EP1049663A1 - Derives organiques nitrile et leur utilisation comme pesticides - Google Patents

Derives organiques nitrile et leur utilisation comme pesticides

Info

Publication number
EP1049663A1
EP1049663A1 EP99907393A EP99907393A EP1049663A1 EP 1049663 A1 EP1049663 A1 EP 1049663A1 EP 99907393 A EP99907393 A EP 99907393A EP 99907393 A EP99907393 A EP 99907393A EP 1049663 A1 EP1049663 A1 EP 1049663A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
halogen
alkoxy
alkenyl
alkinyl
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Withdrawn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
EP99907393A
Other languages
German (de)
English (en)
Inventor
Roger Graham Hall
Arthur Steiger
Ottmar Franz HÜTER
Alfons Pascual
Miroslav Kriz
Stephan Trah
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.)
Syngenta Participations AG
Original Assignee
Novartis Erfindungen Verwaltungs GmbH
Novartis AG
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 Novartis Erfindungen Verwaltungs GmbH, Novartis AG filed Critical Novartis Erfindungen Verwaltungs GmbH
Publication of EP1049663A1 publication Critical patent/EP1049663A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
    • C07C255/66—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms having cyano groups and nitrogen atoms being part of hydrazine or hydrazone groups bound to the same carbon skeleton
    • 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
    • A01N37/34—Nitriles
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/08—Sulfonic acid halides; alpha-Hydroxy-sulfonic acids; Amino-sulfonic acids; Thiosulfonic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • 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
    • C07C323/31—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 having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—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 having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—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 having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/36—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 having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom
    • 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
    • C07C323/50—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 carboxyl groups bound to the same carbon skeleton
    • C07C323/62—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 carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/08—1,2,5-Oxadiazoles; Hydrogenated 1,2,5-oxadiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings 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
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom 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
    • C07D307/70—Nitro radicals
    • C07D307/71—Nitro radicals attached in position 5
    • C07D307/72—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2
    • C07D307/74—Nitro radicals attached in position 5 with hydrocarbon radicals, substituted by nitrogen-containing radicals, attached in position 2 by hydrazino or hydrazono or such substituted radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur 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
    • C07D333/42—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur 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 with nitro or nitroso radicals directly attached to ring carbon atoms
    • C07D333/44—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur 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 with nitro or nitroso radicals directly attached to ring carbon atoms attached in position 5
    • 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

  • the invention relates to a compound of formula
  • Ai and A 2 are independent of one another and in each case represent a monocychc or bicychc aryl or heteroaryl radical, and each heteroaryl radical independently of the other having 1 up to and including 4 hetero atoms selected from the group consisting of N, O and S; and A- is substituted where appropriate with substituent (R 3a )m and A 2 where appropriate with substituent (R 3 b)n2; ni and n 2 are independently of one another 1 , 2, 3 or 4, depending on the possibilities for substitution on ring system A-, and A 2 ; and either
  • R 2 is R 2a or R 2b ;
  • R 3a has one of the meanings defined hereinbefore under (A) or (B),
  • R 2 is R 2a or R 2b ; and in the groups (A), (B) and (C), where appropriate,
  • R 5 is independently H or C ⁇ -C 8 alkyl
  • R 6 is independently H, C Cealkyl, C 3 -C 6 cycloalkyl, phenyl or benzyl, wherein the phenyl or benzyl group is substituted in the aromatic ring where appropriate independently of one another once to three times with substituents selected from the group consisting of halogen, -CN, NO 2 , d-C 6 alkyl, d-C 4 alkoxy, halogen-d-C 6 alkyl and halogen- C ⁇ -C 6 alkoxy; or two alkyl radicals R 6 , together with the nitrogen atom to which they are bonded, form a five to seven-membered ring, wherein a CH 2 group, where appropriate, is substituted by a heteroatom selected from the group consisting of O and S, or is substituted by NH, and wherein the five to seven-membered ring, where appropriate, is substituted once or twice with C* ⁇ -C 4 alkyl;
