WO1997038973A1 - Composes d'hydrazine, procede de preparation desdits composes et insecticides a usage agricole et horticole - Google Patents

Composes d'hydrazine, procede de preparation desdits composes et insecticides a usage agricole et horticole Download PDF

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Publication number
WO1997038973A1
WO1997038973A1 PCT/JP1997/001282 JP9701282W WO9738973A1 WO 1997038973 A1 WO1997038973 A1 WO 1997038973A1 JP 9701282 W JP9701282 W JP 9701282W WO 9738973 A1 WO9738973 A1 WO 9738973A1
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group
carbon atoms
atom
formula
compound represented
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PCT/JP1997/001282
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English (en)
Japanese (ja)
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Shohei Fukuda
Yasuhisa Fukuda
Kiyoshi Tsutsumiuchi
Koichi Goka
Takaaki Kuwata
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Ube Industries, Ltd.
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Priority to AU25221/97A priority Critical patent/AU2522197A/en
Publication of WO1997038973A1 publication Critical patent/WO1997038973A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-nitrogen bonds, e.g. azides, diazo-amino compounds, diazonium compounds, hydrazine derivatives
    • 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
    • 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
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues 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
    • 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
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • 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
    • C07C317/28—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 acyclic carbon atoms of the 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
    • C07C323/46—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 at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/48—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 at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to nitrogen atoms
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3

Definitions

  • Hydrazine compounds their production methods and agricultural and horticultural pesticides
  • the present invention relates to a novel hydrazine compound, a method for producing the same, and a fungicide for agricultural and horticultural use containing the same as an active ingredient.
  • R 1 represents an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, etc .
  • CR 2 R 3 represents an alkylene group
  • R 4 represents a hydrogen atom
  • R 1G represents a hydrogen atom or the like
  • R 11 represents a hydrogen atom, an alkylcarbonyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, one CON RWR (Where R 16 and R 17 each independently represent a hydrogen atom, an alkyl group having from 4 to 4 carbon atoms, etc.); and
  • R 12 and R 13 each independently represent a hydrogen atom
  • the hydrazine compound of the present invention is a novel compound, it is not known that it has an agricultural and horticultural insecticidal activity.
  • An object of the present invention is to provide a novel hydrazine compound, a method for producing the same, and an insecticide for horticulture using the same as an active ingredient. Disclosure of the invention
  • the present inventors have conducted studies to solve the above problems, and as a result, have found that a novel hydrazine compound has a remarkable insecticidal activity for agricultural and horticultural use, and have completed the present invention. That is, the present invention is as follows.
  • the first invention has the following formula (1):
  • R 1 represents an unsubstituted or a phenyl group having a halogen atom as a substituent
  • R 2 represents a hydrogen atom
  • R 3 represents an alkyl group having 1 to 4 carbon atoms or Represents a haloalkyl group having 1 to 4 carbon atoms
  • R 4 represents a hydrogen atom or one CONR 7 R 8
  • R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having up to 4 carbon atoms.
  • R 5 is a hydrogen atom, a haloalkyl group having 1 to 4 carbon atoms, 2 to 5 carbon atoms.
  • R 6 represents an alkoxycarbonyl group having 2 to 5 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, an unsubstituted or substituted C1-C4 alkoxy, halogen, C1-C4 haloalkyl or benzoyl having C1-C4 alkyl, unsubstituted or pyridylcarbonyl having halogen as substituent Group, an alkyl group having 1 to 4 carbon atoms, a phenyl carbamoyl group having an L-diyl group, a hydrogen atom, a non-S-substituted or haloalkyl group having 1 to 4 carbon atoms as a substituent,
  • X represents an alkylene group having 4 to 4 carbon atoms or an oxygen atom; n is 0 to 2; and when X is an alkylene group having 1 to 4 carbon atoms, n represents n. Represents 0 or 1; and when
  • the second invention has the following formula (2):
  • R 1 , R 3 , R 5 , R 6 , X and n are as defined above,
  • R 1 , R 3 , R 5 , R 6 , X and n have the same meanings as described above, and refer to the method for producing a hydrazine compound represented by the following formula.
