Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
  • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
  • C07D233/30—Oxygen or sulfur atoms
  • C07D233/32—One oxygen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
  • C07D263/18—Oxygen atoms
  • C07D263/20—Oxygen atoms attached in position 2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D291/00—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms
  • C07D291/02—Heterocyclic compounds containing rings having nitrogen, oxygen and sulfur atoms as the only ring hetero atoms not condensed with other rings
  • C07D291/04—Five-membered rings
• • 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
  • C07D401/10—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 linked by a carbon chain containing aromatic rings
• • 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
  • C07D401/12—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 linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
  • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
  • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
  • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D419/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms
  • C07D419/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D419/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings

Definitions

• This invention relates to certain f ⁇ ve-membered heterocyclic derivatives, their iV-oxides, salts and compositions suitable for agronomic and nonagronomic uses, including those uses listed below, and methods of their use for controlling invertebrate pests such as arthropods in both agronomic and nonagronomic environments.
• invertebrate pests The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer.
• invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action.
• PCT Patent Publication WO 93/22298 discloses oxazolindine derivatives and pharmaceutically acceptable salts thereof as antihyperlipidemics.
• Japanese Patent Publication 03176476 discloses imidazolidinones as useful chiral auxiliaries for producing penem or carbapenem antibiotics.
• U.S. Patent 4186129 discloses oxazolidinones useful as neuroleptics and phosphodiesterase inhibitors.
• This invention is directed to compounds of Formula 1 including all geometric and stereoisomers, ⁇ f-oxides, and salts thereof, and compositions containing them and their use for controlling invertebrate pests:
• G is O or NR 3 ;
• Z is N or CR 2 ; AMs CR 4 Or N; A 2 is CR 5 or N; A 3 is CR 6 or N; A 4 is CR 7 or N; Q is a 5- or 6-membered saturated or unsaturated heterocycle optionally substituted with one or more substituents independently selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -
• R 1 is cyano; or C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from R 17 ; each R 2 is independently H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulf
• R 4 , R 5 , R 6 and R 7 are independently selected from H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylamino, C 2 -Cg dialkylamino, cyano and nitro; or
• R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing as ring members in addition to the A 3 and A 4 bridgehead atoms, 3 atoms selected from 1 to 2 carbon atoms, O to 2 nitrogen atoms, O to 1 oxygen atom and O to 1 sulfur atom, or 4 atoms selected from 2 to 4 carbon atoms and O to 2 nitrogen atoms; each R 8 , R 12 and R 14 is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 7 alkylcycloalkyl, C 4 -C 7 cycloalkylalkyl, C 2 -C 7 alkylcarbonyl, C 2 ⁇ C 6 alkoxyalkyl or C 2 -C 7 alkoxycarbonyl; each R 9 , R 10
• each R 17 and R 18 is independently halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio,
• each R 19 is independently halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 2 -Cg alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, trimethylsilyl, cyano, nitro or Q 1 ; each Q 1 is independently a phenyl or a 5- or 6-membered saturated or unsaturated heterocycle, each optionally substituted with one or more substituents independently selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1
• This invention also provides a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula 1, an ⁇ f-oxide or a salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent.
• This invention further provides a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula 1, an ⁇ f-oxide or a salt thereof, or the composition described above, and a propellant.
• This invention also provides a bait composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula 1, an N-oxide or a salt thereof, or the composition described above, one or more food materials, optionally an attractant, and optionally a humectant.
• This invention further provides a trap device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
• This invention also provides a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula 1, an ⁇ f-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 ⁇ f-oxide or a salt thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent.
• 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 Af-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 method for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of Formula 1, an iV-oxide or a salt thereof, (e.g., as a composition described herein). DETAILS OF THE INVENTION
• compositions comprising, “comprising,” “includes,” “including,” “has,” “having,” “contains” or “containing,” or any other variation thereof, are intended to cover a non-exclusive inclusion.
• a composition, a mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.
• “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
• invertebrate pest includes arthropods, gastropods and nematodes of economic importance as pests.
• arthropod includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
• gastropod includes snails, slugs and other Stylommatophora.
• helminths includes worms in the phylum of Nemathelminth, Platyhelminth and Acanthocephala such as: round worms, heartworms, and phytophagous nematodes (Nematoda), flukes (Trematoda), tape worms (Cestoda) and throny-headed worms.
• 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 horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential and commercial structures in urban and industrial settings, turf (e.g., sod farm, pasture, golf course, residential lawn, recreational sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
• turf e.g., sod farm, pasture, golf course, residential lawn, recreational sports field, etc.
• wood products e.g., stored product, agro-forestry and vegetation management
• public health (human) and animal health e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife
• alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, /i-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 comprising multiple triple bonds such as 2,5-hexadiynyl.
• Alkoxy includes, for example, methoxy, ethoxy, ⁇ -propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
• Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
• Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group.
• alkylsulfinyl examples include CH 3 S(O)-, CH 3 CH 2 S(O)-, CH 3 CH 2 CH 2 S(O)-, (CHs) 2 CHS(O)- and the different butylsulfinyl, pentylsulfinyl and hexylsulf ⁇ nyl isomers.
• alkylsulfonyl examples include CH 3 S(O) 2 -, CH 3 CH 2 S(O) 2 -, CH 3 CH 2 CH 2 S(O) 2 -, (CH ⁇ 2 CHS(O) 2 -, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
• Alkylamino alkylamino
• dialkylamino and the like, are defined analogously to the above examples.
• Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
• alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, j-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl.
• 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.
• 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 F 3 C-, ClCH 2 -, CF 3 CH 2 - and CF 3 CCl 2 -.
