EP1326827A2 - Insecticidal 1,8-naphthalenedicarboxamides - Google Patents

Insecticidal 1,8-naphthalenedicarboxamides

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Publication number
EP1326827A2
EP1326827A2 EP01987739A EP01987739A EP1326827A2 EP 1326827 A2 EP1326827 A2 EP 1326827A2 EP 01987739 A EP01987739 A EP 01987739A EP 01987739 A EP01987739 A EP 01987739A EP 1326827 A2 EP1326827 A2 EP 1326827A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
formula
compound
halogen
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01987739A
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German (de)
French (fr)
Inventor
Thomas Paul Selby
King-Mo Sun
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1326827A2 publication Critical patent/EP1326827A2/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • A01N37/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides containing at least one oxygen or sulfur atom being directly attached to the same aromatic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/66—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/75—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/48—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C07C255/44—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms at least one of the singly-bound nitrogen atoms being acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C07C255/60—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton at least one of the singly-bound nitrogen atoms being acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C07C323/40—Y being a hydrogen or a carbon atom
    • C07C323/42—Y being a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • C07D231/40—Acylated on said nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C07D233/38—One oxygen atom with acyl radicals or hetero atoms directly attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • This invention relates to certain 1 ,8-naphthalenedicarboxamides, their agriculturally suitable salts and compositions, and methods of their use for controlling invertebrate pests 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, and public and animal health is also important. Many products are commercially available for these pu ⁇ oses, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • EP919542 discloses phthalic diamides of Formula i as insecticides
  • Z 1 and Z 2 are O or S; and R 1 , R 2 and R 3 are, among others, H, alkyl or substituted alkyl.
  • each J is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 5
  • R 5 ; A and B are independently O or S; n is 0 to 4;
  • R 1 is H; or C j -Cg alkyl, C 2 - alkenyl, C 2 -C6 alkynyl or C3-C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO 2 , hydroxy, CpC ⁇ alkoxy, C 1 -C4 alkylthio, C J -C 4 alkylsulfmyl, C r C 4 alkylsulfonyl, C 2 -C4 alkoxycarbonyl, -C4 alkylamino,
  • R 1 is C2-C Q alkylcarbonyl, C 2 -Cg alkoxycarbonyl, C 2 -Cg alkylaminocarbonyl or
  • R 2 is H, Cj-Cg alkyl, C 2 -C6 alkenyl, C 2 -C 6 alkynyl, C3-C5 cycloalkyl, C 1 -C 4 alkoxy, r C 4 alkylamino, C 2 -Cg dialkylamino, C3-C6 cycloalkylamino, C2-Cg alkoxycarbonyl or C 2 -Cg alkylcarbonyl;
  • R 3 is H; or C ⁇ -Cg alkyl, C 2 -C6 alkenyl, C2-Cg alkynyl or C 3 -C 6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO 2 , hydroxy, C 1 -C 4 alkoxy, C 1 -C4 alkylthio, -C4 alkylsulfmyl and C1-C4
  • R 2 and R 3 can be taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring may be optionally substituted with 1 to 4 substituents selected from the group consisting of C1-C 2 alkyl, halogen, CN, NO and C r C 2 alkoxy; and each R4 and each R 5 is independently H, C j -Cg alkyl, C2 ⁇ Cg alkenyl, C2-Cg alkynyl, C 3 -C 6 cycloalkyl, C r C 6 haloalkyl, C 9 -C5 haloalkenyl, C -C6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, CO 2 H, CONH 2 , NO 2 , hydroxy, C r C 4 alkoxy, C 1 -C 4 haloalkoxy, C
  • This invention also pertains to a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I or Formula II and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I or Formula II and an effective amount of at least one additional biologically active compound or agent.
  • This invention also pertains to a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula I or Formula II (e.g., as a composition described herein).
  • This invention also relates to such a method wherein the invertebrate pest or its environment is contacted with composition comprising a biologically effective amount of a compound of Formula I or Formula II or with a composition comprising a compound of Formula I or
  • Formula II and a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, /z-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • alkenyl includes straight-chain or branched alkenes such as 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 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, /z-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • dialkylamino includes amino functions substituted with two alkyl groups that may be the same or different.
  • heterocyclic ring or “heterocyclic ring system” denotes rings or ring systems in which at least one ring atom is not carbon and comprises 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.
  • the heterocyclic ring can be attached through any available carbon or nitrogen by replacement of hydrogen on said carbon or nitrogen.
  • aromatic ring system denotes fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied for the ring system).
  • heterocyclic ring denotes fully aromatic rings in which at least one ring atom is not carbon and comprises 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs (where aromatic indicates that the H ⁇ ckel rule is satisfied).
  • the heterocyclic ring can be attached through any available carbon or nitrogen by replacement of hydrogen on said carbon or nitrogen.
  • aromatic heterocyclic ring system includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied).
  • fused heterobicyclic ring system includes a ring system comprised of two fused rings in which at least one ring atom is not carbon and can be aromatic or non aromatic, as defined above.
  • halogen either alone or in compound words such as “haloalkyl” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and
  • haloalkynyl examples include HOCCHC1, CF 3 C ⁇ C, CC1 3 C ⁇ and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • C C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C3 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 .
  • a compound of Formula 1 contains a heterocyclic ring, all substituents are attached to this ring through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • a group contains a substituent which can be hydrogen, for example R 3 , then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
  • R 3 When the number of optional substituents on a group is 0, for example when n is 0, then it is recognized that this is equivalent to said group being unsubstituted.
  • the substituent When a bond is depicted as floating, the substituent may be attached to any of the available carbons on the ring by replacement of hydrogen; for bicyclic ring systems, the substituent or substituents may be attached to either ring ofthe bicyclic ring system, or both rings.
  • a single R 4 substituent may be attached to Formula I or Formula II at any of the indicated positions 2, 3, 4, 5, 6 or 7; and when n is 2, two independent R 4 substituents may be attached at the 2,3; 2,4; 2,5; 2,6 or 2,7 positions or any other combination of 2 positions.
  • R 2 and R 3 are taken together with the nitrogen to which they are attached to form a ring, said ring can be optionally substituted on any available carbon or optionally nitrogen in said ring.
  • 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.
  • the present invention comprises compounds selected from Formula I or Formula II, iV-oxides and agriculturally suitable salts thereof.
  • 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.
  • tertiary amines can form N-oxides.
  • Synthetic methods for the preparation of iV-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 w-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as /-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as /-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethydioxirane.
  • the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • R 1 is H, C r C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkylcarbonyl or C 2 -Cg alkoxycarbonyl; and n is 0 to 2.
  • R 1 is H, C r C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkylcarbonyl or C 2 -Cg alkoxycarbonyl; and n is 0 to 2.
  • J is a phenyl ring or a 5- or 6-membered heteroaromatic ring selected from the group consisting of J-l, -2, J-3 and J-4, each I ring optionally substituted with 1 to 3 R 5
  • Q is O, S or NR 5 ;
  • W, X, Y and Z are independently N or CR 5 , provided that in J-3 and J-4 at least one of W, X, Y or Z is N;
  • R 2 is H, C,-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkylcarbonyl or C 2 -C alkoxycarbonyl;
  • R 3 is C Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl or C3-C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, C C 2 alkoxy, C C 2 alkylthio, C j -C alkylsulfmyl and C C 2 alkylsulfonyl; one R 4 group is attached to the naphthyl ring system at the 2-
  • Q is NR 5a ;
  • X is N or CH;
  • Y is CH;
  • Z is CR 5b ;
  • R 5a is a phenyl or 2-pyridyl ring substituted with one or two substituents selected from the group consisting of halogen, C 1 -C4 alkyl, C 1 -C4 haloalkyl or C 1 -C 4 haloalkoxy; and
  • R 5b is halogen or CF 3 .
  • Specifically preferred compounds are those selected from the group consisting of N-methyl -N'-(2-bromo-4-fluoropheny)-l,8-naphthalene-dicarboxamide, N-methyl 8-[(3,4-difluorophenyl)carbonylamino]- 1 -naphthalenecarboxamide and N-methyl 8-[(2-thienyl)carbonylamino]-l -naphthalenecarboxamide.
  • This invention also pertains to a composition for controlling invertebrates comprising a biologically effective amount of a compound of Formula I or Formula II and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I or Formula II and an effective amount of at least one additional biologically active compound or agent.
  • Preferred compositions are those comprising compounds of Formula I or Formula II as preferred in Preferred 1 through 9, and the specifically preferred compounds above.
  • This invention also pertains to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound of Formula I or Formula II, and N-oxide or agriculturally suitable salts thereof (e.g. as a composition comprising a compound of Formula I or Formula II).
  • This invention also relates to such a method wherein the invertebrate pest or its environment is contacted with a biologically effective amount of a compound of Formula I or Formula II or a composition comprising a compound of Formula I or Formula II and a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests.
  • Preferred methods are those comprising compounds of Formula I or Formula II as preferred in Preferred 1 through 9, and the specifically preferred compounds above.
  • a and B are independently O or S; m is 1 to 5; n is 0 to 4; R 1 is H; or C Cg alkyl, C 2 -C(5 alkenyl, C 2 -C ⁇ 3 alkynyl or C 3 -Cg cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO 2 , hydroxy, -C4 alkoxy, C 1 -C4 alkylthio, C 1 -C4 alkylsulfmyl, C 1 -C4 alkylsulfonyl, C 2 -C4 alkoxycarbonyl, C 1 -C4 alkylamino, C 2 -Cg dialkylamino and C 3 -Cg cycloalkylamino; or
  • R 1 is C 2 -Cg alkylcarbonyl, C 2 -Cg alkoxycarbonyl, C 2 -Cg alkylaminocarbonyl or
  • R 2 is H, Cj-Cg alkyl, C 2 -Cg alkenyl, C 2 -C6 alkynyl, C -Cg cycloalkyl, C 1 -C4 alkoxy, C j -C alkylamino, C 2 -Cg dialkylamino, C -Cg cycloalkylamino, C 2 -Cg alkoxycarbonyl or C 2 -Cg alkylcarbonyl;
  • R 3 is H; or C Cg alkyl, C 2 - alkenyl, C 2 -C ( 5 alkynyl or C 3 -Cg cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO 2 , hydroxy, C J -C4 alkoxy, C 1 -C 4 alkylthio, C 1 -C4 alkylsulfmyl and C 1 -C 4 alkylsulfonyl; or R 2 and R 3 can be taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring may be optionally substituted with 1 to 4 substituents selected from the group consisting of C ⁇ -C 2 alkyl, halogen, CN, NO 2 and Cj-C 2 alkoxy; and each R 4 and each R 5 is independently H, C Cg alkyl, C 2
  • each R 4 and each R 5 is independently phenyl optionally substituted with C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl,
  • arthropodicidal compositions comprising an arthropodicidally effective amount of a compound of Formula Ih or Formula He noted above and at least one additional component selected from the group consisting of surfactants, solid diluents or liquid diluents.
  • R 3 is C r C 4 alkyl; each R 4 and each R 5 is independently H, C 1 -C 4 alkyl, C C 4 haloalkyl, halogen, CN, NO 2 , C 1 -C4 alkoxy, C 1 -C 4 haloalkoxy, Cj-C 4 alkylthio, C 1 -C4 alkylsulfmyl, C j -
  • a and B are both O; m is 1 to 3; n is 0 to 2;
  • R 1 is H, C r C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkylcarbonyl or C 2 -Cg alkoxycarbonyl; and each R 4 and each R 5 is independently H, C 1 -C4 alkyl, C r C 4 haloalkyl, halogen, CN, NO 2 , C1-C 4 alkoxy, C C haloalkoxy, C 1 -C4 alkylthio, -C 4 alkylsulfmyl, C j - C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl, C j -C haloalkylsulfonyl or C 2 -C4 alkoxycarbonyl. Selection 5. Of note are selected compounds
  • R 2 is H;
  • R 3 is C ⁇ -C 5 alkyl optionally substituted with C 1 -C4 alkoxy or C 1 -C 4 alkylthio;
  • each R 4 and each R 5 is independently H, C 1 -C 4 alkyl, -C 4 haloalkyl, halogen, CN,
  • each J is independently a phenyl ring, a naphthyl ring system, a 5- or
  • each ring or ring system is optionally substituted with 1 to 5 R 5 .
  • the term "optionally substituted" in connection with these J groups refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the arthropodicidal activity possessed by the unsubstituted analog.
  • An example of phenyl optionally substituted with 1 to 5 R 5 is the ring illustrated as U-l in Exhibit 1, wherein R v is
  • R 5 and r is an integer from 1 to 5.
  • An example of a naphthyl group optionally substituted with 1 to 5 R 5 is illustrated as U-85 in Exhibit 1, wherein R v is R 5 and r is an integer from 1 to 5.
  • R 5 include the rings U-2 through U-53 illustrated in Exhibit 1 wherein R v is R 5 and r is an integer from 1 to 5.
  • J-l through J-4 below also denote 5- or 6-membered heteroaromatic rings.
  • U-2 through U-20 are examples of J-l
  • U-21 through U-35 and U-40 are examples of J-2
  • U-41 through U-48 are examples of J-3
  • U-49 through U- 53 are examples of J-4.
  • Examples of aromatic 8-, 9- or 10-membered fused heterobicyclic ring systems optionally substituted with 1 to 4 R 3 include U-54 through U-84 illustrated in
  • R v groups are shown in the structures U-l through U-85, it is noted that they do not need to be present since they are optional substituents. Note that when R v is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or R v . Note that some U groups can only be substituted with less than 5 R v groups (e.g. U-14, U-l 5, U-l 8 through U-
  • the compounds of Formula I and Formula II can be prepared by one or more of the following methods and variations as described in Schemes 1-21.
  • the definitions of R ⁇ R-, R?_ R4 ⁇ A., B, m and n in the compounds described in the Schemes below are as defined above in the Summary of the Invention or their subsets.
  • Compounds of Formula I can be prepared by procedures outlined in Schemes 1-9.
  • Compounds of Formulae la-h are various subsets of the compounds of Fo ⁇ nula I.
  • Typical procedures are described in Scheme 1 and involve either coupling of a isonaphthalimide of Formula 2 with an amine of Formula 3 or coupling of a compound of Formula 4 with an amine of Formula 5 with or without the presence of a base.
  • Typical bases include amine bases such as triethylamine, diisopropylethylamine and pyridine.
  • polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine.
  • amines of Formula 3 and Formula 5 are either commercially available, well represented in the chemical literature, or readily available from established literature procedures.
  • Amides of Formula la can be converted to thioamides of Formula lb using a variety of standard thio transfer reagents including phosphorus pentasulfide and Lawesson's reagent.
  • Id (A and B are independently 0 or S)
  • Compounds of Formula 2 and Formula 4 are typically prepared by coupling of a 1 ,8-naphthaloyl chloride of the Formula 6 with an amine of Formula 7 or an amine of Formula 8 respectively (Scheme 2).
  • Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine.
  • polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine.
  • the amine of Formula 7 can serve as the acid scavenger when used in excess.
  • the compounds of 1 ,8-naphthaloyl chloride of the Formula 6 are well represented in the chemical literature and are typically prepared from the corresponding 1,8-naphthalic acids or the anhydrides with the use of chlorinating reagents commonly used for the transformation of carboxylic acid to carboxylic acid chloride. These commonly used chlorinating reagents include phosphorous oxychloride and phosphorous pentachloride.
  • An alternate procedure for the preparation of compounds of Formula 2 and Formula 4 involves the cyclization of compounds of 8-aminocarbonyl-l-naphthalenecarboxylic acid of Formula 9 and Formula 10 respectively (Scheme 3) with the use of a dehydration reagent in an inert solvent at a temperature in the range of —30 to 30 °C, with or without the presence of an acid scavenger.
  • Typical dehydration reagents include dicyclohexylcarbodiimide and trifluoroacetic anhydride.
  • Polymer supported reagents such as polymer-bound cyclohexylcarbodiimide are useful.
  • Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine. In certain instances it is useful to use polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine.
  • Typical inert solvents include aprotic solvents such as dichloromethane and 1-chlorobutane. A typical range of reaction temperature is from —5 to 25 °C.
  • the preparation of 8-aminocarbonyl-l-naphthalenecarboxylic acids of Formula 9 and Formula 10 involves the coupling of 1,8-naphthalic anhydrides of Formula 11 with amines of Formula 7 or amines of Formula 8 respectively (Scheme 4) in an inert solvent at a temperature in the range of 0 to 30 °C.
  • a typical inert solvent is dimethylformamide.
  • the reaction is commonly conducted in the temperature range of 5 to 10 °C.