  • R 7a is d-Cealkoxy-d-Cealkyl, CH 2 CH 2 CF2CI, d-C ⁇ alkylthio-d-C ⁇ alkyl, acyloxy-d-C 6 alkyl, halogen-C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-C ⁇ -C 6 alkyl, halogen-C 3 -C 6 -cycloalkyl- C ⁇ -C 6 alkyl, aryloxy-d-C 6 alkyl; or phenyl, benzyl, phenoxy or aryloxy-d-Cealkyl, which are substituted with 1 to 3 substituents selected form the group consisting of halogen, nitro, cyano, C C -alkyl, halogen-C ⁇ -C 4 -alkyl and halogen-d-d-alkoxy;
  • R 7b is H, C ⁇ -C 8 alkyl, C 2 -C 8 alkenyl, halo-C C 8 alkyl, halo-C 2 -C 8 alkenyl, d-C 8 alkoxy, halo-C ⁇ -C 8 alkoxy, C 3 -C 6 cycloalkyl, phenyl, benzyl, phenoxy, benzyloxy or -N(R 6 ) 2 (in which the two R 6 are independent of one another);
  • R 8 is C C 8 alkyl, C C 8 alkoxy, halogen-d-C 8 alkyl, halogen-C C 8 alkoxy, C C 8 alkylthio, phenyl, benzyl or -N(R 6 ) (wherein the two R 6 radicals are independent of one another);
  • R 9 is Ci-C ⁇ alkyl, halogen-d-C 4 alkyl or aryl, which is unsubstituted or substituted once to three times, independently of one another, with subsituents selected from the group consisting of C ⁇ -C 6 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkinyl, d-dalkoxy, halogen, cyano, halogen-Crdalkyl, halogen-C 2 -C alkenyl, halogen-C 2 -C alkinyl, halogen-d-C 4 alkoxy and nitro;
  • R 1 0 is H, CrC 6 alkyl, C 3 -C 6 cycloalkyl, phenyl oder benzyl, wherein the phenyl and benzyl radicals are unsubstituted or substituted in the aromatic ring once to three times independently of one another with substituents selected from the group consisting of d-C alkyl, d-dalkoxy, halogen, cyano, halogen-d-C 4 alkyl, halogen-d-C 4 alkoxy and nitro;
  • Rn and R12 are independently of one another H, d-C 6 alkyl, phenyl, -COd-C 6 alkyl,
  • R 13 is H, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkinyl;
  • Groups and compounds containing carbon comprise, unless defined otherwise, in each case 1 to 8 inclusive, preferably 1 to 6 inclusive, more particularly 1 to 4 inclusive, especially 1 or 2, carbon atoms.
  • Alkyl - as a group per se and as a structural component of other groups and compounds, such as alkyl halide, alkoxy or alkylthio - is, in each case with due consideration to the number of carbon atoms in the group or compound concerned, either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • Alkenyl - as a group per se and as a structural component of other groups and compounds, such as alkenoxy, alkenyl halide or alkenoxy halide - is, in each case with due consideration to the number of carbon atoms in the group or compound concerned, either straight-chained, e.g. vinyl, 1 -methylvinyl, allyl, 1 -butenyl oder 2-hexenyl, or branched, such as isopropenyl.
  • Alkinyl - as a group per se and as a structural component of other groups and compounds, such as alkinyl halide - is, in each case with due consideration to the number of carbon - 6 -
  • atoms in the group or compound concerned either straight-chained, e.g. propargyl, 2- butinyl or 5-hexinyl, or branched, such as 2-ethinylpropyl or 2-propargylisopropyl.
  • C 3 -C 6 cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Aryl is phenyl or naphthyl, especially phenyl.
  • Bicyclic heteroaryl is taken to mean a radical which may independently contain one or more heteroatoms only in one ring - such as for example in quinolinyl, quinoxalinyl, indolinyl, benzothiophenyl or benzofuranyl - as well as in both rings - such as for example in pteridinyl or purinyl.
  • Halogen - as a group per se and as a structural component of other groups and compounds, such as alkyl halide, alkenyl halide and alkinyl halide - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, and quite particularly chlorine.
  • Halogen-substituted groups and compounds containing carbon such as alkyl halide, alkenyl halide or alkinyl halide, may be partly halogenated or perhalogenated, where in the case of repeated halogenation the halogen substituents may be the same or different.
  • alkyl halide - as a group per se and as a structural component of other groups and compounds, such as alkenyl halide - are methyl substituted once to three times by fluorine, chlorine and/or bromine, such as CHF 2 or CF 3 ; ethyl substituted once to five times by fluorine, chlorine and/or bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCI 3 , CF 2 CHCI 2 , CF 2 CHF 2 , CF 2 CFCI 2 , CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl substituted once to seven times by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF 3 or CH(CF 3 ) 2 ; and butyl or one of the isomers thereof substituted once to
  • Alkinyl halide is for example CH 2 C ⁇ CF, CH 2 C ⁇ CCH 2 CI or CF 2 CF 2 C ⁇ CCH 2 F.
  • Compounds of formula (I) which show at least one basic centre may form, for example, acid addition salts. These are formed, for example, with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrogen halide, with strong organic carboxylic acids, such as d-dalkanecarboxylic acids substituted if appropriate by halogen, e.g. acetic acid, such as dicarboxylic acids unsaturated if appropriate, e.g. oxalic, malonic, succinic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, e.g.