  • the third invention relates to a compound represented by the above formula Oa)
  • Z represents a leaving group
  • R 7 is as defined above
  • R 1 to R 3, R 4 ′, R 5, R 6, X and n have the same meanings as described above and relate to a method for producing a hydrazine compound represented by The fourth invention provides the following equation (4)
  • R 1 to R 3 , X and n are as defined above;
  • Z ′ represents a leaving group
  • R 1 to R 3, R 5, R 6, X and n are related to the production method of the compound represented by
  • the fifth invention relates to an insecticide for agricultural and horticultural use containing the hydrazine compound represented by the above formula (1) as an active ingredient.
  • the compounds represented by the formulas (1), (2), (la), (3a), (3b), (4) and (5) are converted into the compounds (1), (2) and (1), respectively. a), (3 a), (3 b), (4) and (5).
  • the various substituents represented by the above compounds are as follows.
  • R 1 examples include a phenyl group having a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom) as an unsubstituted or substituted group; preferably, a phenyl group having a halogen atom. And more preferably a phenyl group having a chlorine atom.
  • a halogen atom eg, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
  • the substitution position is not particularly limited; preferably it is at the 4-position.
  • R 2 can include a hydrogen atom.
  • R 3 examples include an alkyl group having 1 to 4 carbon atoms and a haloalkyl group having 1 to 4 carbon atoms.
  • alkyl group examples include straight-chain or branched ones; preferably, CH 3 or C 2 H 5 .
  • haloalkyl group examples include those in which the alkyl is linear or branched and having a halogen atom such as a salt atom, an iodine atom, a bromine atom, and a fluorine atom; Having one child; more preferably CF 3 .
  • R 4 examples include a hydrogen atom, one CONR 7 R 8 , an alkylcarbonyl group having 2 to 5 carbon atoms, and an alkoxycarbonyl group having 2 to 5 carbon atoms.
  • R 7 and R 8 include a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom and CH 3 are preferable.
  • the alkylcarbonyl group is a group having a linear or branched alkyl group having 1 to 4 carbon atoms; preferably —COCH 3 .
  • the alkoxycarbonyl group is a group having a linear or branched alkoxy group having 1 to 4 carbon atoms; preferably —COOC 2 H 5 .
  • the R 5, may be mentioned hydrogen atom, a haloalkyl group having carbon atoms to 4, alkoxyalkyl group and an alkyl group having a carbon number 1-4 carbon atoms having 2-5.
  • haloalkyl group examples include those in which the alkyl moiety is linear or branched and having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; Having a chlorine atom; more preferably, CH 2 CH 2 CI.
  • the alkoxyalkyl group has a total number of carbon atoms of 2 to 5, and has a linear or branched alkoxy group having 1 to 4 carbon atoms and a linear or branched chain having 4 to 4 carbon atoms. it is a branched alkyl group; preferably an CH 2 OC 2 H 5.
  • alkyl group examples include a linear or branched one; preferably, CH 3 .
  • R 6 is an alkoxycarbonyl group having 2 to 5 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, a benzoyl group, a pyridylcarbonyl group, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a hydrogen atom , Phenylcarbamoyl, pyridyl and formyl groups.
  • the alkoxycarbonyl group has a linear or branched alkoxy group having 1 to 4 carbon atoms; preferably, one COOCH 3 , -COOC 2
  • the alkylcarbonyl group has a linear or branched alkyl group having 4 to 4 carbon atoms; preferably, —COCH 3 , —COC 2 H 5 .
  • the benzoyl group may have, as a substituent, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms.
  • alkoxy group for the substituent examples include a linear or branched one; preferably, one is OCH 3 .
  • the position g of the substituent is not particularly limited; however, it is preferably the 4-position.
  • halogen atom for the S-substituent examples include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; preferably a fluorine atom.
  • the position of this substituent is not particularly limited; however, it is preferably at the 2- and / or 4-position.