  • Alternate procedures for the preparation of compounds of 8-aminocarbonyl-l- naphthalenecarboxylic acid of Formula 9 and Formula 10 involve the hydrolysis of compounds of 1 ,8-naphthalimide of Formula 12 and Formula 13 respectively (Scheme 5) using a hydroxide such as sodium hydroxide or potassium hydroxide in a protic solvent system such as water-methanol or water-dioxane at elevated temperature. The reaction is usually conducted at the reflux temperature of the reaction mixture.
  • a hydroxide such as sodium hydroxide or potassium hydroxide in a protic solvent system
  • a protic solvent system such as water-methanol or water-dioxane
  • the compounds of 1 ,8-naphthalimide of Formula 12 and Formula 13 are typically prepared by condensing a 1 ,8-naphthalic anhydride of Formula 1 1 with an amine of Formula 7 or Formula 8 respectively at an elevated temperature, usually in the presence of an acid.
  • a typical reaction involves refluxing the 1,8-naphthalic anhydride of Formula 1 1 and the amine of Formula 7 or Formula 8 in acetic acid.
  • An alternate procedure for the preparation of compounds of Formula I involves the coupling of 8-aminocarbonyl-l-naphthoyl chlorides of Formula 14 and Formula 15 with an amine of Formula 3 or an amine of Formula 5 respectively (Scheme 6), in the presence of an acid scavenger.
  • Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine.
  • polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer- bound dimethylaminopyridine.
  • the reaction temperature range is 0 to 25 °C.
  • 8-Aminocarbonyl-l-naphthoyl chlorides of Formula 14 and Formula 15 are available from coupling the corresponding 1,8-naphthaloyl dichloride of Formula 6 with an amine of Formula 5 or Formula 3 respectively in the presence of an acid scavenger (Scheme 7).
  • Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine.
  • polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine.
  • Another procedure for the preparation of compounds of Formula I involves the stepwise carbamoylation or thiocarbamoylation of a naphthalene of Formula 20 (Schemes and 9).
  • compounds of 1 -naphthalenecarboxamide or 1 -naphthalenethiocarboxamide of Formula 16 or Formula 17 couple with a carbamoyl chloride or thiocarbamoyl chloride of Formula 18 or Formula 19 to provide a compound of Formula I (Scheme 8).
  • Commonly used Lewis acids include aluminum chloride and stannic chloride.
  • the preparation of compounds of 1-naphthalenecarboxamides or 1-naphthalenethiocarboxamides of Formula 16 or Formula 17 involves the coupling of a naphthalene of Formula 20 and a carbamoyl chloride or thiocarbamoyl chloride of Formula 19 or Formula 18 respectively in the presence of a Lewis acid such as aluminum chloride and stannic chloride under Friedel-Crafts reaction conditions.
  • a Lewis acid such as aluminum chloride and stannic chloride under Friedel-Crafts reaction conditions.
  • the naphthalenes of Formula 20, the carbamoyl chlorides and the thiocarbamoyl chlorides of Formula 18 and Formula 19 are commercially available, well described in the chemical literature, or can be prepared following established literature procedures.
  • the compounds of Formula II can be prepared by one or more of the following methods and variations as described in Schemes 10-13.
  • Compounds of Formulae Ila-b are subsets o the compounds of Formula II.
  • a typical procedure is described in Scheme 10 and involves coupling of an 8-amino- naphthalene-1-carboxamide of Formula 21 with a carbonyl chloride of Formula 22 in the presence of an acid scavenger to provide the compounds of Formula Ila, or with thiocarbonyl chloride of Formula 22 in the presence of an areneselenolate to provide the compounds of Formula lib.
  • Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine, other scavengers include hydroxides such as sodium and potassium hydroxide and carbonates such as sodium carbonate and potassium carbonate. In certain instances it is useful to use polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine. Typical areneselenolates include sodium phenylselenolate.
  • the carbonyl chlorides and the thiocarbonyl chlorides of Formula 22 are commercially available, well represented in the chemical literature, or readily prepared according to established literature procedures. Amides of Formula Ila can be converted to thioamides of Formula lib using standard thio transfer reagents such as phosphorus pentasulfide and Lawesson's reagent.
  • Another procedure for the preparation of compounds of Formula Ila involves coupling of an l-amino-naphthalene-8-carboxamide or l-amino-naphthalene-8-thiocarboxamide of Formula 21 with a carboxylic acid of Formula 23 in the presence of a dehydration reagent such as dicyclohexylcarbodiimide (DCC).
  • a dehydration reagent such as dicyclohexylcarbodiimide (DCC).
  • DCC dicyclohexylcarbodiimide
  • Benzoic acids of Formula 23 are commercially available, well represented in the chemical literature, or readily prepared according to established literature procedures.
  • the procedures of Scheme 10 and Scheme 1 1 are only representative examples of useful methods for the preparation of Formula II compounds as the literature is extensive for the preparation of carboxamides.
  • 8-Amino-naphthalene-l-carboxamides and 8-amino-naphthalene-l-thiocarboxamides of Formula 21a are typically available from the corresponding 8-nitro-naphthalene-l- carboxamides and 8-nitro-naphthalene-l-thiocarboxamides of Formula 24 respectively via reduction ofthe nitro group.
  • Typical procedures involve reduction with hydrogen in the presence of a metal catalyst such as palladium on carbon or platinum oxide and in hydroxylic solvents such as ethanol and isopropanol. These procedures are well documented in the chemical literature.
  • R 1 substituents such as alkyl, substituted alkyl and the like can generally be introduced at this stage through known procedures including either direct alkylation or through the generally preferred method of reductive alkylation ofthe amine.
  • a commonly employed procedure is to combine the aminonaphthalene 21a with an aldehyde in the presence of a reducing agent such as sodium cyanoborohydride to produce the compounds of Formula 21 where R 1 is other than H.
  • the intermediate amides of Formula 24 are readily prepared from 8-nitro-naphthalene- -carboxylic acids that are commercially available, known in the literature, or can be prepared by established literature procedures for the derivatization of naphthalenes or aromatic groups in general. Typical methods for amide formation can be applied here. These include direct dehydrative coupling of acids of Formula 25 with amines of Formula 5 using for example DCC, and conversion of the acids to an activated form such as the acid chlorides or anhydrides and subsequent coupling with amines to form amides of formula 24a. Also, diethyl cyanophosphonate is a useful reagent for this type of reaction involving activation of the acid. The chemical literature is extensive on this type of reaction. Amides of Formula 24a are readily converted to thioamides of Formula 24b by using commercially available thio transfer reagents such as phosphorus pentasulfide and Lawesson's reagent.
  • Benzoic acids of Formula 23a (compounds of Formula 23 wherein J is an optionally substituted phenyl ring) are well known in the art. Preparation of certain heterocyclic acids of Formula 4 are described in Schemes 14-21 . A variety of heterocyclic acids and general methods for their synthesis may be found in World Patent Application WO 98/57397.
  • Substituent groups R 5 (c) and R 5 (d) include e.g. alkyl and haloalkyl.
  • the arylating or alkylating agent R 5 (c)-Lg (wherein Lg is a leaving group such as Cl, Br, I, sulfonates such as p-toluenesulfonate or methanesulfonate or sulfates such as -SO 2 OR 5 (c)) includes R 5 (c) groups such as C Cg alkyl, C 2 -C ( 3 alkenyl, C 2 -C6 alkynyl, C 2 -C6 alkylcarbonyl, C 2 -Cg alkoxycarbonyl, C3 ⁇ Cg dialkylaminocarbonyl, C3-C 6 trialkylsilyl; or phenyl, benzyl, benzoyl
  • Lg is a leaving group
  • Lg is a leaving group 40 23d
  • This procedure is particularly useful for preparing 1 -(2-pyridinyl)pyrazolecarboxylic acids of Formula 23e as shown in Scheme 18.
  • Reaction of a pyrazole of Formula 39 with a 2,3-dihalopyridine of Formula 37a affords good yields ofthe 1-pyridylpyrazole of Formula 40a with good specificity for the desired regiochemistry.
  • Metallation and carboxylation of compounds of Formula 40a as described above affords the l-(2-pyridinyl)pyrazolecarboxylic acid of Formula 23e.
  • pyrazoles of Formula 4c are described in Scheme 19. They can be prepared via reaction of an optionally substituted phenyl hydrazine of Formula 41 with a ketopyruvate of Formula 42 to yield pyrazole esters of Formula 43. Hydrolysis of the esters affords the pyrazole acids of Formula 23d. This procedure is particularly useful for the preparation of compounds in which R 5 (c) is optionally substituted phenyl and R 5 (d) is haloalkyl.
  • pyrazole acids of Formula 23d An alternate synthesis of pyrazole acids of Formula 23d is described in Scheme 20. They can be prepared via 3+2 cycloaddition of an appropriately substituted nitrilimine with either substituted propiolates of Formula 45 or acrylates of Formula 47. Cycloaddition with an acrylate requires additional oxidation of the intermediate pyrazoline to the pyrazole. Hydrolysis of the esters affords the pyrazole acids of Formula 23d.
  • Preferred iminohalides for this reaction include the trifluoromethyl iminochloride of Formula 48 and the iminodibromide of Formula 49. Compounds such as 48 are known (J Heterocycl. Chem. 1985, 22(2), 565-8).
  • the starting pyrazoles of Fo ⁇ riula 39 are known compounds.
  • the pyrazole of Fo ⁇ riula 39a (the compound of Formula 39 wherein R 5 (d) is CF3) is commercially available.
  • the pyrazoles of Formula 39c (compounds of Fo ⁇ nula 39 wherein R 5 (d) is Cl or Br) can be prepared by literature procedures (Chem. Ber. 1966, .9.9(10), 3350-7). A useful alternative method for the preparation of compound 39c is depicted in Scheme 21.
  • Step A Preparation of N-methyl 8-r(3,4-difluorophenyl)carbonylamino]-l -naphthalenecarboxamide
  • Step A Preparation of N-methyl 8-nitro-l -naphthalenecarboxamide
  • methylamine (0.22 g, 7.3 mmole)
  • imidazole (0.68 g, 8.3 mmole)
  • diethyl cyanophosphonate (1.24 g, 7.6 mmole
  • reaction mixture was stirred overnight, poured into water (100 mL) and extracted with ethyl acetate (3 x 100 mL). The ethyl acetate extracts were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give a solid which was washed with a small amount of methanol to give the product (0.64 g) which was used without further purification.
  • N-methyl 8-nitro-l-naphthalenecarboxamide (0.5 g, 2.17 mmole) in methanol (5 mL) and dichlomethane (15 mL) was hydrogenated with a catalytic amount of palladium (10% on charcoal) under 30 psi hydrogen pressure for 1 hour.
  • the reaction mixture was suction filtered through celite and concentrated under reduced pressure to provide the product (0.42 g) which was used without further purification.
  • Step C Preparation of N-methyl 8-(T3,4-difluorophenyl)carbonylamino "
  • t is tertiary, s is secondary, n is normal, / is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, t-Bu is tert butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is ethylthio, CN is cyano, NO 2 is nitro, TMS is trimethylsilyl, S(O)Me is methylsulfinyl, and S(O) Me is methylsulfonyl.
  • TJ TJ to to to to TJ j j to to to to to ON 1 I 1 TJ ro cr TJ O O O O 3" T TJ O- al 3 TS TJ J ⁇ j T) Tl Tl Tl Tl O ⁇ ⁇ a. a- to to to TJ Z ⁇ 2 2 3 PS, 5 ⁇ Q
  • TJ TJ TJ T3 ⁇ ⁇ . ra TJ TJ TJ TJ Q TJ 2 2 2 73 o o ⁇ D 2 ⁇ D ⁇ 2> 2 ⁇ D 2 2 m
  • TJ TJ J s 5. o TJ 1 T TJJ J.J TJ TJ TJ TJ TJ ra Tl ra o O ro o
  • Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant.
  • the formulation or composition ingredients are selected to be consistent with the physical properties ofthe active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels.
  • Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient.
  • Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges that add up to 100 percent by weight.
  • Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, rung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-mefhyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
  • Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill.
  • Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084.
  • Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and PCT Publication WO 91/13546.
  • Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

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Abstract

Compounds of Formula I and Formula II, and their N-oxides and agriculturally suitable salts, are disclosed that are useful for controlling invertebrate pests, Formula (I), Formula (II) wherein A, B, J, R1, R2, R3, R4, and n are as defined in the disclosure.Also disclosed are compositions comprising the compounds of Formula I or Formula II and methods for controlling invertebrate pests that involve contacting the invertebrate pests or their environment with an effective amount of a compound of Formula (I) or Formula (II).

Description

TITLE
INSECTICIDAL 1 ,8-NAPHTHALENEDICARBOXAMlDES
BACKGROUND OF THE INVENTION This invention relates to certain 1 ,8-naphthalenedicarboxamides, their agriculturally suitable salts and compositions, and methods of their use for controlling invertebrate pests in both agronomic and nonagronomic environments.
The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these puφoses, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action.
EP919542 discloses phthalic diamides of Formula i as insecticides
wherein, among others, Z1 and Z2 are O or S; and R1, R2 and R3 are, among others, H, alkyl or substituted alkyl.
SUMMARY OF THE INVENTION This invention is directed to compounds of Formula I and Formula II including all geometric and stereoisomers, ZV-oxides and agriculturally suitable salts thereof".
wherein each J is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 5
R5; A and B are independently O or S; n is 0 to 4;
R1 is H; or Cj-Cg alkyl, C2- alkenyl, C2-C6 alkynyl or C3-C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, hydroxy, CpC^ alkoxy, C1-C4 alkylthio, CJ-C4 alkylsulfmyl, CrC4 alkylsulfonyl, C2-C4 alkoxycarbonyl, -C4 alkylamino,
C2-Cg dialkylamino and C3-C6 cycloalkylamino; or R1 is C2-CQ alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg alkylaminocarbonyl or
C3-Cg dialkylaminocarbonyl; R2 is H, Cj-Cg alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C5 cycloalkyl, C1-C4 alkoxy, rC4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-Cg alkoxycarbonyl or C2-Cg alkylcarbonyl; R3 is H; or C^-Cg alkyl, C2-C6 alkenyl, C2-Cg alkynyl or C3-C6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, hydroxy, C1-C4 alkoxy, C1-C4 alkylthio, -C4 alkylsulfmyl and C1-C4 alkylsulfonyl; or
R2 and R3 can be taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring may be optionally substituted with 1 to 4 substituents selected from the group consisting of C1-C2 alkyl, halogen, CN, NO and CrC2 alkoxy; and each R4 and each R5 is independently H, Cj-Cg alkyl, C2~Cg alkenyl, C2-Cg alkynyl, C3-C6 cycloalkyl, CrC6 haloalkyl, C9-C5 haloalkenyl, C -C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, CO2H, CONH2, NO2, hydroxy, CrC4 alkoxy, C1-C4 haloalkoxy, C C4 alkylthio, C]-C4 alkylsulfmyl, Cj-C4 alkylsulfonyl, C1-C4 haloalkylthio, C C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C2-C4 alkoxycarbonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2~Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C8 dialkylaminocarbonyl, or C3"C( trialkylsilyl; or each R4 and each R5 is independently a phenyl, benzyl, phenoxy, 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each ring optionally substituted with one to three substituents independently selected from the group consisting of C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, NO2, CrC4 alkoxy, C1-C4 haloalkoxy, CJ-C4 alkylthio, C1-C4 alkylsulfmyl, C1-C4 alkylsulfonyl, Cj-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C3-C6 (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg alkylaminocarbonyl, C3-C dialkylaminocarbonyl or C3-C6 trialkylsilyl; or (R5)2 when attached to adjacent carbon atoms can be taken together as -OCF2O-,
-CF2CF2O- or -OCF2CF2O-. This invention also pertains to a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I or Formula II and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. This invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I or Formula II and an effective amount of at least one additional biologically active compound or agent. This invention also pertains to a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula I or Formula II (e.g., as a composition described herein). This invention also relates to such a method wherein the invertebrate pest or its environment is contacted with composition comprising a biologically effective amount of a compound of Formula I or Formula II or with a composition comprising a compound of Formula I or
Formula II and a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests.
DETAILS OF THE INVENTION In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, /z-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes such as 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 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, /z-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. "Alkylamino", "alkenylthio", "alkenylsulfinyl", "alkenylsulfonyl", "alkynylthio", "alkynylsulfinyl", "alkynylsulfonyl", and the like, are defined analogously to the above examples. Examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(-O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. Examples of "alkylaminocarbonyl" include CH3NHC(=O), CH3CH2NHC(=O), CH3CH2CH2NHC(=O), (CH3)2CHNHC(=O) and the different butylamino- or pentylaminocarbonyl isomers. The term "dialkylamino" includes amino functions substituted with two alkyl groups that may be the same or different.