  • strong inorganic acids such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrogen halide
  • strong organic carboxylic acids such as d-dalkan
  • compounds of formula (I) with at least one acid group can form salts with bases.
  • Suitable salts with bases are for example metal salts, typically alkali or alkaline earth metal salts, e.g.
  • phenyl especially phenyl, naphthyl, pyridyl or thiadiazolyl, very especially phenyl or pyridyl, in particular phenyl;
  • R 3 corresponds to R 3a and R 3b of formula (I);
  • R 3a and R 3b are independently of one another halogen, -CN, NO 2 , halogen-CrC 2 alkyl, d-C 2 alkoxy or halogen-CrC 2 alkoxy, halogen-C 2 -C 5 alkenoxy or halogen-C 2 -C 5 alkinyloxy; especially chlorine, -CN, CF 3 or OCF 3 ; wherein, if m + n is greater than 1 , the radicals R 3a and R 3b are independent of one another;
  • R is H, d-dalkyl, phenyl or benzyl; especially H and methyl; n is 0 to 5, especially 1 to 3, depending on the possibility for substitution on the ring system, and the values of n in A** are independent of the values of n in A 2 ; m is 0 to 4, depending on the possibility for substitution on the ring system, and the values of m in A- are independent of the values of m in A 2 ; - 9 -
  • R 2 is R 2a or R 2b ;
  • (R 3a )m is Cl, Cl 2 , Cl 3 , -(CF 3 ) 2 , CI-CF 3 , NO 2 , -CN, CI 2 -NO 2 , -OCF 3 , -CF 3 , CI-CF 3 , CI 2 .CF 3 , Cl 2 - OCF 3 , -Cl 2 -F, Cl 2 -Br, CI-CF 3 -F, CI-Br-CH 3 , -(CH 3 ) 2 -Br, CI 3 -CF 3 , CI 2 -F-CF 3 , F 2 -CF 3 -CI, CI 2 -CN, CI 2 -CF 3 , CI 2 -SCF 3 , CI 2 -OCF 3 , CI 2 -O 2 CF 3 , CI 2 -SO 2 CH 3 , CI 2 -OCF 2 Br, CI 2 -OCF 2 H, CI 2 -C 2
  • (R 3b ) n2 is -CN, Cl, Cl 2 , F, F 2 , Br, -NO 2 , -(NO 2 ) 2 , -NO 2 -CF 3 , CF 3 , -(CF 3 ) 2 , -CN-CF 3 , CI-CF 3 , F- CN, -CI-CN, -OCF 3 , -CI-NO 2 , -CH 3 -NO 2 , -OCH 3 -NO 2 , -C 6 H 5 , -C 6 H 4 -F, -C 6 H 4 -CI, -C 6 H 4 -CF 3 , -C 6 H 4 -CF 3 , -C 6 H 4 -NO 2 , -C 6 H 3 -(CF 3 ) 2 , -C 6 H 3 -CI 2 , -C 6 H 3 -(CI-F), -F-CN, F-NO 2 , CI-NO 2
  • 4-CN, 3-CN, 4-CI. 3,4-CI 2 , 2,3-CI 2 , 3,5-CI 2 , 2,5-CI 2 , 3,5-F 2 , 2,6-F 2 , 2-F, 2-NO 2 -4-CF 3 , 4- NO 2 , 3-CF 3) 4-CF 3 , 3,5-(CF 3 ) 2 , 2-CN-4-CF 3 , 2-CI-4-CF 3 , 2-F-4-CN, 3-CI-4-CN, 4-OCF 3 , 3- OCF3, 4-CI-3-NO 2 , 2-CI-4-NO 2 , 3-CH 3 -4-NO 2 , 3-OCH 3 -4-NO 2 , 4-C 6 H 5 , 2-F-4-CN, 2-F-4-NO 2 , 2-CI-4-NO 2 , 4-CI-3-NO 2 , 4-CHO, 4-SCF 3 , 4-SOCF 3 , 4-SO 2 CF 3 or 4-C( O)CF 3 ;
  • Rn and R 12 are independently of one another H, d-C 2 alkyl, phenyl, -COd-C 2 alkyl, -COphenyl, or together form a five or six-membered saturated or unsaturated ring, wherein one of the CH- or CH 2 -groups if applicable is substituted by a heteroatom selected from the group consisting of O, N and S, and wherein the five or six-membered ring if applicable is substituted with 1 or 2 substituents selected from the group consisting of d-C 2 alkyl, d-dhaloalkyl, NO 2 , CN; or the two substituents Rn and R 12 together form a ring X X
  • Rn and R 12 are independently of one another H, d-C 2 alkyl, phenyl, -COC C 2 alkyl, - COphenyl, very especially H, methyl or ethyl.