• halocycloalkyl haloalkoxy
• haloalkylthio CF 3 CH 2 O-
• haloalkylthio examples include CCl 3 S-, CF 3 S-, CCl 3 CH 2 S- and ClCH 2 CH 2 CH 2 S-.
• haloalkylsulfinyl examples include CF 3 S(O)-, CCl 3 S(O)-, CF 3 CH 2 S(O)- and CF 3 CF 2 S(O)-.
• haloalkylsulfonyl examples include CF 3 S(O) 2 -, CCl 3 S(O) 2 -, CF 3 CH 2 S(O) 2 - and CF 3 CF 2 S(O) 2 -.
• Alkylcarbonyl denotes a straight-chain or branched alkyl moieties bonded to a
• C 1 -C 4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
• C 2 alkoxyalkyl designates CH 3 OCH 2
• C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
• C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
• substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents, e.g., (R 2 ) n , n is 1, 2, 3 or 4.
• substituents When 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.
• heterocycle denotes rings or ring systems in which at least one ring atom is not carbon, e.g., nitrogen, oxygen or sulfur.
• a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.
• the heterocyclic ring can be attached through any available carbon or nitrogen by replacement of hydrogen on said carbon or nitrogen.
• the heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satifies the H ⁇ ckel rule, then said ring is also called a "heteroaromatic ring” or "aromatic heterocyclic ring”.
• aromatic ring' or “aromatic ring system” denotes fully unsaturated carbocycles and heterocycles in which at least one ring of the polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied for the ring system).
• fused bicyclic ring system denotes a ring system containing two fused rings in which either ring can be saturated, partially unsaturated, or fully unsaturated.
• fused heterobicyclic ring system denotes a ring system containing two fused rings in which at least one ring atom is not carbon and which can be aromatic or nonaromatic, as defined above.
• optionally substituted in connection with the heterocyclic rings refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated.
• optionally substituted is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.” Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other.
• Q or Q 1 When Q or Q 1 is a 5- or 6-membered nitrogen-containing heterocycle, it may be attached to the remainder of Formula 1 through any available carbon or nitrogen ring atom, unless otherwise indicated.
• pyridinyl and pyridyl are equivalent alternative names for an organic radical formed by removing a hydrogen atom from a pyridine ring to form an attachment point; accordingly “pyridinyl” and “pyridyl” are used herein as synonyms.
• Q 1 can be (among others) phenyl optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of Invention.
• An example of phenyl optionally substituted with from one or more substituents is the ring illustrated as U-I in Exhibit 1, wherein R v is any substituent as defined in the Summary of the Invention for Q 1 and r is an integer from 0 to 5.
• Q or Q 1 can be (among others) 5- or 6-membered saturated or unsaturated heterocycles optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary of Invention.
• Examples of 5- or 6-membered unsaturated aromatic heterocycles optionally substituted with from one or more substituents include the rings U-2 through U-61 illustrated in Exhibit 1 wherein R v is any substituent as defined in the Summary of the Invention for Q or Q 1 , and r is an integer from 0 to 4. Note that some U groups can only be substituted with less than 4 R v groups (e.g., U- 2 through U-5, U-7 through U-48, and U-52 through U-61).
• R v groups are shown in the structures U-I through U-61, it is noted that they do not need to be present since they are optional substituents. Note that when R v is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or R v . Note that when the attachment point between (R v ) r and the U group is illustrated as floating, (R v ) r can be attached to any available carbon atom or nitrogen atom of the U group.
• Q or Q 1 is a 5- or 6-membered saturated or unsaturated non-aromatic heterocycle optionally substituted with one or more substituents selected from the group of substituents as defined in the Summary of Invention for Q or Q 1
• one or two carbon ring members of the heterocycle can optionally be in the oxidized form of a carbonyl moiety.
• 5- or 6-membered saturated or non-aromatic unsaturated heterocycles include the rings Q-I through Q-35 as illustrated in Exhibit 2, wherein R v is any substituent as defined in the Summary of the Invention for Q 1 .
• (R v ) r when the attachment point between (R v ) r and the Q or Q 1 group is illustrated as floating, (R v ) r can be attached to any available carbon atom or nitrogen atom of the U group. Note that when the attachment point on the Q or Q 1 group is illustrated as floating, the Q or Q 1 group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the Q or Q 1 group by replacement of a hydrogen atom.
• the optional substituents can be attached to any available carbon or nitrogen by replacing a hydrogen atom.
• Q or Q 1 comprises a ring selected from Q-28 through Q-35
• Q 2 is selected from O, S or N.
• Q 2 is N, the nitrogen atom can complete its valence by substitution with either H or the substituents as defined in the Summary of Invention for Q or Q l .
• Stereoisomers of this invention can exist as one or more stereoisomers.
• the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
• one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
• the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
• the present invention comprises compounds selected from Formula 1, TV-oxides and agriculturally suitable salts thereof.
• the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.
• nitrogen-containing heterocycles can form TV-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 TV-oxides.
• nitrogen containing heterocycles which can form TV-oxides.
• tertiary amines can form TV-oxides.
• Synthetic methods for the preparation of TV-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as /-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
• MCPBA peroxy acids
• alkyl hydroperoxides such as /-butyl hydroperoxide
• sodium perborate sodium perborate
• dioxiranes such as dimethyldioxirane
• the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
• inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
• the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic moiety such as when Q 1 is phenyl substituted with C(O)OR 22 and R 22 is H.
• organic bases e.g., pyridine or triethylamine
• inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
• the present invention comprises compounds selected from Formula 1, /V-oxides and salts thereof.
• Embodiments of the present invention as described in the Summary of the Invention include:
• Embodiment 1 A compound of Formula 1 wherein G is O.