"Dialkylaminocarbonyl" is defined analogously, and examples include (CH )2NC(=O) and CH3CH2NCH3C(=O).
The term "heterocyclic ring" or "heterocyclic ring system" denotes rings or ring systems in which at least one ring atom is not carbon and comprises 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. The heterocyclic ring can be attached through any available carbon or nitrogen by replacement of hydrogen on said carbon or nitrogen. The term "aromatic ring system" denotes fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied for the ring system). The term "heteroaromatic ring" denotes fully aromatic rings in which at least one ring atom is not carbon and comprises 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs (where aromatic indicates that the Hϋckel rule is satisfied). The heterocyclic ring can be attached through any available carbon or nitrogen by replacement of hydrogen on said carbon or nitrogen. The term "aromatic heterocyclic ring system" includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied). The term "fused heterobicyclic ring system" includes a ring system comprised of two fused rings in which at least one ring atom is not carbon and can be aromatic or non aromatic, as defined above.
The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F3C, C1CH2, CF3CH2 and
CF3CC1 . The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)2C=CHCH and CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HOCCHC1, CF3C≡C, CC13C≡ and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O.
The total number of carbon atoms in a substituent group is indicated by the "Cj-Cj" prefix where i and j are numbers from 1 to 6. For example, C C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2. In the above recitations, when a compound of Formula 1 contains a heterocyclic ring, all substituents are attached to this ring through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
When a group contains a substituent which can be hydrogen, for example R3, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When the number of optional substituents on a group is 0, for example when n is 0, then it is recognized that this is equivalent to said group being unsubstituted. When a bond is depicted as floating, the substituent may be attached to any of the available carbons on the ring by replacement of hydrogen; for bicyclic ring systems, the substituent or substituents may be attached to either ring ofthe bicyclic ring system, or both rings. For example, when n is 1 , a single R4 substituent may be attached to Formula I or Formula II at any of the indicated positions 2, 3, 4, 5, 6 or 7; and when n is 2, two independent R4 substituents may be attached at the 2,3; 2,4; 2,5; 2,6 or 2,7 positions or any other combination of 2 positions. When R2 and R3 are taken together with the nitrogen to which they are attached to form a ring, said ring can be optionally substituted on any available carbon or optionally nitrogen in said ring. Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer 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.
The present invention comprises compounds selected from Formula I or Formula II, iV-oxides and agriculturally suitable salts thereof. One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of iV-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 w-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as /-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-19, A. J. Boulton and A. McKillop, Eds., Pergamon Press; . R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistiy, vol. 43, pp 139-151 , A. R. Katritzky, Ed., Academic Press; M. Tisler and
B. Stanovnik in Advances in Heterocyclic Chemistiy, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistiy, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press. The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
Preferred for reasons including ease of synthesis and/or greater arthropodicidal efficacy are:
Preferred 1. Compounds of Formula I wherein A and B are both O;
R1 is H, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl; and n is 0 to 2.
Preferred 2. Compounds of Formula II wherein A and B are both O;
R1 is H, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl; and n is 0 to 2.
Preferred 3. Compounds of Preferred 1 or Preferred 2 wherein
J is a phenyl ring or a 5- or 6-membered heteroaromatic ring selected from the group consisting of J-l, -2, J-3 and J-4, each I ring optionally substituted with 1 to 3 R5
J-l J-2 J-3 j-4
Q is O, S or NR5;
W, X, Y and Z are independently N or CR5, provided that in J-3 and J-4 at least one of W, X, Y or Z is N; R2 is H, C,-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkylcarbonyl or C2-C alkoxycarbonyl; R3 is C Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl or C3-C5 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, C C2 alkoxy, C C2 alkylthio, Cj-C alkylsulfmyl and C C2 alkylsulfonyl; one R4 group is attached to the naphthyl ring system at the 2-position or 7-position, and said R4 is Cj-C^ alkyl, C1-C4 haloalkyl, halogen, CN, NO , CrC4 alkoxy, CrC4 haloalkoxy, CrC4 alkylthio, CrC alkylsulfmyl, CrC4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; each R5 is independently H, Cj-C4 alkyl, C1-C4 haloalkyl, halogen, CN, NO2, C C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfmyl, C1-C4 alkylsulfonyl, C C4 haloalkylthio, C C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C2-C4 alkoxycarbonyl, C3-C dialkylaminocarbonyl; or each R5 is independently a phenyl, benzyl or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-Cβ cycloalkyl, Cj-C^ haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-Cg halocycloalkyl, halogen,
CN, NO2, CrC4 alkoxy, CrC4 haloalkoxy, CrC4 alkylthio, CrC4 alkylsulfmyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-Cg cycloalkylamino, C -C(5 (alkyl)cycloalkyl amino, C2-C4 alkylcarbonyl, C2-Cg alkoxycarbonyl, C2~C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl; or (R5)2 when attached to adjacent carbon atoms can be taken together as
-OCF2O-, -CF2CF2O- or -OCF2CF2O-; and n is 1 to 2. Preferred 4. Compounds of Formula I of Preferred 3 wherein R2 is H; R3 is C C^ alkyl; and at least one ofthe R5 substituents is ortho to the NRIC(=B) moiety. Preferred 5. Compounds of Preferred 4 wherein R3 is methyl. Preferred 6. Compounds of Formula II of Preferred 3 wherein R1 is H or CrC4 alkyl; R2 is H or CrC4 alkyl;
R3 is CrC alkyl optionally substituted with halogen, CN, OCH3, or S(O)pCH3; one R5 group is attached to the J at the position ortho to the C(=B)NR1 moiety, and said R5 is C1-C4 alkyl, C1-C4 haloalkyl, halogen, CN, NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, Cj-C4 alkylsulfmyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C2-C4 alkoxycarbonyl; C3-Cg dialkylaminocarbonyl or a phenyl, benzyl, or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with halogen, CN, NO2, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; and a second optional R5 group is independently C1-C4 alkyl, C1-C4 haloalkyl, halogen, CN, NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfmyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C2-C4 alkoxycarbonyl; C3-Cg dialkylaminocarbonyl or a phenyl, benzyl, or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with halogen, CN, NO2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-Cg cycloalkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy. Preferred 7. Compounds of Preferred 6 wherein J is phenyl, pyrazole, pyrrole, pyridine or pyrimidine, each substituted with one R5 attached to the J at the position ortho to the C(=B)NR* moiety and a second optional R5. Preferred 8. Compounds of Preferred 7 wherein R1 and R2 are each H; one R4 is attached at the 7-position ortho to the NR1C(=X)J moiety and is selected from the group consisting of Cj-C3 alkyl, CF3, OCF3, OCHF2,
S(O)pCF3, S(O)pCHF2 and halogen and an optional second R4 is attached at the 5-position/>αrø to the NR1C(=X)J moiety and is selected from the group consisting of halogen, C C3 alkyl and C C3 haloalkyl. Preferred 9. Compounds of Preferred 8 wherein J is J-l ;
Q is NR5a; X is N or CH; Y is CH; Z is CR5b; R5a is a phenyl or 2-pyridyl ring substituted with one or two substituents selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 haloalkoxy; and R5b is halogen or CF3. Specifically preferred compounds are those selected from the group consisting of N-methyl -N'-(2-bromo-4-fluoropheny)-l,8-naphthalene-dicarboxamide, N-methyl 8-[(3,4-difluorophenyl)carbonylamino]- 1 -naphthalenecarboxamide and N-methyl 8-[(2-thienyl)carbonylamino]-l -naphthalenecarboxamide.
This invention also pertains to a composition for controlling invertebrates comprising a biologically effective amount of a compound of Formula I or Formula II and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. This invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I or Formula II and an effective amount of at least one additional biologically active compound or agent. Preferred compositions are those comprising compounds of Formula I or Formula II as preferred in Preferred 1 through 9, and the specifically preferred compounds above.
This invention also pertains to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound of Formula I or Formula II, and N-oxide or agriculturally suitable salts thereof (e.g. as a composition comprising a compound of Formula I or Formula II). This invention also relates to such a method wherein the invertebrate pest or its environment is contacted with a biologically effective amount of a compound of Formula I or Formula II or a composition comprising a compound of Formula I or Formula II and a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests. Preferred methods are those comprising compounds of Formula I or Formula II as preferred in Preferred 1 through 9, and the specifically preferred compounds above.
Of note are certain compounds of Formula Ih and Formula lie including all geometric and stereoisomers, and agriculturally suitable salts thereof
wherein:
A and B are independently O or S; m is 1 to 5; n is 0 to 4; R1 is H; or C Cg alkyl, C2-C(5 alkenyl, C2-C<3 alkynyl or C3-Cg cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, hydroxy, -C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfmyl, C1-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl, C1-C4 alkylamino, C2-Cg dialkylamino and C3-Cg cycloalkylamino; or
R1 is C2-Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg alkylaminocarbonyl or
C3-Cg dialkylaminocarbonyl; R2 is H, Cj-Cg alkyl, C2-Cg alkenyl, C2-C6 alkynyl, C -Cg cycloalkyl, C1-C4 alkoxy, Cj-C alkylamino, C2-Cg dialkylamino, C -Cg cycloalkylamino, C2-Cg alkoxycarbonyl or C2-Cg alkylcarbonyl;
R3 is H; or C Cg alkyl, C2- alkenyl, C2-C(5 alkynyl or C3-Cg cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, hydroxy, C J-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfmyl and C1-C4 alkylsulfonyl; or R2 and R3 can be taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring may be optionally substituted with 1 to 4 substituents selected from the group consisting of Cι-C2 alkyl, halogen, CN, NO2 and Cj-C2 alkoxy; and each R4 and each R5 is independently H, C Cg alkyl, C2-Cβ alkenyl, C2-Cg alkynyl,
C3-Cg cycloalkyl, C Cg haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, CO2H, CONH2, NO2, hydroxy, CrC4 alkoxy, Cj-C4 haloalkoxy, C C.4 alkylthio, C1-C4 alkylsulfmyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, -C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C2-C4 alkoxycarbonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C cycloalkylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, or C3-C(5 trialkylsilyl; or each R4 and each R5 is independently phenyl optionally substituted with C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, CrC4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C -Cg halocycloalkyl, halogen, CN, NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfmyl, C1-C4 alkylsulfonyl, C C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C -C6 (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C -Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl.
Also of note are arthropodicidal compositions comprising an arthropodicidally effective amount of a compound of Formula Ih or Formula He noted above and at least one additional component selected from the group consisting of surfactants, solid diluents or liquid diluents.
Also of note are methods for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound of Formula Ih or Formula lie noted above.
Selection 1. Of note are selected compounds of Formula Ih wherein A and B are both O; m is 1 to 3; n is 0 to 2; R1 is H, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl; and each R4 and each R5 is independently H, Cj-C4 alkyl, C1-C4 haloalkyl, halogen, CN, NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, Cj-04 alkylsulfmyl, C C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, Cj-C4 haloalkylsulfonyl or C2-C4 alkoxycarbonyl.
Selection 2. Of note are selected compounds of Selection 1 wherein R2 is H;
R3 is CrC4 alkyl; each R4 and each R5 is independently H, C1-C4 alkyl, C C4 haloalkyl, halogen, CN, NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, Cj-C4 alkylthio, C1-C4 alkylsulfmyl, Cj-
C4 alkylsulfonyl, -C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C2-C4 alkoxycarbonyl; and at least one ofthe R5 substituents is ortho to the amide linkage. Selection 3. Of note are selected compounds of Selection 2 wherein R3 is methyl. Selection 4. Of note are selected compounds of Formula He wherein
A and B are both O; m is 1 to 3; n is 0 to 2;
R1 is H, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl; and each R4 and each R5 is independently H, C1-C4 alkyl, CrC4 haloalkyl, halogen, CN, NO2, C1-C4 alkoxy, C C haloalkoxy, C1-C4 alkylthio, -C4 alkylsulfmyl, Cj- C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, Cj-C haloalkylsulfonyl or C2-C4 alkoxycarbonyl. Selection 5. Of note are selected compounds of Selection 4 wherein
R2 is H; R3 is Cι-C 5 alkyl optionally substituted with C1-C4 alkoxy or C1-C4 alkylthio; each R4 and each R5 is independently H, C1-C4 alkyl, -C4 haloalkyl, halogen, CN,
NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfmyl, C
C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, Cj-C^ haloalkylsulfonyl or C2-C4 alkoxycarbonyl; and at least one ofthe R5 substituents is ortho to the amide linkage.
As noted above, each J is independently a phenyl ring, a naphthyl ring system, a 5- or
6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 5 R5. The term "optionally substituted" in connection with these J groups refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the arthropodicidal activity possessed by the unsubstituted analog. An example of phenyl optionally substituted with 1 to 5 R5 is the ring illustrated as U-l in Exhibit 1, wherein Rv is
R5 and r is an integer from 1 to 5. An example of a naphthyl group optionally substituted with 1 to 5 R5 is illustrated as U-85 in Exhibit 1, wherein Rv is R5 and r is an integer from 1 to 5. Examples of 5- or 6-membered heteroaromatic rings optionally substituted with 1 to 5
R5 include the rings U-2 through U-53 illustrated in Exhibit 1 wherein Rv is R5 and r is an integer from 1 to 5. Note that J-l through J-4 below also denote 5- or 6-membered heteroaromatic rings. Note that U-2 through U-20 are examples of J-l, U-21 through U-35 and U-40 are examples of J-2, U-41 through U-48 are examples of J-3 and U-49 through U- 53 are examples of J-4. Examples of aromatic 8-, 9- or 10-membered fused heterobicyclic ring systems optionally substituted with 1 to 4 R3 include U-54 through U-84 illustrated in
Exhibit 1 wherein Rv is R5 and r is an integer from 1 to 5.
Although Rv groups are shown in the structures U-l through U-85, it is noted that they do not need to be present since they are optional substituents. Note that when Rv is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or Rv. Note that some U groups can only be substituted with less than 5 Rv groups (e.g. U-14, U-l 5, U-l 8 through U-
21 and U-32 throughU-34 can only be substituted with one Rv). Note that when the attachment point between (Rv)r and the U group is illustrated as floating, (Rv)r can be attached to any available carbon atom of the U group. Note that when the attachment point on the U group is illustrated as floating, the U group can be attached to the remainder of
Formula I through any available carbon of the U group by replacement of a hydrogen atom.
Exhibit 1
U-5 U-6 U-7
U-8 U-9 U-10
U-ll U-12 U-13
U-16 U-17
U-27 U-28
U-30 U-31
U-29
U-32 U-33 U-34 U-35
U-44 U-45 U-46 U-47 U-48
U-54 U-55
U-56 U-57 U-58
U-59 U-60 U-61
U-65 U-66
U-67 U-68 U-69
U-70 U-71 U-72
U-73 U-74 U-75
U-76 U-77 U-78
U-79 U-80 U-81 U-82
U-83 U-84
U-85
The compounds of Formula I and Formula II can be prepared by one or more of the following methods and variations as described in Schemes 1-21. The definitions of R\ R-, R?_ R4^ A., B, m and n in the compounds described in the Schemes below are as defined above in the Summary of the Invention or their subsets.
Compounds of Formula I can be prepared by procedures outlined in Schemes 1-9. Compounds of Formulae la-h are various subsets of the compounds of Foπnula I. Typical procedures are described in Scheme 1 and involve either coupling of a isonaphthalimide of Formula 2 with an amine of Formula 3 or coupling of a compound of Formula 4 with an amine of Formula 5 with or without the presence of a base. Typical bases include amine bases such as triethylamine, diisopropylethylamine and pyridine. In certain instances it is useful to use polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine. The amines of Formula 3 and Formula 5 are either commercially available, well represented in the chemical literature, or readily available from established literature procedures. Amides of Formula la can be converted to thioamides of Formula lb using a variety of standard thio transfer reagents including phosphorus pentasulfide and Lawesson's reagent.
Scheme 1
la (A and B are O) lb (A and B are independently 0 or S)
le (A and B are O)
Id (A and B are independently 0 or S)
Compounds of Formula 2 and Formula 4 are typically prepared by coupling of a 1 ,8-naphthaloyl chloride of the Formula 6 with an amine of Formula 7 or an amine of Formula 8 respectively (Scheme 2). Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine. In certain instances it is useful to use polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine. In some instances, the amine of Formula 7 can serve as the acid scavenger when used in excess. The compounds of 1 ,8-naphthaloyl chloride of the Formula 6 are well represented in the chemical literature and are typically prepared from the corresponding 1,8-naphthalic acids or the anhydrides with the use of chlorinating reagents commonly used for the transformation of carboxylic acid to carboxylic acid chloride. These commonly used chlorinating reagents include phosphorous oxychloride and phosphorous pentachloride.
