme 8 is illustrated by Synthesis Example 5.
  • Compounds of Formula 7 can be prepared by the method shown in Scheme 9.
  • An aryl bromide or and aryl iodide of Formula 9 reacts with iodo(trifluoroethenyl)zinc in the presence of a palladium catalyst in a solvent to form trifluorovinyl compounds of Formula 7.
  • Typical palladium catalysts include, but are not limited to, Pd(PPh 3 ) 4 , Pd(o-tolyl) 4 and PdCl2(PPh 3 ) 2 .
  • Typical solvents include, but are not limited to, N,N-dimethylforamide or tetrahydrofuran. Typical reaction temperatures range from 0 °C to the reflux temperature of the solvent.
  • the amount of catalyst can range from 0.02 to 1.0 equivalents, with 0.1 equivalents being the amount typically used.
  • the amount of iodo(trifluoroethenyl)zinc used is typically 1 to 3 molar equivalents.
  • An example of an analogous reaction may be found in J. Fluorine Chem. 2001, 111, 247-252.
  • Compounds of Formula 10 can be prepared using the procedure illustrated in Scheme 11.
  • An aromatic aldehyde of Formula 6 can be treated with 1 to 3 molar equivalents of diethylphosphite in the presence of a base to produce hydroxyl-phosphonates of Formula 12.
  • Typical bases for this reaction include, but are not limited to, alkoxides such as potassium tert-butoxide, carbonates such as potassium carbonate and amines such as triethylamine. Between 1.1 and 3.0 molar equivalents of base are typically used.
  • Typical solvents include N,N-dimethylforamide or tetrahydrofuran. The reactions are typically performed at temperatures ranging from 0 °C up to the reflux temperature of the solvent.
  • An example of an analogous reaction may be found in J. Fluorine Chem. 2011, 132, 636-640.
  • the hydroxyl-phosphonates of Formula 12 can be treated with a fluorinating reagent such as (diethylamino)sulfur trifluoride (DAST) or bis(2-methoxyethyl)aminosulfur trifluoride (Deoxo-Fluor ®) in a solvent such as dichloromethane at temperatures ranging from -78 °C to ambient temperature to form the fluoro-phosphonates of Formula 10.
  • DAST diethylamino)sulfur trifluoride
  • Deoxo-Fluor ® bis(2-methoxyethyl)aminosulfur trifluoride
  • the fluorinating reagents are used in stoichiometric excess, typically 1.1 to 3.0 molar equivalents.
  • An example of an analogous reaction may be found in Synlett 2009, 2180-2182.
  • compounds of Formula If (compounds of Formula 1 wherein L is L-6) can be prepared by the treatment of corresponding hydroxy compounds of Formula 13 with fluorinating reagents such as (diethylamino)sulfur trifluoride (DAST) or bis(2- methoxyethyl)aminosulfur trifluoride (Deoxo-Fluor ®) in solvents, such as diethyl ether, tetrahydrofuran or dichloromethane.
  • fluorinating reagents such as (diethylamino)sulfur trifluoride (DAST) or bis(2- methoxyethyl)aminosulfur trifluoride (Deoxo-Fluor ®) in solvents, such as diethyl ether, tetrahydrofuran or dichloromethane.
  • DAST diethylamino)sulfur trifluoride
  • Deoxo-Fluor ® bis(2- methoxye
  • olefins of Formula 14 can be prepared by reaction of an aldehyde or ketone of Formula 11 with a phophonate of Formula 15 in the presence of a base.
  • bases for the reaction include alkoxide bases such as potassium tert-butoxide in an ethereal solvent such as diethyl ether or tetrahydrofuran, a hydride base such as sodium hydride in an aprotic solvent such as N,N-dimethylforamide or tetrahydrofuran, or an amide base such as lithium diisopropylamide in an aprotic solvent such as tetrahydrofuran.
  • Typical reaction conditions employ the use of one to five molar equivalents of the base at temperatures ranging from -78 °C up to the reflux temperature of the solvent.
  • Compounds of Formula lh (compounds of Formula 1 wherein Rib is F) can be prepared using the procedure illustrated in Scheme 15.
  • Compounds of Formula lh can be formed by the reaction diols of Formula 16 with an excess of two molar equivalents of fluorinating reagents such as (diethylamino)sulfur trifluoride (DAST) or bis(2- methoxyethyl)aminosulfur trifluoride (Deoxo-Fluor ®) in haloalkane solvents, such as dichloromethane or 1 ,2-dichloroethane at temperatures ranging from -78 °C to ambient temperature.
  • fluorinating reagents such as (diethylamino)sulfur trifluoride (DAST) or bis(2- methoxyethyl)aminosulfur trifluoride (Deoxo-Fluor ®) in haloalkane solvents, such as dichloromethane or
  • compounds of Formula li (compounds of Formula 1 wherein L is L-10) can be prepared by ring expanding reaction of corresponding epoxide compounds of Formula lc (wherein R la and R 1 ⁇ are hydrogen).
  • the reagents typically used for this transformation are IV ⁇ SOI in the presence of t-BuOK. This method is known in the chemical literature, for example see, K. Okuma, et al. J. Org. Chem. 1983, 48, 5133.
  • compounds of Formula lj (compounds of Formula 1 wherein L is L-8, L-9, L-10, L-l l, L12) can be prepared by contacting compounds of Formula 17 wherein X 2 is a good leaving group, such as CI, Br, I or OTf, with a compound of Formula 18 (a boronic acid or ester) in the presence of a palladium catalyst.
  • X 2 is a good leaving group, such as CI, Br, I or OTf
  • a compound of Formula 18 a boronic acid or ester
  • a wide variety of palladium-containing compounds and complexes are useful as catalysts for the present method.
  • Examples of palladium-containing compounds and complexes useful as catalysts in the method of Scheme 18 include Pd(OAc) 2 (palladium(II) acetate), PdCl 2 (palladium(II) chloride), PdCl2(PPh 3 ) 2 bis(triphenylphosphine)palladium(II) dichloride, Pd(PPh 3 ) 4 (tetrakis(triphenylphosphine)palladium(O), Pd(C 5 H 7 0 2 )2 (palladium(II) acetylacetonate) and Pd 2 (dba) 3 tris (dibenzylideneacetone)dipalladium(O).
  • Coupling reactions with boronic acids or derivatives in the presence of palladium catalysts can be conducted over a wide range of temperatures, including from about 25 to about 150 °C. Of note are temperatures from about 80 and about 110 °C, which typically provide fast reaction rates and high product yields.
  • Useful solvents include, for example, ethers such as 1 ,2-dimethoxyethane, amides such as N,N-dimethylacetamide, and nonhalogenated aromatic hydrocarbons such as toluene.
  • ethers such as 1 ,2-dimethoxyethane
  • amides such as N,N-dimethylacetamide
  • nonhalogenated aromatic hydrocarbons such as toluene.
  • X 2 is Br, I, OS0 2 CF 3 ;
  • G ⁇ G 2 is CH 2 CH 2 , CH 2 0, OCH 2 , CH 2 S or SCH 2 ;
  • R 20 is H or Me
  • compounds of Formula 17 (wherein G l -G 2 is CH 2 CH 2 , CH 2 0, OCH 2 , CH 2 S orSCH 2 and X 2 is a good leaving group like Br, I orOS0 2 CF 3 ) can be prepared by converting the corresponding alcohol of Formula 19 to a bromide, iodide or trifluoromethanesulfonate derivative.
  • PBr3, CBr4 or MeS0 2 Cl in solvents like dichloromethane or chloroform will provide compounds of Formula 17. This conversion is known in the chemical literature, for example see, M. Meroni, et al. J. Med. Chem. 1979, 22, 183.
  • Scheme 19 is known in the chemical literature, for example see, M. Meroni, et al. J. Med. Chem. 1979, 22, 183.
  • X 2 is Br, I, OS0 2 CF 3 ;
  • G ⁇ G 2 is CH 2 CH 2 , CH 2 0, OCH 2 , CH 2 S or SCH 2
  • compounds of Formula 19 (wherein wherein G l -G 2 is CH 2 CH 2 , CH 2 0, OCH 2 , CH 2 S orSCH 2 ) can be prepared by adding anions generated from compounds of Formula 5 to carbonyl compounds of Formula 20.
  • the anions of Formula 5 can be generated according to the procedures described for Scheme 7.
  • the anions of generated from compounds of Formula 5 can be treated with commercially available or known carbonyl compounds of Formula 20 in solvents, such as tetrahydrofuran, diethyl ether or dioxanes at temperatures in the range of -78 °C to room temperature to generate the desired alcohol compounds of Formula 19.
  • solvents such as tetrahydrofuran, diethyl ether or dioxanes
  • X is H or Br, I
  • G ⁇ G 2 is CH 2 CH 2 , CH 2 0, OCH 2 , CH 2 S or SCH 2
  • compounds of Formula lk (wherein A is CR 3 and L is O) can be formed by contacting pyridines of Formula 21 (wherein X 3 is a leaving group such as F, CI, Br, I or a sulfonate such as methanesulfonate) with a hydroxy aryl compound of Formula 22 in the presence of base such as potassium carbonate or cesium carbonate in a solvent such as, but not limited to, N,N-dimethylformamide, tetrahydrofuran or acetone or a hydride base such as sodium hydride in a solvent such as N,N-dimethylformamide or tetrahydrofuran.