  • Examples of the octaalkyl group as a substituent include those in which the alkyl portion is linear or branched and has a halogen atom such as a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; those having a fluorine ⁇ ; more preferably is CF 3.
  • the position of the substituent is not particularly limited; however, it is preferably the 4-position.
  • the alkyl group of the substituent may be straight-chain or branched; preferably CH 3 .
  • the position S of the substituent is not particularly limited; however, it is preferably the 3-position and / or the 5-position.
  • the pyridylcarbonyl group can have a halogen atom or the like as a substituent.
  • halogen atom for the substituent examples include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; preferably a chlorine atom.
  • the position of the S-substituent is not particularly limited; however, it is preferably the 2-position.
  • alkyl group examples include linear or branched ones; More preferably, it is C 2 H 5 .
  • the phenylcarbamoyl group can have a haloalkyl group having 1 to 4 carbon atoms as a substituent.
  • haloalkyl group for the substituent examples include those in which the alkyl portion is linear or branched and has a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom; Having an atom; more preferably, CF 3 .
  • the position of the substituent is not particularly limited, but is preferably the 4-position.
  • n 0 or 1.
  • X is an oxygen atom
  • n 2
  • alkylene group examples include a linear or branched alkylene group; preferably, CH 2 .
  • Examples of the compound (1) include compounds obtained by combining the above-mentioned various substituents.
  • Preferred compounds from the viewpoint of drug efficacy are as follows.
  • R 1 is a phenyl group
  • R 2 , R 4 and R 5 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 6 is 2 carbon atoms.
  • X is an alkylene group having 1 to 4 carbon atoms
  • n is 0.
  • R 1 is a phenyl group
  • R 2 and R 5 are hydrogen atoms
  • R 4 is -CON R 7 R 8
  • R 3 is an alkyl group having a carbon urine number of ⁇ to 4
  • R 6 is an alkoxycarbonyl group having 2 to 5 carbon atoms
  • X is an alkylene group having 1 to 4 carbon atoms
  • n is 0.
  • R 1 is a phenyl group
  • R 2 , R 4 and R 5 are hydrogen atoms
  • R 3 is a haloalkyl group having 1 to 4 carbon atoms
  • R 6 is a carbon atom number. 2 to 5 alkoxy forces A ruponyl group, wherein X is an oxygen atom and n is 2.
  • R 1 is a phenyl group
  • R 2 , R 4, and R 5 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 6 is 2 to 2 carbon atoms. 5 alkylcarbonyl groups
  • X is an alkylene group having 1 to 4 carbon atoms
  • n is 0.
  • R 1 is a phenyl group
  • R 2 and R 4 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 5 is a haloalkyl group having 1 to 4 carbon atoms.
  • R 6 is an alkoxycarbonyl group having 2 to 5 carbon atoms
  • X is an alkylene group having 1 to 4 carbon atoms
  • ⁇ is 0.
  • R 1 is a phenyl group
  • R 2 and R 4 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 5 is an alkyl group having 1 to 4 carbon atoms
  • R 6 is an alkoxycarbonyl group having 2 to 5 carbon atoms
  • X is an alkylene group having 4 to 4 carbon atoms
  • n is 0.
  • R ⁇ is a phenyl group
  • R 2 , R 4 and R 5 are hydrogen atoms
  • R 3 is the number of carbon atoms!
  • R 4 is a benzoyl group
  • X is an alkylene group having 1 to 4 carbon atoms
  • n is 0.
  • R 1 is a phenyl group
  • R 2 and R 4 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 5 is an alkoxyalkyl group having 2 to 5 carbon atoms
  • R 6 is an alkoxycarbonyl group having 2 to 5 carbon atoms
  • X is an alkylene group having 1 to 4 carbon atoms
  • n is 0.
  • R 1 is a phenyl group
  • R 2 , R 4 and R 5 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 6 is a pyridylcarbonyl group
  • X I is an alkylene group having 1 to 4 carbon atoms
  • n is 0.
  • R 1 is a phenyl group
  • R 2 , R 4, and R 5 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 6 is 2 to 2 carbon atoms.
  • 5 alkoxycals X is an alkylene group having 1 to 4 carbon atoms
  • n is 1.
