Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/44—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom three- or four-membered rings
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

• This invention relates to certain 3-(aryloxy)azocycloalkanes, their N-oxides, salts and compositions suitable for agronomic and nonagronomic uses, 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.
• the control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, turf, wood products, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action.
• PCT Patent Publication WO 2005/115146 Al discloses certain insecticidal, acaricidal molluscicidal and nematicidal compounds comprising a piperazine ring directly bonded to an aromatic or heteroaromatic ring.
• the 3-(aryloxy)azacycloalkanes of the present invention are not disclosed in this publication.
• 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:
• a 1 is N or CR 7 ;
• a 2 is N or CR 8 ;
• a 3 is N or CR 9 ;
• a 4 is N or CR 10 ;
• a 1 , A 2 , A 3 and A 4 are N;
• T is O, S(0) k or NR 36 ;
• Z is O, S(0) m , NR 37 or CR 8 R 39 ;
• R 1 is a phenyl or 5- or 6-membered heteroaromatic ring optionally substituted with up to 5 substituents independently selected from R 14 ;
• R 2 is H, hydroxy, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C3-C7 cycloalkyl, C 4 -C 8 cycloalkylalkyl,
• each R 3 is independently halogen, cyano, C1-C4 alkyl or C1-C4 alkoxy;
• R 4 is H or C!-C4 alkyl
• RS is H or C ⁇ alkyl
• R 6 is a phenyl or 5- or 6-membered heteroaromatic ring optionally substituted with up to 5 substituents independently selected from R 22 ;
• R 7 , R 8 , R 9 and R 10 are independently H, halogen, cyano, nitro, OR 23 , NR 24 R 25 , C r C 6 alkyl, C ⁇ -Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 3 -C 7 cycloalkyl, C 4 -C 8 cycloalkylalkyl, C 5 -C 7 cycloalkenyl, -CHO, C(W )R 26 , C(0)OR 27 , C(0)NR 8 R 29 , S(0) q R 30 ,
• S(0) 2 NR 28 R 29 or OC(0)R 31 or a phenyl or 5- or 6-membered heteroaromatic ring optionally substituted with up to 5 substituents independently selected from R 40 ; or a vicinal pair of R 7 and R 8 , or R 8 and R 9 , or R 9 and R 10 , are taken together with the carbon atoms to which the pair is attached to form a fused 5- or
• R 1 1 and R 12 are independently H, halogen, C ⁇ -C 2 alkyl or C ⁇ -C 2 alkoxy;
• each R 13 , R 14 , R 22 and R 40 is independently halogen, cyano, nitro, OR 23 , NR 24 R 25 ,
• R 15 and R 16 are independently C ⁇ Cg alkyl, C ⁇ Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 3 -C 7 cycloalkyl, C 4 -C 8 cycloalkylalkyl or C 5 -C 7 cycloalkenyl; or phenyl optionally substituted with up to 3 substituents independently selected from halogen, cyano, nitro, OR 23 , NR 24 R 25 , C!-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, -C4 haloalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 4 haloalkenyl, -CHO, C(W 2 )R 26 , C(0)OR 27 , C(0)
• each R 17 and R 20 is independently H, C j -Cg alkyl, C j -Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 3 -C7 cycloalkyl, C 4 - C 8 cycloalkylalkyl or C5-C7 cycloalkenyl; or phenyl optionally substituted with up to 3 substituents independently selected from halogen, cyano, nitro, OR 23 , NR 24 R 25 , C!-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, -Q haloalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 4 haloalkenyl, -CHO, C(W 2 )R 26 , C
• each R 18 , R 21 , R 24 and R 29 is independently H, -Cg alkyl, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl;
• each R 23 and R 31 is independently H, C ⁇ -Cg alkyl or C ⁇ -Cg haloalkyl;
• each R 25 , R 36 and R 37 is independently H, -Cg alkyl, C(0)R 32 or C(0)OR 33 ; each R 28 and R 32 is independently H, C j -Cg alkyl, C j -Cg haloalkyl, C 2 -C 6 alkenyl,
• each R 33 is independently -Cg alkyl, C j -Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6
• haloalkenyl C 2 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 3 -C7 cycloalkyl, C 4 -C 8 cycloalkylalkyl or C5-C7 cycloalkenyl;
• R 34 is H, C!-C 4 alkyl, - ⁇ haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, Ci ⁇ C 4 alkoxy or cyano;
• R 35 is H or methyl
• R 38 is H, OH, halogen, € ⁇ - € 2 alkyl or € ⁇ - € 2 alkoxy;
• R 39 is selected from H, cyano and C ⁇ -C 2 alkyl, and when R 38 is halogen, then R 39 is additionally selected from halogen; or
• R 38 and R 39 together with the carbon atom to which said R 38 and R 39 are attached represent a carbonyl moiety
• W is O or S
• W 1 is O or S
• each W 2 is independently O or S;
• k 0, 1 or 2;
• n 0, 1 or 2;
• n is an integer from 0 to 5;
• p 0, 1 or 2;
• each q is independently 0, 1 or 2;
• s is 1, 2 or 3; and t is 1 or 2;
• this invention relates to a compound selected from Formula 1, an N-oxide, or a salt thereof.
• This invention also provides a composition comprising a compound of Formula 1, an
• 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 optionally further comprising at least one additional biologically active compound or agent.
• This invention further provides a spray composition for controlling an invertebrate pest comprising a compound of Formula 1, an N-oxide, or a salt thereof, or a composition described above, and a propellant.
• This invention also provides a bait composition for controlling an invertebrate pest comprising a compound of Formula 1, an N-oxide, or a salt thereof, or a composition described in the embodiments 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 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 compound of Formula 1, an N-oxide, or a salt thereof (i.e, in a biologically effective amount), 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 protecting a seed or a plant grown therefrom 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 method for protecting an animal from an invertebrate parasitic pest comprising administering to the animal a parasiticidally effective amount of a compound of Formula 1, an N-oxide, or a salt thereof (e.g., as a composition described herein).
• This invention also provides for the use of a compound of Formula 1, an N-oxide, or a salt thereof, (e.g., as a composition described herein) in protecting an animal from an invertebrate pest.
• 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, 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.
• invertebrate pest includes arthropods, gastropods and nematodes of economic importance as pests. More particularly, “invertebrate pest” relates to arthropods and gastropods, and most particularly, “invertebrate pest” relates to arthropods.
• 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.
• 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 (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
• horticultural crops e.g., greenhouse, nursery or ornamental plants not grown in a field
• turf e.g., sod farm, pasture, golf course, lawn, sports field, etc.
• wood products e.g., 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
• alkylating agent refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom. Unless otherwise indicated, the term “alkylating” does not limit the carbon-containing radical to alkyl; the carbon-containing radicals in alkylating agents include the variety of carbon-bound substituent radicals specified for R 4 , R 5 , R 6 and L.
• alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
• Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
• Alkenyl also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl.
• Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
• Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
• Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
• Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 -, CH 3 OCH 2 CH 2 -, CH 3 CH 2 OCH 2 -, CH 3 CH 2 CH 2 CH 2 OCH 2 - and CH 3 CH 2 OCH 2 CH 2 -.
• 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.
• 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-, C1CH 2 -, CF 3 CH 2 - and CF 3 CC1 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-.
• haloalkynyl examples include HC ⁇ CCHC1-, CF 3 C ⁇ C-, CC1 3 C ⁇ C- and FCH 2 C ⁇ CCH 2 -.
• 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 ) n , n is 1, 2, 3, 4 or 5.
• substituents which can be hydrogen, for example R 2 , R 7 , R 8 , R 9 or R 10 , then when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
• variable group When a variable group is shown to be optionally attached to a position, for example (R v ) r in U-30 of Exhibit 1 wherein r may be 0, then hydrogen may be at the position even if not recited in the variable group definition.
• hydrogen atoms When one or more positions on a group are said to be "not substituted” or “unsubstituted”, then hydrogen atoms are attached to take up any free valency.
• ring system denotes two or more fused rings.
• fused ring refers to a ring that is fused to another ring to form a fused bicyclic ring system.
• bicyclic ring system and fused bicyclic ring system denote a ring system consisting of two fused rings, in which either ring can be saturated, partially unsaturated or fully unsaturated unless otherwise indicated. Accordingly either ring can be aromatic or nonaromatic unless otherwise indicated.
• carbocyclic ring denotes a ring or ring system 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".
• heterocyclic ring denotes a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur.
• a heterocyclic ring contains no more than 3 nitrogen atoms, no more than 2 oxygen atoms and no more than 2 sulfur atoms.
• a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring.
• a heterocyclic ring can be aromatic or nonaromatic.
• heterocyclic rings and ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
• Aromatic indicates that each of the ring atoms is essentially in the same plane and has a / ⁇ -orbital perpendicular to the ring plane, and in which (4n + 2) ⁇ electrons, where n is a positive integer, are associated with the ring to comply with Huckel's rule.
• aromatic ring system denotes a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic.
• R 1 , R 6 , R 7 , R 8 , R 9 or R 10 is a 5- or 6-membered nitrogen-containing heteroaromatic ring, it can be attached to the remainder of Formula 1 though any available carbon or nitrogen ring atom, unless otherwise described.
• R 1 , R 6 , R 7 , R 8 , R 9 or R 10 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 one to five substituents is the ring illustrated as U-l in Exhibit 1, wherein R v is R 14 , R 22 or R 40 as defined in the Summary of the Invention for R 1 , R 6 , R 7 , R 8 , R 9 or R 10 , respectively, and r is an integer from 0 to 5.
• R 1 , R 6 , R 7 , R 8 , R 9 or R 10 can be (among others) 5- or 6-membered heteroaromatic ring, which is optionally substituted with substituents up to the number of available positions, and the substituents are independently selected from a group of radicals defined in the Summary of Invention (i.e. R 14 , R 22 or R 40 , respectively).
• Examples of a 5- or 6-membered heteroaromatic ring optionally substituted with from one or more substituents include the rings U-2 through U-61 illustrated in Exhibit 1 wherein R v is any substituent as defined in the Summary of the Invention for R 1 , R 6 , R 7 , R 8 , R 9 or R 10 (i.e.
• 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 v groups are shown in the structures U-l through U-61, it is noted that they do not need to be present since they are optional substituents.