  • base such as potassium carbonate or cesium carbonate
  • a solvent such as, but not limited to, N,N-dimethylformamide, tetrahydrofuran or acetone or a hydride base such as sodium hydride in a solvent such as N,N-dimethylformamide or tetrahydr
  • Typical Scheme 21 reactions employ the use of an excess of base, usually 1.1 to 5.0 molar equivalents and reaction temperatures typically range from 0 °C up to the reflux temperature of the solvent. In certain cases, microwave radiation is used to achieve reaction temperatures that exceed the atmospheric pressure reflux temperatures of the solvent. In certain cases, additives such as copper (0) or copper(I)iodide are added in catalytic amounts to increase the rate of formation of compounds of Formula lk.
  • a related synthesis example may be found in Tetrahedron Lett. 2006, 47, 5045-5048. The method of Scheme 21 is illustrated in Synthesis Example 9.
  • X J is F, CI, Br, I or OS0 2 CF 3
  • compounds of Formula 11 may be prepared by contacting a pyridine of Formula 21 with a aryl thiol of Formula 23 using conditions that are analogous to those described for Scheme 21 reactions.
  • the method of Scheme 22 is illustrated in Synthesis Example 10.
  • an oxidant such as, but not limited to, sodium periodate or Oxone ® in solvents such as tetrahydrofuran, acetonitrile, methanol, ethanol or water (or mixtures of solvents) at temperatures ranging from 0 °C to ambient temperature.
  • peracids such as m-chloroperbenzoic acid or peracetic acid may be used in solvents such as dichloromethane or ethyl acetate at temperatures ranging from 0 °C to ambient temperature.
  • compounds of Formula In (wherein L is NR 7 ) can be prepared by contacting pyridines of Formula 21 with an arylamine of Formula 25 in the presence of an amine base such as triethylamine in a solvent such as l-methyl-2- pyrrolidinone.
  • Typical reaction temperatures range from 100 °C to 250 °C with heating most conveniently supplied by microwave radiation. Analogous reaction procedures may be found in the chemical literature, see for example, Tetrahedron 2010, 66, 2398-2403. The method of Scheme 25 is illustrated in Synthesis Example 11.
  • X J is F, CI, Br, I or OS0 2 CF 3
  • Step A Preparation of 3,5-difluoro-a-[4-[(trifluoromethyl)thio]phenyl]-4- pyridinemethanol
  • Step C Preparation of 3,5-difluoro-a-methyl-a-[4-[(trifluoromethyl)thio]phenyl]-4- pyridinemethanol
  • Step D Preparation of 3,5-difluoro-4-[l-[4-[(trifluoromethyl)thio]phenyl]ethenyl]- pyridine
  • Step E Preparation of 3,5-difluoro-4-[l-[4-[(trifluoromethyl)thio]phenyl]- cyclopropyl]pyridine
  • Step A Preparation of 3-chloro-5-(methylthio)-a-[[4-(trifluoromethoxy)phenyl]- methyl] -4-pyridinemethanol
  • reaction mixture After stirring for 1 h at 66 °C, the reaction mixture is cooled to room temperature and then is added into a solution of 3-chloro-6- thiomethyl-4-pyridinecarboxaldehyde (563 mg, 3.0 mmole) in THF (10 mL) at 0 °C. The reaction mixture was allowed to warm to room temperature and stir for 5 h. The reaction mixture was then treated with saturated aqueous ammonium chloride. The organic phase was separated and the aqueous phase extracted with EtOAc. The combined organic phases were washed with saturated aqueous NaCl solution, dried over sodium sulfate and concentrated.
  • Step B Preparation of 3-chloro-4-[l-fluoro-2-[4-(trifluoromethoxy)phenyl]ethyl]-5-
  • Step A Preparation of 1 -( 1 , 1 -dimethylethyl)-4-( 1 ,2,2-trifluoroethenyl)benzene
  • iodotrifluoroethylene (1.1 mL, 12.1 mmol, condensed in a gas-addition funnel) was added dropwise to a stirred suspension of zinc powder (1.58 g, 24.2 mmol, acid washed and dried before use) and anhydrous DMF (12 mL) while keeping temperature of the exothermic reaction below 30 °C with an ice-water bath.
  • the resulting dark brown suspension of iodo(trifluoroethenyl)zinc (ca. 1.0 molar) was stirred at ambient temperature for 2 h.
  • Step B Preparation of 3,5-dichloro-4-[(lE)-2-[4-(l,l-dimethylethyl)phenyl]-l,2- difluoroethenyljpyridine
  • Step A Preparation of diethyl -[[4-(l , 1 -dimethylethyl)phenyl]hydroxymethyl]- phosphonate
  • the organic phase was concentrated onto silica gel (6 g) and the residue was purified by medium pressure liquid chromatography on a silica column eluting with a gradient of 0% to 100% ethyl acetate in hexanes to give the title compound as a pale yellow viscous oil (1.65 g).
  • Step B Preparation of diethyl -[[4-(l , 1 -dimethylethyl)phenyl]fluoromethyl]- phosphonate
  • Step C Preparation of 3,5-dichloro-4-[(lZ)-2-[4-(l,l-dimethylethyl)phenyl]-2- fluoroethenyljpyridine
  • n-Butyllithium (0.32 mL of a 2.5 M solution in hexanes, 0.80 mmol) was added to a solution of diisopropylamine (0.12 mL, 0.86 mmol) and anhydrous THF (2.6 mL) at -70 °C.
  • the resulting solution was stirred at 0 °C for 15 min, re-cooled to -70 °C, and treated with a solution of diethyl -[[4-(l,l-dimethylethyl)phenyl]fluoromethyl]phosphonate (i.e. the product of Step B) (200 mg, 0.66 mmol) and anhydrous THF.
  • the resulting solution was treated with 3,5-dichloro-4-pyridine carboxaldehyde (105 mg, 0.60 mmol) at -70 °C, stirred at -70 °C for 1 h, stirred at 25 °C for 1 h, and the resulting solution was quenched with saturated aqueous ammonium chloride solution at 0 °C.
  • the resulting mixture was partitioned between diethyl ether and saturated aqueous ammonium chloride solution, the organic phase was washed with saturated aqueous ammonium chloride solution, dried over anhydrous magnesium sulfate, and concentrated onto 1 g of silica gel.
  • Step A Preparation of 3,5-dichloro-4-[(lE)-2-[4-(l,l-dimethylethyl)phenyl]ethenyl]- pyridine
  • Step B Preparation of 4-[l-bromo-2-[4-(l,l-dimethylethyl)phenyl]-2-fluoroethyl]- 3,5-dichloropyridine
  • N-Bromosuccinimide (166 mg, 0.93 mmol) was added to a solution of 3,5-dichloro-4- [(lE)-2-[4-(l,l-dimethylethyl)phenyl]ethenyl]pyridine (i.e. the product of Step A) (190 mg, 0.62 mmol), hydrogen fluoride-pyridine complex (70% HF, 6.2 mL) and diethyl ether (6.2 mL) at 0 °C in a teflon round-bottom flask. The reaction mixture was stirred at 0 °C for 1 h, 25 °C for 2 h and the resulting mixture was poured into 100 g of ice.
  • Step A Preparation of l-(3,5-dichloro-4-pyridinyl)-2-[4-(l,l-dimethylethyl)phenyl]-
  • Methanesulfonamide (0.3 g, 3.2 mmol) was added and the resulting mixture was stirred for 24 h at ambient temperature, diluted with acetonitrile (100 mL) and concentrated onto silica gel. Purification by medium pressure liquid chromatography on a silica column eluting with a gradient of 0% to 100% ethyl acetate in hexanes gave an off-white glassy solid (120 mg).
  • Step B Preparation of 4-[2-[4-(l,l-dimethylethyl)phenyl]-l,2-difluoroethyl]-3,5- dichloropyridine
  • Tables 1A to 121 By the procedures described herein together with methods known in the art, the following compounds of Tables 1A to 121 can be prepared.
  • the following abbreviations are used in Tables 1A to 121 which follow: / is tertiary, s is secondary, n is normal, is iso, Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, S(0)Me is methylsulfmyl and SC ⁇ Me is methylsulfonyl.
  • fragment B is defined to mean the following substructure of Formula 1:
  • Tables 1A-201A pertain to the structure shown below.
  • R 3 is H and R 4 is H
  • the present disclosure also includes Tables 2A through 201 A, each of which is constructed the same as Table 1 A above except that the row heading in Table 1 A (i.e. "R 3 is H and R 4 is H.") below the Markush structure is replaced with the respective row heading shown below.
  • Table 2A the row heading is "R 3 is H and R 4 is F, and B is as defined in Table 1 A above.
  • the first entry in Table 2 A specifically discloses 3-fluoro- 4-[ 1 -(4-chlorophenyl)cyclopropyl]pyridine.