  • R 14 is hydrogen, d-C 2 alkyl, halogen-d-C 2 alkyl, phenyl or benzyl;
  • Ri 5 is methyl or CF 3 ;
  • n 2 1 and
  • (R 3b )n2 is SCH 3 , SCF 3 , SC 2 H 5 , SC 2 F 5 , SOCH 3 , SOC 2 H 5 , SOC 2 F 5 , SO 2 N(CH 3 ) 2 , SO 2 N(C 2 H 5 ) 2 ,
  • R 2 is R 2a or R 2b , especially H, -CH 2 OC 2 H 5 , -COCH 3 , -CH 3 , -CN, -CH 2 C ⁇ CH, -C 2 H 5, -COOCH 3 or -CON(CH 3 )OCH 3 .
  • a further object of the invention is the method for preparing the compounds of formula (I) and where appropriate their E/Z isomers, E/Z isomeric mixtures, and/or tautomers thereof in each case in free form or in the form of a salt, comprising either a) for the preparation of a compound of formula (I), wherein the substituents A, and A 2 are as defined hereinbefore, and R 2 is hydrogen, aa) the diazotization of a compound of formula
  • a 2 is as defined hereinbefore under formula (I) and W is hydrogen or a removable group; or b) for the preparation of a compound of formula
  • A* * , A 2 and R 2 are as defined hereinbefore for R 2a and R 2b in the compounds of formula (I) and Hal is a halogen atom, preferably chlorine or bromine, especially chlorine, with a metal cyanide, preferably an alkaline metal cyanide, especially with sodium cyanide; or c) for the preparation of a compound of formula (I), wherein R 2 is different from H, the reaction of a compound of formula (I), wherein R 2 is hydrogen, with a compound of formula
  • a further object of the invention is a method for the preparation of a compound d) of formula - 15 -
  • Ai, A 2 and R 2 are as defined hereinbefore for R 2a and R 2b in the compounds of formula (I) and Hal is a halogen atom, and where applicable the E/Z isomers and tautomers thereof, in free form or in the form of a salt, comprising the reaction of a compound of formula
  • radicals A, and A. and R 2 have the same meaning as defined hereinbefore under formula (Ma) for R 2a and R 2b , with a halogenation agent, or e) of formula
  • R 2 and the two radicals A, and A 2 have the same meaning as defined hereinbefore for Ai, A , R 23 and R 2b under formula (I) and Hal is a halogen atom, preferably chlorine, comprising the reaction of a compound of formula
  • R 2 and the two radicals A, and A 2 have the same meaning as defined hereinbefore under formula (Mb), with N-bromosuccinimide or N-chlorosuccinimide in the presence of a thio ether, and in each case, if so desired, the conversion of a compound of formula (II) or an E/Z isomer or tautomer thereof in free form or in the form of a salt and obtainable by means of the method or by other means to another compound of formula (II) or an E/Z isomer or tautomer thereof in free form or in the form of a salt, the separation of a mixture of E/Z - 16 -
  • isomers obtainable by means of the method or by other means, and the isolation of the desired isomer, and/or the conversion of a free compound of formula (II) or an E/Z isomer or tautomer thereof, obtainable by means of the method or by other means, to a salt, or the conversion of a salt, obtainable by means of the method or by other means, of a compound of formula (II) or of an E/Z isomer or tautomer thereof to the free compound of formula (II) or an E/Z isomer or tautomer thereof, or to another salt.
  • the reactions described hereinbeore and hereinafter are carried out in known manner, wherein the work may be performed, depending on requirements, with cooling, at room temperature, or with heating, e.g. in a temperature range from about 0°C to the boiling temperature of the reaction medium, preferably from about 20°C to about +120°C, especially at 60°C to 80°C and, if necessary, in a closed container, under pressure and in an inert gas atmosphere, e.g. under nitrogen or argon, and/or under anhydrous conditions. Preferred are reactions carried out at normal pressure under nitrogen.
  • the reaction partners can be reacted with one another as they are, i.e. without the addition of a solvent or diluent, e.g. in the melt. In most cases, however, the addition of an inert solvent or diluent, or a mixture thereof, is of advantage. Especially advantageous reaction conditions are described in the Examples.
  • the isolation of the products takes place according to usual methods, e.g. by filtration, crystallization, distillation or chromatography or any suitable combination of these methods.
  • mineral acids e.g. perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrogen halide
  • the reaction takes place in a temperature range from about -10°C to about +20°C, or if necessary even at a higher temperature, for example at 60°C to 80°C.
  • the reaction time is preferably about 1 to about 2 hours.
  • the product is usually not isolated, but processed further in the next reaction step.