• Embodiment 2. A compound of Formula 1 wherein G is NR 3 .
• Embodiment 3. A compound of Formula 1 wherein R 3 is H or cyano; or C 1 -C 4 alkyl optionally substituted with one or more substituents selected from halogen.
• Embodiment 4 A compound of Embodiment 3 wherein R 3 is CH 3 , CH 2 CH 3 or
• Embodiment 6 A compound of Formula 1 wherein Z is CR 2 .
• Embodiment 7 A compound of Formula 1 wherein each R 2 is independently selected from H, halogen or C 1 -C 2 haloalkyl.
• Embodiment 8 A compound of Embodiment 7 wherein each R 2 is independently H, halogen or CF 3 .
• Embodiment 9 A compound of Formula 1 wherein A 1 is CR 4 .
• Embodiment 10 A compound of Formula 1 wherein A 2 is CR 5 .
• Embodiment 11 A compound of Formula 1 wherein A 3 is CR 6 .
• Embodiment 12 A compound of Formula 1 wherein A 4 is CR 7 .
• Embodiment 13 A compound of Formula 1 wherein R 4 and R 5 are independently selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano and nitro.
• Embodiment 14 A compound for Formula 1 wherein R ⁇ and R 7 are independently selected from H, halogen, Ci-C ⁇ alkyl, C 1 -C 3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing as ring members in addition to the A 3 and A 4 bridgehead atoms, 4 atoms selected from 3 to 4 carbon atoms and 0 to 1 nitrogen atom.
• Embodiment 15 A compound of Embodiment 14 wherein R 6 and R 7 are independently selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano and nitro.
• Embodiment 16 A compound of Embodiment 14 wherein R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing as ring members in addition to the A 3 and A 4 bridgehead atoms, 4 atoms selected from 3 to 4 carbon atoms and 0 to 1 nitrogen atom.
• Embodiment 17 A compound of Embodiment 14 or 16 wherein the fused aromatic ring contains 4 carbon atoms as ring members in addition to the A 3 and A 4 bridgehead atoms.
• Embodiment 18 A compound of Formula 1 wherein Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl ring, an imidazolyl ring, an oxazolyl ring, an isoxazolyl ring, a thiazolyl ring or an isothiazolyl ring, each ring optionally substituted with one or more substituents independently selected from halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1
• Embodiment 19 A compound of Embodiment 18 wherein Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl ring, an imidazolyl ring, an oxazolyl ring, an isoxazolyl ring, a thiazolyl ring or an isothiazolyl ring, each ring optionally substituted with one or more substituents independently selected from halogen, C 1 -Cg alkyl, C 1 -Cg haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl
• Embodiment 20 A compound of Embodiment 19 wherein Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted with one or more substituents independently selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylamino, C 2 -C 4 dialkylamino, cyano, nitro, C(O)NR 8 R 9 , C(O)OR 10 , phenyl and pyridinyl, each phenyl and pyridinyl optionally substituted with one or more substituents independently selected from
• Embodiment 21 A compound of Embodiment 20 wherein Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted with one or more substituents independently selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, cyano, nitro, C(O)NR 8 R 9 and C(O)OR 10 .
• Embodiment 22 A compound of Embodiment 21 wherein Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted with one or more substituents independently selected from halogen, C 1 -C 3 alkyl and C 1 -C 3 haloalkyl.
• Embodiment 23 A compound of Embodiment 22 wherein Q is a triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted with one or more substituents independently selected from halogen, C 1 -C 3 alkyl and C 1 -C 3 haloalkyl.
• Embodiment 24 A compound of Formula 1 wherein each R 8 is independently H, C 1 -C 6 alkyl, C 2 -Cy alkylcarbonyl or C 2 -C 7 alkoxycarbonyl.
• Embodiment 25 A compound of Embodiment 24 wherein each R 8 is H.
• Embodiment 26 A compound of Formula 1 wherein each R 9 is independently H; or
• C 1 -C 4 alkyl C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 19 .
• Embodiment 27 A compound of Embodiment 26 wherein each R 9 is independently
• Embodiment 28 A compound of Embodiment 27 wherein each R 9 is independently C 1 -C 4 alkyl optionally substituted with one Q 1 and optionally substituted with one or more substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 - C 4 alkylthio, C 1 -C 4 alkylsulfonyl and cyano.
• Embodiment 29. A compound of Formula 1 wherein each R 10 is independently H; or
• C 1 -C 4 alkyl C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 19 .
• Embodiment 30 A compound of Embodiment 29 wherein each R 10 is independently C 1 -C 4 alkyl optionally substituted with one or more substituents selected from R l9 .
• Embodiment 31 A compound of Embodiment 30 wherein each R 10 is independently
• C 1 -C 4 alkyl optionally substituted with one Q 1 and optionally substituted with one or more substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl and cyano.
• Embodiment 32 A compound of Formula 1 wherein each R 19 is independently selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl, cyano, nitro and Q 1 .
• Embodiment 33 A compound of Embodiment 32 wherein each R 19 is independently selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl and cyano.
• Embodiment 35 A compound of Formula 1 wherein R 12 is H, C 1 -C6 alkyl, C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl.
• Embodiment 36 A compound of Embodiment 35 wherein R 12 is H.
• Embodiment 37 A compound of Formula 1 wherein R 13 is H; or C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 19 .
• Embodiment 38 A compound of Embodiment 37 wherein R 13 is H; or Cj-C 4 alkyl optionally substituted with one or more substituents selected from R 19 .
• Embodiment 39 A compound of Embodiment 37 wherein R 13 is H; or Cj-C 4 alkyl optionally substituted with one or more substituents selected from R 19 .