  • R 3 is F and R 4 is F
  • R 3 is F and R 4 is CI
  • R 3 is F and R 4 is Br
  • R 3 is F and R 4 is I
  • R 3 is F and R 4 is Me
  • R 3 is F and R 4 is Et
  • R 3 is F and R 4 is n-Pr
  • R 3 is F and R 4 is z ' -Pr
  • R 3 is F and R 4 is «-Bu
  • R 3 is F and R 4 is z ' -Bu
  • R 3 is CI and R 4 is SEt 182A R 3 is Me and R 4 is SEt
  • R 3 is CI and R 4 is S(0)Et 183A R 3 is Me and R 4 is S(0)Et
  • R 3 is CI and R 4 is S0 2 Et 184A R 3 is Me and R 4 is S0 2 Et
  • R 3 is CI and R 4 is S- «-Pr 185 A R 3 is Me and R 4 is S-n-Pr
  • R 3 is CI and R 4 is S(0)- «-Pr 186A R 3 is Me and R 4 is S(0)- «-Pr
  • R 3 is CI and R 4 is S0 2 - «-Pr 187 A
  • R 3 is Me and R 4 is S0 2 -»-Pr
  • R 3 is CI and R 4 is S(0)-z-Pr 189 A R 3 is Me and R 4 is S(0)-z-Pr
  • R 3 is CI and R 4 is S0 2 -z-Pr 190 A R 3 is Me and R 4 is S0 -z-Pr
  • R 3 is CI and R 4 is is SCH 2 CF 3 191A
  • R 3 is Me and R 4 is is SCH 2 CF 3
  • R 3 is CI and R 4 is S(0)CH 2 CF 3 192 A R 3 is Me and R 4 is S(0)CH 2 CF 3
  • R 3 is CI and R 4 is S0 2 CH 2 CF 3 193A
  • R 3 is Me and R 4 is S0 2 CH 2 CF 3
  • R 3 is CI and R 4 is 2-Pyridinyl 195A R 3 is Me and R 4 is 2-Pyridinyl
  • R 3 is CI and R 4 is 1- imidazole 199 A R 3 is Me and R 4 is 1 -imidazole
  • R 3 is CI and R 4 is 1- 1,2,3-triazole 200A
  • R J is Me and R 4 is 1-1,2,3-triazole
  • R 3 is CI and R 4 is 2- 1,2,3-triazole 201A R 3 is Me and R 4 is 2-1,2,3-triazole
  • Table IB is identical to Table 1A, except that the chemical structure in the Table IB heading is replaced with the following structure:
  • the first compound in Table IB is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2B through 20 IB are constructed in a similar manner as Tables 2 A through 201A. TABLE 1C
  • Table 1C is identical to Table 1A, except that the chemical structure in the Table 1C heading is replaced with the following structure:
  • the first compound in Table 1C is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2C through 201C are constructed in a similar manner as Tables 2A through 201A.
  • Table ID is identical to Table 1A, except that the chemical structure in the Table ID heading is replaced with the foll ing structure:
  • the first compound in Table ID is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2D through 20 ID are constructed in a similar manner as Tables 2 A through 201A.
  • Table IE is identical to Table 1A, except that the chemical structure in the Table IE heading is replaced with the following structure:
  • the first compound in Table IE is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2E through 20 IE are constructed in a similar manner as Tables 2 A through
  • Table IF is identical to Table 1A, except that the chemical structure in the Table IF heading is replaced with the foll ing structure:
  • the first compound in Table IF is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2F through 20 IF are constructed in a similar manner as Tables 2 A through 201A.
  • Table IG is identical to Table 1A, except that the chemical structure in the Table IG heading is replaced with the following structure:
  • the first compound in Table IG is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2G through 201G are constructed in a similar manner as Tables 2A through 201A.
  • Table 1H is identical to Table 1A, except that the chemical structure in the Table 1H heading is replaced with the followin structure:
  • the first compound in Table 1H is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2H through 201H are constructed in a similar manner as Tables 2 A through 201A.
  • Table II is identical to Table 1A, except that the chemical structure in the Table II heading is replaced with the followin structure:
  • the first compound in Table II is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 21 through 2011 are constructed in a similar manner as Tables 2 A through 201A.
  • Table 1J is identical to Table 1A, except that the chemical structure in the Table 1J heading is replaced with the following structure:
  • the first compound in Table 1J is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2 J through 201J are constructed in a similar manner as Tables 2 A through 201A.
  • Table IK is identical to Table 1A, except that the chemical structure in the Table IK heading is replaced with the followin structure:
  • the first compound in Table IK is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2K through 20 IK are constructed in a similar manner as Tables 2 A through 201A.
  • Table 1L is identical to Table 1A, except that the chemical structure in the Table 1L heading is replaced with the following structure:
  • the first compound in Table 1L is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl. TABLES 2L-201L
  • Tables 2L through 201L are constructed in a similar manner as Tables 2A through 201A.
  • Table 1M is identical to Table 1A, except that the chemical structure in the Table 1M heading is replaced with the following structure:
  • the first compound in Table 1M is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2M through 201M are constructed in a similar manner as Tables 2 A through 201A.
  • Table IN is identical to Table 1A, except that the chemical structure in the Table IN heading is replaced with the following structure:
  • the first compound in Table IN is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2N through 20 IN are constructed in a similar manner as Tables 2A through 201A.
  • Table 10 is identical to Table 1A, except that the chemical structure in the Table 10 heading is replaced with the following structure:
  • the first compound in Table 10 is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 20 through 2010 are constructed in a similar manner as Tables 2A through
  • Table IP is identical to Table 1A, except that the chemical structure in the Table IP heading is replaced with the following structure:
  • the first compound in Table IP is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2P through 20 IP are constructed in a similar manner as Tables 2 A through 201A.
  • Table 1Q is identical to Table 1A, except that the chemical structure in the Table 1Q heading is replaced with the following structure:
  • the first compound in Table 1Q is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl. TABLES 2Q-201Q
  • Tables 2Q through 201Q are constructed in a similar manner as Tables 2A through 201A.
  • Table IR is identical to Table 1A, except that the chemical structure in the Table IR heading is replaced with the followin structure:
  • the first compound in Table IR is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2R through 20 IR are constructed in a similar manner as Tables 2 A through 201A.
  • Table IS is identical to Table 1A, except that the chemical structure in the Table IS heading is replaced with the following structure:
  • the first compound in Table IS is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2S through 20 IS are constructed in a similar manner as Tables 2A through 201A.
  • fragment B is defined to mean the following substructure of Formula 1:
  • Tables 1T-147T pertain to the structure shown below.
  • R 3 is F and R 4 is F
  • the present disclosure also includes Tables 2T through 147T, each of which is constructed the same as Table IT above except that the row heading in Table IT (i.e. "R 3 is F and R 4 is F.") below the Markush structure is replaced with the respective row heading shown below.
  • Table 2T the row heading is "R 3 is F and R 4 is CI, and B is as defined in Table IT above.
  • the first entry in Table 2T specifically discloses 3- chloro-4-(4-chlorophenoxy)-5-fluoropyridine.