  • R 1 is a phenyl group
  • R 2 , R 4 and R 5 are hydrogen atoms
  • R 3 and R 6 are an alkyl group having 1 to 4 carbon atoms
  • X is 1 to 4 carbon atoms.
  • R ⁇ is a phenyl group
  • R 2 , R 4 , R 5 and R 6 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • X is 1 to 4 carbon atoms.
  • R 1 is a phenyl group
  • R 2 , R 4 and R 5 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 6 is a phenylcarbamoyl group
  • X is an alkylene group having 1 to 4 carbon atoms
  • ⁇ is 0.
  • R 1 is a phenyl group
  • R 2 and R 5 are a hydrogen atom
  • R 3 is a haloalkyl group having 1 to 4 carbon atoms
  • R 4 is an alkyl carbonyl group having 2 to 5 carbon atoms
  • R 6 is an alkoxycarbonyl group having 2 to 5 carbon atoms
  • X is an oxygen atom
  • n is 2.
  • R 1 is a phenyl group
  • R 2 , R 4, and R 5 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 6 is 2 to 2 carbon atoms.
  • 5 is an alkoxycarbonyl group, wherein X is an oxygen atom and n is 2.
  • R 1 is a phenyl group
  • R 2 , R 4 and R 5 are hydrogen atoms
  • R 3 is an alkyl group having 1 to 4 carbon atoms
  • R 6 is a formyl group
  • n is 0.
  • ⁇ 1 31 can be mentioned.
  • Compound (II) can be synthesized by the following synthesis method 1, 2, or 3.
  • Compound (1a) (when R 4 is a hydrogen atom in compound (1)) can be synthesized by reducing compound (2) in a solvent as shown below.
  • R 1 , R 3 , R 5, Re, X and n have the same meanings as described above.
  • the method of transporting compound (2) is not particularly limited, and a method using a transport agent, contact water An additional method can be used.
  • the carrier is not particularly limited, and examples thereof include sodium borohydride, sodium trimethoxyborohydride, sodium cyanoborohydride, lithium aluminum hydride, and lithium hydride.
  • Metal-hydrogen complex compounds such as ethoxyminium lithium, hydrogen sulfide and getyl aluminum dimethylaluminum, can be used.
  • the amount of the reducing agent used is 0.001 to 5 times the molar amount of the compound (2).
  • a Lewis acid such as titanium tetrachloride, aluminum chloride or boron trifluoride can be added to adjust the reducing power.
  • the type of the solvent is not particularly limited as long as it does not directly participate in the reaction.
  • Organic bases such as pendecar 7-ene; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; and mixtures of the above solvents.
  • the amount of the solvent used may be such that the concentration of the compound (2) is in the concentration range of 0.1 to 80% by weight; preferably 0.5 to 70% by weight.
  • reaction temperature is not particularly limited, it is generally in the range of from 120 ° C to the boiling point of the solvent used or lower.
  • the reaction time varies depending on the above-mentioned temperature and temperature; it is usually from 0.3 to 24 hours.
  • the catalyst is not particularly limited, and examples thereof include ordinary hydrogenation catalysts such as palladium, palladium-carbon, nickel, and Raney nickel.
  • the amount of the catalyst to be added is 0.001 to 1 times the molar amount of the compound (2).
  • Compound (2) can be synthesized by dehydrating and condensing compound (6) and compound (5) as shown below.
  • R 1 , R 3 , R 5 , R 6 , X and n are as defined above.
  • R 1 and R 3 are as defined above; n ′ represents 0 or 1; and Z represents a leaving group.
  • compound (7) can be synthesized, for example, according to the method described in Org. Synh, IV, 921 (1963).
  • Compound (6) can be synthesized by reacting compound (9) with compound (10) as shown below when X is O (compound (6c)).
  • R 1 8 3 and ⁇ is an as defined above; Z 'represents a leaving group.
  • Compound (9) can be produced, for example, from the corresponding carboxylic acid ester by Fries transfer reaction. Some can be used as commercial products.