• the nitrogen atoms that require substitution to fill their valence are substituted with H or R v .
• (R v ) r can be attached to any available carbon atom or nitrogen atom of the U group.
• the U group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the U group by replacement of a hydrogen atom.
• 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).
• a vicinal pair of R 7 and R 8 , or R 8 and R 9 , or R 9 and R 10 can be taken together with the carbon atoms to which they are attached to form a fused 5- or 6-membered aromatic or nonaromatic ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from N, O and S.
• This ring comprising R 7 and R 8 , or R 8 and R 9 , or R 9 and R 10 is fused to the 6-membered aromatic ring comprising A 1 , A 2 , A 3 and A 4 , and thus is at least partially unsaturated, and may be fully unsaturated.
• Compounds 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). 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.
• Compounds of this invention can exist as one or more conformational isomers due to restricted rotation about the amide bond in Formula 1.
• This invention comprises mixtures of conformational isomers.
• this invention includes compounds that are enriched in one conformer relative to others.
• 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 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 biologically suitable salts thereof.
• reference to Formula 1 includes 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 A 1 is N.
• Embodiment 2 A compound of Formula 1 wherein A 1 is CR 7 .
• Embodiment 3 A compound of Formula 1 or Embodiment 1 or 2 wherein A 2 is CR 8 .
• Embodiment 4. A compound of Formula 1 or any one of Embodiments 1 through 3 wherein A 3 is CR 9 .
• Embodiment 5. A compound of Formula 1 or any one of Embodiments 1 through 4 wherein A 4 is CR 10 .
• Embodiment 6 A compound of Formula 1 or any one of Embodiments 1 through 5 wherein R 7 , R 8 , R 9 and R 10 are independently H, halogen, cyano, nitro, OR 23 , NR24R 25 , C !-C 6 alkyl, C Y -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl,
• Embodiment 7 A compound of Embodiment 6 wherein R 7 , R 8 , R 9 and R 10 are
• Embodiment 8 A compound of Formula 1 or any one of Embodiments 1 through 7 wherein independently when R 7 , R 8 , R 9 or R 10 is separate (i.e. not taken together to form a ring), then said R 7 , R 8 , R 9 or R 10 is independently H, halogen, C j -C 4 alkyl, C j -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 3 -C 4 haloalkynyl, C 3 -C 6 cycloalkyl, C j -C 4 alkoxy, C j -C 4 haloalkoxy, C j -C 4 alkylthio, C ⁇ -C 4 haloalkylthio or cyano.
• Embodiment 9 A compound of Embodiment 8 wherein independently when R 7 , R 8 , R 9 or R 10 is separate, then said R 7 , R 8 , R 9 or R 10 is independently H, halogen or C ⁇ -C 4 haloalkyl.
• Embodiment 10 A compound of Formula 1 or any one of Embodiments 1 through 9 wherein when R 7 is separate, then R 7 is H or halogen.
• Embodiment 1 A compound of Embodiment 10 wherein when R 7 is separate, then R 7 is H or F.
• Embodiment 12 A compound of Embodiment 1 1 wherein when R 7 is separate, then R 7 is H.
• Embodiment 13 A compound of Formula 1 or any one of Embodiments 1 through 12 wherein when R 8 is separate, then R 8 is H, halogen or C ⁇ -C 2 haloalkyl.
• Embodiment 14 A compound of Embodiment 13 wherein when R 8 is separate, then R 8 is H, halogen or C ⁇ fluoroalkyl (i.e. fluoromethyl, including CH 2 F, CHF 2 and CF 3 ).
• Embodiment 15 A compound of Embodiment 14 wherein when R 8 is separate, then R 8 is H, halogen or CF 3 .
• Embodiment 16 A compound of Embodiment 15 wherein when R 8 is separate, then R 8 is H, F, CI or CF 3 .
• Embodiment 17 A compound of Embodiment 15 wherein when R 8 is separate, then R 8 is halogen or CF 3 .
• Embodiment 18 A compound of Embodiment 17 wherein when R 8 is separate, then R 8 is F, CI or CF 3 .
• Embodiment 19 A compound of Formula 1 or any one of Embodiments 1 through 18 wherein when R 9 is separate, then R 9 is H, halogen or C1-C2 haloalkyl.
• Embodiment 20 A compound of Embodiment 19 wherein when R 9 is separate, then R 9 is H, halogen or C ⁇ fluoroalkyl (i.e. fluoromethyl).
• Embodiment 21 A compound of Embodiment 20 wherein when R 9 is separate, then R 9 is H, halogen or CF 3 .
• Embodiment 22 A compound of Embodiment 21 wherein when R 9 is separate, then R 9 is H, CI or CF 3 .
• Embodiment 23 A compound of Formula 1 or any one of Embodiments 1 through 22 wherein when R 10 is separate, then R 10 is H or halogen.
• Embodiment 24 A compound of Embodiment 23 wherein when R 10 is separate, then R 10 is H or F.
• Embodiment 25 A compound of Embodiment 24 wherein when R 10 is separate, then R 10 is H.
• Embodiment 27 A compound of Formula 1 or any one of Embodiments 1 through 26 wherein one vicinal pair of R 7 and R 8 , or R 8 and R 9 , or R 9 and R 10 , are taken together with the carbon atoms to which they are attached to form a fused ring as described.
• Embodiment 28 A compound of Formula 1 or any one of Embodiments 1 through 27 wherein a vicinal pair of R 7 and R 8 are taken together with the carbon atoms to which they are attached to form a fused ring as described.
• Embodiment 29 A compound of Formula 1 or any one of Embodiments 1 through 27 wherein a vicinal pair of R 8 and R 9 are taken together with the carbon atoms to which they are attached to form a fused ring as described.
• Embodiment 30 A compound of Formula 1 or any one of Embodiments 1 through 27 wherein a vicinal pair of R 9 and R 10 are taken together with the carbon atoms to which they are attached to form a fused ring as described.
• Embodiment 31 A compound of Formula 1 or any one of Embodiments 1 through 25 wherein each of R 7 , R 8 , R 9 and R 10 is separate (i.e. not taken together to form a fused ring).
• Embodiment 34 A compound of Formula 1 or any one of Embodiments 1 through 33 wherein R 1 1 and R 12 are independently H, halogen or methyl.
• Embodiment 35 A compound of Embodiment 34 wherein R 1 1 and R 12 are
• Embodiment 36 A compound of Embodiment 35 wherein R 1 1 and R 12 are H.
• Embodiment 37 A compound of Formula 1 or any one of Embodiments 1 through 32 wherein L is 1 ,4-diphenylene optionally substituted with up to 4 substituents independently selected from R 13 .
• Embodiment 38 A compound of Formula 1 or any one of Embodiments 1 through 31 wherein L is -C(R 3 )(R 35 )-Z-, wherein the carbon atom bonded to R 34 and R 35 is also bonded to CR R 5 and Z is bonded to R 6 .
• Embodiment 39 A compound of Formula 1 or any one of Embodiments 1 through 31 or Embodiment 38 wherein R 34 is H or C1-C4 alkyl.
• Embodiment 40 A compound of Embodiment 39 wherein R 34 is H or C1-C2 alkyl.
• Embodiment 41 A compound of Embodiment 40 wherein R 34 is H or methyl.
• Embodiment 42 A compound of Embodiment 41 wherein R 34 is H.
• Embodiment 43 A compound of Formula 1 or any one of Embodiments 1 through 31 or 38 through 42 wherein R 35 is H.
• Embodiment 44 A compound of Formula 1 or any one of Embodiments 1 through 31 or 38 through 43 wherein Z is O, S, NR 37 or CR 38 R 39 (i.e. m is 0).
• Embodiment 45 A compound of Embodiment 44 wherein Z is O, S or NR 37 .
• Embodiment 46 A compound of Embodiment 45 wherein Z is O or NR 37 .
• Embodiment 47 A compound of Embodiment 46 wherein Z is O.
• Embodiment 48 A compound of Formula 1 or any one of Embodiments 1 through 47 wherein R 37 is H.
• Embodiment 49 A compound of Formula 1 or any one of Embodiments 1 through 48 where R 38 and R 39 are H.
• Embodiment 50 A compound of Formula 1 or any one of Embodiments 1 through 49 wherein when L comprises 1 ,4-diphenylene, then said 1 ,4-diphenylene is optionally substituted with up to 2 substituents independently selected from R 13 .
• Embodiment 51 A compound of Embodiment 50 wherein when L comprises
• Embodiment 52 A compound of Formula 1 or any one of Embodiments 1 through 51 wherein each R 13 is independently halogen or C1-C4 alkyl.
• Embodiment 53 A compound of Embodiment 52 wherein each R 13 is independently halogen or methyl.
• Embodiment 54 A compound of Formula 1 or any one of Embodiments 1 through 53 wherein R 1 is a phenyl or 5- or 6-membered heteroaromatic ring optionally substituted with up to 4 substituents independently selected from R 14 .
• Embodiment 55 A compound of Embodiment 54 wherein R 1 is a phenyl or pyridinyl ring optionally substituted with up to 4 substituents independently selected from
• Embodiment 56 A compound of Embodiment 55 wherein R 1 is a phenyl ring
• Embodiment 57 A compound of Embodiment 55 wherein R 1 is a pyridinyl ring
• Embodiment 58 A compound of Embodiment 57 wherein R 1 is a 4-pyridinyl ring optionally substituted with up to 4 substituents independently selected from R 14 .
• Embodiment 59. A compound of Embodiment 58 wherein R 1 is a 4-pyridinyl ring substituted with 1 to 3 substituents independently selected from R 14 , wherein one of said substituents is located at the 2-position of the 4-pyridinyl ring (i.e. ortho to the pyridinyl ring nitrogen atom and meta to the bond connecting the pyridinyl ring to the remainder of Formula 1).
• Embodiment 60 A compound of Embodiment 59 wherein R 1 is a 4-pyridinyl ring substituted with 1 substituent selected from R 14 , wherein said substituent is located at the 2-position of the 4-pyridinyl ring.
• Embodiment 61 A compound of Formula 1 or any one of Embodiments 1 through 60 wherein each R 14 is independently halogen, C1-C4 alkyl, C1-C4 haloalkyl, cyano, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C3-C4 haloalkynyl, C 3 -C 6 cycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio or C1-C4 haloalkylthio.