  • the reaction usually takes place in the presence of water and preferably in the presence of an organic carboxylic acid, such as formic acid, chloroacetic acid, trifluoroacetic acid, cyanoacetic acid, oxalic, malonic, succinic, maleic, fumaric or phthalic acid; especially preferred is the addition of acetic acid.
  • an organic carboxylic acid such as formic acid, chloroacetic acid, trifluoroacetic acid, cyanoacetic acid, oxalic, malonic, succinic, maleic, fumaric or phthalic acid; especially preferred is the addition of acetic acid.
  • a removable group W is taken to mean an electrophilic group which is readily removable under the prevailing reaction conditions.
  • the reaction is advantageously carried out within a temperature range of about -10°C to about +30°C, preferably from about 0°C to about +25°C.
  • reaction time of about 0.5 to about 8 hours is preferred, especially about 2 to about 4 hours.
  • transition metal cyanides such as CuCN or Ni(CN) 2
  • alkaline earth and alkaline metal cyanides especially KCN and NaCN.
  • solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyi ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether,
  • the reaction is advantageously carried out within a temperature range from about 0°C to about 80°C, preferably from about 20°C to about 30°C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture. - 18 -
  • reaction time of about 0.1 to about 24 hours is preferred, especially about 3 to about 5 hours.
  • a compound of formula (II) is reacted in an ethanol / water mixture with sodium cyanide at room temperature.
  • Suitable leaving groups Q in compounds of formula (V) are for example hydroxy, d-C 8 alkoxy, halogen-d-C 8 alkoxy, Crdalkanoyloxy, mercapto, d-C 8 alkylthio, halogen- CrC 8 alkylthio, d-C 8 alkanesulfonyloxy, halogen-CrC 8 alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy, trifluoromethanesulfonyloxy or halogen, especially halogen, in particular bromine or chlorine.
  • Suitable bases for facilitating the reaction are e.g. alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, cycloalkylamines (N-alkylated where appropriate and unsaturated where appropriate), basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Examples are: sodium hydroxide, hydride, amide, methanolate, acetate, and carbonate, potassium tert-butanolate, hydroxide, carbonate, hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N- dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N- methylmorpholine, benzyltrimethylammonium hydroxide and 1 ,5-diazabicyclo[5.4.0]undec-5- ene (DBU).
  • Preferred are alkaline metal and earth alkaline metal carbonates, alkylamines and alkaline metal or earth alkaline metal alkanolates.
  • solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons, typically benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethylether, dimethoxydiethylether, tetrahydrofuran or dioxan; esters, such as ethyl acetate and methyl acetate; and sulfoxides, such as dimethyl sulfoxide.
  • the reaction is advantageously carried out within a temperature range from about 0°C to about +120°C, preferably from about 0°C to about +80°C.
  • reaction time of about 0.1 to about 24 hours is preferred, especially about 0.5 to about 2 hours.
  • the reaction preferably takes place in the presence of an acid catalyst, for example in the presence of a carboxylic acid, such as formic acid, acetic acid, malonic acid or oxalic acid, or also a sulfonic acid, such as d-dalkane or arylsulfonic acid substituted if necessary for example by halogen, e.g. methane, trifluoromethane or p-toluenesulfonic acid.
  • a carboxylic acid such as formic acid, acetic acid, malonic acid or oxalic acid
  • a sulfonic acid such as d-dalkane or arylsulfonic acid substituted if necessary for example by halogen, e.g. methane, trifluoromethane or p-toluenesulfonic acid.
  • solvents which are suited to azeotropic removal of water.
  • solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, dimethoxydiethyl ether; ketones, such as methyl isobutyl ketone;
  • the reaction is advantageously carried out within a temperature range of about 60°C to about 180°C, preferably 80°C to about 130°C, in many cases at the reflux temperature of the reaction medium.
  • the preferred reaction time is about 6 to about 72 hours, especially about 12 to about 48 hours.
  • the reaction is carried out at 80° C to 140°C in an alcohol or an aromatic hydrocarbon in the presence of d-dcarboxylic acid.
  • Preferred halogenation agents are Cl 2 , Br 2 , SOCI 2 , SO 2 CI 2 , POCI 3 , PCI 3 , PCI 5 and COCI 2 .
  • solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethene or - 20 -
  • aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetrachloromethane,
  • esters such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxan; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; amides, such as N,N-dimethylformamide, N,N diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles, such as acetonitrile or propionitrile.
  • ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene
  • the reaction is advantageously carried out within a temperature range from about 0°C to about 180°C, preferably from about 50°C to about 100°C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.
  • reaction time is not critical; a reaction time of about 0.1 to about 24 hours is preferred, especially about 3 to about 6 hours.