  • R 3 is F and R 4 is CI 51T R 3 is CI and R 4 is CI
  • R is F and R 4 is Br 52T R 3 is CI and R 4 is Br
  • R 3 is F and R 4 is I 53T R 3 is CI and R 4 is I
  • R 3 is F and R 4 is Me 54T R 3 is CI and R 4 is Me
  • R 3 is F and R 4 is Et 55T R 3 is CI and R 4 is Et
  • R is F and R 4 is n-Pr 56T R 3 is CI and R 4 is n-Pr
  • R is F and R 4 is z ' -Pr 57T R 3 is CI and R 4 is z ' -Pr Table Table Headings Table Table Headings
  • R 3 is F and R 4 is «-Bu 58T R 3 is CI and R 4 is «-Bu
  • R 3 is F and R 4 is z ' -Bu 59T R 3 is CI and R 4 is z-Bu
  • R 3 is F and R 4 is i-Bu 60T R 3 is CI and R 4 is t-B
  • R 3 is F and R 4 is C ⁇ CH 61T R 3 is CI and R 4 is C ⁇ CH
  • R 3 is F and R 4 is CF 3 63T R 3 is CI and R 4 is CF 3
  • R 3 is F and R 4 is CF 2 CF 3 64T R 3 is CI and R 4 is CF 2 CF 3
  • R 3 is F and R 4 is O-w-Pr 67T R 3 is CI and R 4 is ⁇ - ⁇ -Pr
  • R 3 is F and R 4 is O-z-Pr 68T R 3 is CI and R 4 is O-z ' -Pr
  • R 3 is F and R 4 is O-i-Bu 69T R 3 is CI and R 4 is O-t-B
  • R 3 is F and R 4 is OCH 2 CF 3 70T R 3 is CI and R 4 is OCH 2 CF 3
  • R 3 is F and R 4 is OCH 2 CHF 2 71T R 3 is CI and R 4 is OCH 2 CHF 2
  • R 3 is F and R 4 is OCH 2 CH 2 F 72T R 3 is CI and R 4 is OCH 2 CH 2 F
  • R 3 is F and R 4 is CH 2 OMe 73T R 3 is CI and R 4 is CH 2 OMe
  • R 3 is F and R 4 is CH 2 OEt 74T R 3 is CI and R 4 is CH 2 OEt
  • R 3 is F and R 4 is OCH 2 CH 2 OMe 75T R 3 is CI and R 4 is OCH 2 CH 2 OMe
  • R 3 is F and R 4 is OCH 2 CH 2 OEt 76T R 3 is CI and R 4 is OCH 2 CH 2 OEt
  • R 3 is F and R 4 is SMe 77T R 3 is CI and R 4 is SMe
  • R 3 is F and R 4 is S0 2 Me 79T R 3 is CI and R 4 is S0 2 Me
  • R 3 is F and R 4 is SEt SOT R 3 is CI and R 4 is SEt
  • R 3 is F and R 4 is S(0)Et 81T R 3 is CI and R 4 is S(0)Et
  • R 3 is F and R 4 is S0 2 Et 82T R 3 is CI and R 4 is S0 2 Et
  • R 3 is F and R 4 is S- «-Pr 83T R 3 is CI and R 4 is S- «-Pr
  • R 3 is F and R 4 is S(0)- «-Pr 84T R 3 is CI and R 4 is S(0)- «-Pr
  • R 3 is F and R 4 is S0 2 - «-Pr 85T R 3 is CI and R 4 is S0 2 - «-Pr
  • R 3 is F and R 4 is S-z-Pr 86T R 3 is CI and R 4 is S-z-Pr
  • R 3 is F and R 4 is S(0)-z-Pr 87T R 3 is CI and R 4 is S(0)-z-Pr
  • R 3 is F and R 4 is S0 2 - -Pr 88T R 3 is CI and R 4 is S0 2 -z-Pr
  • R 3 is F and R 4 is SCH 2 CF 3 89T R 3 is CI and R 4 is is SCH 2 CF 3
  • R 3 is F and R 4 is S(0)CH 2 CF 3 90T R 3 is CI and R 4 is S(0)CH 2 CF 3
  • R 3 is F and R 4 is S0 2 CH 2 CF 3 91T R 3 is CI and R 4 is S0 2 CH 2 CF 3
  • R 3 is F and R 4 is Ph 92T R 3 is CI and R 4 is Ph Table Table Headings Table Table Headings
  • R 3 is F and R 4 is 2-Pyridinyl 93T R 3 is CI and R 4 is 2-Pyridinyl
  • R 3 is F and R 4 is 3-Pyridinyl 94T R 3 is CI and R 4 is 3-Pyridinyl
  • R 3 is F and R 4 is 4-Pyridinyl 95T R 3 is CI and R 4 is 4-Pyridinyl
  • R 3 is F and R 4 is 1-pyrazole 96T R 3 is CI and R 4 is 1-pyrazole
  • R 3 is F and R 4 is 1 -imidazole 97T R 3 is CI and R 4 is 1 -imidazole
  • R 3 is F and R 4 is 1 -1 ,2,3-triazole 98T R 3 is CI and R 4 is 1-1,2,3-triazole
  • R 3 is F and R 4 is 2-1,2,3-triazole 99T R 3 is CI and R 4 is 2-1,2,3-triazole
  • R 3 is Me and R 4 is Br 124T R 3 is Me and R 4 is OCH 2 CH 2 OEt
  • R 3 is Me and R 4 is CF 2 CF 3 136T R 3 is Me and R 4 is S0 2 -; ' -Pr
  • R 3 is Me and R 4 is O-w-Pr 139T R 3 is Me and R 4 is S0 2 CH 2 CF 3
  • R 3 is Me and R 4 is OCH 2 CHF 2 143T R 3 is Me and R 4 is 4-Pyridinyl
  • R 3 is Me and R 4 is OCH 2 CH 2 F 144T R 3 is Me and R 4 is 1-pyrazole
  • R 3 is Me and R 4 is OCH 2 CH 2 OMe 147T R 3 is Me and R 4 is 2-1,2,3-triazole
  • Table 1U is identical to Table IT, except that the chemical structure in the Table 1U heading is replaced with the following structure:
  • the first compound in Table 1U is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2U through 147U are constructed in a similar manner as Tables 2T through
  • Table IV is identical to Table IT, except that the chemical structure in the Table IV heading is replaced with the followin structure:
  • the first compound in Table IV is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl.
  • Tables 2V through 147V are constructed in a similar manner as Tables 2T through
  • Table IW is identical to Table IT, except that the chemical structure in the Table IW heading is replaced with the followin structure:
  • the first compound in Table IW is the structure shown immediately above wherein R 3 is H, R 4 is H and B is 4-chlorophenyl. TABLES 2W-147W
  • Tables 2W through 147W are constructed in a similar manner as Tables 2T through
  • Tables 11-121 pertain to the structure shown below.
  • the present disclosure also includes Tables 12 through 121, each of which is constructed the same as Table II above except that the row heading in Table II (i.e. "R 3 is SMe and R 4 is H.") below the Markush structure is replaced with the respective row heading shown below.
  • the row heading is "R 3 is SMe and R 4 is F
  • B is as defined in Table II above.
  • the first entry in Table 12 specifically discloses 3-fluoro- a- [4-( 1 , 1 -dimethylethyl)phenyl] -a-methyl-5 -(methylthio)-4-pyridinemethanol.
  • R 3 is SEt and R 4 is CI
  • R 3 is S(0)Et and R 4 is H
  • R 3 is S(0)Et and R 4 is F
  • R 3 is S(0)Et and R 4 is CI
  • R 3 is S0 2 Et and R 4 is H
  • R 3 is S0 2 Et and R 4 is F
  • R 3 is OMe and R 4 is H
  • R 3 is OMe and R 4 is F
  • a compound of this invention 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.
  • a composition i.e. formulation
  • 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.
  • Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions 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 and suspo-emulsion.
  • 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. 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), 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, triacetin, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl
  • Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), 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 can be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation.
  • alkylated fatty acids e.g., methylated, ethylated, butylated
  • Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
  • the solid and liquid compositions of the present invention often include one or more surfactants.
  • surfactants also known as “surface-active agents”
  • 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.
  • 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 are 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
  • 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 invention can also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which can be considered to also function as solid diluents, liquid diluents or surfactants).
  • formulation auxiliaries and additives can 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 ⁇ can be wet milled using media mills to obtain particles with average diameters below 3 ⁇ .
  • 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. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 um range. 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.
  • 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.
  • compound 7 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
  • compound 21 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
  • compound 46 10.0% imidacloprid 5.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0%) styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0%> silicone based defoamer 0.1 % l,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon 20.0% water 53.7%
  • invertebrate pests include invertebrates inhabiting a variety of environments such as, for example, plant foliage, roots, soil, harvested crops or other foodstuffs, building structures or animal integuments.
  • These pests 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
  • present compounds and compositions are thus useful agronomically for protecting field crops from phytophagous invertebrate pests, and also nonagronomically for protecting other horticultural crops and plants from phytophagous invertebrate pests.
  • 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.
  • Transgenic plants can be modified to express multiple traits.
  • plants containing 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 ® , and herbicide-tolerant varieties of corn, cotton, soybean and rapeseed such as ROUNDUP READY ® , LIBERTY LINK ® ,
  • the present compounds and compositions may interact synergistically with traits introduced by genetic engineering or modified by mutagenesis, thus enhancing phenotypic expression or effectiveness of the traits or increasing the invertebrate pest control effectiveness of the present compounds and compositions.
  • the present compounds and compositions may interact synergistically with the phenotypic expression of proteins or other natural products toxic to invertebrate pests to provide greater-than-additive control of these pests.
  • compositions of this invention 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.
  • 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 invention which further comprise at least one plant nutrient can be in the form of liquids or solids.
  • Solid formulations comprising a fertilizer composition can be prepared by mixing the compound or composition of the present invention 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 invention 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.
  • 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 fugiperda J. E.
  • Noctuidae e.g., pink stem borer (Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioides Lefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm (Spodoptera fugiperda J. E.
  • 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 orders Hemiptera and Homoptera 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.
  • 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 fiat or rusty grain beetle (Cryptolestis ferrugineus).
  • Compounds of the invention show particularly high activity against pests in the order Lepidoptera (e.g., Alabama argillacea Hiibner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus (European leaf roller) and other Archips species, Chilo suppressalis Walker (rice stem borer), Cnaphalocrosis medinalis Guenee (rice leaf roller), Crambus caliginosellus Clemens (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hiibner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco bud
  • Homoptera including: Acyrthosiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum a
  • Compounds of this invention may 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-Schaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp.
  • Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower 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 the present invention also have activity on members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e.
  • compounds of this invention for controlling potato leafhopper (Empoasca fabae). Of note is use of compounds of this invention for controlling corn planthopper (Peregrinus maidis). Of note is use of compounds of this invention for controlling cotton melon aphid ⁇ Aphis gossypii). Of note is use of compounds of this invention for controlling green peach aphid ⁇ Myzus persicae). Of note is use of compounds of this invention for controlling diamondback moth ⁇ Plutella xylostella). Of note is use of compounds of this invention for controlling fall armyworm ⁇ Spodoptera frugiperda).