• Embodiment 62 A compound of Embodiment 61 wherein each R 14 is independently halogen or C1-C4 haloalkyl.
• Embodiment 63 A compound of Embodiment 62 wherein each R 14 is independently F,
• Embodiment 64 A compound of Embodiment 63 wherein each R 14 is CI.
• Embodiment 65 A compound of Formula 1 or any one of Embodiments 1 through 64 wherein R 2 is H, C1-C4 alkyl, C1-C4 alkoxy, C 2 -C 5 alkoxyalkyl, C 2 -C 5 alkoxycarbonyl or C2-C5 alkylcarbonyl;
• Embodiment 66 A compound of Embodiment 65 wherein R 2 is H, methyl, methoxy,
• Embodiment 67 A compound of Embodiment 66 wherein R 2 is H, methyl,
• Embodiment 68 A compound of Embodiment 67 wherein R 2 is H.
• Embodiment 69 A compound of Formula 1 or any one of Embodiments 1 through 68 wherein each R 3 is independently C1-C4 alkyl.
• Embodiment 70 A compound of Embodiment 69 wherein each R 3 is methyl.
• Embodiment 71 A compound of Formula 1 or any one of Embodiments 1 through 70 wherein R 4 is H or C ⁇ -C 4 alkyl.
• Embodiment 72 A compound of Embodiment 71 wherein R 4 is H or 1-C2 alkyl.
• Embodiment 73. A compound of Embodiment 72 wherein R 4 is H or methyl.
• Embodiment 74 A compound of Embodiment 73 wherein R 4 is H.
• Embodiment 75 A compound of Formula 1 or any one of Embodiments 1 through 74 wherein R 5 is H.
• Embodiment 76 A compound of Formula 1 or any one of Embodiments 1 through 75 wherein R 6 is a phenyl ring optionally substituted with up to 5 substituents independently selected from R 22 or a pyridinyl ring optionally substituted with up to 4 substituents independently seleted from R 22 .
• Embodiment 77 A compound of Embodiment 76 wherein R 6 is a phenyl or pyridinyl ring substituted with 1 to 3 substituents independently selected from R 22 wherein one substituent is at the para position (relative to the bond connecting the ring to the remainder of Formula 1).
• Embodiment 78 A compound of Embodiment 77 wherein R 6 is a phenyl or pyridinyl ring substituted with 1 or 2 substituents independently selected from R 22 wherein one substituent is at the para position.
• Embodiment 79 A compound of Embodiment 78 wherein R 6 is a phenyl or pyridinyl ring substituted at the para position with a substituent independently selected from R 22 and optionally substituted at an ortho position with a substituent independently selected from R 22 .
• Embodiment 80 A compound of Embodiment 79 wherein R 6 is a phenyl or pyridinyl ring substituted at the para position with a substituent selected from R 22 .
• Embodiment 81 A compound of Formula 1 or any one of Embodiments 1 through 80 wherein when R 6 comprises a pyridinyl ring, said ring is bonded at the 2-position to the remainder of Formula 1.
• Embodiment 82 A compound of Formula 1 or any one of Embodiments 1 through 80 wherein R 6 is a phenyl ring substituted as described.
• Embodiment 83 A compound of Formula 1 or any one of Embodiments 1 through 81 wherein R 6 is a pyridinyl ring substituted as described.
• Embodiment 84 A compound of Embodiment 76 wherein R 6 is a phenyl ring
• Embodiment 85 A compound of Embodiment 84 wherein R 6 is a phenyl ring
• Embodiment 86 A compound of Embodiment 85 wherein R 6 is a phenyl ring
• Embodiment 87 A compound of Formula 1 or any one of Embodiments 1 through 86 wherein each R 22 is independently halogen, cyano, Ci ⁇ C 6 alkyl, Ci ⁇ C 6
• haloalkyl C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl,
• Embodiment 88 A compound of Embodiment 87 wherein each R 22 is independently F, CI, Br, cyano, CH 3 , CF 3 , cyclopropyl, HC ⁇ C, CH 3 0 or CF 3 0.
• Embodiment 89 A compound of Embodiment 88 wherein each R 22 is independently F,
• Embodiment 90 A compound of Embodiment 89 wherein each R 22 is independently F, CI, Br or CF 3 .
• Embodiment 91 A compound of Embodiment 90 wherein each R 22 is independently F,
• Embodiment 92 A compound of Embodiment 91 wherein each R 22 is F or CI.
• Embodiment 93 A compound of Formula 1 or any one of Embodiments 1 through 92 wherein T is O, S or NR 36 (i.e. k is 0).
• Embodiment 94 A compound of Embodiment 93 wherein T is O or NR 36 .
• Embodiment 95 A compound of Embodiment 94 wherein T is O.
• Embodiment 96 A compound of Formula 1 or any one of Embodiments 1 through 95 wherein R 36 is H.
• Embodiment 97. A compound of Formula 1 or any one of Embodiments 1 through 96 wherein W is O.
• Embodiment 98 A compound of Formula 1 or any one of Embodiments 1 through 97 wherein W 1 is O.
• Embodiment 99 A compound of Formula 1 or any one of Embodiments 1 through 98 wherein each W 2 is O.
• Embodiment 100 A compound of Formula 1 or any one of Embodiments 1 through 99 wherein n is an integer from 0 to 2.
• Embodiment 101 A compound of Embodiment 100 wherein n is 0 or 1.
• Embodiment 102 A compound of Embodiment 101 wherein n is 0.
• Embodiment 103 A compound of Formula 1 or any one of Embodiments 1 through 102 wherein p is 0 or 2.
• Embodiment 104 A compound of Embodiment 103 wherein p is 0.
• Embodiment 105 A compound of Formula 1 or any one of Embodiments 1 through 104 wherein s is 1.
• Embodiment 106 A compound of Formula 1 or any one of Embodiments 1 through 105 wherein t is 1.
• Embodiment 107 A compound described in the Summary of the Invention or any one of Embodiments 1 through 106 that is not in the form of an N-oxide.
• Embodiment 108. A compound of Embodiment 107 that is not in the form of an N- oxide or a salt.
• Embodiment 109 A compound described in the Summary of the Invention or any one of Embodiments 1 through 108 wherein R 7 is other than NH 2 .
• Embodiment 110 A compound of Embodiment 109 wherein R 7 is other than NR 24 R 25 .
• Embodiments of this invention including Embodiments 1-110 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 1-110 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.
• Embodiment Al A compound of Formula 1 wherein
• T O
• Z is O
• R 1 is a 4-pyridinyl ring substituted with 1 to 3 substituents independently selected from R 14 , wherein one of said substituents is located at the 2-position of the 4-pyridinyl ring;
• R 2 is H, methyl, C2-C5 alkoxyalkyl or C2-C4 alkoxycarbonyl;
• R 4 is H or -C4 alkyl
• R 5 is H
• R 6 is a phenyl ring optionally substituted with up to 5 substituents independently selected from R 22 or a pyridinyl ring optionally substituted with up to 4 substituents independently seleted from R 22 ;
• R 7 , R 8 , R 9 and R 10 are independently H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 3 -C 4 haloalkynyl, C 3 -C 6 cycloalkyl, Ci ⁇ C 4 alkoxy, Ci ⁇ C 4 haloalkoxy, Ci ⁇ C 4 alkylthio, Ci ⁇ C 4 haloalkylthio or cyano, or a vicinal pair of R 7 and R 8 , or R 8 and R 9 , or R 9 and
• R 10 are taken together with the carbon atoms to which they are attached to form a 5- or 6-membered aromatic or nonaromatic ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from N, O and S;
• R 1 1 and R 12 are independently H, halogen or methyl
• each R 13 is halogen or methyl
• each R 14 is independently halogen, C j -C 4 alkyl, C j -C 4 haloalkyl, cyano, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 3 -C 4 haloalkynyl, C 3 -C 6 cycloalkyl, C j -C 4 alkoxy, C j -C 4 haloalkoxy, C j -C 4 alkylthio or C j -C 4 haloalkylthio;
• each R 22 is independently halogen, cyano, Ci ⁇ C 6 alkyl, Ci ⁇ C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, Ci ⁇ C 6 alkoxy or C ⁇ -C6 haloalkoxy;
• R 34 is H or C ⁇ alkyl
• R 5 is H
• W is O
• n 0;
• s 1 ;
• Embodiment A2 A compound of Embodiment A 1 wherein
• a 1 is N or CR 7 ;
• a 2 is N or CR 8 ;
• a 3 is N or CR 9 ;
• a 4 is CR 10 ;
• R 1 is a 4-pyridinyl ring substituted with 1 substituent selected from R 14 , wherein said substituent is located at the 2-position of the 4-pyridinyl ring;
• R 2 is H;
• R 4 is H or methyl;
• R 6 is a phenyl or pyridinyl ring substituted with 1 to 3 substituents independently selected from R 22 wherein one substituent is at the para position;
• R 7 , R 8 , R 9 and R 10 are independently H, halogen or C1-C4 haloalkyl;
• R 11 and R 12 are H
• each R 14 is independently halogen or C1-C4 haloalkyl
• each R 22 is independently F, CI, Br, cyano, CH 3 , CF 3 , cyclopropyl, HC ⁇ C, CH 3 0 or CF3O;
• R 34 is H or methyl.
• Embodiment A3 A compound of Embodiment A2 wherein
• R 6 is a phenyl or pyridinyl ring substituted at the para position with a substituent independently selected from R 22 and optionally substituted at an ortho position with a substituent independently selected from R 22 ;
• R 7 is H or F
• R 8 and R 9 are independently H, halogen or C1-C4 haloalkyl
• R 10 is H or F
• each R 14 is independently F, CI, Br or CF 3 ;
• each R 22 is independently F, CI, Br, CF 3 or CF 3 0.
• Embodiment A4 A compound of Embodiment A3 wherein
• R 6 is a phenyl ring substituted at the para position with a substituent selected from
• R 7 is H
• R 8 is H, halogen or CF 3 ;
• R 9 is H, halogen or CF 3 ;
• R 10 is H
• R 14 is CI
• R 22 is F, CI, Br or 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 of any of the preceding Embodiments, as well as any other embodiments described herein, and any combinations thereof, and at least one additional component selected from the group consisting of a surfactant, a solid diluent and a liquid diluent, said compositions optionally further comprising at least one additional biologically active compound or agent.