An alternate procedure for the preparation of compounds of Formula 2 and Formula 4 involves the cyclization of compounds of 8-aminocarbonyl-l-naphthalenecarboxylic acid of Formula 9 and Formula 10 respectively (Scheme 3) with the use of a dehydration reagent in an inert solvent at a temperature in the range of —30 to 30 °C, with or without the presence of an acid scavenger. Typical dehydration reagents include dicyclohexylcarbodiimide and trifluoroacetic anhydride. Polymer supported reagents such as polymer-bound cyclohexylcarbodiimide are useful. Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine. In certain instances it is useful to use polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine. Typical inert solvents include aprotic solvents such as dichloromethane and 1-chlorobutane. A typical range of reaction temperature is from —5 to 25 °C. Scheme 3
10
The preparation of 8-aminocarbonyl-l-naphthalenecarboxylic acids of Formula 9 and Formula 10 involves the coupling of 1,8-naphthalic anhydrides of Formula 11 with amines of Formula 7 or amines of Formula 8 respectively (Scheme 4) in an inert solvent at a temperature in the range of 0 to 30 °C. A typical inert solvent is dimethylformamide. The reaction is commonly conducted in the temperature range of 5 to 10 °C.
Alternate procedures for the preparation of compounds of 8-aminocarbonyl-l- naphthalenecarboxylic acid of Formula 9 and Formula 10 involve the hydrolysis of compounds of 1 ,8-naphthalimide of Formula 12 and Formula 13 respectively (Scheme 5) using a hydroxide such as sodium hydroxide or potassium hydroxide in a protic solvent system such as water-methanol or water-dioxane at elevated temperature. The reaction is usually conducted at the reflux temperature of the reaction mixture. The compounds of 1 ,8-naphthalimide of Formula 12 and Formula 13 are typically prepared by condensing a 1 ,8-naphthalic anhydride of Formula 1 1 with an amine of Formula 7 or Formula 8 respectively at an elevated temperature, usually in the presence of an acid. A typical reaction involves refluxing the 1,8-naphthalic anhydride of Formula 1 1 and the amine of Formula 7 or Formula 8 in acetic acid.
Scheme 5
An alternate procedure for the preparation of compounds of Formula I involves the coupling of 8-aminocarbonyl-l-naphthoyl chlorides of Formula 14 and Formula 15 with an amine of Formula 3 or an amine of Formula 5 respectively (Scheme 6), in the presence of an acid scavenger. Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine. In certain instances it is useful to use polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer- bound dimethylaminopyridine. Typically, the reaction temperature range is 0 to 25 °C.
8-Aminocarbonyl-l-naphthoyl chlorides of Formula 14 and Formula 15 are available from coupling the corresponding 1,8-naphthaloyl dichloride of Formula 6 with an amine of Formula 5 or Formula 3 respectively in the presence of an acid scavenger (Scheme 7). Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine. In certain instances it is useful to use polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine. Scheme 6
le (A and B are O)
14 (R2 and R3 are not H)
If (A and B are independently 0 or S) (R2 and R3 are not H)
S)
Scheme 7
15
Another procedure for the preparation of compounds of Formula I involves the stepwise carbamoylation or thiocarbamoylation of a naphthalene of Formula 20 (Schemes and 9). Upon treatment with a Lewis acid under Friedel-Crafts reaction conditions, compounds of 1 -naphthalenecarboxamide or 1 -naphthalenethiocarboxamide of Formula 16 or Formula 17 couple with a carbamoyl chloride or thiocarbamoyl chloride of Formula 18 or Formula 19 to provide a compound of Formula I (Scheme 8). Commonly used Lewis acids include aluminum chloride and stannic chloride.
The preparation of compounds of 1-naphthalenecarboxamides or 1-naphthalenethiocarboxamides of Formula 16 or Formula 17 (Scheme 9) involves the coupling of a naphthalene of Formula 20 and a carbamoyl chloride or thiocarbamoyl chloride of Formula 19 or Formula 18 respectively in the presence of a Lewis acid such as aluminum chloride and stannic chloride under Friedel-Crafts reaction conditions. The naphthalenes of Formula 20, the carbamoyl chlorides and the thiocarbamoyl chlorides of Formula 18 and Formula 19 are commercially available, well described in the chemical literature, or can be prepared following established literature procedures.
Scheme 9
20
The compounds of Formula II can be prepared by one or more of the following methods and variations as described in Schemes 10-13. Compounds of Formulae Ila-b are subsets o the compounds of Formula II. A typical procedure is described in Scheme 10 and involves coupling of an 8-amino- naphthalene-1-carboxamide of Formula 21 with a carbonyl chloride of Formula 22 in the presence of an acid scavenger to provide the compounds of Formula Ila, or with thiocarbonyl chloride of Formula 22 in the presence of an areneselenolate to provide the compounds of Formula lib. Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine, other scavengers include hydroxides such as sodium and potassium hydroxide and carbonates such as sodium carbonate and potassium carbonate. In certain instances it is useful to use polymer supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound dimethylaminopyridine. Typical areneselenolates include sodium phenylselenolate. The carbonyl chlorides and the thiocarbonyl chlorides of Formula 22 are commercially available, well represented in the chemical literature, or readily prepared according to established literature procedures. Amides of Formula Ila can be converted to thioamides of Formula lib using standard thio transfer reagents such as phosphorus pentasulfide and Lawesson's reagent.
Scheme 10
Another procedure for the preparation of compounds of Formula Ila involves coupling of an l-amino-naphthalene-8-carboxamide or l-amino-naphthalene-8-thiocarboxamide of Formula 21 with a carboxylic acid of Formula 23 in the presence of a dehydration reagent such as dicyclohexylcarbodiimide (DCC). Polymer supported reagents such as polymer- bound cyclohexylcarbodiimide are useful. Benzoic acids of Formula 23 are commercially available, well represented in the chemical literature, or readily prepared according to established literature procedures. The procedures of Scheme 10 and Scheme 1 1 are only representative examples of useful methods for the preparation of Formula II compounds as the literature is extensive for the preparation of carboxamides. Scheme 1
21
8-Amino-naphthalene-l-carboxamides and 8-amino-naphthalene-l-thiocarboxamides of Formula 21a are typically available from the corresponding 8-nitro-naphthalene-l- carboxamides and 8-nitro-naphthalene-l-thiocarboxamides of Formula 24 respectively via reduction ofthe nitro group. Typical procedures involve reduction with hydrogen in the presence of a metal catalyst such as palladium on carbon or platinum oxide and in hydroxylic solvents such as ethanol and isopropanol. These procedures are well documented in the chemical literature. R1 substituents such as alkyl, substituted alkyl and the like can generally be introduced at this stage through known procedures including either direct alkylation or through the generally preferred method of reductive alkylation ofthe amine. A commonly employed procedure is to combine the aminonaphthalene 21a with an aldehyde in the presence of a reducing agent such as sodium cyanoborohydride to produce the compounds of Formula 21 where R1 is other than H.
Scheme 12
21 (R1 is other than H)
The intermediate amides of Formula 24 are readily prepared from 8-nitro-naphthalene- -carboxylic acids that are commercially available, known in the literature, or can be prepared by established literature procedures for the derivatization of naphthalenes or aromatic groups in general. Typical methods for amide formation can be applied here. These include direct dehydrative coupling of acids of Formula 25 with amines of Formula 5 using for example DCC, and conversion of the acids to an activated form such as the acid chlorides or anhydrides and subsequent coupling with amines to form amides of formula 24a. Also, diethyl cyanophosphonate is a useful reagent for this type of reaction involving activation of the acid. The chemical literature is extensive on this type of reaction. Amides of Formula 24a are readily converted to thioamides of Formula 24b by using commercially available thio transfer reagents such as phosphorus pentasulfide and Lawesson's reagent.
Benzoic acids of Formula 23a, (compounds of Formula 23 wherein J is an optionally substituted phenyl ring) are well known in the art. Preparation of certain heterocyclic acids of Formula 4 are described in Schemes 14-21 . A variety of heterocyclic acids and general methods for their synthesis may be found in World Patent Application WO 98/57397.
The synthesis of representative pyridine acids (23b) is depicted in Scheme 14. This procedure involves the known synthesis of pyridines from β-ketoesters and
4-aminobutenones (29). Substituent groups R5(c) and R5(d) include e.g. alkyl and haloalkyl.
Scheme 14
The synthesis of representative pyrimidine acids (23c) is depicted in Scheme 15. This procedure involves the known synthesis of pyrimidines from vinylidene-β-ketoesters (33) and amidines (34). Substituent groups R5(c) and R5(d) include e.g. alkyl and haloalkyl.
Scheme 15
heat
35 23c
Syntheses of representative pyrazole acids (23d) are depicted in Schemes 16-21. The synthesis of 23d in Scheme 16 involves as the key step introduction of the R5(c) substituent via arylation or alkylation ofthe pyrazole. The arylating or alkylating agent R5(c)-Lg (wherein Lg is a leaving group such as Cl, Br, I, sulfonates such as p-toluenesulfonate or methanesulfonate or sulfates such as -SO2OR5(c)) includes R5(c) groups such as C Cg alkyl, C2-C(3 alkenyl, C2-C6 alkynyl, C2-C6 alkylcarbonyl, C2-Cg alkoxycarbonyl, C3~Cg dialkylaminocarbonyl, C3-C6 trialkylsilyl; or phenyl, benzyl, benzoyl, 5- or 6-membered heteroaromatic ring each ring or ring system optionally substituted. Oxidation of the methyl group affords the pyrazole carboxylic acid. Some of the more preferred R5(d) groups include haloalkyl.
Scheme 16
Lg is a leaving group
Synthesis of pyrazoles of Fomiula 23d are described in Scheme 17. These acids may be prepared via metallation of compounds of Formula 40 with lithium diisopropylamide (LDA) followed by quenching of the lithium salt with carbon dioxide affords metallation using lithium diisoprylamide (LDA) and carboxylation of compounds of Formula 40 as the key step. The R5(c) group is introduced in a manner similar to that of Scheme 16, i.e. via alkylation or arylation with a compound of Formula 37. Representative R5(d) groups include e.g. cyano, haloalkyl and halogen.
Scheme 17
39
Lg is a leaving group 40 23d
This procedure is particularly useful for preparing 1 -(2-pyridinyl)pyrazolecarboxylic acids of Formula 23e as shown in Scheme 18. Reaction of a pyrazole of Formula 39 with a 2,3-dihalopyridine of Formula 37a affords good yields ofthe 1-pyridylpyrazole of Formula 40a with good specificity for the desired regiochemistry. Metallation and carboxylation of compounds of Formula 40a as described above affords the l-(2-pyridinyl)pyrazolecarboxylic acid of Formula 23e.
Scheme 18
The synthesis of pyrazoles of Formula 4c is described in Scheme 19. They can be prepared via reaction of an optionally substituted phenyl hydrazine of Formula 41 with a ketopyruvate of Formula 42 to yield pyrazole esters of Formula 43. Hydrolysis of the esters affords the pyrazole acids of Formula 23d. This procedure is particularly useful for the preparation of compounds in which R5(c) is optionally substituted phenyl and R5(d) is haloalkyl. Scheme 19
An alternate synthesis of pyrazole acids of Formula 23d is described in Scheme 20. They can be prepared via 3+2 cycloaddition of an appropriately substituted nitrilimine with either substituted propiolates of Formula 45 or acrylates of Formula 47. Cycloaddition with an acrylate requires additional oxidation of the intermediate pyrazoline to the pyrazole. Hydrolysis of the esters affords the pyrazole acids of Formula 23d. Preferred iminohalides for this reaction include the trifluoromethyl iminochloride of Formula 48 and the iminodibromide of Formula 49. Compounds such as 48 are known (J Heterocycl. Chem. 1985, 22(2), 565-8). Compounds such as 49 are available by known methods (Tetrahedron Letters 1999, 40, 2605). These procedures are particularly useful for the preparation of compounds where R5(c) is optionally substituted phenyl and R5(d) is haloalkyl or bromo.
Scheme 20
49
48 The starting pyrazoles of Foπriula 39 are known compounds. The pyrazole of Foπriula 39a (the compound of Formula 39 wherein R5(d) is CF3) is commercially available. The pyrazoles of Formula 39c (compounds of Foπnula 39 wherein R5(d) is Cl or Br) can be prepared by literature procedures (Chem. Ber. 1966, .9.9(10), 3350-7). A useful alternative method for the preparation of compound 39c is depicted in Scheme 21. Metallation ofthe sulfamoyl pyrazole of Formula 50 with /z-butyllithium followed by direct halogenation of the anion with either hexachloroethane (for R5(d) being Cl) or 1,2-dibromotetrachloroethane (for R5(d) being Br) affords the halogenated derivatives of Formula 51. Removal ofthe sulfamoyl group with trifluoroacetic acid (TFA) at room temperature proceeds cleanly and in good yield to afford the pyrazoles of Formula 39c. One skilled in the art will recognize that Formula 39c is a tautomer of Formula 39b.
Scheme 21
39b 39c
(R5(d) is α < 3r Br)
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I and Formula II may not be compatible with certain functional groups present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I and II. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I and II. One skilled in the art will also recognize that compounds of Formula I and II and the inteπriediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. JH NMR spectra are reported in ppm downfield from tetramethylsilane: s is singlet, d is doublet, t is triplet, q is quartet, m is multiplet, dd is doublet of doublets, dt is doublet of triplets, br s is broad singlet, m. p. is melting point.
EXAMPLE 1
Preparation of N-methyl -N'-f2-bromo-4-fluoropheny)-l,8-naphthalene-dicarboxamide Step A: Preparation of 8-[(methylamino)carbonyl1-l-naphthalenecarboxylic acid
To a stirred solution of 1,8-naphthalic anhydride (5 g, 25.3 mmole) in NN-dimethylformamide (50 mL) at room temperature, methylamine (0.82 g, 26.5 mmole) in NN-dimethylformamide (5 mL) was added. The reaction mixture was stirred for 2.5 hours. The solvent was removed under reduced pressure. The crude solid thus obtained was washed with a small amount of diethyl ether and air dried to give the product (5 g), containing 8-[(methylamino)carbonyl]-l-naphthalenecarboxylic acid and 1,8-naphthalic anhydride in a ratio of ~7 to 1 determined by ΝMR analysis. This material was used for the subsequent reaction without further purification. ltt ΝMR (DMSO-d6) δ: 2.77 (doublet, 3H), 7.55-7.65 (multiplet,3H), 7.83 (doubleflH), 8.03-8.12 (multiplet,2H), 8.39 (quarteflH). Step B: Preparation of N-methyl -N-(2-bromo-4-fluorophenv)-1.8-naphthalene- dicarboxamide
To a stirred solution of 8-[(methylamino)carbonyl]-l-naphthalenecarboxylic acid (22.3 g, 97.4 mmole) prepared as described in Step A and pyridine (15.4 g, 0.195 mole) in dichloromethane (300 mL) cooled to ~5 °C under nitrogen atmosphere, trifluroacetic anhydride ( 22.5 g, 0.107 mole) diluted in dichloromethane (50 mL) was added in a dropwise manner. After the addition, the reaction mixture was further stirred at ambient temperature for one half of an hour. A small amount of solid was filtered off. The filtrate was concentrated under reduced pressure to a solid that was extracted with hot hexane (3 x 250 ml). The hexane extracts were combined and concentrated under reduced pressure to give a crude product of 3-(methylimino)-l H,3H-naphtho[l ,8-cd]pyran-l -one ( 15 g). The 3-(methylimino)- l H,3H-naphtho[l ,8-cd]pyran-l-one (0.25 g, 1.19 mmole) thus obtained was dissolved in dichloromethane (3 ml) and 2-bromo-4-fluoroaniline (0.17 g, 1.45 mmole) was added. The reaction mixture was stirred at room temperature for 48 hours. The solid was filtered, collected and washed with a small amount of methanol in dichloromethane and air dried to give N-methyl N'-(2-methyl-4-fluoropheny)- 1,8- naphthalene-dicarboxamide (0.12 g, m. p. 249 °C).
*H ΝMR (DMSO-d6) δ: 2.37 (singlet, 3H), 2.72 (doublet, 3H), 7.05-7.12 (multiplet, 2H), 7.54-7.64 (multiplet, 3H), 7.75-7.83 (multiplet, 2H), 8.05-8.10 (multiplet, 2H), 8.33 (quartet, I H), 9.84 (singlet, I H).