  • the compounds of formulae (I), (lla), (lib) und (VIII) may be present in the form of one of the possible isomers or as a mixture thereof, depending for example on the number and the absolute and relative configuration of the asymmetric carbon atoms as pure isomers, such as enantiomers and/or diastereomers or isomer mixtures, such as mixtures of enantiomers, for example racemates; the invention relates both to the pure isomers and to all possible isomeric mixtures, and is hereinbefore and hereinafter understood as doing so, even if stereochemical details are not specifically mentioned in every case.
  • Diastereomer mixtures and racemate mixtures of compounds of formulae (I), (lla), (lib) and (VIII), obtainable as described in the method - depending on the starting materials and working procedures selected- or by other means, can, owing to the physicochemical differences of the constituents, be separated in known manner into the pure diastereomers or racemates, for example by fractionated crystallization, distillation and/or chromatography.
  • the resolution of correspondingly obtainable mixtures of enantiomers, such as racemates, can be achieved by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, e.g. high-pressure liquid chromatography (HPLC) on acetyl cellulose, by the use of suitable microorganisms, by cleavage with specific immobilized enzymes, through the formation of inclusion compounds, e.g. using chiral crown ether, wherein only one enantiomer is complexed.
  • HPLC high-pressure liquid chromatography
  • the invention relates to all those forms of the method, according to which one starts from a compound obtainable as a primary material or an intermediate at any stage of the method and carries out all or some of the missing steps, or uses, or - especially under the reaction conditions - produces a starting material in the form of a derivative or a salt and/or its racemate or enantiomer.
  • the starting materials and intermediates used are preferably those that lead to the compounds of formula (I) described at the beginning as being especially useful.
  • the invention relates in particular to the manufacturing processes described in Examples H1 , H2, H4 and H5.
  • a further object of the invention is a method for controlling pests using a compound of formula (I), wherein A**, A 2 and R 2 have the same meaning as defined hereinbefore for formula (I).
  • the compounds of formula (I) according to the invention are active substances of preventive and/or curative merit for use in pest control and offer a very favourable spectrum - 22 -
  • compositions according to the invention are active against all or individual development stages of animal pests showing normal sensitivity, and also of those showing resistance, for example insects or members of the order acarina.
  • the insecticidal, ovicidal, and/or acaricidal effect of the compositions of the invention can manifest itself directly, i.e. killing the pests either immediately or after some time has elapsed, for example when moulting occurs, or the eggs thereof, or indirectly, e.g. reducing the number of eggs laid and/or the hatching rate, good efficacy corresponding to a destruction rate (mortality) of at least 50 to 60%.
  • the animal pests include for example:
  • Pests of said type which occur on plants, especially on crops and ornamentals in agriculture, horticulture and forestry, or on parts of such plants, such as fruits, blooms, leaves, stems, tubers or roots, can be controlled, i.e. kept in check or eradicated, using the active ingredients of the invention, this protection remaining for parts of some plants whose growth does not occur until later.
  • Target crops within the scope of this application include especially cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beet, such as sugar beet or fodder beet; fruit, e.g. pomes, drupes and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, e.g.
  • strawberries, raspberries or blackberries leguminous plants, such as beans, lentils, peas or soybean; oleaginous fruits, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as pumpkins, cucumbers or melons; fibrous plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or paprika; lauraceae, such as avocado, cinnamon or camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, banana plants, natural rubber plants and ornamentals.
  • the active ingredients of the invention are especially suitable for the control of insects and members of the order acarina, in particular crop-eating and damaging insects, such as - 23 -
  • the invention therefore relates also to pesticides which comprise a compound of formula (I), wherein A**, A 2 and R 2 have the same meaning as defined hereinbefore for formula (I), with the exception of 1 -phenylhydrazono-2-nitriloethylbenzene, such as emulsifiable concentrates, suspension concentrates, ready-to-spray or ready-to-dilute solutions, coatable pastes, dilute emulsions, spray powders, soluble powders, dispersible powders, wettable powders, dusts, granulates or encapsulations in polymeric substances (chosen in accordance with the intended objectives and prevailing circumstances), comprising at least one active ingredient of the invention.
  • 1 -phenylhydrazono-2-nitriloethylbenzene such as emulsifiable concentrates, suspension concentrates, ready-to-spray or ready-to-dilute solutions, coatable pastes, dilute emulsions
  • the active ingredient is employed in pure form, the solid active ingredients in a specific particle size, or preferably together with - at least - one of the adjuvants conventionally used in the art of formulation, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).
  • the adjuvants conventionally used in the art of formulation, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).
  • Suitable adjuvants such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, and anionic surfactants in the compositions used according to the invention, are the same as those which are described in EP-A-736'252 (CASE 20400) and which are included in the present object of the invention by reference.