• Embodiments of the 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 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, 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, alone or in combination.
• 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, alone or in combination, 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 (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 methods for protecting a seed from an invertebrate pest comprising contacting the seed with a biologically effective amount of a compound of any of the preceding Embodiments, alone or in combination.
• 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, 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.
• 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.
• Embodiments of the invention also include any of the preceding embodiments (alone or in combination) wherein the invertebrate pest is an arthropod.
• the arthropod is selected from the group consisting of insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
• the arthropod is an insect.
• Embodiments of the invention also include any of the preceding embodiments (alone or in combination) wherein the invertebrate pest is a gastropod.
• Embodiments of the invention also include any of the preceding embodiments wherein the gastropod is selected from the group consisting of snails, slugs and other Stylommatophora.
• One or more of the following methods and variations as described in Schemes 1-27 can be used to prepare the compounds of Formula 1.
• a 1 , A 2 , A 3 , A 4 , L, T, R 1 , R 2 , R 3 , R4, R 5 , R 6 , R 36 , W, k, n, s and t in the compounds of Formulae 1-34 below are as defined above in the Summary of the Invention unless otherwise noted.
• Formulae la- Id, 11a, 17a-17d, 20a, 22a, 24a, 26a-26c, 30a and 31a are various subsets of Formulae 1, 11, 17, 20, 22, 24, 26, 30 and 31, respectively. All substituents for Formulae la-Id are as defined above for Formula 1 unless otherwise noted.
• a compound of Formula la i.e. Formula 1 wherein R 5 is H
• a compound of Formula la is prepared by reacting an azetidine of Formula 2 with an aldehyde or ketone of Formula 3 and a suitable reducing agent, for example NaHB(OAc)3 or NaH 3 BCN, in a suitable solvent, for example tetrahydrofuran (THF) or 1,2-dichloroethane.
• a suitable solvent for example tetrahydrofuran (THF) or 1,2-dichloroethane.
• THF tetrahydrofuran
• the method of Scheme 1 is illustrated by Step D of Synthesis Example 4, Step D of Synthesis Example 6, Step E of Synthesis Example 7 and Step D of Synthesis Example 8.
• a compound of Formula 1 is prepared by reacting an azetidine of Formula 2 with an alkylating agent of Formula 4 wherein X 1 is a leaving group (i.e. nucleofuge) such as a halide (e.g., Br, I) or a sulfonate (e.g., mesylate, triflate) in the presence of an appropriate base such as triethylamine, N,N-diisopropyl- ethylamine or potassium carbonate in a suitable solvent, for example acetonitrile, N,N-dimethylformamide (DMF) or THF.
• a suitable solvent for example acetonitrile, N,N-dimethylformamide (DMF) or THF.
• DMF N,N-dimethylformamide
• a compound of Formula la is prepared by reacting an azetidine of Formula 2 with an aldehyde of Formula 5 (or paraformaldehyde for R 4 being H) and a boronic acid (Formula 6, Y is OH) or derivative such as a boronate ester (e.g., Formula 6 wherein is -OCMe2CMe20-) or fluoroborate salt (Formula 7 wherein M ® is a counterion), optionally in the presence of a Lewis acid catalyst (such as BF3-OEt2 or T1F4), in a suitable solvent such as toluene, 1 ,2-dichloroethane, 1,4-dioxane or ethanol.
• a Lewis acid catalyst such as BF3-OEt2 or T1F4
• the reaction is typically conducted at between ambient temperature and the boiling point of the solvent, and the reaction mixture can be heated using microwave radiation. Examples of such conditions are found in numerous literature references such as Tetrahedron Lett. 2004, 3471-3474; Tetrahedron Lett. 2005, 8027-8031; and Chemtracts 2001, 14(14), 796-801 and the references cited therein.
• the method of Scheme 3 is illustrated by Step F of Synthesis Example 1.
• a compound of Formula 1 wherein R 2 is other than H is prepared by reacting a compound of Formula lb (i.e. Formula 1 wherein R 2 is H) with a suitable base, for example sodium hydride or lithium hexamethyldisilazide (LiHMDS), and a compound of Formula 9 wherein X 2 is a leaving group such as a halide (e.g., CI, Br) or a sulfonate (e.g., mesylate, triflate), in a suitable solvent such as THF or DMF.
• a suitable solvent such as THF or DMF.
• R is other than H.
• an azetidine intermediate of Formula 2 is prepared from a suitably protected derivative of Formula 10 wherein Pg is a protecting group, for example, tert-butoxycarbonyl (BOC), benzyl, benzhydryl or, especially when T is NH, trifluoroacetyl by deprotection under conditions well known to those skilled in the art and reviewed in T. W. Greene and P. G. Wuts, Protecting Groups in Organic Synthesis, Wiley, 1991, pages 327-329 and 364-365.
• the method of Scheme 5 wherein Pg is BOC is illustrated by Step E of Synthesis Example 1, Step D of Synthesis Example 4, Step C of Synthesis Example 5, Step C of Synthesis Example 6, Step D of Synthesis Example 7 and Step C of Synthesis Example 8.
• a compound of Formula 10 is prepared by reacting an amino compound of Formula 11 (wherein Pg is as defined in Scheme 5) with an acid or derivative of Formula 12 (wherein, e.g., X 3 is OH or CI) under a variety of conditions known to those skilled in the art and described in numerous texts such as J. March, Advanced Organic Chemistry, Wiley, 1992, pages 417-421.
• Exemplary conditions include treating an amino compound of Formula 11 with RiCOCl (as Formula 12) in the presence of a suitable base, such as triethylamine in a suitable solvent, for example THF or CH 2 Cl2, or by treating the amino compound of Formula 11 with a R!CC ⁇ H (as Formula 12) and an activating agent, for example (benzotriazol-l-yloxy)tris(dimethylamino)phosphonium hexafluoro- phosphate (CAS # 56602-33-6, BOP Reagent), in the presence of a suitable base, such as 4-methylmorpholine, in suitable solvent, for example DMF.
• a suitable base such as triethylamine
• a suitable solvent for example THF or CH 2 Cl2
• an activating agent for example (benzotriazol-l-yloxy)tris(dimethylamino)phosphonium hexafluoro- phosphate (CAS # 56602-33-6, BOP Reagent)
• Compounds of Formula 10 wherein Pg is an oxidative ly stable protecting group such as BOC, T is S(0)k and k is 1 or 2 can be prepared from corresponding compounds of Formula 10 wherein k is a lower integer by oxidation with a suitable oxidizing agent such as 2-chloroperbenzoic acid (MCPBA) or potassium peroxymonosulfate (OXONE®) in a suitable solvent such as dichloromethane or a water-methanol mixture, respectively.
• MCPBA 2-chloroperbenzoic acid
• OXONE® potassium peroxymonosulfate
• a base such as sodium hydrogencarbonate can be included in the reaction mixture.
• the oxidation is typically conducted at ambient temperature, although temperatures as low as -20 °C or as high as 80 °C may prove beneficial.
• a compound of Formula 11 (wherein Pg is as defined for Scheme 5) in which R 2 is other than H is prepared by reacting a compound of Formula 11a (i.e. Formula 11 wherein R 2 is H) with a compound of Formula 13 wherein X 4 is a suitable leaving group, typically with use of a base in an appropriate solvent.
• Typical leaving groups include halides (e.g., CI, Br, I) and sulfonates (e.g., mesylate, triflate). Iodo is particularly useful when R 2 is an alkyl group.
• a variety of bases can be used, depending upon choice of Formula 13 and whether the base is used to deprotonate the amino group of Formula 11a or merely as a scavenger of acid byproduct from the reaction.
• Strong bases such as sodium hydride are useful for deprotonation, while tertiary amine bases such as triethylamine are useful as acid scavengers in reactions wherein R 2 is an acyl group.
• Useful solvents include polar aprotic solvents such as THF and DMF. Dichloromethane is particularly useful when R 2 is an acyl group and the base is a tertiary amine.
• the reaction is typically conducted at ambient temperature, although cooling to -20 °C or heating to the lesser of 120 °C or the boiling point of the solvent may be beneficial.
• Scheme 8 illustrates the preparation of amino compounds of Formula 11a (where Pg is as defined in Scheme 5) by reduction of the corresponding nitro compounds of Formula 14 by catalytic hydrogenation when the substituents R 7 , R 8 , R 9 and R 10 are compatible or by dissolving metal reduction.
• a hydrogen source such as molecular hydrogen (preferably at a pressure ranging from atmospheric pressure to 350 kPa, although higher pressures can be used) or 1 ,4-cyclohexadiene or ammonium formate
• a metal catalyst such as palladium (preferably supported on carbon or other substrate such as calcium carbonate) or platinum (optionally supported on carbon or alumina) in elemental form or in the form of its oxide.
• the reaction is typically conducted in ethanol, methanol or ethyl acetate and at ambient temperature, although elevated temperatures up to the boiling point of the solution can be employed. Careful selection of conditions (i.e. low pressure, short reaction times) is required in the cases where Pg is benzyl or benzhydryl.
• Examples of dissolving metal reduction include the use of finely powdered iron (for example with a particle size of 10 ⁇ ) in either acetic acid or in aqueous ethanol containing a catalyst such as ammonium chloride.
• the reaction is conducted at elevated temperature, preferably ranging from 70 °C to the boiling point of the solvent. These conditions are preferred when other reducible functionality (e.g., alkenes, aromatic halides) is present in the compound.
• the dissolving metal reduction method of Scheme 8 is illustrated by Step C of Synthesis Example 1 , Step B of Synthesis Example 4 and Step B of Synthesis Example 6.
• Pg is as defined in Scheme 5, and T is other than NH) are prepared by Curtius Rearrangement of the acyl azides formed in situ by treatment of carboxylic acids of Formula 15 with, for example, diphenyl phosphoryl azide, or prepared from the acids of Formula 15 by conversion to the acid chloride (e.g., by treatment with oxalyl chloride) and then reaction with an azide source such as sodium azide in the presence of a base such as triethylamine.