EXAMPLE 2
Preparation of N-methyl 8-r(3,4-difluorophenyl)carbonylamino]-l -naphthalenecarboxamide Step A: Preparation of N-methyl 8-nitro-l -naphthalenecarboxamide To a stirred solution of 8-nitro-l -naphthalenecarboxylic acid (1.5 g, 6.9 mmole), methylamine (0.22 g, 7.3 mmole), and imidazole (0.68 g, 8.3 mmole) in NN-dimethylformamide (12 mL) at room temperature, diethyl cyanophosphonate (1.24 g, 7.6 mmole) was added. The reaction mixture was stirred overnight, poured into water (100 mL) and extracted with ethyl acetate (3 x 100 mL). The ethyl acetate extracts were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give a solid which was washed with a small amount of methanol to give the product (0.64 g) which was used without further purification.
'H ΝMR (DMSO-d6) δ: 2.76 (doublet, 3H), 7.72-8.37 (multiplet, 6H), 8.66 (broad quartet, IH). Step B: Preparation of Ν-methyl 8-amino-l -naphthalenecarboxamide
N-methyl 8-nitro-l-naphthalenecarboxamide (0.5 g, 2.17 mmole) in methanol (5 mL) and dichlomethane (15 mL) was hydrogenated with a catalytic amount of palladium (10% on charcoal) under 30 psi hydrogen pressure for 1 hour. The reaction mixture was suction filtered through celite and concentrated under reduced pressure to provide the product (0.42 g) which was used without further purification.
'H ΝMR (DMSO-d6) δ: 2.82 (doublet, 3H), 5.46 (singlet, 2H), 6.81-7.85 (multiplet, 6H), 8.59 (broad quartet, IH).
Step C: Preparation of N-methyl 8-(T3,4-difluorophenyl)carbonylamino"|-l- naphthalenecarboxamide To a stirred solution of N-methyl 8-amino-l -naphthalenecarboxamide (0.2 g,
1 mmole) and pyridine (0.24 g, 3 mmole) in dichloromethane (10 mL), actyl chloride (94.2 mg, 1.2 mmole) in dichloromethane (2 mL) was added in portions. The mixture was stirred for 3 hours. The solid was collected with suction filtration (110 mg, m. p. >250 °C). !H ΝMR (DMSO-dό) δ: 2.43 (doublet, 3H), 7.46-8.10 (multiplet, 9H), 8.51 (broad quartet, 1 H), 10.13 (singlet, 1 H). EXAMPLE 3
Preparation of N-methyl 8-r(2-thienyl)carbonylaminol-l -naphthalenecarboxamide To a stirred solution of N-methyl 8-amino-l -naphthalenecarboxamide (0.2 g, 1 mmole) and pyridine (0.24 g, 3 mmole) in dichloromethane (10 mL), 2-thiophenecarboxylic acid chloride (176 mg, 1.2 mmole) in dichloromethane (2 mL) was added in portions. The mixture was stirred for 3 hours. The reaction mixture was washed sequentially with dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, and water. The solvent was partially removed under reduced pressure. The solid thus formed was collected with suction filtration (36 mg, m. p. 210 °C). H ΝMR (DMSO-d6) δ: 2.53 (doublet, 3H), 7.26-8.10 (multiplet, 9H), 8.66 (broad quartet, IH), 10.07 (singlet, IH).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 10 can be prepared. The following abbreviations are used in the Tables: t is tertiary, s is secondary, n is normal, / is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, t-Bu is tert butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is ethylthio, CN is cyano, NO2 is nitro, TMS is trimethylsilyl, S(O)Me is methylsulfinyl, and S(O) Me is methylsulfonyl.
Table 1
2 2 2 2 2 cn 2 2 2 2 2 2 2 2 2 2 2 2 2 m
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X L
2 2 2 2 2 2 2 π> 2 α> 2 π> 2 2 2 r
V 3
K K s ac ϊ i E a g 2 - oτι o
^ - 3 -5 I??
X ip
2 2 cn 2 2 2 2 2 2 2 2 2 2 2 2 m 2
<τ -r PP.
]TJ
X -p-
O O 2 2 ro 2 <D 2 <τ> 2 π> 2 ΓD 2 ΓD τι θ , 1 —J - -Ωy ? _ t "π- 2 π> 2 π> 2 π> 2 π> r2s n2 ta
tfl 2 2 2 o 2 re 2 2 2 2 2 2 2
2 2 2 X 3- K X X X -∑; x x x x x x P°
1 --
O O o o ro ro o o o O o ro o O O O O O O o
Tl T
Tl X o ω o π Tl n O
Ti Tl π Tl π O O O O
Tl Tl l o π o O O ro n 5θ
Tl X o r
T to to
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
x x x X X X X X X X X X X X X X X X X X X X X X X X X KB
n o o o o o X X X X X X X X X X X X X X X X X X X X X X X X F I cr
o O > O O r « o o ro O CD O O O O O O
Tl Tl τι T <~l> o
X Q ro O O
T π T] J Tl o O O
T] Tl o O J τι π
X o ro
Tl Tl Tl w π Q ro o 1^
~ OJ ^ ~ I cr to
2 rD 2r 2o 2rD m^ 2rc 2rD 2D 2r 2rD 2r 2r 2rD 2O 2rD 2rD 2o 2rD r2D 2rD 2rD 2rD 2rD 2 2rD 2 m 2 ? 2 2 2 rπ 2 2 2 l^
2 2 2 2π) 2-. 2i) 2ri) 2o 2rc 2ri) 2(T) 2r 2D 2Q 2rD 2α) 2rt 2 2rt) 2rD 2ri) 2-. 2 2rD 2r!3 2rD 2τj 2π) 2 2ri) 2n) 2τ) 2rιι 2rβ 2π) 2ϋ 2t) ] ftc-
X X X X X X X X X X X X X X X X X X X X X X X X X X X 4-. cr
o O
X X τ 2 2 Q TJ ? m 2 2 2 2 m 73 On
2 2 2 2 2 2 2 2 m 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 m 2 ? 2 n 2a n2 m |?,
n o o o o o n o o o n o o o π o o o o o o o o o o n o o o o o o o o o n o 50
^ ώ ^ S K -t S ^ K I -ϊ C o Tl o TJ 2 2 2 2 2 2 2 ro 2 2 Q TJ m 2 2 0 ro 2 2 5
- ' -
2 2 2 2 2 2 2 2 2 2 2 2 2 2 ?
o r o ro o 0 O 0 o ro o o r Cl 170
0 ro o 0 0
X 0 0 0 0 0 0 0 0 0 τι τι o o o o Tl 12 ° 00 TJ o o Tj o Tl o or O
Tl X TJ Tl o to
2 2 2 o 2 ro 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 ro 2 -D 2 2 O5J
Q Q. Q Q 1 X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 7°
.---. ----. ----. ----. ----. o o o o o 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 •fc. cr
OJ OJ OJ CO CD CD D TI O O O O to to t to
TJ TJ to to to to I I
TJ TJ to to to TJ j j to to to to ON 1 : I 1 TJ ro cr TJ O O O O 3" T TJ O- al 3 TS TJ J τj T) Tl Tl Tl Tl O ^ ^ a. a- to to to TJ Z ό 2 2 3 PS, 5^ Q|
^ ^ ^ ^ o J TJ TJ TJ TJ
TJ J J J cr TJ TJ J T cr cr cr cr cr cr cr cr i-,;- ^
^< u- <---. α al cr cr :
O O O O
CD o Q 0 ro o O O 0 0 0
Tl J o ro o _ TJ L
~ OJ — -> X O CD O O 0 0 0 0 0 0 o! τι 2? Q τι | on
TJ ^ cr to
m £ 2 2 2 2 2 2 2 2 2 2 2 S 2 m 2 2 2 m
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o 73
13
S I --C S K II S K 3, -- l--; -l. l-C -I. !--! I cr
X o o 2 2 2 ΓD 2 ΓD 2 ΓD 2 2 m 2 2 2 2 m m pi i Ji
2 2 2 2 ΓP 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2 ΓD 2ΓD 2ΓD 2CD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2 2 73 I J O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O ?3
03 CD CD CD O O to
TJ to to to to to to
TJ to to to CΛ to l τι O cr "T1 to to ^ o
X X X "T* Tl
TJ TJ TJ TJ . OJ TJ TJ TJ TJ T Tl Tl ro O O O o (73
^ O to to to TJ z
^ ^ v; TJ J J l TJ J J TJ TJ TJ cr J J cr cr tr cr t-L α- 5.' a- cr pr r cr cr cr
" ^< D. a. ^< α.
Q w - J Q! O QJ I cy,
Table 2
R-- R4a R4b R5a R5b El g4a E^ R5a R5b
Me H Me H CF3 Me H H H CF3
Me H Me H OCF3 Me H H H OCF3
Et H Me H OCF3 Et H H H OCF3
Me H Me Me Br Me H H Me Br
Me H Me Et Br Me H H Et Br
Me H Me Me Cl Me H H Me Cl
Me H Me Et Cl Me H H Et Cl
Me H Me Me I Me H H Me I
Me H Me Me CF3 Me H H Me CF3
Me H Me Me OCF3 Me H H Me OCF3
Et H Me Me CF3 Et H H Me CF3
Me H Me Me SCF3 Me H H Me SCF3
Me H Me Me SCHF2 Me H H Me SCHF2
Me H Me Me OCHF2 Me H H Me OCHF2 n-Pr H Me Me CF3 n-Pr H H Me CF3
Me H Me Me C2F5 Me H H Me C2F5
Et H Me Me C2FS Et H H Me C2F5
Me H Me Et CF3 Me H H Et CF3
Me H Me n-Pr CF3 Me H H n-Pr CF3
Me H Me i-Pr CF3 Me H H i-Pr CF3
Me H Me Cl CF3 Me H H Cl CF3
Me H Me F CF3 Me H H F CF3
Me H Me Me SMe Me H H Me SMe
Me H Me Me OMe Me H H Me OMe
Me H Me Me OEt Me H H Me OEt
Me H Me Me n-C3F Me H H Me n-C3F7
Me H Me Me i-C3F7 Me H H Me Ϊ-C3F7
Me I-I Me Me Et Me 1-1 I-I Me Et 2 2 2 2 2 2 2 2 2 2 n 2 2 2 2 2 m 2 2 2 2 I?, 3
i — i _-u 3- -H -C X-, hU i-E ϊ h-C nn !-u 3- 3π hC --C 3→ 3C 3
X X X X *• I cr
o O O O O
n cn n 2 ΓD 2 ΓD Γ 2D 2 ΓD 2 ΓD 2 ΓD 2 73 ΓD I OJ
2 2 2 2 2 2 2 2 2 X X X X X X Pt
X EC EE X EC EC EC X EC EC EC EC EC X 2 rt> 2 ΓD 2 ΓD 2 ro 2 2 2 73 r
OJ OJ OJ OJ l-J OJ OJ OJ OJ OJ ro ro ro ro TJ o O O O O
3
U TJ 2 2 2 2 m cn tO t tO tO ^ 2 ^ Q tO f-j tO tO tO tO l-J
X X 3 TJ TJ CL n CL • • TJ TJ TJ TJ TJ 1 3 "* *≤- < *≤- to "3 ^ ^ ^ S;I * α:- * 5 A ----- ' ■≥. o; < ■ ; o-;
£2 o o o o o ' ' to ° to o o ° o ∞ O O o o O O o o
Tl TJ ι TJ TJ o c
TJ o o o co ro o o O Tl O CD O O CO
Tl J j Tl τι Tl Tl τι TJ Tl T O
OJ o 73
■n J on to to OJ OJ OJ TJ I cr t
2 2 2 2 2 2 2 2 2 2 m 2 ΓD ?J 2Γ 2ΓD 2ΓD m,→' 2ΓD 2ΓD 2 ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2 ΓD 2 ΓD 2 ΓD 2 ro 2 ΓD 2 ΓD 2 ΓD 73
X X X X EC X X ]
X X X X 3. 1 o O O O O O O O O O O O O O O O O O O O O O O 173
X EC EC X EC X X X X X X 1 cr
2 ΓD 2O 2ΓD 2ΓD 2T> τι ' — '
2 2 2 2 2 2 2 2 2 2 m 2 2 2 2 2 2 2 170 I OJ
2 ro 2o 2π> 2rιι 2α 2rD 2rp 2rD 2rD 2ro 2ro 2rD 2ro 2rD 2rD 2ro 2rD 2ro 2rD 2ro 2-τ- 2o 2π- 2ro 2ro 2ro 2rD 2ro 2rD 2rD 2θ 2o 2ro 2ro 2ro 2ro 2rτ- K| &i
X X X X X EC 3- 3. X EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EE EC EC EC EC EC EC 11
>>> '>> to to to t to to . -
Q 2 ro o "< ^ TJ TJ TJ o o
-α *τ-l TJ TJ TJ TJ TJ Tj _ rL 2 Tl o Tl 2 ro 2 2 73 on
2 2 2 ΓD 2 ΓD 2 Γ 2 2 n D ΓD ro 2 ro 2 ro 2 ro 2 2 2 73
3
X X X X X X EC X EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC EC
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O 73 I cr
Ml 2 2 2 cn 2 2 2 2 2 2 2 2 IT?,
o o o o o o o o o o o o o o o o o o 2 2
[73
X X JΛ
CD CO CD CO O τι O
V TJ O O to to to to to to t
2 2 2 2 cπ cn V T
T; ^ . 2 Q f 2 n J τ
Q T>' Jo cπ l o n
"3 "≤. f to ^ al O- 5-. CL a CLl 5. 5." 5 1 i 5." cr cr
o ro o o o o O o O O O O 73
Tl Tl O o O τι
■ ■ -^ -^ <2 K? -3 »-- o r τι o ro o J1 ^ 5 - Q X τι I cr t
4
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
o o o o o o o o o o o o o o o o o o o o o x x x X X 7 -fc-
X X X X X X X X X X X X X X X X X X X X Q O O o o o o o o o o o 3 1 cr
C •-O. CO 03 CO O Q o O
2 CD o O O O TJ •ή" cr E-r cr 2 ^ O to to to 2 | a. o? TJ TJ cr cr — cr cr cr cr " > "3 ^ ^ ^ " Λ: ^ a. O
CL a. α." al CL cr
* 05
o o
n 73 2 2 2 2 ro 2 2 2 2 2 2 2 2 2 2 2 1?,
x x x 73 O O O O O O O O O O O O O O O O O
D -^ --. o ro ro O O n )τj to o O n o O O O O 173 C-r, Tl O ro Tl o O
Tl Tl T o O J O C Tl TJ TI O ~ — -, j j yj ^ J Tl '-n
OJ OJ ' on Tl OJ OJ OJ OJ J TX O ] Tl OJ OJ OJ OJ OJ J 1 cr to
2 ro 2 2 2 2 2 2 2 2 2 2 2 cπ 2 2 cπ 73
X X X X X X X X X X X X X X X X X Pi
2 ro 2 2 2 2 2 2 2 2 2 2
<τ> cr
X X X X x x x S o TJ o Tl s 5--. ? ? τι θ ? tτi 2 2 2 2 2 2 2 173
S S ^ X ^ S I E ^ S PC S K ffi W K ffi ffi ffi ffi E PC
73
X X X X X X X X X X X X X X X -t-
- cr
O
X X X X X X X X X X X o Ci 2 -n 2 2 2 2 2 τι θ ÷J ? m
OJ OJ E-- T i -J 2 -D 2ro 2 2o 2r 2 2 2 Pi r o l Ea
cπ 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 pi
2 2 x x x x x x x x x X X X X 73
x x x x 2 2 2 2 2 2 2 2 2 2 2 2 7
ΓD 2ΓD 2ΓD 2ΓD 2 2 2 2 2 2 2 2 2 2 2 2 2 2 I -c£r-
F o3n
GO
CD o o o o O o O O o O O O O O O O τι Tl T T| Tl T| T| Tl T J O CD 0 8 O °l o J - OJ OJ X o ro o o TJ τι τi τι T) O CO o O O o 70
TJ o TJ Tl OJ OJ OJ OJ OJ OJ OJ OJ OJ X J TI O u τι ω o to OJ Tl to
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
O O O X X X EC X X X X X X cr
CD CD CD CO -ι * to to to
TJ TJ o o o o o to to to to I I to to to to O m J TJ Tl
TJ TJ TJ TJ TJ ό ό ό ό ^ ^ TJ TJ TJ — 73 J TJ TJ Tl T1 TJ Tl O CO os *< o n
^ o O to to to TJ TJ TJ TJ TJ Q^ g TJ TJ J TJ cr J TJ J cr cr cr cr -<- ^-ς-
LL CL α. α. al al α. al a- α cr - cr cr cr cr cr cr o OS ; os os
O GO
_ o o ro o ro O O O O O ro O O O O
TJ TJ TJ Tl o o T| J τι O O
T] T| Tl Tl T o
Tl Tl O CO I
OJ OJ OJ OJ X o π
OJ OJ OJ OJ OJ X ° T r- ° τ ro o 3
OJ τ J _ OJ OJ OJ Tl Tl OJ J I cr to to
2 2 2 2 2 2 2 2 2 2 2 2 2 2 1
70
X X
I cr
o
X X X o TJ 2 2 2 2 2 2 o Ό ^ w 2 2 2 2 2 2 cπ m 3
O
4
2 2 2 2 2 2 m 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 m 2 ? 2 2 2 πι 2 2 73 OJ
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 3
4=-
I w o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o 70 cr
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 73
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 [73 ^
1 o
cn o
O τ-| α o o O o O O O 3 τ CD o o O O O
X X CD o O O O
Tl -π Tl or o o o Tl o ro o 7 J O
X
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 73
O x 73
X X X X X X X
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
I cr
GO o J o to o o o ro 8 ° o O
TJ τι o
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o TO
4--
X X X X X X X 70 I cr
f I o
2π> 2ro 2ro I 2T) 2 ΓD 2ro 2ro 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
X X
%
2 2 2 cn ro ro cD cTπ rD ro ro rD ro ro ro cπ 2 I I? OJ.