  • Compounds of this invention 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 invention also pertains to a composition
  • a composition comprising a biologically effective amount of a compound of Formula 1, an N-oxide, or salt thereof, 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, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, bensultap, bifenthrin, bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-
  • insecticides such as abamectin, acetamiprid, acrinathrin, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, 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, endosulfan, esfenvalerate, dinote
  • One embodiment of biological agents for mixing with compounds of this invention 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 nucleopolyhedr
  • a composition of the present invention 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.
  • additional biologically active compounds or agents include, but are not limited to, sodium channel modulators such as bifenthrin, cypermethrin, cyhalothrin, lambda- cyhalothrin, cyfluthrin, beta-cyfluthrin, deltamethrin, dimefluthrin, esfenvalerate, fenvalerate, indoxacarb, metofluthrin, profluthrin, pyrethrin and tralomethrin; cholinesterase inhibitors such as chlorpyrifos, methomyl, oxamyl, thiodicarb and triazamate; neonicotinoids such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid and thiamethoxam; insecticidal macrocyclic lactones such as spinetoram,
  • biologically active compounds or agents with which compounds of this invention can be formulated are: fungicides such as l-[4-[4-[5-(2,6-difluorophenyl)- 4,5 -dihydro-3 -isoxazolyl] -2-thiazolyl] - 1 -piperidinyl]-2- [5 -methyl-3 -(trifluoromethyl)- 1H- pyrazol-l-yl]ethanone, acibenzolar, aldimorph, amisulbrom, azaconazole, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, binomial, biphenyl, bitertanol, blasticidin-S, Bordeaux mixture (Tribasic copper sulfate), boscalid/nicobifen, bromuconazole, bupirimate, buthiobate, car
  • fungicides and compositions comprising fungicides such as l-[4-[4-[5- (2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-l-piperidinyl]-2-[5-methyl-3- (trifluoromethyl)-lH-pyrazol-l-yl]ethanone, azoxystrobin, copper hydroxide, cymoxanil, cyproconazole, difenoconazole, famoxadone, fenoxanil, ferimzone, flusilazole, flutolanil, fthalide, furametpyr, hexaconazole, isoprothiolane, isotianil, kasugamycin, mancozeb, metominostrobin, orysastrobin, pencycuron, penthiopyrad, picoxystrobin, probenazole, prop
  • combinations of a compound of this invention with other biologically active (particularly invertebrate pest control) compounds or agents can result in a greater-than-additive (i.e. synergistic) effect. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable.
  • synergism of invertebrate pest control active ingredients 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 invention 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 effect of the exogenously applied invertebrate pest control compounds of this invention may be synergistic with the expressed toxin proteins.
  • the weight ratio of these various mixing partners (in total) to the compound of Formula 1, an N- oxide, or salt thereof is typically between about 1 :3000 and about 3000: 1.
  • 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. It will be evident that including these additional components can expand the spectrum of invertebrate pests controlled beyond the spectrum controlled by the compound of Formula 1 alone.
  • Table A lists specific combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the present invention.
  • the first column of Table A lists the specific invertebrate pest control agents (e.g., "Abamectin" in the first line).
  • the second column of Table A lists the mode of action (if known) or chemical class of the invertebrate pest control agents.
  • the third column of Table A lists embodiment(s) of ranges of weight ratios for rates at which a compound of Formula 1 can be applied relative to an invertebrate pest control agent (e.g., "50:1 to 1 :50" of a compound of Formula 1 relative to abamectin by weight).
  • the first line of Table A specifically discloses the combination of a compound of Formula 1 with abamectin can be applied in a weight ratio between 50: 1 to 1 :50.
  • the remaining lines of Table A are to be construed similarly.
  • Table A lists specific combinations of a compound of Formula 1 with other invertebrate pest control agents illustrative of the mixtures, compositions and methods of the present invention and includes additional embodiments of weight ratio ranges for application rates.
  • Azadirachtin ecdysone agonists 100 1 to 1 120
  • Chlorantraniliprole ryanodine receptor ligands 100:1 to 1:120

Abstract

L'invention concerne des composés de Formule 1, les N-oxydes et les sels de ceux-ci, formule dans laquelle R2, R4, R5, R6, A, L, Q et n 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 nuisible invertébré, comprenant la mise en contact du nuisible invertébré ou de son environnement avec une quantité biologiquement efficace d'un composé ou d'une composition de l'invention.
PCT/US2013/035873 2012-04-17 2013-04-10 Composés hétérocycliques pour la lutte contre des animaux nuisibles invertébrés WO2013158422A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105116093A (zh) * 2015-09-08 2015-12-02 山东省农业科学院农业质量标准与检测技术研究所 一种检测苹果和土壤中虱螨脲残留的快速分析方法
WO2016068301A1 (fr) * 2014-10-31 2016-05-06 石原産業株式会社 Agent de lutte contre les parasites
US9638690B2 (en) 2014-11-07 2017-05-02 The University Of British Columbia Compounds and compositions for use as alkylating agent sensors and methods of use thereof
JP2017524704A (ja) * 2014-08-13 2017-08-31 シャンハイ シェイルテック テクノロジー カンパニー リミテッド カルボン酸化合物、その製造方法および使用
WO2017159618A1 (fr) * 2016-03-18 2017-09-21 石原産業株式会社 Agent de lutte contre les animaux nuisibles
US10030004B2 (en) 2014-01-01 2018-07-24 Medivation Technologies Llc Compounds and methods of use
WO2020171129A1 (fr) * 2019-02-20 2020-08-27 住友化学株式会社 Composé éther et composition de lutte contre les arthropodes nuisibles le contenant
WO2022271901A1 (fr) * 2021-06-24 2022-12-29 Fmc Corporation Composés azole pour lutter contre des invertébrés nuisibles

Citations (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891855A (en) 1954-08-16 1959-06-23 Geigy Ag J R Compositions and methods for influencing the growth of plants
US3060084A (en) 1961-06-09 1962-10-23 Du Pont Improved homogeneous, readily dispersed, pesticidal concentrate
US3235361A (en) 1962-10-29 1966-02-15 Du Pont Method for the control of undesirable vegetation
US3299566A (en) 1964-06-01 1967-01-24 Olin Mathieson Water soluble film containing agricultural chemicals
US3309192A (en) 1964-12-02 1967-03-14 Du Pont Method of controlling seedling weed grasses
GB1164471A (en) * 1966-09-10 1969-09-17 Union Carbide Corp Novel Oxetanes and use thereof
DE2054142A1 (de) * 1969-11-12 1971-06-03 Ciba Geigy AG , Basel (Schweiz) Pyridinsulfonsauren
US3852416A (en) 1971-05-27 1974-12-03 L Grubb Tick and flea collar of solid solution plasticized vinylic resin-carbamate insecticide
US3920442A (en) 1972-09-18 1975-11-18 Du Pont Water-dispersible pesticide aggregates
US3950360A (en) 1972-06-08 1976-04-13 Sankyo Company Limited Antibiotic substances
US3984564A (en) 1972-06-08 1976-10-05 Sankyo Company Limited Antibiotic substances B-41, their production and their use as insecticides and acaricides
US4144050A (en) 1969-02-05 1979-03-13 Hoechst Aktiengesellschaft Micro granules for pesticides and process for their manufacture
US4172714A (en) 1976-12-20 1979-10-30 E. I. Du Pont De Nemours And Company Dry compactible, swellable herbicidal compositions and pellets produced therefrom
US4199569A (en) 1977-10-03 1980-04-22 Merck & Co., Inc. Selective hydrogenation products of C-076 compounds and derivatives thereof
US4224901A (en) 1979-04-16 1980-09-30 Carey Jr Sam H Combination inner flea-tick collar and outer protective collar, for animals
US4310519A (en) 1976-04-19 1982-01-12 Merck & Co., Inc. Novel substances and process for their production
US4311857A (en) 1979-02-05 1982-01-19 Schering Corporation 1-Aryl-2-acylamido-3-fluoro-1-propanol acylates, methods for their manufacture and intermediates useful therein, methods for their use as antibacterial agents and compositions useful therefor
GB2095558A (en) 1981-03-30 1982-10-06 Avon Packers Ltd Formulation of agricultural chemicals