• a compound of Embodiment 38 wherein R 13 is H; or C 1 -C 4 alkyl optionally substituted with one Q 1 and optionally substituted with one or more substituents selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio,
• Embodiment 40 A compound of Embodiment 39 wherein R 13 is H; or C 1 -C 4 alkyl optionally substituted with one Q 1 and optionally substituted with one or more fluorine.
• Embodiment 41 A compound of Formula 1 wherein each R 19 is independently selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, Cj-C 4 alkylthio, C 1 -C 4 alkylsulfinyl,
• Embodiment 42 A compound of Embodiment 41 wherein each R 19 is independently selected from halogen and Q 1 .
• Embodiment 43 A compound of Formula 1. wherein each Q 1 is independently selected from phenyl, pyridinyl and thiazolyl, each optionally substituted with one or more substituents independently selected from halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano, phenyl and pyridinyl.
• Embodiment 44 A compound of Embodiment 43 wherein Q 1 is phenyl, pyridinyl or thiazolyl.
• Embodiment 45 A compound of Embodiment 18 wherein Q is R 16 .
• Embodiment 46 A compound of Embodiment 18 wherein Q is S(O) 2 NR 14 R 15 .
• Embodiment 47 A compound of Formula 1 wherein R 14 is H, C 1 -C ⁇ alkyl, C 2 -C 7 alkylcarbonyl Or C 2 -C 7 alkoxycarbonyl.
• Embodiment 48 A compound of Embodiment 47 wherein R 14 is H.
• Embodiment 49 A compound of Formula 1 wherein R 15 is H; or C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 19 .
• Embodiment 50 A compound of Embodiment 49 wherein R 15 is H; or C 1 -C 4 alkyl optionally substituted with one or more substituents selected from R 19 .
• Embodiment 51 A compound of Embodiment 50 wherein R 15 is H; or C 1 -C 4 alkyl optionally substituted with one or more substituents selected from halogen,
• Embodiment 52 A compound of Embodiment 51 wherein R 15 is H; or C 1 -C 4 alkyl optionally substituted with one or more fluorine and at most one Q 1 .
• Embodiment 53 A compound of Formula 1 wherein Q is other than R 16 .
• Embodiment 54 A compound of Formula 1 wherein R 16 is halogen, C 1 -C3 haloalkyl, C2-C 4 dialkylamino, cyano or nitro.
• Embodiment 55 A compound of Formula 1 wherein R 1 is C 1 -C3 alkyl optionally substituted with one or more substituents independently selected from R 17 .
• Embodiment 56 A compound of Embodiment 55 wherein R 1 is C 1 -C 3 alkyl substituted with one or more halogen.
• Embodiment 57 A compound of Embodiment 56 wherein R 1 is CF 3 .
• Embodiment 58 A compound of Formula 1 wherein n is 1 or 2.
• Embodiment 59 A compound of Formula 1 wherein at most 3 of A 1 , A 2 , A 3 and A 4 are
• Embodiment 60 A compound of Embodiment 59 wherein at most 2 of A 1 , A 2 , A 3 and A 4 are N.
• Embodiment 61 A compound of Embodiment 60 wherein at most 1 of A*, A 2 , A 3 and
• Embodiment 62 A compound of Embodiment 61 wherein A 1 , A 2 , A 3 and A 4 are each other than N.
• Embodiment 63 A compound of Formula 1 wherein when Z is CH, and one R 2 is attached to the phenyl ring at the 4-position, then said R 2 is other than C 1 -Cg alkoxy.
• Embodiments of this invention including Embodiments 1-64 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.
• embodiments of this invention including Embodiments 1-64 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
• Q is a pyridinyl ring, a pyrimidinyl ring, a triazinyl ring, a pyrazolyl ring, a triazolyl ring, an imidazolyl ring, an oxazolyl ring, an isoxazolyl ring, a thiazolyl ring or an isothiazolyl ring, each ring optionally substituted with one or more substituents independently selected from halogen, C ] -Cg alkyl, CpCg haloalkyl, C ⁇ -Cg cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -Cg alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfin
• Z is CR 2 ;
• R 1 is C 1 -C 3 alkyl optionally substituted with one or more substituents independently selected from R 17 ;
• each R 2 is independently selected from H, halogen or C 1 -C 2 haloalkyl;
• R 3 is H or cyano; or C 1 -C 4 alkyl optionally substituted with one or more substituents selected from halogen;
• R 4 and R 5 are independently selected from halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano and nitro;
• R 6 and R 7 are independently selected from halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing as ring members in addition to the A 3 and A 4 bridgehead atoms, 4 atoms selected from 3 to 4 carbon atoms and O to 1 nitrogen atom;
• each R 8 is independently H, C 1 -C 6 alkyl, C 2 -C 7 alkylcarbonyl or C 2 -C 7 alkoxycarbonyl;
• each R 9 and R 10 is independently H; or C 1
• R 13 and R 15 are independently H; or C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3- C 4 cycloalkyl, C 4 -C 7 alkylcycloalkyl or C 4 -C 7 cycloalkylalkyl, each optionally substituted with one or more substituents selected from R 19 ;
• R 16 is halogen, C 1 -C 3 haloalkyl, C 2 -C 4 dialkylamino, cyano or nitro; each R 19 is independently selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfonyl, cyano, nitro and Q 1 ; each Q 1 is independently selected from phenyl, pyridinyl and thiazolyl, each optionally substituted with one or more substituents independently selected from
• Q is a pyrazolyl ring, a triazolyl ring or an imidazolyl ring, each ring attached through nitrogen and optionally substituted with one or more substituents independently selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C]-C 4 alkoxy, C 1 -C 4 haloalkoxy, cyano, nitro, C(O)NR 8 R 9 and C(O)OR 10 ; or Q is C(O)NR 12 R 13 ; R 1 is CF 3 ;
• R 6 and R 7 are independently selected from H, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano and nitro; or R 6 and R 7 are taken together to form a fused aromatic ring, the fused aromatic ring containing 4 carbon atoms as ring members in addition to the A 3 and A 4 bridgehead atoms; each R 8 is H; each R 9 and R 10 is independently C 1 -C 4 alkyl optionally substituted with one Q 1 and optionally substituted with one or more substituents selected from halogen,
• R 12 is H;
• R 13 is H; or C 1 -C 4 alkyl optionally substituted with one or more substituents selected from R 19 ; and each R 19 is independently selected from halogen and Q 1 .