170
X X X X X X X X X X X X X X X X X X X X X X X -p-.
2 2 2 2
2 2 2 2 2 cπ 2 2 2 2 2 2 2 2 2 2 cn 2 cπ 2 χ χ χ 73
2 2 2 2 2 2 2 2 m 2 2 2 2 2 2 2 2 2 2 cπ 2 cπ 2 173
2 2 2 ro 2 o 2 2 2 2 2 2 2 2 2 2 2 2 73
- --. |70
X X X X X 4-.
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 73
I cr
2 2 2 2 7 1
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X p x X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 7
I cr
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
X x X 3
X X
] cr
O O O TJ cr cr ? TJ Tl 2 2 2 TJ tg 2 2 2 2 2 CU •? 73 ro I y cr cr SJ CL
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 cn 2 ξ, 2 2 2 w 2 2 2 2 2 |?
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o 73
to t to to r TJ TJ n O !) () O o; O O
TJ J TJ J J cr cr τι TJ ro ro ro ro ro ro ro 2 ro 2 n 2 ro ^ -r ? -? w — - 2 ro 2ro 2ro 2ro 2ro 2ro 2ro 2r -o 2ro 2ro m - 2 |^
^r* 3" cr cr cr CL o-S
? 2 2 2 m 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
o n o o o o o o o o o o o ^~ 2 2 2 2 2 2 F
X X X X X X cr
o o o o o O O o o o o o ro ω o co o O O O O o o o o o O O O O O
X τι X o r τι o τι X o
t
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 ^ 2 2 (V 2 2 2 2
O O O O O O O O O O O O O O O x X X X X X X 70 I P
170 X X X X X X X X X X O O O o o o o o o o o o o o o o o o o 4L
I cr
O o o n O -π O O o o GO O O O o o
TJ o O tn
O ra 2 TJ O co 8 SJ ~ nπ o O o O o O O O 170
X O
2 X
2 2 2 ro 2r. 2ro ra 2 2 2 2 2 2 2 2 2 2 2 0 I OJ
X t O O O O O O O O o o o o o o o o π
oj C K nl ° TI ro 1 „2 o ra oI
Rl Ri R4b R5a R5b R! R4a R^ R5a R5b
Et H Me Me CH2CF3 Et H H Me CH7CF-3
Me H Me Me Et Me H H Me Et
Me H Me Me n-Pr Me H H Me n-Pr
Me H Me Me CH2C2F5 Me H H Me CH2C2F5 n-Pr H Me Me CH2CF3 n-Pr H H Me CH2CF3
Me H Me Me CF3 Me H H Me CF3
Et H Me Me C2F5 Et H H Me C2F5
Me H Me Et CHF2 Me H H Et CHF2
Me H Me n-Pr CH2CF3 Me H H n-Pr CH2CF3
Me H Me i-Pr CHF2 Me H H i-Pr CHF2
Me H Me Cl CH2CF3 Me H H Cl CH2CF3
Me H Me F CH2CF3 Me H H F CH2CF3
Me H Me Me CH2C1 Me H H Me CH2C1
Me H Me Me CC1F2 Me H H Me CC1F2
Me H Me Me CH2CH2C1 Me H H Me CH2CH2C1
Me H Me Me n-C3F7 Me H H Me n-C3F7
Me H Me Me i-C3F7 Me H H Me i-C3F7
Me H Me Me Allyl Me H H Me Allyl
Me H Me Et CF2CHF, Me H H Me CF2CHF2
Me H Me Et i-C3F7 Me H H Me i-C3F7
Me H Me i-Pr CF2CHF2 Me H H Me CF2CHF2
Me H Me n-Pr CF2CHF2 Me H H Me CF2CHF2
Me H Me CF3 CF2CHF2 Me PI H CF3 CF2CHF2
Me H Me CF3 Me Me H H CF3 Me
Me H Me OMe CH2CF3 Me H H OMe CH2CF3
Me H Me H CH2CF3 Me H H H CH2CF3
Me H Me H CH2CF3 Me H H H CH2CF3
Me H Me H C2F5 Me H H H C2F5
Et H Me H C2FS Et H H H C2F5
Me 11 Me H C2F5 Me H H H C2F5
Me H Me H CF2CHF2 Me H H H CF2CHF2
Me H Me i-Pr CH2CF3 Me H H H CH2CF3
Me H Me H n-C3F7 Me H H H n-C F7
Me H Me H i-C3F7 Me H H H i-C F
Me H Me Ph CH2CF3 Me H H H CH2CF3
Me H Me Ph CF2CHF2 Me I-I H H CF2CHF2
Me H Me Ph CHF, Me I-I I-I I-I CHF? 2 2 2 2 m 2 2 2 173
ΓD 2ΓD 2ΓD 2ΓD 2 ro 2 ro 2 ro 2 ro 2 ro 2 ro 2 ro 2 ro 2 π> 2 ro 2 ro 2 2 2 2 ΓD 2ΓD 2ΓD Γ 2D 2ro !
2 2 2 2 2 2 2 173
X X X X X X X X X X X X X X X X X X X X X X X X 45-
2 c 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 ro 2 ro
X X X X X X X X X X X X Pi o o o o o x x 73
X X X x X X 45-
1 cr
2 ro 2 ro 2 ro 2 2 2 2 2 2 TJ 2 2 2 cn r 2 2 73 o ΓD I OJ
2 2 2 2 2 2 2 2 2 2 2 2 I X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 173 x x x x I cr
O O
X X X X τι Tl 2 2 Q Tj' TJ cπ
2 2 2 2 cπ 2 2 2 2 2 2 2 2 2 2 2 2 2 m
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 7
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
X X X X X X X X X X o TJ o TJ 2 2 2 73
Q TJ' TJ ro c 2o 2ro 2ro α- ro ro ro
2 2 2 2 2 2 o 2 73
2 2 2 2 173
Q Q Q ≤ ro ro - 1
2 o 2 2 2 ro 2 2 2 2 ro 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
70
Q Q Q Q x x x X X
X X X X o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o 70
1 cr
2 ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2ΓD 2 2 2ro 2ΓD 2ΓD 2ΓD 2 cπ ro -o m 2 2ro o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o 170
45.
1 »
to to t t O CO CD CD to -ι O to to to TJ O O —- - 1 — '
2 ό 2 W O to to to ra ro o Q Q to t'o to to
TJ TJ TJ T3 ^ α. ra TJ TJ TJ TJ Q TJ 2 2 2 73 o o ΓD 2 ΓD Π 2> 2 ΓD 2 2 m
TJ TJ TJ TJ TJ J cr J TJ Cr cr "3 oc
3" cr cr ^
3" -=. to I •g ^ ^
*<_ > 5_ * 5_." ^ 5- ----- al
2 2 2 2 ro 2 o 2 ro 2 π> 2 π> 2 ro 2 ro 2 σ- 2 2 2 2 2 2 2 2 π 2 2 2 2 2 ΓD Γ 2D 2 ΓD 2 ΓD 2 3 ΓD 2 7 ΓD
O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O n
X X X X X X X X X X
I cr
2 2 2 2 o 2 rs cπ ro -o 2 cπ cπ 173
X X X X X X X X X X X X X X X X X X X X 73
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 I 4-. cr
O cn a lϊ O oJ O o m o g 2 ^ o o o o . Q 00 r iw
X o o o ω ω o o y> yt ra TJ 2 ar ra ra ra ra o ra X τι Tl ra π 0 O r ra Urai ° , τι
-J -o to to - - -■ " JP J ^ l-3"
si R4a R4b R5a R5b R! l R4b R5a ^
Me H Me Me OCF2CHF2 Me H H Me OCF2CHF2
Me H Me Me SCF2CHF2 Me H H Me SCF2CHF2
Me H Me Me S02Me Me H H Me S02Me
Me H Me Me S02CF3 Me H H Me S02CF3
Me H Me CF3 CF3 Me H H CF3 CF3
Me H Me CF3 Me Me H H CF3 Me
Me H Me OMe CF3 Me H H OMe CF3
Me H Me H CF3 Me H H H CF3
Me H Me H OCHF2 Me H H H OCHF2
Me H Me H C2F5 Me H H H C2F5
Et H Me H C2F5 Et H H H C F5
Me H Me H OCF3 Me H H H OCF3
Me H Me H OCF2CHF2 Me H H H OCF2CHF2
Me H Me H SCF2CHF2 Me H H H SCF2CHF2
Me H Me H n-C F7 Me H H H n-C3F7
Me H Me H ι-C3F7 Me H H H i-C3F7
Me H Me H Br Me H H H Br
Me H Me H Cl Me H H H Cl
Me H Me H SCF3 Me H H H SCF3
Me H Me Ph CF3 Me H H Ph CF3
Me H Me Ph Cl Me H H Ph Cl
Me H Me Ph Br Me H H Ph Br
Me H Me 2-pyπdyl CF3 Me H H 2-pyridyl CF3
Me H Me 2-pyridyl Cl Me H H 2-pyridyl Cl
Me H Me 2-ClPh CF3 Me H H 2-ClPh CF3
Me H Me 2-ClPh OCF3 Me H H 2-ClPh OCF3
Me H Me 2-ClPh Br Me H H 2-ClPh Br
Me H Me 2-ClPh Cl Me H H 2-ClPh Cl
Me H Me 2-ClPh SCHF2 Me H H 2-ClPh SCHF2
Me H Me 2-BrPh CF3 Me H H 2-BrPh CF3
Me H Me 2-MePh CF3 Me H H 2-MePh CF3
Me I-I Me 2-CNPh CF3 Me H H 2-CNPh CF3
Me H Me 2-FPh CF3 Me H H 2-FPh CF3
Me H Me 2,6-F2Ph CF3 Me PI II 2,6-F2Ph CF3
Me H Me 2,4-F2Ph CF3 Me H H 2,4-F2Ph CF3
Me H Me 2,5-F2Ph CF3 Me I-I I I 2,5-F2Ph CF
Me H Me 2-MeOPh CF3 Me I-I H 2-MeOPh CF3 2 2 2 2 m m 2 2 2 73
2 2 2 2 2 2 2 2 2 2 X X X X X X X F 4 ro 2 ro 2 2 x x I » 2 2 2 2 2 |73
X X X X X X X X X X X 2 I 45. cr
co ro c "^o ro ra O O O O O )
2 2 2 2 2 2 π to to to to "≤ O m 2 2 fl X X X TJ TJ ra F a. TJ TJ TJ on
■3 os
CL CL CL CL os oe; OS O
O O J ar O O ( to o o 00 o O o o o 00 o O r r o o HH o o ro ro ° o ° o y o ro o o o O O o ro o o a ra ra ra ra F a X X ra ra Tl ra τι X ra toar to ra to ra
2 2 n 2 2 cπ 2 ro 2 re 2 ro r 2o 2 ro 2 ro 2 ro 2 2
X X X X X X X X X X X X X X X X X X X X X X X X X X X X 45.
I t) o o o o o o o o o o o o o o o o o o o o o o x x x x F
I cr
ra
m 2 2 2 2 70
2ro 2 2 2 2 2 2ro 2 2 2 2 2 2 2ro 2 2 F 45.
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 73
I cr
2 2 2 2 2 2 2 2 2 2 2 ro 2 2 2 2 2 2 2 2 2 2 2 2 2 2 m 2 2 2 2 2 2 2 2 2 2 2 70
I OJ
X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o F I cr
to to to to to to to to to to to to to a^ to J TJ ra ar ra ra ( 1 ro O O O O O TJ TJ X X X X X X X X X X o to to TJ Z 2 ro 2 2 2 F On
TJ TJ cr TJ 'U TJ TJ 3" J J TJ TJ •3 cr X X o ra o ra ro 1 J 3- 3- cr cr cr cr cr cr cr <<
00 00 O
>—. 3 r O 00 o a
O O O O O ra o o O 00 O ra ra ra ra ra ar o ra CD Caj τ πι r, ° τι ro o o oo
Tl O CD o t to to O O o a
O O r Tl
Tl ra to to to to Fn ra r Tl n r, ra ra ra X ra ra O cr to ^1 X X on r t ra ra 2 O o 1
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Formulation/Utility
Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties ofthe active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible
("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges that add up to 100 percent by weight. Weight Percent
Active
Ingredient Diluent Surfactant
Water-Dispersible and Water-soluble 5-90 0-94 1-15
Granules, Tablets and Powders.
Suspensions, Emulsions, Solutions 5-50 40-95 0-15
(including Emulsifiable
Concentrates)
Dusts 1-25 70-99 0-5
Granules and Pellets 0.01-99 5-99.99 0-15
High Strength Compositions 90-99 0-10 0-2
Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, rung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-mefhyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and PCT Publication WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
For further information regarding the art of formulation, see T. S. Woods, "The Formulator's Toolbox - Product Forms for Modern Agriculture" in Pesticide Chemistiy and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41 ; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; lingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Table A.
Example A
Wettable Powder
Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
Example B
Granule
Compound 7 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example C Extruded Pellet
Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%>. Example D Emulsifiable Concentrate
Compound 7 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%).
Example E Granule
Compound 1 0.5% cellulose 2.5% lactose 4.0% cornmeal 93.0%.