• the rearrangement is preferably conducted at an elevated temperature from 60 °C up to the boiling point of the solution, in for example toluene as solvent. Hydrolysis of the mixture then liberates the amino compound of Formula 11a.
• the rearrangement can be conducted in an alcoholic solvent such tert-butanol as solvent, which provides the aniline in BOC-protected form.
• the amino compound of Formula 11a is then liberated by treatment with a strong acid such as trifluoroacetic acid or hydrogen chloride in an ethereal solvent.
• a strong acid such as trifluoroacetic acid or hydrogen chloride in an ethereal solvent.
• Pg is generally chosen to be an acid- resistant group such as benzyl to prevent loss during the treatment with strong acid.
• the Curtius Rearrangement is summarized in J. March, Advanced Organic Chemistry, Wiley, 1992, pages 1091-1092; see also Org. Synth., Coll. Vol. 6: 910-913.
• a compound of Formula 14 is prepared by reacting a compound of Formula 16 wherein X 5 is a suitable leaving group such as a halide, with a protected azetidinol of Formula 17 (wherein Pg is as defined for Scheme 5) in the presence of a suitable base, for example sodium hydride, sodium hydroxide or potassium carbonate, and in a suitable solvent, for example DMF, acetonitrile, THF or toluene.
• a suitable base for example sodium hydride, sodium hydroxide or potassium carbonate
• a suitable solvent for example DMF, acetonitrile, THF or toluene.
• T is S(C% and k is 1 or 2
• Suitable oxidation conditions are the same as those already described under Scheme 6 for preparing compounds of Formula 10 wherein T is S(0 and k is 1 or 2 from corresponding compounds of Formula 10 wherein k is a lower integer.
• an ester of Formula 19 wherein R a is lower alkyl e.g., methyl, ethyl, tert-butyl
• R a is lower alkyl
• X 5 is a suitable leaving group such as a halide
• Pg is as defined for Scheme 5
• X 5 is preferably F
• a 1 is N
• X 5 being CI also generally works well.
• ester of Formula 19 is converted to the carboxylic acid of Formula 15 by saponification using aqueous base (e.g., NaOH), followed by acidification, in the case of methyl and ethyl esters or by treatment with a strong acid, for example trifluoroacetic acid or a solution of hydrogen chloride in ethanol or dioxane, in the case of tert-butyl esters.
• aqueous base e.g., NaOH
• a strong acid for example trifluoroacetic acid or a solution of hydrogen chloride in ethanol or dioxane, in the case of tert-butyl esters.
• Co- solvents such as dichloromethane can be added to improve solubility.
• Ethanol and dioxane are particularly useful as co-solvents for improving solubility of esters of Formula 19 in aqueous saponification mixtures.
• the conversion of the ester of Formula 19 to the carboxylic acid of Formula 15 is typically conducted at ambient temperature, although cooling to -20 °C or heating to the lesser of 100 °C or the boiling point of the solvent may be beneficial. Many other conditions will also effect this transformation and a variety of carboxylic acid protecting groups besides R a being lower alkyl can be used in the method of Scheme 11.
• Pertinent literature references can be found in T. W. Greene and P. G. Wuts, Protecting Groups in Organic Synthesis, Wiley, 1991, pages 229-263.
• R a is lower alkyl (e.g., methyl, ethyl, feri-butyl)
• compounds of Formula 22 are also prepared by reacting a hydroxy aromatic compound of Formula 20 with an azetidine of Formula 21 having an appropriate leaving group (X 6 ) such as mesylate or bromide in the presence of a suitable base (such as K2CO3, NaH or LiHMDS).
• a suitable base such as K2CO3, NaH or LiHMDS.
• R is a carboxylic acid protecting group such as lower alkyl.
• G is a protecting group Pg as defined for Scheme 6 or CR 4 R 5 -L-R 6 .
• Compounds of Formula 20 can be prepared by a wide variety of methods known in the art of organic chemical synthesis. Of note is preparation of compounds of Formula 20 wherein T is S from corresponding compounds of Formula 20 wherein T is O by the use of the Newman-Kwart Rearrangement (see Dirk Kusch, Specialty Chemicals Magazine 2003,
• R is a carboxylic acid protecting group such as lower alkyl.
• G is a protecting group Pg as defined for Scheme 6 or CR 4 R 5 -L-R 6 .
• R B is preferably Et or z-Pr.
• compounds of Formula 1 are alternatively prepared by acylation of anilines of Formula 24 with a suitable acid derivative of Formula 12 wherein X 3 is, e.g., OH or CI by analogy to the chemistry described above for Scheme 6.
• X 3 is, e.g., OH or CI by analogy to the chemistry described above for Scheme 6.
• the disclosure provided for the method of Scheme 6 extends to the method of Scheme 14.
• the method of Scheme 14 is illustrated by Step D of Synthesis Example 2.
• a compound of Formula 24 wherein R 2 is other than H is prepared by reacting a compound of Formula 24a (i.e. Formula 24 wherein R 2 is H) with a compound of Formula 13 wherein X 4 is a suitable leaving group, typically with use of a base in an appropriate solvent, analogous to the method described above for Scheme 7.
• a compound of Formula 24a i.e. Formula 24 wherein R 2 is H
• a compound of Formula 13 wherein X 4 is a suitable leaving group
• an amino compound of Formula 24a is prepared by reduction of the corresponding nitro compound of Formula 25, analogous to the method described above in Scheme 8.
• the disclosure provided for the method of Scheme 8 extends to the method of Scheme 16.
• the method of Scheme 16 involving dissolving metal reduction is illustrated by Step C of Synthesis Example 2.
• a nitro compound of Formula 25 is prepared by reaction of a compound of Formula 16 wherein X 5 is a suitable leaving group such as a halide, with an azetidinol of Formula 26 in the presence of a suitable base and solvent, analogous to the method described above for Scheme 10.
• the disclosure provided for the method of Scheme 10 extends to the method of Scheme 17.
• conducting the reaction at temperatures up to 120 °C or the boiling point of the solvent may be beneficial.
• the method of Scheme 17 is illustrated by Step B of Synthesis Example 2.
• Aromatic compounds of Formulae 16, 18 and 20 can be prepared by a wide variety of methods known in the art of organic chemical synthesis.
• Compounds of Formula 26 can be also be prepared by a variety of methods. The following method of Scheme 18 is particularly useful for preparing compounds of Formula 26 wherein Y is O, and s and t are each 1.
• an azetidinol of Formula 26a i.e.
• Formula 26 wherein Y is O, and s and t are each 1) can be prepared by reacting an amine of Formula 28 with an epihalohydrin of Formula 27 wherein X 6 is CI, Br or I and most typically CI, or a derivative, optionally in the presence of additives such as triethylamine or magnesium bromide, according to published procedures (e.g., J. Het. Chem. 1971, 8, 1059-1062; J. Org. Chem. 1967, 32, 2972-2976; Tetrahedron Lett. 1997, 6059-6062).
• the method of Scheme 18 is illustrated by Step A of Synthesis Example 2.
• Amines of Formula 28 can be made by methods known in the art; for example, cinnamylamines can be prepared according to the general method described in J. Org. Chem. 1982, 47, 5395-5397.
• Scheme 19 illustrates a method, analogous to the method of Scheme 18, for preparing hydroxy-substituted protected azetidines (i.e. protected azetidinols) of Formula 17a (i.e. Formula 17 wherein T is O) wherein Pg is, for example, benzhydryl or benzyl.
• a protected azetidinol of Formula 17a is prepared by reacting a protected amine of Formula 29 with an epihalohydrin of Formula 27 using procedures analogous to those described for Scheme 18.
• general methods well known in the art e.g., T. W. Greene and P. G.
• the protecting group can be removed from the azetidinol of Formula 17a wherein Pg is, for example benzhydryl or benzyl, and then another protecting group can be attached to form a protected azetidinol of Formula 17a wherein Pg is, for example BOC.
• an azetidinol of Formula 26b (i.e. Formula 26 wherein R 3 is not attached to the 3-position of the azetidine ring) wherein n' is an integer from 0 to 4 can also be prepared by reducing an azetidinone of Formula 30 with a reducing agent, such as sodium borohydride in methanol or ethanol, using procedures similar to those described in U.S. Patent 3668196.
• a reducing agent such as sodium borohydride in methanol or ethanol
• a protected azetidinol of Formula 17b (i.e. Formula 17 wherein T is O, and R 3 is not attached to the 3-position of the azetidine ring) wherein n' is an integer from 0 to 4, and Pg is a protecting group as defined for Scheme 5, can be prepared by reducing an azetidinone of Formula 31 with a reducing agent, analogous to the method of Scheme 20.
• an azetidinol of Formula 26c (i.e. Formula 26 wherein an R 3 (as R 3a ) is attached to the 3-position of the azetidine ring) wherein n' is an integer from 0 to 4 and R 3a is alkyl is prepared by the addition of an organometallic reagent of Formula 32 (e.g., an organolithium or Grignard reagent) to an azetidinone of Formula 30 in an ethereal solvent, such as diethyl ether or THF, at ambient temperature, of if preferred, cooling to temperatures as low as -78 °C, using general procedures known in the art (e.g., Tetrahedron Lett. 1972, 5063-5064; U.S. Patent 3668196).
• M 2 is, e.g., Li, MgCl, MgBr.
• a protected azetidinol of Formula 17c (i.e. Formula 17 wherein T is O, and an R 3 (as R 3a ) is attached to the 3-position of the azetidine ring), wherein n' is an integer from 0 to 4, R 3a is alkyl and Pg is a protecting group as defined for Scheme 5, is prepared by the addition of an organometallic compound of Formula 32 to a protected azetidinone of Formula 31 in an ethereal solvent analogous to the method of Scheme 22.
• M 2 is, e.g., Li, MgCl, MgBr.
• Azetidinones of Formulae 30 and 31 can be prepared by general methods known in the art. For example, as shown in Scheme 24, geminally disubstituted azetidinones of Formula 30a (i.e. Formula 30 in which the 2-position of the azetidine ring is substituted with two R 3 ) can be prepared by treatment of corresponding l-bromo-2-butanones of Formula 33 with a base such as sodium hydrogencarbonate in a solvent such as DMF or aqueous methanol, using procedures similar to those described in U.S. Patent 3668196.