EP0097480A1 (fr) * 1982-06-17 1984-01-04 Pfizer Limited Agents fongicides triazoliques
DE3246493A1 (de) 1982-12-16 1984-06-20 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von wasserdispergierbaren granulaten
US4582918A (en) 1984-09-19 1986-04-15 Schering Corporation Preparation of intermediates for (threo)-1-aryl-2-acylamido-3-fluoro-1-propanols
US4743700A (en) 1984-02-03 1988-05-10 Zambon S.P.A. Process for fluorinating 1-phenyl-2-amino-1,3-propanediol compounds
US4820695A (en) 1982-09-13 1989-04-11 Eli Lilly And Company C-20-dihydro-deoxy-(cyclic amino)-derivatives of macrolide antibiotics
US4876352A (en) 1988-09-14 1989-10-24 Schering Corporation Pressurized fluorination of hydroxy alkyl groups
US4916154A (en) 1986-09-12 1990-04-10 American Cyanamid Company 23-Imino derivatives of LL-F28249 compounds
US4973750A (en) 1984-09-19 1990-11-27 Schering Corporation Preparation of (threo)-1-aryl-2-acylamido-3-fluoro-1-propanols
WO1991013546A1 (fr) 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Granules pesticides dispersibles ou solubles dans l'eau, obtenus a partir de liants thermo-actives
US5089480A (en) 1985-07-27 1992-02-18 Pfizer Inc. Antiparasitic agents
US5105009A (en) 1983-06-02 1992-04-14 Zambon S.P.A. Intermediates for the preparation of 1-(phenyl)-1-hydroxy-2-amino-3-fluoropropane derivatives
US5180587A (en) 1988-06-28 1993-01-19 E. I. Du Pont De Nemours And Company Tablet formulations of pesticides
US5184573A (en) 1992-02-21 1993-02-09 Stevens Jr John L Animal collar
US5208030A (en) 1989-08-30 1993-05-04 Imperial Chemical Industries Plc Active ingredient dosage device
US5227494A (en) 1988-09-14 1993-07-13 Schering Corporation Process for preparing oxazoline compounds
US5232701A (en) 1990-10-11 1993-08-03 Sumitomo Chemical Company, Limited Boron carbonate and solid acid pesticidal composition
US5288710A (en) 1990-06-28 1994-02-22 Merck & Co., Inc. Stable salts of 4"-deoxy-4"-epi-methylamino avermectin Bla/Blb
US5352832A (en) 1992-12-18 1994-10-04 Schering Corporation Asymmetric process for preparing florfenicol, thiamphenicol chloramphenicol and oxazoline intermediates
US5382673A (en) 1990-10-25 1995-01-17 Schering Corporation Process for preparing florfenicol, its analogs and oxazoline intermediates thereto
US5399717A (en) 1993-09-29 1995-03-21 Merck & Co., Inc. Glycosidation route to 4"-epi-methylamino-4"-deoxyavermectin B1
US5554620A (en) * 1993-09-14 1996-09-10 Sterling Winthrop Inc. Substituted 6,11-ethano-6,11-dihydrobenzo[b] quinolizinium salts and compositions and methods of use thereof
US5555848A (en) 1995-05-17 1996-09-17 Trujillo; Wendy J. Pet/flea collar
US5567844A (en) 1984-02-03 1996-10-22 Zambon S.P.A. Process for preparing 1-phenyl-2-amino-3-fluoro-1-propanols
US5663361A (en) 1996-08-19 1997-09-02 Schering Corporation Process for preparing intermediates to florfenicol
US5958888A (en) 1996-07-02 1999-09-28 Merial, Inc. Water miscible macrolide solutions
US5994374A (en) * 1995-11-10 1999-11-30 Merck Sharp & Dohme Ltd. Substituted 1-indolylpropyl-4-benzyl-tetrahydropyridine derivatives
US6054434A (en) 1997-09-10 2000-04-25 Merck & Co., Inc. 8a-azalides as veterinary antimicrobal agents
US6239112B1 (en) 1998-07-09 2001-05-29 Merial, Inc. Water miscible macrolide solutions
US6271255B1 (en) 1996-07-05 2001-08-07 Biotica Technology Limited Erythromycins and process for their preparation
US6270768B1 (en) 1999-01-28 2001-08-07 Pfizer Inc Azalides and methods of making same
US6339063B1 (en) 1997-09-10 2002-01-15 Merck & Co., Inc. 9a-azalides as veterinary antimicrobial agents
US6406690B1 (en) 1995-04-17 2002-06-18 Minrav Industries Ltd. Bacillus firmus CNCM I-1582 or Bacillus cereus CNCM I-1562 for controlling nematodes
US6472371B1 (en) 1998-01-02 2002-10-29 Pfizer, Inc. Macrolides
US6514945B1 (en) 2000-01-27 2003-02-04 Pfizer Inc. Azalide antibiotic compositions
WO2003024222A1 (fr) 2001-09-21 2003-03-27 E. I. Du Pont De Nemours And Company Traitement arthropodicide a l'anthranilamide
US20030064939A1 (en) 2001-04-27 2003-04-03 Constantine Sklavounos Process for preparing 4"-substituted-9-deoxo-9a-aza-9a-homoerythromycin a derivatives
US20050182059A1 (en) 2003-12-31 2005-08-18 Schering-Plough Animal Health Corporation Control of parasites in animals by the use of imidazo[1,2-b]pyridazine derivatives
US7041670B2 (en) 2002-03-08 2006-05-09 Schering-Plough Animal Health Corporation Florfenicol-type antibiotics
WO2006059149A1 (fr) 2004-12-01 2006-06-08 Merck Sharp & Dohme Limited Derives de l'arylsulfonylnaphtalene utilises en tant qu'antagonistes de 5ht2a
WO2006106241A1 (fr) 2005-04-08 2006-10-12 Les Laboratoires Servier Derives de piperazine et leur utilisation comme inhibiteurs de recapture de la serotonine ou comme antagonistes de neurokinine
WO2006113704A2 (fr) 2005-04-18 2006-10-26 Neurogen Corporation Antagonistes cb1 heteroaryle substitue
US20060281695A1 (en) 2005-06-09 2006-12-14 Schering-Plough Animal Health Corporation Control of parasites in animals by N-[(phenyloxy)phenyl]-1,1,1-trifluoromethanesulfonamide and N-[(phenylsulfanyl)phenyl]-1,1,1-trifluoromethanesulfonamide derivatives
US7153842B2 (en) 2003-12-23 2006-12-26 Schering-Plough Animal Health Corporation Florfenicol prodrug having improved water solubility
US7312248B2 (en) 2004-09-23 2007-12-25 Schering-Plough Animal Health Corporation Control of parasites in animals by the use of novel trifluoromethanesulfonanilide oxime ether derivatives
US7361689B2 (en) 2003-12-31 2008-04-22 Schering-Plough Animal Health Corporation Antibacterial 1-(4-mono- and di-halomethylsulphonylphenyl)-2-acylamino-3-fluoroproponals and preparation thereof
US20080262057A1 (en) * 2007-04-20 2008-10-23 Dow Agrosciences Llc Diarylisoxazolines
WO2009154775A1 (fr) 2008-06-20 2009-12-23 Amgen Inc. Agonistes du récepteur s1p1 et utilisations
EP2210879A1 (fr) * 2008-12-30 2010-07-28 Bayer CropScience AG Dérivés de pyrimidine et leur utilisation pour combattre la croissance indésirable de plantes
WO2011014515A1 (fr) 2009-07-30 2011-02-03 Irm Llc Composés et compositions utilisés comme inhibiteurs de la syk kinase
WO2012042006A1 (fr) * 2010-10-01 2012-04-05 Basf Se Imines
WO2012087630A1 (fr) * 2010-12-20 2012-06-28 E.I. Du Pont De Nemours And Company Composés de pyridine et de pyrimidine utilisés pour lutter contre des nuisibles invertébrés

Patent Citations (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891855A (en) 1954-08-16 1959-06-23 Geigy Ag J R Compositions and methods for influencing the growth of plants
US3060084A (en) 1961-06-09 1962-10-23 Du Pont Improved homogeneous, readily dispersed, pesticidal concentrate
US3235361A (en) 1962-10-29 1966-02-15 Du Pont Method for the control of undesirable vegetation
US3299566A (en) 1964-06-01 1967-01-24 Olin Mathieson Water soluble film containing agricultural chemicals
US3309192A (en) 1964-12-02 1967-03-14 Du Pont Method of controlling seedling weed grasses
GB1164471A (en) * 1966-09-10 1969-09-17 Union Carbide Corp Novel Oxetanes and use thereof
US4144050A (en) 1969-02-05 1979-03-13 Hoechst Aktiengesellschaft Micro granules for pesticides and process for their manufacture
DE2054142A1 (de) * 1969-11-12 1971-06-03 Ciba Geigy AG , Basel (Schweiz) Pyridinsulfonsauren
US3852416A (en) 1971-05-27 1974-12-03 L Grubb Tick and flea collar of solid solution plasticized vinylic resin-carbamate insecticide
US3950360A (en) 1972-06-08 1976-04-13 Sankyo Company Limited Antibiotic substances
US3984564A (en) 1972-06-08 1976-10-05 Sankyo Company Limited Antibiotic substances B-41, their production and their use as insecticides and acaricides
US3920442A (en) 1972-09-18 1975-11-18 Du Pont Water-dispersible pesticide aggregates
US4310519A (en) 1976-04-19 1982-01-12 Merck & Co., Inc. Novel substances and process for their production
US4172714A (en) 1976-12-20 1979-10-30 E. I. Du Pont De Nemours And Company Dry compactible, swellable herbicidal compositions and pellets produced therefrom
US4199569A (en) 1977-10-03 1980-04-22 Merck & Co., Inc. Selective hydrogenation products of C-076 compounds and derivatives thereof
US4311857A (en) 1979-02-05 1982-01-19 Schering Corporation 1-Aryl-2-acylamido-3-fluoro-1-propanol acylates, methods for their manufacture and intermediates useful therein, methods for their use as antibacterial agents and compositions useful therefor
US4224901A (en) 1979-04-16 1980-09-30 Carey Jr Sam H Combination inner flea-tick collar and outer protective collar, for animals
GB2095558A (en) 1981-03-30 1982-10-06 Avon Packers Ltd Formulation of agricultural chemicals