  • the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of - at least - one solid or liquid adjuvant, wherein 0 to 25%, especially 0.1 to 20%, of the composition may as a rule be surfactant (% in each case meaning percent by weight).
  • the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient.
  • Preferred compositions are thus composed in particular as described in EP-A-736'252 .
  • compositions of the invention can be substantially broadened and adapted to prevailing circumstances by adding other insecticidal, acaricidal, and/or - 24 -
  • compositions of the invention can also comprise other solid or liquid adjuvants, such as stabilizers, e.g. vegetable oils, epoxidized where appropriate (e.g. epoxidized coconut oil, rapeseed oil or soya oil), antifoams, e.g. silicone oil, preservatives, viscosity modulators, binders and/or tackifiers, and also fertilizers or other active ingredients to achieve specific effects, e.g. acaricides, bactericides, nematocides, molluscicides or selective herbicides.
  • stabilizers e.g. vegetable oils, epoxidized where appropriate (e.g. epoxidized coconut oil, rapeseed oil or soya oil), antifoams, e.g. silicone oil, preservatives, viscosity modulators, binders and/or tackifiers, and also fertilizers or other active ingredients to achieve specific effects, e.g. acaricide
  • compositions of the invention are prepared in a known manner, in the absence of adjuvants, for example, by grinding and/or sieving a solid active ingredient or active ingredient mixture, e.g. to a specific particle size, and in the presence of at least one adjuvant, for example, by intimately mixing and/or grinding the active ingredient or the mixture of active ingredients with the adjuvant(s).
  • adjuvants for example, by grinding and/or sieving a solid active ingredient or active ingredient mixture, e.g. to a specific particle size
  • at least one adjuvant for example, by intimately mixing and/or grinding the active ingredient or the mixture of active ingredients with the adjuvant(s).
  • compositions i.e. the methods of controlling pests of said type, such as spraying, atomizing, dusting, coating, dressing, scattering or pouring (chosen in accordance with the intended objectives and prevailing circumstances), and the use of the compositions for controlling pests of said type are further objects of the invention.
  • Typical concentrations of active ingredient are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm.
  • a preferred method of application for crop protection is to apply the active ingredient to the foliage of the plants (leaf application), the number of applications and the rate of application depending on the intensity of infestation by the pest in question.
  • the active ingredients can also penetrate the plant through the roots via the soil (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). With paddy rice cultures, granules may be metered into the flooded paddy field. 25 -
  • compositions of the invention are also suitable for protecting plant propagation material, e.g. seeds, such as fruits, tubers or grains, or plant seedlings, from fungal infections and animal pests.
  • the propagation material can be treated with the composition before the start of cultivation, seeds for example being dressed before they are sown.
  • the active ingredients of the invention can also be applied to seeds (coating) by either soaking the seeds in a liquid composition or coating them with a solid composition.
  • the composition can also be given when the propagation material is introduced to the place of cultivation, e.g. when the seeds are sown in the seed furrow.
  • the treatment procedures for plant propagation material and the propagation material thus treated are further objects of the invention.
  • Example H3 The other compounds listed in Table 1 can be prepared in a manner analogous to that described under Example H2.
  • Example H5 Preparation of 4- ⁇ 1 -[(2,6-dichloro-4-trifluoromethylphenyl)-N-methyl-N- methoxycarbamoylhydrazono]-2-nitriloethyl ⁇ nitrobenzene of formula - 28 -
  • Example 6 The other compounds listed in Tables 2 and 3 can also be prepared in a manner analogous to that described under Example H5.