• Embodiment D A compound of Embodiment C wherein each R 2 is independently H, halogen or CF 3 ;
• R 3 is CH 3 , CH 2 CH 3 , or CH 2 CF 3 .
• Embodiment E A compound of Embodiment D wherein G is O; and provided that A 1 , A 2 , A 3 and A 4 are each other than N.
• 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 for controlling an invertebrate pest comprising a biologically effective amount of 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 composition optionally further comprising a biologically effective amount of at least one additional biologically active compound or agent.
• Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of any of the preceding
• Embodiments e.g., as a composition described herein.
• Embodiments of the invention also include a composition comprising a compound of any of the preceding Embodiments, in the form of a soil drench liquid formulation.
• Embodiments of the invention further include methods for controlling an invertebrate pest comprising contacting the soil with a liquid composition as a soil drench comprising a biologically effective amount of a compound of any of the preceding Embodiments.
• Embodiments of the invention also include a spray composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding Embodiments and a propellant.
• Embodiments of the invention further include a bait composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of any of the preceding Embodiments, one or more food materials, optionally an attractant, and optionally a humectant.
• Embodiments of the invention also include a device for controlling an invertebrate pest comprising said bait composition and a housing adapted to receive said bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to said bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
• a compound of Formula 1 can be prepared by treating an amine of Formula 2 with an appropriate reagent of Formula 3 (where L is a suitable nucleophilic reaction leaving group such as halogen or imidazole) in the presence of a base (e.g. triethylamine, JV. ⁇ f-diisopropylethylamine or sodium hydrogen carbonate).
• a base e.g. triethylamine, JV. ⁇ f-diisopropylethylamine or sodium hydrogen carbonate.
• polymer-supported acid scavengers such as polymer-bound equivalents of N Jt- diisopropylethylamine and 4-(dimethylamino)pyridine, for example, iV-[(4-ethenylphenyl]- methyl)]-.V-methyl-4-pyridinamine polymer with diethenylbenzene and ethenylbenzene (CAS Registry Number 82942-26-5, hereafter identified as "PS-DMAP").
• the reaction can be conducted neat or in an solvent such as dichloromethane, chloroform, tetrahydrofuran, acetonitrile or 1,2-dichloroethane. Temperatures for this reaction can range from 0 to 90 0 C.
• the method of Scheme 1 is illustrated in Step F of Example 1, Step D of Example 2, and Example 3.
• Compounds of Formula 2a can be made by the ring- opening of an appropriate epoxide of Formula 4 by treatment with an amine of Formula 5 in a solvent such as methanol, ethanol, chloroform, tetrahydrofuran, acetonitrile or 1,2-dichloroethane at temperatures ranging from 25 to 90 0 C, as depicted in Scheme 2.
• a solvent such as methanol, ethanol, chloroform, tetrahydrofuran, acetonitrile or 1,2-dichloroethane at temperatures ranging from 25 to 90 0 C, as depicted in Scheme 2.
• the method of Scheme 2 is illustrated in Step E of Example 1 and Step C of Example 2.
• Epoxides of Formula 4 can be prepared from ketones of Formula 6 by treatment with a sulfonium ylide, which is typically generated in situ by reacting a trimethylsulfoxonium halide of Formula 7 with an appropriate base such as sodium hydride, potassium hydride or sodium re/t-butoxide, in a suitable solvent such as dimethyl sulfoxide, MN-dimethylformamide or tert-butanol, as depicted in Scheme 3.
• a suitable solvent such as dimethyl sulfoxide, MN-dimethylformamide or tert-butanol
• Trimethylsulfoxonium halides of Formula 7 are commercially available.
• ketones of Formula 6 can be obtained by treating compounds of Formula 8 with lithium metal, an organolithium reagent such as, n-butyllithium, sec-butyllithium or terf-butyllithium, or an alkylmagnesium halide such as ethyl or methyl magnesium bromide or chloride at temperatures typically between -78 0 C and room temperature, to form the lithio or Grignard intermediate, respectively.
• This intermediate is then reacted with a reagent of Formula 9 where L 1 is a leaving group such as Cl, Br, OCH3 or OCOCF3 to give the ketone of Formula 6.
• the reaction is run in an organic solvent, preferably tetrahydrofuran or diethyl ether.
• the method of Scheme 4 is illustrated in Step C of Example 1.
• compounds of Formula Ia can be prepared from oxazolidinones of Formula 10 by reacting with aromatic halide intermediates of Formula 11 (where L2 is a leaving group such as F or Cl) as illustrated in Scheme 5.
• oxazolidinone of Formula 10 is contacted with a base, such as sodium hydride or potassium rerf-butoxide, and then subsequently treated with a compound of Formula 11 typically in a solvent (e.g., iV.N-dimethylformamide or dimethyl sulfoxide).
• a base such as sodium hydride or potassium rerf-butoxide
• a compound of Formula 11 typically in a solvent (e.g., iV.N-dimethylformamide or dimethyl sulfoxide).