• a base such as sodium hydrogencarbonate
• a solvent such as DMF or aqueous methanol
• R JU and R ⁇ are independently alkyl.
• protected geminally disubstituted azetidinones of Formula 31a i.e. Formula 31 in which the 2-position of the azetidine ring is substituted with two R 3 ), wherein Pg is a suitable protecting group such as benzhydryl or benzyl, can be prepared by treatment of corresponding l-bromo-2-butanones of Formula 34, using reaction conditions similar to those described for the method of Scheme 24.
• R 3b and R 3c are independently alkyl.
• a thiol compound of Formula 17d (i.e. Formula 17 wherein T is S) can be prepared by treatment of a corresponding compound of Formula 21 (where X 6 is as defined in Scheme 12) with the thiol nucleophile Na 2 S.
• a suitable thiol nucleophile in the form of PgSH (where Pg is suitable protecting group such as benzyl (Bn)) can be used in the presence of a suitable base such as NaH, followed by deprotection using, for example, sodium in liquid ammonia.
• DMF is a particularly good solvent for this displacement reaction involving a thiol nucleophile, and mild heating (for example to 80 °C) is beneficial.
• Compounds of Formula 21 can be prepared by a wide variety of methods known in the art of organic chemical synthesis, including preparation from corresponding compounds of Formula 17 wherein T is O.
• Compounds of Formula 21 wherein Pg is BOC, n is 0, and X 6 is I or OMs are commercially available for each of the present values of s and t.
• Certain other compounds of Formula 21 where Pg is another protecting group such as trifluoroacetyl, carboxybenzyl (CBz) or benzhydryl are also commercially available.
• compounds of Formula lc can be prepared by thionation of corresponding compounds of Formula Id (i.e. Formula 1 wherein W is O).
• Thionation involves treatment with a thionating reagent, for example phosphorus pentasulfide, or 2,4-bis(4-methoxyphenyl)-l,3,2,4-dithiadiphosphetane, 2,4-disulfide (Lawesson's Reagent), or 2,4-bis(4-phenoxyphenyl)-l,3,2,4-dithiadiphos- phetane, 2,4-disulfide (Belleau's Reagent).
• the reaction is preferably conducted in solvents such as toluene, xylenes or dioxane and at elevated temperature from 80 °C to the boiling point of the solvent.
• Mass spectra are reported as the molecular weight of the highest isotopic abundance positively charged parent ion (M+1) formed by addition of H + (molecular weight of 1) to the molecule or the highest isotopic abundance negatively charged ion (M-1) formed by loss of H + (molecular weight of 1), observed by mass spectrometry using electrospray ionization (ESI) where "amu” stands for atomic mass units.
• Step B Preparation of 1 , 1 -dimethylethyl 3 - [ [3 -nitro-6-(trifluoromethyl)-2-pyridinyl] - oxy]- 1 -azetidinecarboxylate
• Step C Preparation of 1,1-dimethylethyl 3-[[3-amino-6-(trifluoromethyl)-
• Step D Preparation of 1,1-dimethylethyl 3-[[3-[[(2-chloro-4-pyridinyl)carbonyl]- amino]-6-(trifluoromethyl)-2-pyridinyl]oxy]-l -azetidinecarboxylate
• Step E Preparation of N- [2-(3 -azetidinyloxy)-6-(trifluoromethyl)-3 -pyridinyl] -
• reaction mixture was concentrated under reduced pressure, dissolved in dichloromethane, washed with 10% aqueous sodium hydrogencarbonate solution and dried (Na 2 S0 4 ). The residue after concentration was triturated with diethyl ether to give the title product as a yellow solid (275 mg).
• Step F Preparation of 2-chloro-N-[2-[[l-[(2E)-3-(4-chlorophenyl)-2-propen-l-yl]-
• Step A Preparation of l-[(2E)-3-(4-chlorophenyl)-2-propen-l-yl]-3-azetidinol
• Step B Preparation of l-[(2E)-3-(4-chlorophenyl)-2-propen-l-yl]-3-(4,5-dichloro-
• Step C Preparation of 4,5-dichloro-2-[[l-[(2E)-3-(4-chlorophenyl)-2-propen-l-yl]-
• Step D Preparation of 2-chloro-N-[4,5-dichloro-2-[[l-[(2E)-3-(4-chlorophenyl)-
• Example 2 the product of Example 2) (56 mg, 0.11 mmol) in dichloromethane (3 mL) with a solution of oxalic acid (4.8 mg, 53 ⁇ ) in ethanol (100 ⁇ ), followed by concentration and trituration with ethyl ether gave the title oxalate salt product, a compound of the present invention, as a light brown solid (29 mg).
• Step A Preparation of 1,1-dimethylethyl 3-[(5-chloro-3-nitro-2-pyridinyl)oxy]-l- azetidinecarboxylate
• Step B Preparation of 1 , 1 -dimethylethyl 3 - [(3 -amino-5 -chloro-2-pyridinyl)oxy] - 1 - azetidinecarboxylate
• Step C Preparation of 1,1 -dimethylethyl 3-[[5-chloro-3-[[(2-chloro-4- pyridinyl)carbonyl]amino]-2-pyridinyl]oxy]- 1 -azetidinecarboxylate
• Step D Preparation of 2-chloro-N-[5-chloro-2-[[l-[(2E)-3-(4-chlorophenyl)-
• reaction mixture was concentrated in vacuo, treated with saturated aqueous sodium hydrogencarbonate solution and extracted with dichloromethane (3 ⁇ ).
• the combined organic phase was dried (MgSC ⁇ ) and concentrated in vacuo to give a product containing N-[2-(3-azetidinyloxy)-5-chloro-3-pyridinyl]-2-chloro-4-pyridinecarboxamide as a white solid (0.18 g, approximately 50% pure), which was used without further purification.
• Step A Preparation of 1,1-dimethylethyl 3-[(3-amino-5,6-dichloro-2-pyridinyl)oxy]- 1-azetidinecarboxylate
• Step B Preparation of 1,1-dimethylethyl 3-[[5,6-dichloro-3-[[(2-chloro-
• Step D Preparation of N-[2-[[l-[2-(4-bromophenoxy)ethyl]-3-azetidinyl]oxy]-
• the cooled solution was treated with saturated aqueous sodium bicarbonate solution (2 mL) and water (2 mL), and then diluted with dichloromethane before being filtered through a tube containing Celite® diatomaceous filter aid, eluting with dichloromethane.
• the residue after concentration was purified by chromatography (silica gel, ethyl acetate to 5% methanol in ethyl acetate) to give the title product, a compound of the present invention, as a pale yellow oil (84 mg).
• Step A Preparation of 1,1 -dimethylethyl 3-[(6-chloro-3-nitro-2-pyridinyl)oxy]-l- azetidinecarboxylate
• Step B Preparation of 1 , 1 -dimethylethyl 3-[[6-chloro-3-[[(2-chloro-4-pyridinyl)- carbonyl]amino]-2-pyridinyl]oxy]- 1 -azetidinecarboxylate
• Step C Preparation of N-[2-(3-azetidinyloxy)-6-chloro-3-pyridinyl]-2-chloro-
• Step D Preparation of 2-chloro-N-[6-chloro-2-[[l-[(2E)-3-(4-chlorophenyl)-l- methyl-2-propen-l-yl]-3-azetidinyl]oxy]-3-pyridinyl]-4-pyridinecarboxamide
• N-[2-(3-azetidinyloxy)-6-chloro-3-pyridinyl]-2-chloro-4-pyridine- carboxamide i.e.
• Step C) the product of Step C) (79 mg, 0.23 mmol) was added (3E)-4-(4-chloro- phenyl)-3-buten-2-one (48 mg, 0.28 mmol), sodium triacetoxyborohydride (59 mg, 0.28 mmol), THF (3 mL) and acetic acid (16 ⁇ ), and the mixture was stirred at ambient temperature overnight. The mixture was treated with saturated aqueous sodium hydrogencarbonate solution and extracted with dichloromethane (2x).
• Step B Preparation of 1 , 1 -dimethylethyl 3 - [(5 -chloro-6-fluoro-3 -nitro-2- pyridinyl)oxy]- 1 -azetidienecarboxylate
• 3-hydroxyazetidine (3.29 g, 1 equiv) and sodium carbonate (3.02 g, 1.5 equiv) were combined in toluene (50 mL), and the resultant mixture was stirred at ambient temperature overnight. The mixture was then diluted with ethyl ether, washed with water (3 X ) and dried (MgSOzj). The residue after concentration was purified by chromatography (silica gel, 5% to 15% ethyl acetate in hexanes) to give the title product (0.68 g, 80%> pure) which was used in the next step without further purification.
• Step D Preparation of N- [6-amino-2-( 1 -azetidinyloxy)-5 -chloro-3 -pyridinyl] -
• Step E Preparation of N-[6-amino-5-chloro-2-[[l-[(2E)-3-(4-chlorophenyl)-2-propen-
• Step A Preparation of 1 , 1 -dimethylethyl 3-[(4-amino-6-chloro-3-pyridazinyl)oxy]-
• Step B Preparation of 1 , 1 -dimethylethyl 3-[[6-chloro-4-[[(2-chloro-4-pyridinyl)- carbonyl]amino]-3-pyridazinyl]oxy]-l -azetidinecarboxylate
• Step D Preparation of of 2-chloro-N-[6-chloro-3-[[l-[(2E)-3-(4-chlorophenyl)-
• the present disclosure also includes Tables 2 through 30, each of which is constructed the same as Table 1 above, except that the row heading in Table 1 (i.e. "A 1 is CH; R 2 is H; R 10 is H; (R 1 ) a is 2-Cl; s is 1 ; and t is 1”) is replaced with the respective row heading shown below.
• Table 2 the row heading is "A 1 is CH; R 2 is H; R 10 is H; (R 14 ) a is 2,5-di-Cl; s is 1 and t is 1", and R 8 , R 9 and R 22 are as defined in Table 1 above.
• Table 2 specifically discloses 2,5-dichloro-N-[2-[[l-[(2E)- 3 -(4-chlorophenyl)-2-propen- 1 -yl] -3 -azetidinyljoxy] -4,5 -difluorophenyl]-4-pyridine- carboxamide.