  • C 3 H 3 F 2 cyc is 2,2-difluoro-cycloprop-1 -yl
  • CD CD CD CD CD CD ⁇ CD en 00 CD en 4 - CO ro o CD 00 en en 4 s - CO IV) o CO oo -*J CD en 4 s - ⁇ ro o CD o so
  • formulations of compounds of the invention i.e. solutions, granulates, dusts, wettable powders, emulsifiable concentrates, coated granules, and suspension concentrates are of the types listed for instance in EP-A-580'553(Case 19164), Examples F1 to F10. - 56 -

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  • Thiazole And Isothizaole Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

Composés de formule (I) dans laquelle A1 et A2 représentent séparément un radical aryle ou hétéroaryle; et A1, lorsque cela est approprié, est substitué par un substituant (R3a)n1 et A2, lorsque cela est approprié, par un substituant (R3b)n2; n1 et n2 valent séparément 0, 1, 2, 3 ou 4; et soit R3a et R3b représente séparément, par exemple, halogène, C1-C6alkyle, C2-C4alkinyle, halogène-C1-C6alkyle, halogène-C2-C4alkinyle, C1-C6alcoxy, halogène-C1-C6alcoxy, C2-C6alcènyloxy, C2-C6alkinyloxy ou halogène-C2-C6alcényloxy; et R2 représente R¿2a?; R2a représente par exemple, -C1-C6alkyle-NR11R12, -COC9-C20alkyle, -C1-C6alkyle-O-C1-C6alkyle-O-C1-C6alkyle ou -CH2O(C=O)C1-C6alkyle; soit au moins un des radicaux R3a ou R3b représente -CR5=CR5R14, -NR11R12, -C(=O)CN, -C(=O)C(=O)O-C1-C6alkyle, -CR7=NOR10, ou un cycle hétéroaryle à six éléments, lié par un atome de carbone; R2 représente R2a ou R2b, R2a étant tel que défini précédemment; et R2b représentant, par exemple, hydrogène, -OH, C1-C6alkyle ou C1-C6alcoxy; R14 représente, par exemple, hydrogène, halogène, C1-C6alkyle ou halogène-C1-C6alkyle; X représente O ou S; p vaut 0, 1 ou 2; R5 représente séparément H ou C1-C8alkyle; R6 représente, par exemple, séparément, H, C1-C8alkyle ou C3-C6cycloalkyle; R7 représente par exemple H, C1-C8alkyle, C2-C8alcényle ou halogène-C1-C8alkyle; R8 représente par exemple C1-C8alkyle, C1-C8alcényle ou halogène-C1-C8alkyle; R9 représente C1-C6alkyle, halogène-C1-C4alkyle ou aryle; R10 représente H, C1-C6alkyle, C3-C6cycloalkyle, phényle ou benzyle; R11 et R12 représentent, par exemple, séparément H, C1-C6alkyle ou phényle; et lorsque c'est applicable, les éventuels isomères E/Z, les mélanges d'iomères E/Z et/ou les tautomères de ceux-ci, sous forme libre ou sous une forme acceptable du point de vue argochimique, peuvent être utilisés comme principes actifs agrochimiques et peuvent être préparés de la manière connue en soi.
EP99907393A 1998-01-22 1999-01-20 Derives organiques nitrile et leur utilisation comme pesticides Withdrawn EP1049663A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CH14998 1998-01-22
CH14998 1998-01-22
CH96398 1998-04-29
CH96398 1998-04-29
PCT/EP1999/000363 WO1999037603A1 (fr) 1998-01-22 1999-01-20 Derives organiques nitrile et leur utilisation comme pesticides

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EP1049663A1 true EP1049663A1 (fr) 2000-11-08

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JP (1) JP2002501038A (fr)
KR (1) KR20010034302A (fr)
CN (1) CN1288459A (fr)
AU (1) AU744872B2 (fr)
BR (1) BR9907741A (fr)
CA (1) CA2316835A1 (fr)
TW (1) TW436475B (fr)
WO (1) WO1999037603A1 (fr)

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Publication number Priority date Publication date Assignee Title
EP1338589A4 (fr) 2000-11-02 2004-03-17 Nippon Soda Co Compose organique possedant un groupe cyano et insecticides / miticides
DE10353205A1 (de) * 2003-11-13 2005-06-16 Aventis Pharma Deutschland Gmbh Ortho-substituierte Pentafluorsulfuranyl-Benzole, Verfahren zu ihrer Herstellung sowie ihre Verwendung als wertvolle Synthese-Zwischenstufen
TW201029997A (en) * 2008-12-23 2010-08-16 Basf Se Imine compounds for combating invertebrate pests
CA2878815A1 (fr) 2012-07-10 2014-01-16 Dana-Farber Cancer Institue, Inc. Composes anti-proliferatifs et utilisations associees
CN103224470A (zh) * 2013-05-17 2013-07-31 南京农业大学 一类喹喔啉-6-苯腙衍生物的制备方法及其用途

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NZ241574A (en) * 1991-02-22 1993-08-26 Ishihara Sangyo Kaisha Substituted phenyl derivatives of hydrazone and pesticidal compositions
TW268881B (fr) * 1992-07-07 1996-01-21 Ciba Geigy Ag
TR199900124T2 (xx) * 1996-07-24 1999-03-22 Novartis Ag Ha�ere �ld�r�c� bile�imler

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See references of WO9937603A1 *

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AU2718199A (en) 1999-08-09
CN1288459A (zh) 2001-03-21
CA2316835A1 (fr) 1999-07-29
AU744872B2 (en) 2002-03-07
KR20010034302A (ko) 2001-04-25
BR9907741A (pt) 2000-10-17
WO1999037603A1 (fr) 1999-07-29
TW436475B (en) 2001-05-28
JP2002501038A (ja) 2002-01-15

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