EP0097480A1 (fr) * 1982-06-17 1984-01-04 Pfizer Limited Agents fongicides triazoliques
US4820695A (en) 1982-09-13 1989-04-11 Eli Lilly And Company C-20-dihydro-deoxy-(cyclic amino)-derivatives of macrolide antibiotics
DE3246493A1 (de) 1982-12-16 1984-06-20 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von wasserdispergierbaren granulaten
US5105009A (en) 1983-06-02 1992-04-14 Zambon S.P.A. Intermediates for the preparation of 1-(phenyl)-1-hydroxy-2-amino-3-fluoropropane derivatives
US4743700A (en) 1984-02-03 1988-05-10 Zambon S.P.A. Process for fluorinating 1-phenyl-2-amino-1,3-propanediol compounds
US5567844A (en) 1984-02-03 1996-10-22 Zambon S.P.A. Process for preparing 1-phenyl-2-amino-3-fluoro-1-propanols
US4582918A (en) 1984-09-19 1986-04-15 Schering Corporation Preparation of intermediates for (threo)-1-aryl-2-acylamido-3-fluoro-1-propanols
US4973750A (en) 1984-09-19 1990-11-27 Schering Corporation Preparation of (threo)-1-aryl-2-acylamido-3-fluoro-1-propanols
US5089480A (en) 1985-07-27 1992-02-18 Pfizer Inc. Antiparasitic agents
US4916154A (en) 1986-09-12 1990-04-10 American Cyanamid Company 23-Imino derivatives of LL-F28249 compounds
US5180587A (en) 1988-06-28 1993-01-19 E. I. Du Pont De Nemours And Company Tablet formulations of pesticides
US4876352A (en) 1988-09-14 1989-10-24 Schering Corporation Pressurized fluorination of hydroxy alkyl groups
US5227494A (en) 1988-09-14 1993-07-13 Schering Corporation Process for preparing oxazoline compounds
US5208030A (en) 1989-08-30 1993-05-04 Imperial Chemical Industries Plc Active ingredient dosage device
WO1991013546A1 (fr) 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Granules pesticides dispersibles ou solubles dans l'eau, obtenus a partir de liants thermo-actives
US5288710A (en) 1990-06-28 1994-02-22 Merck & Co., Inc. Stable salts of 4"-deoxy-4"-epi-methylamino avermectin Bla/Blb
US5232701A (en) 1990-10-11 1993-08-03 Sumitomo Chemical Company, Limited Boron carbonate and solid acid pesticidal composition
US5382673A (en) 1990-10-25 1995-01-17 Schering Corporation Process for preparing florfenicol, its analogs and oxazoline intermediates thereto
US5184573A (en) 1992-02-21 1993-02-09 Stevens Jr John L Animal collar
US5352832A (en) 1992-12-18 1994-10-04 Schering Corporation Asymmetric process for preparing florfenicol, thiamphenicol chloramphenicol and oxazoline intermediates
US5554620A (en) * 1993-09-14 1996-09-10 Sterling Winthrop Inc. Substituted 6,11-ethano-6,11-dihydrobenzo[b] quinolizinium salts and compositions and methods of use thereof
US5399717A (en) 1993-09-29 1995-03-21 Merck & Co., Inc. Glycosidation route to 4"-epi-methylamino-4"-deoxyavermectin B1
US6406690B1 (en) 1995-04-17 2002-06-18 Minrav Industries Ltd. Bacillus firmus CNCM I-1582 or Bacillus cereus CNCM I-1562 for controlling nematodes
US5555848A (en) 1995-05-17 1996-09-17 Trujillo; Wendy J. Pet/flea collar
US5994374A (en) * 1995-11-10 1999-11-30 Merck Sharp & Dohme Ltd. Substituted 1-indolylpropyl-4-benzyl-tetrahydropyridine derivatives
US5958888A (en) 1996-07-02 1999-09-28 Merial, Inc. Water miscible macrolide solutions
US6271255B1 (en) 1996-07-05 2001-08-07 Biotica Technology Limited Erythromycins and process for their preparation
US6437151B2 (en) 1996-07-05 2002-08-20 Biotica Technology Limited Erythromycins and process for their preparation
US5663361A (en) 1996-08-19 1997-09-02 Schering Corporation Process for preparing intermediates to florfenicol
US6054434A (en) 1997-09-10 2000-04-25 Merck & Co., Inc. 8a-azalides as veterinary antimicrobal agents
US6339063B1 (en) 1997-09-10 2002-01-15 Merck & Co., Inc. 9a-azalides as veterinary antimicrobial agents
US6472371B1 (en) 1998-01-02 2002-10-29 Pfizer, Inc. Macrolides
US6239112B1 (en) 1998-07-09 2001-05-29 Merial, Inc. Water miscible macrolide solutions
US6270768B1 (en) 1999-01-28 2001-08-07 Pfizer Inc Azalides and methods of making same
US6514945B1 (en) 2000-01-27 2003-02-04 Pfizer Inc. Azalide antibiotic compositions
US20030064939A1 (en) 2001-04-27 2003-04-03 Constantine Sklavounos Process for preparing 4"-substituted-9-deoxo-9a-aza-9a-homoerythromycin a derivatives
WO2003024222A1 (fr) 2001-09-21 2003-03-27 E. I. Du Pont De Nemours And Company Traitement arthropodicide a l'anthranilamide
US7041670B2 (en) 2002-03-08 2006-05-09 Schering-Plough Animal Health Corporation Florfenicol-type antibiotics
US7153842B2 (en) 2003-12-23 2006-12-26 Schering-Plough Animal Health Corporation Florfenicol prodrug having improved water solubility
US7361689B2 (en) 2003-12-31 2008-04-22 Schering-Plough Animal Health Corporation Antibacterial 1-(4-mono- and di-halomethylsulphonylphenyl)-2-acylamino-3-fluoroproponals and preparation thereof
US20050182059A1 (en) 2003-12-31 2005-08-18 Schering-Plough Animal Health Corporation Control of parasites in animals by the use of imidazo[1,2-b]pyridazine derivatives
US7312248B2 (en) 2004-09-23 2007-12-25 Schering-Plough Animal Health Corporation Control of parasites in animals by the use of novel trifluoromethanesulfonanilide oxime ether derivatives
WO2006059149A1 (fr) 2004-12-01 2006-06-08 Merck Sharp & Dohme Limited Derives de l'arylsulfonylnaphtalene utilises en tant qu'antagonistes de 5ht2a
WO2006106241A1 (fr) 2005-04-08 2006-10-12 Les Laboratoires Servier Derives de piperazine et leur utilisation comme inhibiteurs de recapture de la serotonine ou comme antagonistes de neurokinine
WO2006113704A2 (fr) 2005-04-18 2006-10-26 Neurogen Corporation Antagonistes cb1 heteroaryle substitue
US20060281695A1 (en) 2005-06-09 2006-12-14 Schering-Plough Animal Health Corporation Control of parasites in animals by N-[(phenyloxy)phenyl]-1,1,1-trifluoromethanesulfonamide and N-[(phenylsulfanyl)phenyl]-1,1,1-trifluoromethanesulfonamide derivatives
US20080262057A1 (en) * 2007-04-20 2008-10-23 Dow Agrosciences Llc Diarylisoxazolines
WO2009154775A1 (fr) 2008-06-20 2009-12-23 Amgen Inc. Agonistes du récepteur s1p1 et utilisations
EP2210879A1 (fr) * 2008-12-30 2010-07-28 Bayer CropScience AG Dérivés de pyrimidine et leur utilisation pour combattre la croissance indésirable de plantes
WO2011014515A1 (fr) 2009-07-30 2011-02-03 Irm Llc Composés et compositions utilisés comme inhibiteurs de la syk kinase
WO2012042006A1 (fr) * 2010-10-01 2012-04-05 Basf Se Imines
WO2012087630A1 (fr) * 2010-12-20 2012-06-28 E.I. Du Pont De Nemours And Company Composés de pyridine et de pyrimidine utilisés pour lutter contre des nuisibles invertébrés

Non-Patent Citations (62)

* Cited by examiner, † Cited by third party
Title
"Developments in formulation technology", 2000, PJB PUBLICATIONS
"McCutcheon's Emulsifiers and Detergents", MCCUTCHEON'S DIVISION
"McCutcheon's Volume 2: Functional Materials", MCCUTCHEON'S DIVISION
"Perry's Chemical Engineer's Handbook, 4th Ed.", MCGRAW-HILL, pages: 8 - 57
A. R. KATRITZKY AND C. W. REES: "Comprehensive Heterocyclic Chemistry", 1984, PERGAMON PRESS
A. R. KATRITZKY, C. W. REES AND E. F. V. SCRIVEN: "Comprehensive Heterocyclic Chemistry II", 1996, PERGAMON PRESS
A. S. DAVIDSON; B. MILWIDSKY: "ynthetic Detergents, Seventh Edition,", 1987, JOHN WILEY AND SONS
A. V. KUZENKOV: "Synthesis of substituted 2-azolyl-1-pyridylethan-1-ols", CHEMISTRY OF HETEROCYCLIC COMPOUNDS, vol. 39, no. 11, 2003, pages 1492 - 1495, XP002713328 *
A.J.KAY ET AL.: "Simple zwitterionic merocyanines as potential NLO chromophores", JOURNAL OF MATERIALS CHEMISTRY, vol. 11, 2001, pages 2271 - 2281, XP002713329 *
B. LV ET AL., BIO. & MED. CHEM. LETT., vol. 1.9, 2009, pages 6877
BROWNING: "Agglomeration", CHEMICAL ENGINEERING, 4 December 1967 (1967-12-04), pages 147 - 48
C. D. S. TOMLIN,: "The Pesticide Manual, 13th Edition,", 2003, BRITISH CROP PROTECTION COUNCIL
D. S. KETTLE: "Medical and Veterinary Entomology", JOHN WILEY & SONS
D. YANG ET AL., J. ORG. CHEM., vol. 60, 1995, pages 3887 - 9
DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 1961, Namirski, Pawel Nantka: "Carboline Synthesis by the method of Graebe Ullman I", XP002713330, Database accession no. 57:83135 *
DATABASE CA [Online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 1962, Nantka-Namirski, Pawel: "Carboline synthesis by the method of Graebe-Ullman. III. Synthesis and inhibitory effect of certain derivatives of .gamma.-carboline", XP002713331, Database accession no. 59:82218 *
E. J. L. SOULSBY: "Helminths, Arthropods and Protozoa, (6th Edition of Monnig's Veterinary Helminthology and Entomology", THE WILLIAMS AND WILKINS CO.