• Tables 3 through 30 are constructed similarly.
• R 2 is CH
• R 2 is H
• R 10 is H
• (R 14 ) a is 2,5-di-Cl
• s is 1
• t is 1.
• R 3 is CH; R 2 is H; R 10 is H; (R 14 ) a is 2,6-di-Cl; s is 1; and t is 1.
• R 12 is CH; R 2 is MeOC(O)-; R 10 is H; (R 14 ) a is 2-Cl; s is 1 ; and t is 1.
• R 13 is CH; R 2 is EtOCH 2 -; R 10 is H; (R 14 ) a is 2-Cl; s is 1 ; and t is 1.
• R 14 is CF; R 2 is H; R 10 is H; (R 14 ) a is 2-Cl; s is 1 ; and t is 1.
• IS H R 10 is H; (R 14 ) a is 2-Cl, 5-F; s is 1; and t is 1.
• A is N; R 2 is H; R 10 is CI; (R 14 ) a is 2-Cl; s is 1; and t is 1.
• A is : R 2 is MeOC(O)-; R 10 is H; (R 14 ) a is 2-Cl; s is 1 ; and t is 1.
• R 2 is EtOCH 2 -; R 10 is H; (R 14 ) a is 2-Cl; s is 1; and t is 1.
• A is CH R 2 is H R 10 is H; (R 14 ) a is 2-Cl; s is 2; and t is 2.
• A is CH R 2 is H R 10 is H; (R 14 ) a is 2-F; s is 2; and t is 2.
• A is CH R 2 is H R 10 is H; (R 14 ) a is 2-CF 3 ; s is 2; and t is 2.
• R 2 is H
• R 10 is H
• (R 14 ) a is 2-Cl
• s is 2
• t is 2.
• R 2 is H
• R 10 is H
• (R 14 ) a is 2-F
• s is 2
• t is 2.
• A is N: R 2 is H .
• R 10 is H; (R 14 ) a is 2-CF 3 ; s is 2; and t is 2.
• A is CH; R 2 is H; R 10 is H; (R 14 ) a is 2-Cl; s is 2; and t is 1.
• a 1 is CH; R 2 is H; R 10 is H; (R 14 ) a is 2-Cl; s is 3; and t is 1.
• a 1 is CH; R 2 is H; R 10 is H; and (R 14 ) a is 2-Cl.
• the present disclosure also includes Tables 42 through 70, each of which is constructed the same as Table 41 above, except that the row heading in Table 41 (i.e. "A 1 is CH; R 2 is H; R 10 is H; and (R 1 ) a is 2-CL”) is replaced with the respective row heading shown below.
• Table 40 the row heading is "A 1 is CH; R 2 is H; R 10 is H; and (R 14 ) a is 2,5-di-CL", and R 8 , R 9 and R 22 are as defined in Table 41 above.
• Table 40 specifically discloses 2,5-dichloro-N-[2-[[l-[(4'-chloro[l,l'-biphenyl]- 4-yl)methyl]-3-azetidinyl]oxy]-4,5-difluorophenyl]-4-pyridinecarboxamide.
• Tables 43 through 70 are constructed similarly.
• Al is CH; (R 3 ) N is 2-Me; and R 4 , R11 and R!2 are H.
• Tables 73 through 85 each of which is constructed the same as Table 72 above, except that the row heading in Table 72 (i.e. "Al is CH; (R ) n is 2-Me; and R 11 and R 12 are H.") is replaced with the respective row heading shown below.
• Table 73 the row heading is "A 1 is CH; (R ) n is 3-Me; and R 1 1 and R 12 are H.”, and R 8 and R 9 are as defined in Table 72 above.
• Table 73 specifically discloses 2-chloro-N-[2-[[l-[(2E)-3-(4-chlorophenyl)-2-propen-l-yl]- 3-methyl-3-azetidinyl]oxy]-4,5-difluorophenyl]-4-pyridinecarboxamide.
• Tables 74 through 85 are constructed similarly.
• a 1 is CH; (R 3 ) n is 2-Me; and R 4 is H.
• Tables 87 through 91 each of which is constructed the same as Table 86 above, except that the row heading in Table 86 (i.e. "A 1 is CH; (R ) n is 2-Me; and R 4 is H.") is replaced with the respective row heading shown below.
• Table 87 the row heading is "A 1 is CH; (R ) n is 3-Me; and R 4 is H.”
• R 8 and R 9 are as defined in Table 86 above.
• Table 87 specifically discloses 2-chloro-N-[4,5-difluoro-2-[[l-[(4'-fluoro[l, -biphenyl]-4-yl)methyl]-3-methyl-3- azetidinyl]oxy]phenyl]-4-pyridinecarboxamide.
• Tables 88 through 91 are constructed similarly.
• the present disclosure also includes Tables 93 through 110, each of which is constructed the same as Table 92 above, except that the row heading in Table 92 (i.e. "A 1 is CH; R 34 is H; Z is CH; s is 1; and t is 1.”) is replaced with the respective row heading shown below.
• Table 93 the row heading is "A 1 is N; R 34 is H; Z is CH; s is 1; and t is 1."
• R 8 , R 9 and R 22 are as defined in Table 92 above.
• Table 93 specifically discloses 2-chloro-N-[2-[[l-[2-(4-chlorophenoxy)ethyl]-3-azetidinyl]oxy]- 5,6-difluoro-3-pyridinyl]-4-pyridinecarboxamide.
• Tables 94 through 110 are constructed similarly.
• a 1 is N; R 34 is H; Z is CH; s is 1; and t is 1.
• a 1 is N; R 34 is Me; Z is CH; s is 1; and t is 1.
• a 1 is CH; R 34 is H; Z is CH; s is 2; and t is 2.
• 101 A 1 is N; R 34 is H; Z is CH; s is 2; and t is 2.
• 102 A 1 is CH; R 34 is Me; Z is CH; s is 2; and t is 2.
• a 1 is N; R 34 is Me; Z is CH; s is 2; and t is 2.
• 104 A 1 is CH; R 34 is H; Z is CH; s is 2; and t is 1.
• 105 A 1 is N; R 34 is H; Z is CH; s is 2; and t is 1.
• a 1 is CH; R 34 is Me; Z is CH; s is 2; and t is 1.
• 109 A 1 is CH; R 34 is H; Z is CH; s is 3; and t is 1.
• the present disclosure also includes Tables 112 through 114, each of which is constructed the same as Table 111 above, except that the row heading in Table 111 (i.e. "R22b i s 2-F; and R 34 is H.") is replaced with the respective row heading shown below.
• Table 112 the row heading is "R 22b is 3-F; and R 34 is H.” and R 8 , R 9 and R 22a are as defined in Table 111 above.
• the first entry in Table 112 specifically discloses
• Tables 113 through 114 are constructed similarly.
• R 22b is 3_ F . and R 34 is H Table Row Heading
• R 22b is 3_ F . and R 34 is Me _
• the present disclosure also includes Tables 116 through 118, each of which is constructed the same as Table 115 above, except that the row heading in Table 115 (i.e. "s is 1; and t is 1.") is replaced with the respective row heading shown below.
• Table 116 the row heading is "s is 2; and t is 2.”
• R 9 , R 14 and R 22 are as defined in Table 115 above.
• Table 116 specifically discloses 2-chloro-N-[6-chloro- 3-[[ 1 -[(2E)-3-(4-f uorophenyl)-2-propen- 1 -yl]-4-piperidinyl]oxy]-4-pyridazinyl]-4-pyridine- carboxamide.
• Tables 117 through 118 are constructed similarly.
• 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.
• 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, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy- 4-methyl-2-pentan
• Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C 6 -C 2 2), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof.
• plant seed and fruit oils e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel
• animal-sourced fats e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil
• Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation.
• 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 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 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 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 ⁇ 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 2 65.0% dodecylphenol polyethylene glycol ether 2.0%> sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
• Compound 1 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0% U.S.S. No. 25-50 sieves)
• Compound 2 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0%> sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
• Compound 1 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%
• Compound 31 65.0% dodecylphenol polyethylene glycol ether 2.0%> sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0%> montmorillonite (calcined) 23.0%
• insects include, for example, invertebrates feeding on foliage (including leaves, stems, flowers and fruits), seeds, wood, textile fibers or animal blood or tissues, and thereby causing injury or damage to, for example, growing or stored agronomic crops, forests, greenhouse crops, ornamentals, nursery crops, stored foodstuffs or fiber products, or houses or other structures or their contents, or being harmful to animal health or public health.
• foliage including leaves, stems, flowers and fruits
• seeds wood, textile fibers or animal blood or tissues
• the 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.
• 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 particularly 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).
• External parasitic or disease transmitting pests include, for example, chiggers, ticks, lice, mosquitoes, flies, mites and fleas.
• 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 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.
• fatalities and performance reduction in terms of meat, milk, wool, skins, eggs, honey, etc.
• 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.
• 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 (Tetranychus mcdanieli McGregor)); flat mites in the family Tenuipalpidae (e.g., citrus flat mite ⁇ Brevipalpus lewisi McGregor)); rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e.
• Tetranychidae e.g., European red mite ⁇ Panonychus ulmi Koch
• two spotted spider mite Tetranychus urticae Koch
• McDaniel mite Tetranychus 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 spp., Odontotermes obesus Rambur), Kalotermitidae (e.g., Cryptotermes spp.), and Rhinotermitidae (e.g., Reticulitermes spp., Coptotermes spp., 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).
• 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 Hubner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm),
• Compounds of the invention also have significant activity on members from the order 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), Hyalopter
• Compounds of this invention also have activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say (chinch bug), Cimex lectularius Linnaeus (bed bug) Corythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-S chaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp.
• Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and the order Coleoptera (e.g., Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius).
• Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower thrips), Scirthothrips citri Moulton (citrus thrips), Sericothrips variabilis Beach (soybean thrips), and Thrips tabaci Lindeman (onion thrips); and
• compounds of this invention for controlling silverleaf whitefiy (Bemisia argentifolii).
• compounds of this invention for controlling western flower thrip (Frankliniella occidentalis).
• compounds of this invention for controlling green peach aphid (Myzus persicae).
• compounds of this invention for controlling diamondback moth (Plutella xylostella).