  • the compound (10) can be obtained as a commercial product.
  • the compound (10) in the case of sulfonyl chloride, the compound (10) can also be synthesized by reacting a corresponding mercaptan with chlorine or the like.
  • R ⁇ , R 3 , R 4 , R5 to R7, X and n are as defined above.
  • the type of the solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, and methylene chloride.
  • Chlorinated or non-chlorinated aromatic, aliphatic, and lipophilic hydrocarbons such as chloroform, dichloroethane, trichloroethylene, and cyclohexane; Ethers; ketones such as acetone, methyl ethyl ketone, etc .; alcohols such as methanol, ethanol, ethylene glycol and the like, or hydrates thereof; N, N-dimethylformamide, N, N-dimethyla Amides such as cetamide, etc .; Nitriles such as pionitoltril; organic bases such as triethylamine, pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] pentacar 7-ene; 1 , 3-dimethyl-2-imidazolidinone; dimethylsulfoxide; mixtures of the above-mentioned solvents.
  • the solvent can be used in such an amount that the compound (1a) is used in an amount of 0.1 to 80% by weight; preferably 0.5 to 70% by weight.
  • the reaction temperature is not particularly limited, but is 0 to 20 (within the temperature range of TC; preferably room temperature to 100 ° C).
  • the reaction time varies depending on the concentration and the temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours.
  • the amount of the starting compound to be used is 0.5 to 50 times mol of compound (3) relative to compound (1a); preferably 0.8 to 10 times mol.
  • a base such as triethylamine, pyridine, 4-N, N-dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] ]
  • Organic bases such as pendecar 7-ene; sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate It is possible to use an inorganic base such as trium in an amount of 0.001 to 1 mol based on the compound (1a).
  • Compound (1a) can be produced by Synthesis Method 1 or Synthesis Method 3.
  • Some of the compounds (3) can be used as commercial products, and for example, can be produced by reacting the corresponding amine with trichlorochloroformate (TCF).
  • TCF trichlorochloroformate
  • Some compounds (3a) can be used as commercial products, and can be produced, for example, by reacting the corresponding primary amine with trichlorochloroformate (TCF).
  • TCF trichlorochloroformate
  • the compound (1a) (in the case where R 4 is a hydrogen atom in the compound (1)) is prepared by reacting the compound (4) with the compound (5) in the absence or in the solvent as shown below. In this way, it can be synthesized.
  • R ⁇ to R3, R5, R6, X and n are as defined above.
  • the type of solvent is not particularly limited as long as it does not directly affect the reaction, and examples thereof include benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, and chloride.
  • Chlorinated or unchlorinated aromatic, aliphatic or cycloaliphatic hydrocarbons such as methylene, chloroform, dichloroethane, trichloroethylene, cyclohexane; such as getyl ether, tetrahydrofuran, dioxane, etc.
  • Ethers ketones such as acetone and methyl ketone; alcohols such as methanol, ethanol, ethylene glycol and the like; and hydrates thereof; N, N-dimethylformamide, N, N-dimethylacetamide Amides such as acetonitrile, pro Nitriles such as binitronitrile; organics such as triethylamine, pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] Base; 1,3-dimethyl-2-imidazolidinone; dimethylsulfoxide; a mixture of the above solvents.
  • the solvent may be used in such a manner that the total amount of the compound (4) and the compound (5) is 5 to 80% by weight; preferably 5 to 70% by weight.
  • the reaction temperature is not particularly limited, but is in a temperature range of 0 ⁇ to 200; preferably room temperature to 100 ° C.
  • the reaction time varies depending on the concentration and the temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours.
  • the amount of the starting compound to be used is 0.5 to 50 times mol of compound (5) relative to compound (4); preferably 0.8 to 10 times mol.
  • a base such as triethylamine, pyridine, 4-N, N-dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4. 0]
  • Organic bases such as pendecar 7-ene; sodium hydride, sodium amide, sodium hydroxide, hydroxylated lithium
  • Inorganic bases such as calcium, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate can be used in an amount of 0.001 to 1 mol per 1 mol of compound (1a).