Compounds of this invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and non- agronomic invertebrate pests. (In the context of this disclosure "invertebrate pest control" means inhibition of invertebrate pest development (including mortality) that causes significant reduction in feeding or other injury or damage caused by the pest; related expressions are defined analogously.) As referred to in this disclosure, the term "invertebrate pest" includes arthropods, gastropods and nematodes of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term "gastropod" includes snails, slugs and other Stylommatophora. The term "nematode" includes all ofthe helminths, such as: roundworms, heartworms, and phytophagous nematodes (Nematoda), flukes (Tematoda), Acanthocephala, and tapeworms (Cestoda). Those skilled in the art will recognize that not all compounds are equally effective against all pests. Compounds of this invention display activity against economically important agronomic, forest, greenhouse, nursery, ornamentals, food and fiber, public and animal health, domestic and commercial structure, household, and stored product pests. These include larvae o the order Lepidoptera, such as armyworms, cutworms, loopers, and heliothines in the family Noctuidae (e.g., fall armyworm (Spodoptera fugiperda J. E. Smith), beet armyworm (Spodoptera exigua Hϋbner), black cutworm (Agrotis ipsilon Hufnagel), cabbage looper (Trichoplusia ni Hiibner), tobacco budworm (Heliothis virescens Fabricius)); borers, casebearers, webworms, coneworms, cabbageworms and skeletonizers from the family Pyralidae (e.g., European corn borer (Ostrinia nubilalis Hϋbner), navel orangeworm (Amyelois transϊtella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworm (Herpetogramma licarsisalis Walker)); leafrollers, budworms, seed worms, and fruit worms in the family Tortricidae (e.g., codling moth (Cydia poinonella Linnaeus), grape berry moth [Endopiza viteana Clemens), oriental fruit moth (Grapliolita molesta Busck)); and many other economically important lepidoptera (e.g., diamondback moth (Plutella xylostella Linnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth (Lymantria dispar Linnaeus)); nymphs and adults of the order Blattodea including cockroaches from the families Blattellidae and Blattidae (e.g., oriental cockroach (Blatta orientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo), German cockroach (Blattella germanica Linnaeus), brownbanded cockroach (Supella longipalpa Fabricius), American cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Madeira cockroach (Leucophaea maderae Fabricius)); foliar feeding larvae and adults ofthe order Coleoptera including weevils from the families Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil (Anthonomus grandis Boheman), rice water weevil (Lissorhoptrus oiyzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)); flea beetles, cucumber beetles, rootworms, leaf beetles, potato beetles, and leafminers in the family Chrysomelidae (e.g., Colorado potato beetle (Leptinotarsa decemlineata Say), western corn rootworm (Diabrotica virgifera virgifera LeConte)); chafers and other beetles from the family Scaribaeidae (e.g., Japanese beetle (Popillia japonica Newman) and European chafer (Rhizotrogus majalis Razoumowsky)); carpet beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae. In addition it includes: adults and larvae of the order Dermaptera including earwigs from the family Forficulidae (e.g., European earwig (Forficula auricularia Linnaeus), black earwig (Chelisoches mono Fabricius)); adults and nymphs ofthe orders Hemiptera and Homoptera such as, plant bugs from the family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g. Empoasca spp.) from the family Cicadellidae, planthoppers from the families Fulgoroidae and Delphacidae, treehoppers from the family Membracidae, psyllids from the family Psyllidae, whiteflies from the family Aleyrodidae, aphids from the family Aphididae, phylloxera from the family Phylloxeridae, mealybugs from the family Pseudococcidae, scales from the families Coccidae, Diaspididae and Margarodidae, lace bugs from the family Tingidae, stink bugs from the family Pentatomidae, cinch bugs (e.g., Blissus spp.) and other seed bugs from the family Lygaeidae, spittlebugs from the family Cercopidae squash bugs from the family Coreidae, and red bugs and cotton stainers from the family Pyrrhocoridae. Also included are adults and larvae ofthe order Acari (mites) such as spider mites and red mites in the family Tetranychidae (e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdanieli McGregor)), flat mites in the family Tenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor)), rust and bud mites in the family Eriophyidae and other foliar feeding mites and mites important in human and animal health, i.e. dust mites in the family Epidermoptidae, follicle mites in the family Demodicidae, grain mites in the family Glycyphagidae, ticks in the order Ixodidae (e.g., deer tick (Lxodes scapularis Say), Australian paralysis tick (Lxodes holocyclus Neumann), American dog tick (Dermacentor variabilis Say), lone star tick (Amblyoinma americanum Linnaeus) and scab and itch mites in the families Psoroptidae, Pyemotidae, and Sarcoptidae; adults and immatures ofthe order Orthoptera including grasshoppers, locusts and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury), desert locust (Schistocerca gregaria Forskal), migratory locust (Locusta migratoria Linnaeus), house cricket (Acheta domesiicus Linnaeus), mole crickets (Giyllotalpa spp.)); adults and immatures of the order Diptera including leafminers, midges, fruit flies (Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots, house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g., Fannia canicularis Linnaeus, 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., Cluysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids, and other Nematocera; adults and immatures ofthe order Thysanoptera including onion thrips (Thrips tabaci Lindeman) and other foliar feeding thrips; insect pests of the order Hymenoptera including ants (e.g., red carpenter ant
(Camponotiis ferrugineus Fabricius), black carpenter ant (Camponotus pennsylvanicus De Geer), Pharaoh ant (Monomorium pharaonis Linnaeus), little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), red imported fire ant (Solenopsis invicta Buren), Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Para trech ina longicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus), cornfield ant (Lasius alienus Fδrster), odorous house ant (Tapinoma sessile Say)), bees (including carpenter bees), hornets, yellow jackets and wasps; insect pests ofthe order Isoptera including the eastern subterranean termite (Reticulitermes flavipes Kollar), western subterranean termite (Reticulitermes esperus Banks), Formosan subterranean termite (Coptoterines formosanus Shiraki), West Indian drywood termite (Incisitermes immigrans Snyder) and other termites of economic importance; insect pests of the order Thysanura such as silverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobia domestica Packard); insect pests of the order Mallophaga and including the head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanus humanus Linnaeus), chicken body louse (Menacanthus stramineus Nitszch), dog biting louse (Trichodectes canis De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus euiysteriuis Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and chewing parasitic lice that attack man and animals; insect pests of the order Siphonoptera including the oriental rat flea (Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felis Bouche), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), sticktight flea (Echidiiophaga gallinacea Westwood), human flea (Pulex irritans Linnaeus) and other fleas afflicting mammals and birds. Additional arthropod pests covered include: spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik) and the black widow spider (Latrodectiis mactans Fabricius), and centipedes in the order Scutigeromorpha such as the house centipede (Scutigera coleoptrata Linnaeus). Activity also includes members ofthe Classes Nematoda, Cestoda, Trematoda, and Acanthocephala including economically important members of the orders Strongylida, Ascaridida, Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited to economically important agricultural pests (i.e. root knot nematodes in the genus Meloidogyne, lesion nematodes in the genus Pratylenchiis, stubby root nematodes in the genus Trichodorus, etc.) and animal and human health pests (i.e. all economically important flukes, tapeworms, and roundworms, such as Strongylus vulgaris in horses, Toxocara canis in dogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs, Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.).
Compounds ofthe invention show particularly high activity against pests in the order Lepidoptera (e.g., Alabama argillacea Hϋbner (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 (com root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoverpa armigera Hϋbner (American bollworm), Helicoverpa zea Boddie (com earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis & Schiffermϋller (grape berry moth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistis citrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (large white butterfly), Pieris rapae Linnaeus (small white butterfly), Plutella xylostella Linnaeus (diamondback moth), Spodoptera exigua Hϋbner (beet armyworm), Spodoptera lititra Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hϋbner (cabbage looper) and Tut a absoluta Meyrick (tomato leafminer)). Compounds of the invention also have commercially significant activity on members from the order Homoptera including: Acyrthisiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (blaϋk bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis po i De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosip/ion fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis eiysimi Kaltenbach (turnip aphid), Metopolophiuin dirrhodum Walker (cereal aphid), Macrosipum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maiclis Fitch (co leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry- oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Therioap is maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii Boyer de Fonscolombe (black citms aphid), and Toxoptera citricida Kirkaldy (brown citms aphid); Adelges spp. (adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisia argentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citri Ashmead (citms whitefly) and Trialeurodes vaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris (potato leafhopper), Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestes quadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler (green leafhopper), Nephotettix nigropictus Stal (rice leafhopper), Nilaparvata lugens Stal (brown planthopper), Peregrinus maidis Ashmead (com planthopper), Sogatella furcifera Horvath (white-backed planthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAtee white apple leafhopper, Erythroneoura spp. (grape leafhoppers); Magicidada septendecim Linnaeus (periodical cicada); Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotus perniciosus Comstock (San Jose scale); Planococcus citri Risso (citms mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla). These compounds also have activity on members from the order Hemiptera including: Acrosternum hilare Say (green stink bug), Anasa tristis De Geer (squash bug), Blissus leucopteriis leucopterus Say (chinch bug), Coiythuca gossypii Fabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servus Say (brown stink bug), Euchistus variolarius Palisot de Beauvois (one-spotted stink bug), Graptosthetus spp. (complex of seed bugs), Leptoglossus corculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (southern green stink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltus fasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper). Other insect orders controlled by compounds of the invention include Thysanoptera (e.g., FrankHniella occidentalis Pergande (western flower thrip), Scirthothrips citri Moulton (citrus thrip),
Sericot rips variabilis Beach (soybean thrip), and Thrips tabaci Lindeman (onion thrip); and the order Coleoptera (e.g., Leptinotarsa decemUneata Say (Colorado potato beetle), Epilachna varivestis Mulsant (Mexican bean beetle) and wireworms of the genera Agriotes, Athous or Limonius).
Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators such as rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, vims or fungi to form a multi-component pesticide giving an even broader spectmm of agricultural utility. Thus compositions of the present invention can further comprise a biologically effective amount of at least one additional biologically active compound or agent. Examples of such biologically active compounds or agents with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, acetamiprid, avermectin, azadirachtin, azinphos-methyl, bifenthrin, binfenazate, buprofezin, carbofuran, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothicarb, fenoxycarb, fenpropathrin, fenproximate, fenvalerate, fipronil, flonicamid, flucythrinate, tau-fluvalinate, flufenoxuron, fonophos, halofenozide, hexaflumuron, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, methoxyfenozide, nithiazin, novaluron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, pymetrozine, pyridalyl, pyriproxyfen, rotenone, spinosad, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, trichlorfon and triflumuron; fungicides such as acibenzolar, azoxystrobin, benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, (S)-3,5-dichloro-N-(3-chloro-l-ethyl-l-methyl-2-oxopropyl)-4- methylbenzamide (RH 7281), diclocymet (S-2900), diclomezine, dicloran, difenoconazole, (S)-3,5-dihydro-5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4N-imidazol-4-one (RP 407213), dimethomo h, dimoxystrobin, diniconazole, diniconazole-M, dodine, edifenphos, epoxiconazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramid (SZX0722), fenpiclonil, fenpropidin, fenpropimoφh, fentin acetate, fentin hydroxide, fluazinam, fludioxonil, flumetover (RPA 403397), fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, furametapyr (S-82658), hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mepronil, metalaxyl, metconazole, metomino- strobin/fenominostrobin (SSF-126), myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propamocarb, propiconazole, pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon, quinoxyfen, spiroxamine, sulfur, tebuconazole, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, triadi efon, triadimenol, tricyclazole, trifloxystrobin, triticonazole, validamycin and vinclozolin; nematocides such as aldicarb, oxamyl and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus thuringiensis including ssp. aizawai and kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, vims and fungi.
A general reference for these agricultural protectants is The Pesticide Manual, 12th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2000.
Preferred insecticides and acaricides for mixing with compounds of this invention include pyrethroids such as cypermethrin, cyhalothrin, cyfluthrin, beta-cyfluthrin, esfenvalerate, fenvalerate and tralomethrin; carbamates such as fenothicarb, methomyl, oxamyl and thiodicarb; neonicotinoids such as clothianidin, imidacloprid and thiacloprid; neuronal sodium channel blockers such as indoxacarb; insecticidal macrocyclic lactones such as spinosad, abamectin, avermectin and emamectin; γ-aminobutyric acid (GABA) antagonists such as endosulfan, ethiprole and fipronil; insecticidal ureas such as flufenoxuron and triflumuron; juvenile hormone mimics such as diofenolan and pyriproxyfen; pymetrozine; and amitraz. Preferred biological agents for mixing with compounds of this invention include Bacillus thuringiensis and Bacillus thuringiensis delta endotoxin as well as naturally occurring and genetically modified viral insecticides including members ofthe family Baculoviridae as well as entomophagous fungi.
Most preferred mixtures include a mixture of a compound of this invention with cyhalothrin; a mixture of a compound of this invention with cyfluthrin; a mixture of a compound of this invention with beta-cyfluthrin; a mixture of a compound of this invention with esfenvalerate; a mixture of a compound of this invention with methomyl; a mixture of a compound of this invention with imidacloprid; a mixture of a compound of this invention with thiacloprid; a mixture of a compound of this invention with indoxacarb; a mixture of a compound of this invention with abamectin; a mixture of a compound of this invention with endosulfan; a mixture of a compound of this invention with ethiprole; a mixture of a compound of this invention with fipronil; a mixture of a compound of this invention with flufenoxuron; a mixture of a compound of this invention with pyriproxyfen; a mixture of a compound of this invention with pymetrozine; a mixture of a compound of this invention with amitraz; a mixture of a compound of this invention with Bacillus thuringiensis and a mixture of a compound of this invention with Bacillus thuringiensis delta endotoxin. In certain instances, combinations with other invertebrate pest control compounds or agents having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management. Thus, compositions of the present invention can further comprise an biologically effective amount of at least one additional invertebrate pest control compounds or agents having a similar spectmm of control but a different mode of action. Contacting a plant genetically modified to express a plant protection compound (e.g., protein) or the locus o the plant with a biologically effective amount of a compound of invention can also provide a broader spectmm of plant protection and be advantageous for resistance management. Invertebrate pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more ofthe compounds of this invention, in an effective amount, to the environment ofthe pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus, the present invention further comprises a method for the control of foliar- and soil-inhabiting invertebrates and protection of agronomic and/or nonagronomic crops, comprising contacting the invertebrates or their environment with a biologically effective amount of one or more ofthe compounds ofthe invention, or with a composition comprising at least one such compound or a composition comprising at least one such compound and an effective amount of at least one additional biologically active compound or agent. A preferred method of contact is by spraying. Alternatively, a granular composition comprising a compound ofthe invention can be applied to the plant foliage or the soil. Compounds of this invention are effective in delivery 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. Other methods of contact include application of a compound or a composition of the invention by direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.
The compounds of this invention can be incorporated into baits that are consumed by the invertebrates or within devices such as traps and the like. Granules or baits comprising between 0.01—5% active ingredient, 0.05-10% moisture retaining agent(s) and 40-99% vegetable flour are effective in controlling soil insects at very low application rates, particularly at doses of active ingredient that are lethal by ingestion rather than by direct contact. The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy.
The rate of application required for effective control (i.e. "biologically effective amount") will depend on such factors as the species of invertebrate to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg/hectare may be sufficient or as much as 8 kg/hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required. One skilled in the art can easily determine the biologically effective amount necessary for the desired level of invertebrate pest control. The following Tests in the Biological Examples of the Invention demonstrate the control efficacy of compounds of this invention on specific pests. "Control efficacy" represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-E for compound descriptions. The following abbreviations are used in the Index Tables that follow: t is tertiary, n is normal, is iso, s is secondary, Me is methyl, Et is ethyl, Pr is propyl and Bu is butyl; accordingly /-Pr is isopropyl, -s-Bu is secondary butyl, etc. Ac is COCH3. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.
INDEX TABLE A
Compound R^ R3 R4 R5 m.p. °C
1 (Ex. 1 ) Me H H ? 2-Me-4-F 249
2 /-Pr H H 2 2-MC-4-C1 >250
3 /;-Pr H I-I 2 2-Me-4-Cl 212 o (
-=
H U α.
CN N —'
-E K X X X
a to -w cυ cυ tυ cu <u o tυ ti> i> -J tD --υ υ --U (D tU (υ u ^ s =
o
o O
42 Me H H 1 4-C02Et 202
43 Me H H 1 4-NMeAc 210
44 Me H H 2 2,6-di-Me >250
45 Me H H 1 2-(pyrrol- l-yl) 208
46 Me H H 1 4-N02 224
47 Me H H 1 3-OCH2Ph 214
48 Me H H 2 2,4-di-Me 213
49 Me H H 3-CN 200
50 Me H H 3-OCF3 >250
51 Me H H 2 2-Me-3-N02 233
52 Me H H 2-OEt 224
53 Me H H 4-(4-ClPhO) 224
54 Me H H 4-CH3 248
55 Me H H 4-0-/-Pr 183
56 Me H H 4-F 247
57 Me H H 2-SMe 204
58 Me H H 2-Z-Bu 248 9 Me H H 3-SMe 218 0 Me H H 4-OEt 195 1 Me H H 2-CH2CN 191 2 Me H H 3 2-Et 200 i-Pr H 4-N02/ 2 2-Me-4-CI ***
5-N02
( 1/1 mixture) 4 Me H 4-Br/ 2 2-Me-4-Cl *
5-Br
(1/1 mixture)
Me H H 1 2-CONH(/-Pr)-6-Me 248 * Me H H 2 2-Me-4-Cl *-k * * Me H H 2 2-Me-4-OCF3 ***
Me H H 2 2-Me-5-N02 242
Me H H 2 2-Me-4-CF3 250
Me H H 1 4-CF3 246
Me H H 1 2-Ph 163
Me H H 2 2-( ~Me-tetrazol-5-yl)-6-Me 202
Me H H 1 2-CONHMe 235
Me I-l H 2 2-Me-6-Cl 231
Me H H 2 3-N02-4-Mc 223 76 Me H H 3 2-F~4-Cl-5-N02 250
77 Me H H 2 2-Br-4-Me 198
78 Me H H 3 2-Br-4,6-di-F 197
79 Me H H 2 2,5-di-N02 223
80 Me H H 2 2-F-4-C1 250
81 Me H H 2 2-Me-3-F 242
82 Me H H 2 2-Br-4-F 126.5
83 Me H H 1 2-(morpholin-4-yl) 193
84 Me II H 2 3-NC-2-4-F 248
85 Me H H 2 3,4-di-F 1 10
86 Me H H 2 2-C1-4-F 250
87 Me H H 1 2-CF3 217
88 Me H H 2 2-CN-4-C1 250
89 Me H H 1 2-Ac 237
90 Me H H 1 2-OCF3 209
91 Me H H 1 2-SCF3 21 1
92 Me H H 2 2-CF3-4-Br 250
* This sample contained 25% by weight of 1,8-naphthalene-anhydride. *** See Index Table E for NMR data.