• 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, 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, acetoprole, acrinathrin, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole (3-bromo-l- (3 -chloro-2-pyridinyl)-N- [4-cyano-2-methyl-6- [(methylamin
• insecticides such as abamectin, acetamiprid, acrinathrin, amitraz, avermectin, azadirachtin, 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
• One embodiment of biological agents for mixing with compounds of this invention includes entomopathogenic bacteria such as Bacillus thuringiensis, and the encapsulated delta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII); 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 nucleopolyhedro virus
• HzNPV Helicoverpa zea nucleopolyhedrovirus
• AfNPV Anagrapha
• 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, mepyrflutrin, metofluthrin, profluthrin, pyrethrin, tetramethylfluthrin and tralomethrin; cholinesterase inhibitors such as chlorpyrifos, methomyl, oxamyl, thiodicarb and triazamate; neonicotinoids such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid and thiamethoxam;
• fungicides such as acibenzolar (i.e. acibenzolar-iS*- methyl), aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), benodanil, benomyl, benthiavalicarb, benthiavalicarb- isopropyl, bethoxazin, binapacryl, binomial, biphenyl, bitertanol, bixafen, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), boscalid/nicobifen, bromuconazole, bupirimate, buthiobate, carboxin, carpropamid, captafol, captan, carbendazim, chinomethionat, chloroneb
• acibenzolar i.e. acibenzolar-iS*-
• phthalide picobenzamid, picoxystrobin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propamocarb-hydrochloride, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyrifenox, pyriofenone, pyrrolnitrin, pyroquilon, quinconazole, quinoxyfen, quintozene, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquin, tecloftalam,
• 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 is typically between about 1 :3000 and about 3000: 1. Of note are weight ratios between about 1 :300 and about 300: 1 (for example ratios between about 1 :30 and about 30: 1).
• 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 the invertebrate pest control agent can be applied relative to a compound of Formula 1 (e.g., "50: 1 to 1 :50" of abamectin relative to a compound of Formula 1 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
• Fenoxycarb juvenile hormone mimics 500:1 to 1:100
• Hydramethylnon mitochondrial electron transport inhibitors 150:1 to 1:250 are Hydramethylnon mitochondrial electron transport inhibitors 150:1 to 1:250
• Methoprene juvenile hormone mimics 500:1 to 1:100
• Pymetrozine 200 1 to 1 : 100
• Pyriproxyfen juvenile hormone mimics 500 1 to 1 100
• Tebufenozide ecdysone agonists 500 1 to 1 250
• Tetramethylfluthrin sodium channel modulators 100 1 to 1 :40
• Thiosultap-sodium 150 1 to 1 100
• NPV e.g., Gemstar biological agents 50: 1 to 1 : 10
• composition of the present invention comprising at least one additional biologically active compound or agent is selected from the Invertebrate Pest Control Agents listed in Table A above.
• the weight ratios of a compound, including a compound of Formula 1, an N-oxide or a salt thereof, to the additional invertebrate pest control agent typically are between 1000:1 and 1 : 1000, with one embodiment being between 500: 1 and 1 :500, another embodiment being between 250:1 and 1 :200 and another embodiment being between 100:1 and 1 :50.
• Tables B1-B45 are embodiments of specific compositions comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Tables A-F) and an additional invertebrate pest control agent.
• Table Bl Listed below in Tables B1-B45 are embodiments of specific compositions comprising a compound of Formula 1 (compound numbers (Cmpd. No.) refer to compounds in Index Tables A-F) and an additional invertebrate pest control agent.
• A-35 1 and Hydramethylnon A-71 1 and NPV e.g., Gemstar
• Tables B2 through B45 are each constructed the same as Table B 1 above except that entries below the "Cmpd. No" column heading are replaced with the respective Cmpd. No. Column Entry shown below. Thus, for example, in Table B2 the entries below the "Cmpd. No.” column heading all recite “Compound 2", and the first line below the column headings in Table B2 specifically discloses a mixture of Compound 2 with abamectin. Tables B3 through B45 are constructed similarly.
• Invertebrate pests are controlled in agronomic and nonagronomic applications by applying one or more compounds of this invention, typically in the form of a composition, in a biologically effective amount, to the environment of the pests, including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
• the present invention comprises a method for controlling an invertebrate pest in agronomic and/or nonagronomic applications, comprising contacting the invertebrate pest or its environment with a biologically effective amount of one or more of the compounds of the invention, or with a composition comprising at least one such compound or a composition comprising at least one such compound and a biologically effective amount of at least one additional biologically active compound or agent.
• a plant in the environment of the invertebrate pest is contacted with a biologically effective amount of a compound of the invention (e.g., in the form of a composition of the invention).
• the compound or composition is typically applied to the seed of the crop before planting, to the foliage (e.g., leaves, stems, flowers, fruits) of crop plants, or to the soil or other growth medium before or after the crop is planted.
• foliage e.g., leaves, stems, flowers, fruits
• a method of contact is by spraying.
• a granular composition comprising a compound of the invention can be applied to the plant foliage or the soil.
• Compounds of this invention can also be effectively delivered through plant uptake by contacting the plant with a composition comprising a compound of this invention applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants.
• a composition of the present invention in the form of a soil drench liquid formulation.
• a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of the present invention or with a composition comprising a biologically effective amount of a compound of the present invention.
• this method wherein the environment is soil and the composition is applied to the soil as a soil drench formulation.
• compounds of this invention are also effective by localized application to the locus of infestation.
• Other methods of contact include application of a compound or a composition of the invention by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols, dusts and many others.
• One embodiment of a method of contact is a dimensionally stable fertilizer granule, stick or tablet comprising a compound or composition of the invention.
• the compounds of this invention can also be impregnated into materials for fabricating invertebrate control devices (e.g., insect netting). Compounds of this invention are also useful in seed treatments for protecting seeds from invertebrate pests.
• treating a seed means contacting the seed with a biologically effective amount of a compound of this invention, which is typically formulated as a composition of the invention.
• This seed treatment protects the seed from invertebrate soil pests and generally can also protect roots and other plant parts in contact with the soil of the seedling developing from the germinating seed.
• the seed treatment may also provide protection of foliage by translocation of the compound of this invention or a second active ingredient within the developing plant.
• an aspect of this invention is a method for protecting a seed, or a plant grown therefrom, 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 formulated composition).
• Seed treatments can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin or those expressing herbicide resistance such as glyphosate acetyltransferase, which provides resistance to glyphosate.
• compositions formulated for seed treatment generally comprise a film former or adhesive agent. Therefore typically a seed coating composition of the present invention comprises a biologically effective amount of a compound of Formula 1, an N-oxide, or a salt thereof, and a film former or adhesive agent. Treatment with this composition thus involves coating the seed with a compound of Formula 1, an N-oxide, or a salt thereof (i.e. in a biologically effective amount) formulated as a composition comprising a film former or adhesive agent. Seed can be coated by spraying a flowable suspension concentrate directly into a tumbling bed of seeds and then drying the seeds.
• the treated seed typically comprises a compound of the present invention in an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. from about 0.0001 to 1% by weight of the seed before treatment) to provide a biologically effective amount.
• a flowable suspension formulated for seed treatment typically comprises from about 0.5 to about 70% of the active ingredient, from about 0.5 to about 30% of a film-forming adhesive, from about 0.5 to about 20% of a dispersing agent, from 0 to about 5% of a thickener, from 0 to about 5% of a pigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0 to about 1% of a preservative, and from 0 to about 75% of a volatile liquid diluent.
• the compounds of this invention can be incorporated into a bait composition that is consumed by an invertebrate pest or used within a device such as a trap, bait station, and the like.
• a bait composition can be in the form of granules which comprise (a) active ingredients, namely a biologically effective amount of a compound of Formula 1, an N-oxide, or a salt thereof; (b) one or more food materials; optionally (c) an attractant, and optionally (d) one or more humectants.
• granules or bait compositions which comprise between about 0.001-5% active ingredients, about 40-99%) food material and/or attractant; and optionally about 0.05-10% humectants, which are effective in controlling soil invertebrate pests at very low application rates, particularly at doses of active ingredient that are lethal by ingestion rather than by direct contact.
• Some food materials can function both as a food source and an attractant.
• Food materials include carbohydrates, proteins and lipids. Examples of food materials are vegetable flour, sugar, starches, animal fat, vegetable oil, yeast extracts and milk solids.
• attractants are odorants and flavorants, such as fruit or plant extracts, perfume, or other animal or plant component, pheromones or other agents known to attract a target invertebrate pest.
• humectants i.e. moisture retaining agents, are glycols and other polyols, glycerine and sorbitol.
• a bait composition (and a method utilizing such a bait composition) used to control at least one invertebrate pest selected from the group consisting of ants, termites and cockroaches.
• a device for controlling an invertebrate pest can comprise the present bait composition and a housing adapted to receive the bait composition, wherein the housing has at least one opening sized to permit the invertebrate pest to pass through the opening so the invertebrate pest can gain access to the bait composition from a location outside the housing, and wherein the housing is further adapted to be placed in or near a locus of potential or known activity for the invertebrate pest.
• the compounds of this invention can be applied without other adjuvants, but most often application will be of a formulation comprising one or more active ingredients with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
• One method of application involves spraying a water dispersion or refined oil solution of a compound of the present invention. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy.
• Such sprays can be applied from spray containers such as a can, a bottle or other container, either by means of a pump or by releasing it from a pressurized container, e.g., a pressurized aerosol spray can.
• Such spray compositions can take various forms, for example, sprays, mists, foams, fumes or fog.
• Such spray compositions thus can further comprise propellants, foaming agents, etc. as the case may be.
• a spray composition comprising a biologically effective amount of a compound or a composition of the present invention and a carrier.
• a spray composition comprises a biologically effective amount of a compound or a composition of the present invention and a propellant.
• propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing.
• a spray composition (and a method utilizing such a spray composition dispensed from a spray container) used to control at least one invertebrate pest selected from the group consisting of mosquitoes, black flies, stable flies, deer flies, horse flies, wasps, yellow jackets, hornets, ticks, spiders, ants, gnats, and the like, including individually or in combinations.

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• 2011
  • 2011-07-19 WO PCT/US2011/044436 patent/WO2012012366A1/fr active Application Filing
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