• a solvent e.g., iV.N-dimethylformamide or dimethyl sulfoxide
• the reaction can be conducted with two equivalents of a base such as potassium carbonate and in the presence of a copper(I) catalyst such as copper(I) iodide (typically 3-5 mol %) and fr ⁇ /is-cyclohexanediamine (to solubilize the CuI) using the method described in Organic Letters 2003, 5, 963-965.
• a base such as potassium carbonate
• a copper(I) catalyst such as copper(I) iodide (typically 3-5 mol %) and fr ⁇ /is-cyclohexanediamine (to solubilize the CuI) using the method described in Organic Letters 2003, 5, 963-965.
• compounds of Formula Ia can also be prepared by a copper-mediated iV-arylation reaction of an oxazolidinone of Formula 10 with a compound of Formula 12, where M is a group such as boronic acid, boronic ester, biarylbismuthane, trialkylstannane or trialkylsiloxane.
• the reaction can be run in an solvent such as dichloromethane, chloroform or tetrahydrofuran, and in the presence of a copper salt such as copper (II) acetate and a base (e.g., triethylamine, or pyridine), as depicted in Scheme 6.
• a copper salt such as copper (II) acetate and a base (e.g., triethylamine, or pyridine
• Oxazolidinones of Formula 10 can be prepared by the reaction of amino alcohols of Formula 13 with triphosgene or triphosgene substitutes that result in carbonylation (e.g., diphosgene, phosgene, (bis(trichloromethyl) carbonate) or 1,1' -carbon yl-diimidazole).
• the reaction is run in a suitable organic solvent, such as dichloromethane, 1,2-dichloroethane or tetrahydrofuran in the presence of a base such as triethylamine, sodium hydrogen carbonate or sodium carbonate as depicted in Scheme 7.
• Amino alcohols of Formula 13 can be prepared by the reduction of cyanohydrins of Formula 14 with a reducing agent such as lithium tetrahydroaluminate in a suitable organic solvent such as diethyl ether or tetrahydrofuran as depicted in Scheme 8.
• a reducing agent such as lithium tetrahydroaluminate
• a suitable organic solvent such as diethyl ether or tetrahydrofuran
• Cyanohydrins of the Formula 14 can be prepared from the corresponding ketones (i.e., Formula 6) via one of a variety of cyanation methods well known in the art (see, for example, North, M. Science of Synthesis 2004, 19, 235-284).
• Compounds of Formula Ib can be prepared by reduction of the imide of Formula 15 with sodium borohydride in a suitable solvent such as methanol and then reducing the resulting 5-hydroxy intermediate with sodium borohydride and trifluoroacetic acid.
• a suitable solvent such as methanol
• Methods for reduction of ketones and alcohols are well document in the art see, for example, Mehrotra, M. M., et al.; Journal of Medicinal Chemistry 2004, 47, 2037-2061 and Johnson, M. R.; Rickbom, B.; Journal of Organic Chemistry 1970, 35, 1041-1045.
• the method of Scheme 9 is illustrated in Example 5, Steps E and F as well as Example 6, Steps B and C.
• compounds of Formula 15 can be prepared from cyclization of ureas of Formula 16 by treatment with aqueous hydrochloric acid according to the general method described by Cook, A. H.; Hunter, G. D.; Journal of the Chemical Society 1952, 3789-3796.
• R 3 is other than H
• a suitable base such as sodium hydride
• compounds of Formula 16 can be obtained by reacting ⁇ -aminonitriles of Formula 17 with isocyanates of Formula 18 according to the general method of Van Dort, M. E.; Jung, Y.-W.; Bioorganic & Medicinal Chemistry Letters 2004, 74(21), 5285-5288.
• Compounds of Formula 17 can be obtained by coverting ketones of Formula 6 to the corresponding imines 20, followed by addition of a cyanide source (e.g., HCN) to the imine intermediates, followed by the addition of cyanide, which are well documented in the art
• a cyanide source e.g., HCN
• a ketone of Formula 6 is first treated with lithium bis(trimethylsily])amide, which results in the formation of an imine intermediate 19, which is then solvolyzed in methanol to afford a stable imine 20 according to the general method of Gosselin, F. et al Organic Letters 2005, 7, 355-358.
• compounds of Formula 15 can be prepared by heating compounds of Formula 21 with amines of Formula 5 (see Scheme 13) in the presence of a catalyst such as 4-(dimethylamino)pyridine or trifluoroacetic acid.
• a catalyst such as 4-(dimethylamino)pyridine or trifluoroacetic acid.
• the cyclized hydantoins formed can then be treated with L ⁇ -R 3 in the presence of a base such as sodium hydride to form compounds of Formula 15.
• a catalyst such as 4-(dimethylamino)pyridine or trifluoroacetic acid.
• the cyclized hydantoins formed can then be treated with L ⁇ -R 3 in the presence of a base such as sodium hydride to form compounds of Formula 15.
• a base such as sodium hydride
• compounds of Formula 21 can be obtained by reacting ⁇ -ketoesters of Formula 22 with benzyl carbamate, after dehydration to form imines of Formula 23, followed by addition of the Grignard intermediates 24, which can be derived from compounds of Formula 8 as described previously for the method of Scheme 4.
• Grignard intermediates 24 can be derived from compounds of Formula 8 as described previously for the method of Scheme 4.
• Step A Preparation of 4-(acetylamino)-2-methyl-iv * -(2,2,2-trifluoroethyl)benzamide
• Step B Preparation of 4-amino-2-methyI-JV-(2,2,2-trifluoroethyl)benzamide
• Step A) was added concentrated hydrochloric aeid, and the reaction mixture was heated to 100 0 C for 2 h.
• the reaction mixture was cooled using an external ice/water bath, and aqueous sodium hydroxide (50 wt%, 20 mL) was added until the reaction mixture was neutralized, causing a solid to precipitate.