  • the hydroxyl form [compound (4a)] can be synthesized according to a known method such as transferring the corresponding ketone form.
  • R 1 to R 3 , X and n have the same meanings as described above.
  • Some of the compounds (5) can be used as a commercial product.
  • one of R 5 and R 6 is an alkoxycarbonyl group
  • a known method such as the method described in JP-A-58-203980 can be used. It can be synthesized according to it.
  • the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, reduction, erythrification, etc., and if necessary, recrystallization, various chromatographies, etc. Can be appropriately purified by known means.
  • Examples of the compound (1) include compounds 1 to 31 shown in Table 1 below.
  • compound 1 is a compound represented by the formula (1), wherein R 1 is a 4-phenylphenyl group, R 2 is a hydrogen atom, R 3 is an ethyl group, R 4 is a hydrogen atom, and R 5 is A hydrogen atom and R 6 are an ethoxycarbonyl group.
  • the pests in agricultural and horticultural activities which are controlled by the compound (1) of the present invention include agricultural and horticultural insect pests (for example, Hemiptera (Lepidoptera, Lepidoptera, Aphids, Whitefly), Lepidoptera) (Eg, beetles such as lotus beetle, horn moth, locust beetles, pygmy beetles, sink beetles, cabbage butterfly, etc.), Coleoptera (e.g., Tenebrion beetles, Diptera, Pentatomidae, Scarabaeidae, etc.) Family, such as citrus red and yellow, and phytoseiid family citrus sabidae)), sanitary pests (for example, flies, power, cockroaches, etc.), and stored grain pests (e.g. Corn root worms, root-knotting, pine-nosed tick, and spider mite in soil it can.
  • the insecticide of the present invention has
  • the compound (1) can be used alone, but it is usually compounded with a carrier, a surfactant, a dispersant, an auxiliary agent and the like (for example, a powder, an emulsion, a fine granule, a granule) by an ordinary method. , A wettable powder, oily suspension, aerosol, etc.).
  • the carrier examples include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, cas sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.), aromatics Hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone Hexone, hexanone, isophorone, etc., esters (ethyl ethyl sulphate, ethylene glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n- Liquid carriers such as xanol, ethylene glycol, polar solvents (dimethylformamide, dimethylsulfoxide, etc.), water
  • surfactants and dispersants that can be used to improve the performance of this agent, such as adhesion to animals and plants, improved absorption, and dispersion, emulsification, and spreading of drugs, include alcohol sulfates and alkyl sulfones. Acid salts, ligninsulfonates, polysuccinic renderichol ethers, and the like. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as adjuvants.
  • the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in appropriate combination, respectively, depending on the purpose of each.
  • the active ingredient is usually 1 to 50% by weight for emulsions, usually 0.3 to 25% for powders, and usually 1 to 90% for wettable powders. %, Usually 0.5 to 10% by weight for granules, 0.5 to 5% for oils, and 0.1 to 5% for azole.
  • Titanium tetrachloride (2.1 g) was dissolved in 1,2-dimethyloxetane (4 Om I), and sodium borohydride (0.8 g) was obtained at 0 ° C.
  • reaction mixture was poured into 400 ml of a saturated sodium hydrogen carbonate solution, and extracted with ethyl acetate.
  • the acid ethyl solution was washed with saturated saline and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • N- [4-Chloro-4 '-(ethylthiomethyl) diphenylmethyl] -N'-Ethoxycarbonylhydrazine (1.1 g) and triethylamine (0.1 g) are dissolved in toluene (20 ml), and the mixture is dissolved at room temperature. Under stirring, methyl isocyanate (0.2 g) was added.
  • the ethyl sulphate solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
  • Titanium tetrachloride (3 g) was dissolved in 1,2-dimethyloxetane (5 Om I), and sodium borohydride (1.8 g) was added at 0 ° C.
  • reaction mixture was poured into 500 ml of a saturated sodium hydrogen carbonate solution, and extracted with ethyl acetate.
  • the acid ethyl solution was washed with a saturated saline solution, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • reaction mixture was poured into water and extracted with toluene.
