EP1326827A2 - Insecticidal 1,8-naphthalenedicarboxamides - Google Patents

Insecticidal 1,8-naphthalenedicarboxamides

Info

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Withdrawn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
Other languages
German (de)
English (en)
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Withdrawn legal-status Critical Current

Links

Classifications

    • 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%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP01987739A 2000-10-17 2001-10-11 Insecticidal 1,8-naphthalenedicarboxamides Withdrawn EP1326827A2 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US24089000P 2000-10-17 2000-10-17
US240890P 2000-10-17
US32383301P 2001-09-21 2001-09-21
US323833P 2001-09-21
PCT/US2001/042632 WO2002032856A2 (en) 2000-10-17 2001-10-11 Insecticidal 1,8-naphthalenedicarboxamides

Publications (1)

Publication Number Publication Date
EP1326827A2 true EP1326827A2 (en) 2003-07-16

Family

ID=26933807

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01987739A Withdrawn EP1326827A2 (en) 2000-10-17 2001-10-11 Insecticidal 1,8-naphthalenedicarboxamides

Country Status (5)

Country Link
EP (1) EP1326827A2 (enrdf_load_stackoverflow)
JP (1) JP2004511538A (enrdf_load_stackoverflow)
CN (1) CN1429199A (enrdf_load_stackoverflow)
BR (1) BR0107384A (enrdf_load_stackoverflow)
WO (1) WO2002032856A2 (enrdf_load_stackoverflow)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE396985T1 (de) * 2001-08-15 2008-06-15 Du Pont Orthosubstituierte arylamide zur bekämpfung von wirbellosen schädlingen
UA96565C2 (ru) 2004-09-02 2011-11-25 Дженентек, Инк. Пиридильные ингибиторы хеджхоговской передачи сигнала
WO2007069684A1 (ja) * 2005-12-15 2007-06-21 Nihon Nohyaku Co., Ltd. フタルアミド誘導体及び農園芸用殺虫剤並びにその使用方法
CL2008002242A1 (es) 2007-07-31 2009-08-21 Bayer Cropscience Ag Compuestos derivados de n-cicloalquil-n-carboxamida, tiocarboxamida, biciclicas o derivados de carboximidamida n-sustituida; composicion fungicida; y metodo para controlar los hongos fitopatogenos de los cultivos.
CN102428957A (zh) * 2011-12-20 2012-05-02 湖北仙隆化工股份有限公司 一种复配杀虫组合物
EP3643711A1 (en) * 2018-10-24 2020-04-29 Bayer Animal Health GmbH New anthelmintic compounds
KR20220097418A (ko) * 2019-11-01 2022-07-07 신젠타 크롭 프로텍션 아게 살충 활성 융합된 바이사이클릭 이종방향족 화합물
WO2021177334A1 (ja) * 2020-03-04 2021-09-10 国立大学法人山口大学 新規なフルオロアルカン誘導体及びそれらを用いたゲル化剤
CN113214106B (zh) * 2021-06-22 2023-05-09 河南师范大学 一种高效合成伯酰胺、n-甲基仲酰胺类化合物的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0346841A3 (de) * 1988-06-16 1991-01-09 Ciba-Geigy Ag 1-Aryl-naphthoesäureamide und diese enthaltende mikrobizide Mittel
TW515786B (en) * 1997-11-25 2003-01-01 Nihon Nohyaku Co Ltd Phthalic acid diamide derivatives, agricultural and horticultural insecticides, and a method for application of the insecticides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0232856A2 *

Also Published As

Publication number Publication date
WO2002032856A9 (en) 2004-04-08
CN1429199A (zh) 2003-07-09
BR0107384A (pt) 2002-09-24
JP2004511538A (ja) 2004-04-15
WO2002032856A2 (en) 2002-04-25
WO2002032856A3 (en) 2002-07-04

Similar Documents

Publication Publication Date Title
AU2002331706B2 (en) Ortho-substituted aryl amides for controlling invertebrate pests
AU2002254107B2 (en) Heterocyclic diamide invertebrate pest control agents
US7541377B2 (en) Substituted anthranilamides for controlling invertebrate pests
US7629463B2 (en) Ortho-heterocyclic substituted aryl amides for controlling invertebrate pests
AU2002305669B2 (en) Diamide invertebrate pest control agents containing a non-aromatic heterocyclic ring
AU2002331706A1 (en) Ortho-substituted aryl amides for controlling invertebrate pests
AU2002326748A1 (en) Substituted anthranilamides for controlling invertebrate pests
WO2003106427A2 (en) Pyrazolecarboxamide insecticides
AU2009202871A1 (en) Quinazoline(DI)ones for invertebrate pest control
US20040110777A1 (en) Quinazolinones and pyridinylpyrimidinones for controlling invertebrate pests
US7157475B2 (en) Diamide invertebrate pest control agents
US20040235959A1 (en) Insecticidal diamides
AU2002343512A1 (en) Iminobenzoxazines, iminobenzthiazines and iminoquinazolines for controlling invertebrate pests
EP1511385B1 (en) Insecticidal amides with nitrogen-containing benzo-fused bicyclic ring systems
EP1326827A2 (en) Insecticidal 1,8-naphthalenedicarboxamides
US20040053786A1 (en) Insecticidal 1,8-naphthalenedicarboxamides
AU2003202966A1 (en) Diamide invertebrate pest control agents
AU2002331708A1 (en) Ortho-heterocyclic substituted aryl amides for controlling invertebrate pests

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030331

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17Q First examination report despatched

Effective date: 20031212

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH CY DE ES FR GB IT LI

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20040623