• the solid was filtered, washed with water and dried in a vacuum oven at 60 0 C overnight to provide the title compound as a white powder (0.89 g).
• Step F 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)-3-oxazolidinyl]- 2-methyl-7V-(2,2,2-trifluoroethyl)benzamide
• More l.T-carbonyldiimidazole (0.05 g, 0.31 mmol) was added. After stirring for 22 h, more l,l'-carbonyldiimidazole (0.047 g, 0.28 mmol) and PS-DMAP (0.10 g, 0.14 mmol) were added. After stirring for 4 h, the reaction mixture was concentrated under reduced pressure, and the resulting residue was dissolved in ethyl acetate (60 mL), washed with water (3 x 30 mL), filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to give a solid.
• Step A Preparation of 4-(acetylamino)-2-methyl-iV-(2-pyridinylmethyl)benzamide A mixture of 4-(acetylamino)-2-methylbenzoic acid (5.0 g, 25.9 mmol),
• Step C Preparation of 4-[[2-(3,5-dichlorophenyl)-2-hydroxy- 3,3,3-trifluoropropyl]amino]-2-methyl- ⁇ r -(2-pyridinylmethyl)benzamide
• Step D) (0.75 g) and 4-amino-2-methyI--V-(2-pyridinylmethyl)benzamide (i.e. product of Step B) (0.39 g, 1.7 mmol) in anhydrous ethanol (6 mL) was heated at 65 0 C for 7O h.
• the reaction mixture was concentrated under reduced pressure, and the residue was purified by medium pressure silica gel chromatography using ethyl acetate/hexanes (6:8) as eluant to provide the title compound as an off-white glassy solid (0.28 g).
• Step D Preparation of 4-[5-(3,5-dichlorophenyl)-2-oxo-5-(trifluoromethyl)- 3-oxazolidinyl-2-methyl-7V-(2-pyridinylmethyl)benzamide
• Step A Preparation of 2-nitro-5-[2-oxo-5-phenyl-5-(trifluoromethyl)-3-oxazolidinyl]benzonitrile
• Step A Preparation of 5-phenyI-5-(trifluoromethyl)-2-oxazolidinone
• a cold (below 20 0 C) solution of lithium tetrahydroaluminate (10.0 mL, 1.0 M solution in diethyl ether) was added a solution of ⁇ -hydroxy- ⁇ -(trifluoromethyl)benzeneacetonitrile (Aldrich, 2.01 g, 10.0 mmol) in anhydrous diethyl ether (10 mL).
• Aldrich 2.01 g, 10.0 mmol
• the reaction mixture was stirred at ambient temperature for 1 h.
• the solvent phases were separated, and the organic phase was washed with water, 1 N aqueous hydrochloric acid, and saturated aqueous sodium chloride solution.
• the organic extracts were dried (MgSC ⁇ ), filtered and the solvent was concentrated under reduced pressure to provide the title compound as a white solid (1.35 g).
• Step A Preparation of 3,3,3-trifluoro-2-hydroxy-N-[(phenylmethoxy)carbonyl]alanine ethyl ester
• Step D Preparation of 4-[4-(3,5-dichlorophenyl)-2,5-dioxo-4-(trifluorornethyl)- l-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide
• Step E Preparation of 4-[4-(3,5-dichlorophenyl)-5-hydroxy-2-oxo-4-(trifluoromethyl)- l-imidazolidinyl]-2-methyl-.V-(2-pyridinylrnethyl)benzamide
• Step F Preparation of 4-[4-(3,5-dichlorophenyl)-2-oxo-4-(trifluoromethyl)- l-imidazolidinyl]-2-methyl- ⁇ f-(2-pyridinylmethyl)benzamide
• 4-[4-(3,5-dichlorophenyl)-5-hydroxy-2-oxo-4-(trifluoromethyl)- l-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide i.e.
• Step E the product of Step E) (0.18 g, 0.33 mmol) in trifluoroacetic acid (4 mL) at ice-bath temperature was added sodium borohydride (0.10 g, 2.6 mmol) in two batches. After the initial vigorous reaction had subsided, the reaction mixture was stirred at room temperature. An additional batch of sodium borohydride (0.048 g) was added after 2 h. The reaction mixture was stirred for 18 h, and then water (5 mL) was added. The reaction mixture was cooled with an external ice/water bath, and then a solution of sodium hydroxide (4.1 g of 50% aqueous solution and 10 mL of water) was added.
• reaction mixture was extracted with ethyl acetate (2 X 25 mL), and the combined organic layers were filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to give a gummy solid.
• Another run was conducted using 90 mg of product from Step E, 2 mL of trifluoroacetic acid, and 67 mg of sodium borohydride under similar conditions.
• the crude products from these two runs were combined and purified by medium pressure silica gel chromatography using ethyl acetate/hexanes (45%-65%) as eluant to provide the title compound, a compound of the present invention, as an off-white solid (0.18 g).
• Step A Preparation of 4-[4-(3,5-dichlorophenyl)-3-methyl-2,5-dioxo- 4-(trifluorometh y I)- 1 -imi dazolidinyl]-2-meth yl- ⁇ T-(2-pyridinylmethyl)benzamide
• 4-[4-(3,5-dichlorophenyl)-2,5-dioxo-4-(trifluoromethyl)- l-imidazolidinyl]-2-methyl- ⁇ /'-(2-pyridinylmethyl)benzamide i.e.
• Step D of Example 5 the product of Step D of Example 5 (0.39 g, 0.73 mmol) in ⁇ /,-V-dimethylformamide (4 mL) was added sodium hydride (60% oil dispersion, 0.0335 g, 2.3 mmol). After stirring for 15 min, iodomethane (0.179 g, 1.26 mmol) was added. The reaction mixture was stirred for 45 min and then partitioned between ethyl acetate (50 mL) and water (25 mL).