E. J. L. SOULSBY: "Textbook of Veterinary Clinical Parasitology, Volume 1, Helminths", vol. 1, F. A. DAVIS CO.
F. BELLINA ET AL., SYNTHESIS, vol. 15, 2004, pages 2419 - 2440
G. W. H. CHEESEMAN; E. S. G. WERSTIUK: "Advances in Heterocyclic Chemistry", vol. 22, ACADEMIC PRESS, pages: 390 - 392
GREENE, T. W.; WUTS, P. G. M.: "Protective Groups in Organic Synthesis, 2nd ed.", 1991, WILEY
HANCE ET AL.: "Weed Control Handbook, 8th Ed.", 1989, BLACKWELL SCIENTIFIC PUBLICATIONS
J. AM. CHEM. SOC., vol. 123, 2001, pages 1365 - 1371
J. FLUORINE CHEM., vol. 111, 2001, pages 247 - 252
J. FLUORINE CHEM., vol. 132, 2011, pages 636 - 640
J. FLUORINE CHEM., vol. 25, 1984, pages 169 - 193
J. FLUORINE CHEM., vol. III, 2001, pages 247 - 252
J. J. LI, G. W. GRIBBLE,: "Palladium in Heterocyclic Chemistry: A Guide for the Synthetic Chemist", 2000
J. MEDICINAL CHEM., vol. 51, 2008, pages 2708
J. ORG. CHEM., no. 58, 1993, pages 6996 - 7000
K. OKUMA ET AL., J. ORG. CHEM., vol. 48, 1983, pages 5133
K. VARAZO ET AL., TETRAHEDRON LETT., vol. 49, 2008, pages 5293
KAZUHIRO KOBAYASHI ET AL: "Synthesis of 4-Aryl-1,7-naphthyridine-2(1H)-thiones by the Electrocyclic Reaction of 4-(1-Arylalk-1-enyl)-3-isothiocyanatopyridines Generated in situ from the Corresponding Isocyanides", HELVETICA CHIMICA ACTA, vol. 95, no. 4, 11 April 2012 (2012-04-11), pages 556 - 563, XP055079869, ISSN: 0018-019X, DOI: 10.1002/hlca.201100408 *
KLINGMAN: "Weed Control as a Science", 1961, JOHN WILEY AND SONS, INC., pages: 81 - 96
L. G. COPPING,: "The BioPesticide Manual, 2nd Edition,", 2001, BRITISH CROP PROTECTION COUNCIL
M. MERONI ET AL., J. MED. CHEM., vol. 22, 1979, pages 183
M. R. GRIMMETT; B. R. T. KEENE: "Advances in Heterocyclic Chemistry", vol. 43, ACADEMIC PRESS, pages: 149 - 161
M. TISLER; B. STANOVNIK: "Advances in Heterocyclic Chemistry", vol. 9, ACADEMIC PRESS, pages: 285 - 291
M. TISLER; B. STANOVNIK: "Comprehensive Heterocyclic Chemistry", vol. 3, PERGAMON PRESS, pages: 18 - 20
M. W. C. ROBINSON ET AL., TETRAHEDRON, vol. 66, 2010, pages 8377
MARSDEN: "Solvents Guide, 2nd ed.", 1950, INTERSCIENCE
ORG. LETT., vol. 13, 2011, pages 102 - 105
P. ESPINET; A. M. ECHAVARREN, ANGEWANDTE CHEMIE, INTERNATIONAL EDITION, vol. 43, 2004, pages 4704 - 4734
P. KOSTERS ET AL.: "Seed Treatment: Progress and Prospects", 1994
PICHOWICZ M ET AL: "Microwave-assisted synthesis of 4-amino-3,5-dihalopyridines", TETRAHEDRON, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 66, no. 13, 27 March 2010 (2010-03-27), pages 2398 - 2403, XP026932591, ISSN: 0040-4020, [retrieved on 20100202], DOI: 10.1016/J.TET.2010.01.101 *
PROUDFOOT J R ET AL: "A NOVEL SMILES REARRANGEMENT GIVES ACCESS TO THE A-RING PYRIDINE ISOMERS OF THE NEVIRAPINE RING SYSTEM", THE JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY [NOT]ETC., vol. 58, no. 25, 3 December 1993 (1993-12-03), pages 6996 - 7000, XP009006676, ISSN: 0022-3263, DOI: 10.1021/JO00077A016 *
Q. HU ET AL., J. MED. CHEM., vol. 53, 2010, pages 5049
R. J. MATTSON ET AL., J. ORG. CHEM., vol. 55, 1990, pages 3410
SISELY; WOOD: "Encyclopedia of Surface Active Agents", 1964, CHEMICAL PUBL. CO., INC.
SØREN EBDRUP ET AL: "Synthesis and Structure-Activity Relationship for a Novel Class of Potent and Selective Carbamate-Based Inhibitors of Hormone Selective Lipase with Acute In Vivo Antilipolytic Effects", JOURNAL OF MEDICINAL CHEMISTRY, vol. 50, no. 22, 5 October 2007 (2007-10-05), pages 5449 - 5456, XP055080028, ISSN: 0022-2623, DOI: 10.1021/jm0607653 *
SYNLETT, 2009, pages 2180 - 2182
T. FRANCOIS ET AL., TETRAHEDRON, vol. 56, 2000, pages 1349
T. L. GILCHRIST: "Comprehensive Organic Synthesis", vol. 7, PERGAMON PRESS, pages: 748 - 750
T. S. WOODS: "Pesticide Chemistry and Bioscience, The Food-Environment Challenge", 1999, THE ROYAL SOCIETY OF CHEMISTRY, article "The Formulator's Toolbox - Product Forms for Modem Agriculture", pages: 120 - 133
TETRAHEDRON LETT., vol. 37, 1996, pages 5609 - 5612
TETRAHEDRON LETT., vol. 37, 1996, pages 629 - 632
TETRAHEDRON LETT., vol. 47, 2006, pages 5045 - 5048
TETRAHEDRON, vol. 66, 2010, pages 2398 - 2403
TORONTO: "Control of Arthropod Pests of Livestock: A Review of Technology", CRC PRESS
WATKINS: "Handbook of Insecticide Dust Diluents and Carriers, 2nd ed.", DORLAND BOOKS
YA-BO HE ET AL: "(E)-1,2-Difluoro-1-iodo-2-trialkylsilanesA useful synthon for the addition of the [IFCCF] unit to activated electrophiles", JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER, NL, vol. 132, no. 11, 14 July 2011 (2011-07-14), pages 940 - 944, XP028389353, ISSN: 0022-1139, [retrieved on 20110723], DOI: 10.1016/J.JFLUCHEM.2011.07.013 *
ZHOU LI ET AL: "One-Pot Arylative Epoxidation of Ketones by Employing Amphoteric Bromoperfluoroarenes", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 51, no. 5, 27 January 2012 (2012-01-27), pages 1225 - 1227, XP055079629, ISSN: 1433-7851, DOI: 10.1002/anie.201106969 *

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