INDEX TABLE B
Compound R2 R3 R4 m..pp. °C
INDEX TABLE C
Compound R^ R3 R4 R5 m.p. °C
98 (Ex. 2) /-Pr H H 2 3.4-di-F 227
99 /-Pr H H 2 2,3-di-Me 242
100 /-Pr I-I H 2 2,4-di-F 204
101 -Pr H H 1 4-OCF3 186
102 /-Pr H H 1 4-C1 218
103 /-Pr H H 1 4-Et 206 104 /-Pr H H 1 4-CF3 165
105 Me H H 2 3,4-di-F 250
106 Me H H 2 2,3-di-Me 184.5
107 Me H H 2 2,4-di-F 207
108 Me H H 4-C1 250
109 Me H H 4-Et 250
110 Me H H 4-CF3 208
111 Me H H 4-OCF3 144
112 Me H H 2-Me 173.5
113 /-Pr H H 2-Me 176.5
114 /-Pr H H 2 2-Me-4-0-CF3 173.5
115 /-Pr H H 2 2-Me-4-CF3 194.5
116 Me H H 2 2-Me-4-OCF3 173.5
117 Me H H 2 2-Me-4-CF3 204.5 Index Table D
Compound R2 R3 R" J m.p. °C
118 /-Pr H H 1 -naphthyl 210
119 /-Pr H H 2-thienyl 208
20 (Ex.3) Me H H 2-thienyl 215
121 Me H H 1 -naphthyl 214
INDEX TABLE E
Cmpd No. ' H NMR Data (CDC13 solution unless indicated otherwise)a
4 (DMSO-d6) δ: 0.9 (m, 6H), 2.37 (s, 3H), 3.01 (m, IH), 3.96 (d, 2H), 7.27-8.48 (m, 10H), 9.84 (br s, IH).
5 (DMSO-d6) δ: 2.36 (s, 3H), 2.88 (s, 3H), 2.94 (s, 3H), 7.28-8.08 (m, 10H), 9.99 (s, IH).
6 (DMSO-d6) δ: 1.07 (t, 3H), 2.37 (s, 3H), 3.22 (m, 2H), 7.30-8.06 (m, 9H), 8.40 (t, I H), 9.86 (s, IH).
10 (DMSO-d6) δ: 2.36 (s, 3H), 7.25-8.08 (m, 1 IH), 9.88 (s, IH).
63 (DMSO-d6) δ: 1.09 (d, 6H), 2.36 (s, 3H), 4.03 (m, IH), 7.27-8.52 (m, 9H), 10.04 (s, IH).
64 (DMSO-d6) δ: 2.36 (s, 3H), 2.69 (d, 3H), 7.33-8.84 (m, 8H), 8.45 (br q, IH), 9,98 (s, IH).
66 (DMSO-d6) δ: 2.37 (s, 3H), 2.71 (d, 3H), 7.27-8.10 (m, 9H), 8.34 (br q, lH), 9.88 (s, IH).
67 (DMSO-d6) δ: 2.41 (s, 3H), 2.72 (d, 3H), 7.26-8.08 (m, 9H), 8.36 (br q, IH), 9.95 (s, IH). a I H NMR data are in ppm downfϊeld from tetramethylsilane. Couplings are designated by (s)-singlet,
(d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br s)-broad singlet, (bs q)-broad quartet.
BIOLOGICAL EXAMPLES OF THE INVENTION
TEST A For evaluating control of fall armyworm (Spodoptera frugiperda) the test unit consisted of a small open container with a 4-5-day-old corn (maize) plant inside. This was pre-infested with 10-15 1 -day-old larvae on a piece of insect diet by use of a core sampler to remove a plug from a sheet of hardened insect diet having many larvae growing on it and transfer the plug containing larvae and diet to the test unit. The larvae moved onto the test plant as the diet plug dried out.
Test compounds were formulated using a solution containing 10% acetone, 90% water and 300 ppm X-77© Spreader Lo-Foam Formula non-ionic surfactant containing alkylarylpolyoxyethylene, free fatty acids, glycols and isopropanol (Loveland Industries, Inc.), unless otherwise indicated. The formulated compounds were applied in 1 mL of liquid through a SUJ2 atomizer nozzle with 1/8 JJ custom body (Spraying Systems Co,) positioned 1.27 cm (0.5 inches) above the top of each test unit. All experimental compounds in this screen were sprayed at 250 ppm and replicated three times. After spraying of the formulated test compound, each test unit was allowed to dry for 1 hour and then a black, screened cap was placed on top. The test units were held for 6 days in a growth chamber at 25 °C and 70% relative humidity. Plant feeding damage was then visually assessed.
Of the compounds tested, the following provided excellent levels of plant protection (10% or less feeding damage): 1 , 7, 1 1, 16, 48, 66 and 67. TEST B
For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of a small open container with a 6-7 day old cotton plant inside. This was pre- infested with 8 2-day-old larvae on a piece of insect diet by use of a core sampler as described for Test A. Test compounds were formulated and sprayed at 250 ppm as described for Test A.
The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test A.
Ofthe compounds tested, the following provided excellent levels of plant protection (10% or less feeding damage): 1, 7 and 16. TEST C
For evaluating control of diamondback moth (Plutella xylostella) the test unit consisted of a small open container with a 12-14-day-old radish plant inside. This was pre- infested with 10—15 neonate larvae on a piece of insect diet by use of a core sampler as described for Test A. Test compounds were formulated and sprayed at 250 ppm as described for Test A.
The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test A.
Ofthe compounds tested, the following provided excellent levels of plant protection (10% or less feeding damage): 1, 7, 11, 12, 14, 16, 20, 24, 37, 48, 51, 54, 55, 56, 61 , 66, 67, 69, 70, 72, 75, 81, 85, 86, 89, 90, 91, 93 and 97.
TEST D For evaluating control of beet armyworm (Spodoptera exigua) the test unit consisted of a small open container with a 4-5-day-old corn plant inside. This was pre-infested with 10-15 1 -day-old larvae on a piece of insect diet by use of a core sampler as described for Test A.
Test compounds were formulated and sprayed at 250 ppm as described for Test A. The applications were replicated three times. After spraying, the test units were maintained in a growth chamber and then visually rated as described for Test A.
Of the compounds tested, the following provided excellent levels of plant protection (10% or less feeding damage): 1 , 40 and 54.

Claims

CLAIMS What is claimed is:
1. A compound selected from Formula I or Formula II, and N-oxides and agriculturally suitable salts thereof,
wherein each J is independently a phenyl ring, a naphthyl ring system, a 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system wherein each ring or ring system is optionally substituted with 1 to 5 5;
A and B are independently O or S; n is 0 to 4;
R1 is H; or CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CΝ, ΝO2, hydroxy, C1-C4 alkoxy, C1-C4 alkylthio, CJ-C4 alkylsulfmyl, C1-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl, C1-C4 alkylamino, C2-Cg dialkylamino and C3-Cg cycloalkylamino; or
R1 is C2-C6 alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-C(5 alkylaminocarbonyl or C3-C8 dialkylaminocarbonyl;
R2 is H, CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, CrC4 alkoxy, Cj-C4 alkylamino, C2-Cg dialkylamino, C -Cg cycloalkylamino, C2-Cg alkoxycarbonyl or C2-Cg alkylcarbonyl;
R3 is H; or C Cg alkyl, C^- alkenyl, C2-C6 alkynyl or Cβ-Cg cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, hydroxy, C1-C4 alkoxy, CrC alkylthio, C1-C4 alkylsulfmyl and C1-C4 alkylsulfonyl; or
R2 and R3 can be taken together with the nitrogen to which they are attached to form a ring containing 2 to 6 atoms of carbon and optionally one additional atom of nitrogen, sulfur or oxygen, said ring may be optionally substituted with 1 to 4 substituents selected from the group consisting of Cι-C2 alkyl, halogen, CN, NO2 and CrC7 alkoxy; and each R4 and each R5 is independently H, Cj-C6 alkyl, C2-C6 alkenyl, C2-C(5 alkynyl, C3-C6 cycloalkyl, C Cg haloalkyl, C2-Cg haloalkenyl, C2-C haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, CO2H, CONH2, NO2, hydroxy, CrC4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfmyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C -C4 alkoxycarbonyl, CJ-C4 alkylamino, C2-Cg dialkylamino, C3-Cg cycloalkylamino, C2-Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg alkylaminocarbonyl, C -Cg dialkylaminocarbonyl, or C3-C6 trialkylsilyl; or each R4 and each R5 is independently a phenyl, benzyl, phenoxy, 5- or 6-membered heteroaromatic ring or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each ring optionally substituted with one to three substituents independently selected from the group consisting of C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-Cg cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C -C4 haloalkynyl, C3-Cg halocycloalkyl, halogen, CN, NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfmyl, CJ-C4 alkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-Cg cycloalkylamino, C3-Cg (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C<5 trialkylsilyl; or (R5)2 when attached to adjacent carbon atoms can be taken together as -OCF2O-,
-CF2CF2O- or -OCF2CF2O-.
2. The compound of Formula I of Claim 1 wherein A and B are both O;
R1 is H, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl; and n is 0 to 2.
3. The compound of Formula II of Claim 1 wherein A and B are both O;
R1 is H, C C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl; and n is 0 to 2.
4. The compound of Claim 2 or Claim 3 wherein
J is a phenyl ring or a 5- or 6-membered heteroaromatic ring selected from the group consisting of J-l , J-2, J-3 and J-4, each J ring optionally substituted with 1 to 3 R5
J-l J-2 J-3 J-4
Q is O, S or NR5;
W, X, Y and Z are independently N or CR5, provided that in J-3 and J-4 at least one of W, X, Y or Z is N; R2 is H, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl; R3 is Cj-Cg alkyl, C2-C<5 alkenyl, C -C(3 alkynyl or C3-Cg cycloalkyl each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, Cj-C2 alkoxy, C}-C2 alkylthio, Cι-C2 alkylsulfmyl and C1-C2 alkylsulfonyl; one R4 group is attached to the naphthyl ring system at the 2-position or 7-position, and said R4 is Cj-C alkyl, CrC haloalkyl, halogen, CN, NO2, -C4 alkoxy, C]-C4 haloalkoxy, Cj-C4 alkylthio, -C4 alkylsulfmyl, C C4 alkylsulfonyl, C1-C4 haloalkylthio, CJ-C4 haloalkylsulfinyl or Cj-C4 haloalkylsulfonyl; each R5 is independently H, C1-C4 alkyl, C1-C4 haloalkyl, halogen, CN, NO2, -C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C C4 alkylsulfmyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C2-C4 alkoxycarbonyl, C -Cg dialkylaminocarbonyl; or each R5 is independently a phenyl, benzyl or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with C1-C4 alkyl, C2-C4 alkenyl, C -C4 alkynyl,
C3-Cg cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, NO2, C C.4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, Cj-C4 alkylsulfmyl, CJ-C4 alkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-Cg cycloalkylamino, yC (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, C7-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl; or (R5)2 when attached to adjacent carbon atoms can be taken together as -OCF2O-,
-CF2CF2O- or -OCF2CF2O-; and n is 1 to 2.
5. The compound of Formula I of Claim 4 wherein R2 is H; R3 is C1-C4 alkyl; and at least one of the R5 substituents is ortho to the NR1C(=B) moiety.
6. The compound of Claim 5 wherein R3 is methyl.
7. The compound of Formula II of Claim 4 wherein R1 is H or CrC4 alkyl; R2 is H or CrC4 alkyl;
R3 is CrC4 alkyl optionally substituted with halogen, CN, OCH3, or S(O)pCH3; one R5 group is attached to the J at the position ortho to the C(=B)NR1 moiety, and said R5 is CrC alkyl, CrC haloalkyl, halogen, CN, NO , CrC4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, Cj-C4 alkylsulfmyl, C C4 alkylsulfonyl,
C1-C4 haloalkylthio, C[-C4 haloalkylsulfinyl, C C4 haloalkylsulfonyl or C2-C4 alkoxycarbonyl; C3-Cg dialkylaminocarbonyl or a phenyl, benzyl, or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with halogen, CN, NO2, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, CrC4 haloalkyl, C C4 alkoxy or Cj-C4 haloalkoxy; and a second optional R5 group is independently C C4 alkyl, C C4 haloalkyl, halogen, CN, NO2, Cj-C alkoxy, CrC haloalkoxy, C1 -C4 alkylthio, C C4 alkylsulfmyl, Cj-C4 alkylsulfonyl, C]-C4 haloalkylthio, Cj-C4 haloalkylsulfinyl, Cj-C haloalkylsulfonyl or C2-C4 alkoxycarbonyl; C3-Cg dialkylaminocarbonyl or a phenyl, benzyl, or a 5- or 6-membered heteroaromatic ring, each ring optionally substituted with halogen, CN, NO2, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-Cg cycloalkyl, C1-C4 haloalkyl, C C.4 alkoxy or Cι-C4 haloalkoxy.
7. The compound of Claim 6 wherein J is phenyl, pyrazole, pyrrole, pyridine or pyrimidine, each substituted with one R5 attached to the J at the position ortho to the
C(=B)NR1 moiety and a second optional R5.
8. The compound of Claim 7 wherein R1 and R2 are each H; one R4 is attached at the 7-position ortho to the NR1C(=X)J moiety and is selected from the group consisting of CrC3 alkyl, CF3, OCF3, OCHF2. S(O)pCF3,
S(O)pCHF2 and halogen and an optional second R4 is attached at the 5-position para to the NR1C(=X)J moiety and is selected from the group consisting of halogen, Cj-C3 alkyl and C1-C3 haloalkyl.
9. The compound of Claim 8 wherein J is J-l ;
Q is NR5a; X is N or CH; Y is CH; Z is CR5b; R5a is a phenyl or 2-pyridyl ring substituted with one or two substituents selected from the group consisting of halogen, CrC alkyl, CpC4 haloalkyl or CrC4 haloalkoxy; and R5b is halogen or CF3.
10. The compound of Claim 1 selected from the group consisting of N-methyl -N'-(2-bromo-4-fluoropheny)-l,8-naphthalene-dicarboxamide, N-methyl 8-[(3,4-difluorophenyl)carbonylamino]-l -naphthalenecarboxamide and N-methyl 8-[(2-thienyl)carbonylamino]- 1 -naphthalenecarboxamide.
1 1. A composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.
12. The composition of Claim 11 further comprising an effective amount of at least one additional biologically active compound or agent.
13. The composition of Claim 12 wherein at least one additional biologically active compound or agent is selected from arthropodicides of the group consisting of pyrethroids, carbamates, neonicotinoids, neuronal sodium channel blockers, insecticidal macrocyclic lactones, γ-aminobutyric acid (GABA) antagonists, insecticidal ureas and juvenile hormone mimics.
14. The composition of Claim 12 wherein at least one additional biologically active compound or agent is selected from insecticide, nematocide, acaricide or biological agents in the group consisting of abamectin, acephate, acetamiprid, avermectin, azadirachtin, azinphos-methyl, bifenthrin, binfenazate, buprofezin, carbofuran, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothicarb, fenoxycarb, fenpropathrin, fenproximate, fenvalerate, fipronil, flonicamid, flucythrinate, tau-fluvalinate, flufenoxuron, fonophos, halofenozide, hexaflumuron, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, methoxyfenozide, nithiazin, novaluron, oxamyl, parathion, parathion-methyl, permefhrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, pymetrozine, pyridalyl, pyriproxyfen, rotenone, spinosad, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, trichlorfon and triflumuron, aldicarb, oxamyl, fenamiphos, amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben, tebufenpyrad, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.
15. The composition of Claim 14 wherein at least one additional biologically active compound or agent is selected from the group consisting of cypermethrin, cyhalothrin, cyfluthrin, beta-cyfluthrin, esfenvalerate, fenvalerate, tralomethrin, fenothicarb, methomyl, oxamyl, thiodicarb, clothianidin, imidacloprid, thiacloprid, indoxacarb, spinosad, abamectin, avermectin, emamectin, endosulfan, ethiprole, fipronil, flufenoxuron, triflumuron, diofenolan, pyriproxyfen, pymetrozine, amitraz, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin and entomophagous fungi.
16. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Claim 1 or a composition of Claim 1 1.
EP01987739A 2000-10-17 2001-10-11 Insecticidal 1,8-naphthalenedicarboxamides Withdrawn EP1326827A2 (en)

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