• Step C Preparation of 4-[4-(3,5-dichlorophenyl)-3-methyl-2-oxo-4-(trifluoromethyl)- l-imidazolidinyl]-2-methyl-N-(2-pyridinylmethyl)benzamide
• reaction mixture was cooled with an external ice/water bath, and then a solution of sodium hydroxide (6 mL g of 50% aqueous solution and 20 mL of water) was added.
• the reaction mixture was extracted with ethyl acetate (1 X 50 mL, 1 X 35 mL), and the combined organic layers were filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian), and concentrated under reduced pressure to give a gummy solid, which was purified by medium pressure silica gel chromatography using ethyl acetate/hexanes (45%-65%) as eluant to provide the title compound, a compound of the present invention, as a white solid (0.2O g).
• m 1, 2, 3, 4 or 5.
• W-I W-2 W-3 W-4 wherein m is 1, 2, 3, 4 or 5.
• m 1, 2, 3, 4 or 5.
• Compounds of this invention can generally be used as an invertebrate pest control active ingredient in a composition, i.e. formulation, with a carrier suitable for agronomic or nonagronomic uses comprising at least one of a liquid diluent, a solid diluent or a surfactant.
• a carrier suitable for agronomic or nonagronomic uses comprising at least one of a liquid diluent, a solid diluent or a surfactant.
• the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
• Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels.
• 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.
• 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 emulsif ⁇ able granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. Hugh-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, ⁇ iV-dimethylalkanamides (e.g., TvyV-dimethylformarnide), limonene, dimethyl sulfoxide, ⁇ f-alkylpyrrolidones (e.g., JV-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
• Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C ( j— C 22 ).
• glycerol esters of saturated and unsaturated fatty acids typically C ( j— C 22 ).
• 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
• mixtures thereof e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil
• Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation.
• alkylated fatty acids e.g., methylated, ethylated, butylated
• Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses.
• 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 may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene
• 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 Hgnosulfonates; 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 ⁇ f-alkyl propanediamines, tripropylenetriamines and dipropylene- tetramines, 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 diquatemary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
• amines such as ⁇ f-alkyl propanediamines, tripropylenetriamines and dipropylene- tetramines, and
• 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 may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants).
• formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes.
• Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes.
• formulation auxiliaries and additives include those listed in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
• the compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent.
• Solutions, including emulsifiable concentrates can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water.
• Active ingredient slurries, with particle diameters of up to 2,000 ⁇ m can be wet milled using media mills to obtain particles with average diameters below 3 ⁇ m.
• Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 ⁇ m 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 12 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
• Compound 16 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0%
• Compound 18 20.00% polyvinylpyrrolidone-vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water 65.75%
• 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 com, 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 ® , Evil ® , STS ® and CLEARFIELD ® , as well as crops expressing JV-acetyltransferase (GAT) to provide resistance to glyphosate herbicide, or crops containing the HRA gene providing resistance to herbicides inhibiting acetolactate synthase (ALS).
• GAT JV-acetyltransferase
• 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.
• Nonagronomic uses refer to invertebrate pest control in the areas other than fields of crop plants.
• Nonagronomic uses of the present compounds and compositions include control of invertebrate pests in stored grains, beans and other foodstuffs, and in textiles such as clothing and carpets.
• Nonagronomic uses of the present compounds and compositions also include invertebrate pest control in ornamental plants, forests, in yards, along roadsides and railroad rights of way, and on turf such as lawns, golf courses and pastures.
• Nonagronomic uses of the present compounds and compositions also include invertebrate pest control in houses and other buildings which may be occupied by humans and/or companion, farm, ranch, zoo or other animals.
• Nonagronomic uses of the present compounds and compositions also include the control of pests such as termites that can damage wood or other structural materials used in buildings.
• Nonagronomic uses of the present compounds and compositions also include protecting human and animal health by controlling invertebrate pests that are parasitic or transmit infectious diseases.
• the controlling of animal parasites includes controlling external parasites that are parasitic to the surface of the body of the host animal (e.g., shoulders, armpits, abdomen, inner part of the thighs) and internal parasites that are parasitic to the inside of the body of the host animal (e.g., stomach, intestine, lung, veins, under the skin, lymphatic tissue).
• External parasitic or disease transmitting pests include, for example, chiggers, ticks, lice, mosquitoes, flies, mites and fleas.
• Internal parasites include heartworms, hookworms and helminths.
• Compounds and compositions of the present invention are suitable for systemic and/or non-systemic control of infestation or infection by parasites on animals.
• Compounds and compositions of the present invention are particularly suitable for combating external parasitic or .disease transmitting pests.
• Compounds and compositions of the present invention are suitable for combating parasites that infest agricultural working animals, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalos, rabbits, hens, turkeys, ducks, geese and bees; pet animals and domestic animals such as dogs, cats, pet birds and aquarium fish; as well as so-called experimental animals, such as hamsters, guinea pigs, rats and mice.
• Examples of 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 ⁇ Forf ⁇ cula 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.
• eggs, larvae, nymphs and adults of the order Acari 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 (JTetranychus mcdanieli McGregor)); flat mites in the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e.
• Tetranychidae e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (JTetranychus mcdanie
• 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 (lncisitermes immigran
• 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).
• Compounds of the present invention also have activity on members of the Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchus, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e.
• Compounds of the invention show particularly high activity against pests in the order Lepidoptera (e.g., Alabama argillacea 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

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• 2007
  • 2007-04-13 MX MX2008013305A patent/MX2008013305A/es not_active Application Discontinuation
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