  • the toluene solution was washed with a saturated saline solution, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.
  • the resulting oil is subjected to column chromatography ( ⁇ Ko-gel C-200, toluene).
  • the residue was purified by crystallization with hexane and then recrystallized with hexane to obtain 3.9 g of the target compound as colorless needles.
  • Compound 1 was 5 parts by weight, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neseki Rex Powder (trade name, manufactured by Kao Corporation) and 2 parts by weight of sodium ligninsulfonate were uniformly mixed. Next, a small amount of water was added and kneaded, followed by granulation and drying to obtain granules.
  • To 20 parts by weight of Compound 1 and 70 parts by weight of xylene 10 parts by weight of Toxanone (trade name; manufactured by Sanyo Danisei Kogyo Co., Ltd.) was added, mixed uniformly, and dissolved to obtain an emulsion.
  • Toxanone trade name; manufactured by Sanyo Danisei Kogyo Co., Ltd.
  • a powder was obtained by uniformly mixing 5 parts by weight of compound 40, 50 parts by weight of talc and 45 parts by weight of strength olin.
  • Each wettable powder of the compound (1) shown in Table 1 prepared according to Example 2 was diluted to 300 ppm with water containing a surfactant (0.01%), and the capillaries were added to these solutions.
  • the leaf pieces (5 cm x 5 cm) were spread for 30 seconds, placed in each plastic cup and air-dried.
  • Each wettable powder of the compound (1) shown in Table 1 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%).
  • the soybean leaves were 3 ⁇ 43 ⁇ 4 ⁇ ⁇ ⁇ ⁇ for 30 seconds, placed one in each plastic cup, and air-dried.
  • each of the 10 cups (10th instar larvae) was released into each of these cups, covered and left in a 25 "constant room.
  • the number of live and dead insects in each cup was counted and the mortality was calculated.
  • the results of the evaluation of the insecticidal effect are shown in Table 4 using the four-step evaluation method described in (1) above.
  • Each wettable powder of the compound (1) shown in Table 1 prepared according to Example 2 was diluted to 300 ppm with water containing a surfactant (0.01%), and the rice was added to each of these solutions. Seedlings were soaked for 30 seconds, air-dried, and inserted into glass cylinders.
  • novel hydrazine compound of the present invention has excellent pesticidal activity for agricultural use, and provides an insecticide for agricultural use containing this as an active ingredient.

Abstract

Composés d'hydrazine de formule générale (1), procédé de préparation desdits composés et insecticides à usage agricole et horticole contenant lesdits composés en tant qu'ingrédients actifs. Dans ladite formule, R1 est phényle substitué ou non substitué; R2 est hydrogène; R3 est alkyle C¿1?-C4 ou haloalkyle C1-C4; R?4¿ est hydrogène ou alkylcarbonyle C¿2?-C5; R?5¿ est hydrogène, haloalkyle C¿1?-C4, alcoxyalkyle C2-C5 ou alkyle C1-C4; R?6¿ est alcoxycarbonyle C¿2?-C5, alkylcarbonyle C2-C5, benzoyle, pyridylcarbonyle, alkyle C1-C4, phényle, hydrogène, phénylcarbamyle, pyridyle ou formyle; X est alkylène C1-C4 ou oxygène; et n est 0 à 2, à condition que lorsque X est alkylène C1-C4, n soit 0 ou 1, et que n soit 2 lorsque X est oxygène.
PCT/JP1997/001282 1996-04-16 1997-04-14 Composes d'hydrazine, procede de preparation desdits composes et insecticides a usage agricole et horticole WO1997038973A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6924313B1 (en) 1999-09-23 2005-08-02 Pfizer Inc. Substituted tertiary-heteroalkylamines useful for inhibiting cholesteryl ester transfer protein activity
US7122536B2 (en) 1999-09-23 2006-10-17 Pfizer Inc. (R)-chiral halogenated substituted fused heterocyclic amino compounds useful for inhibiting cholesterol ester transfer protein activity
WO2008061866A1 (fr) * 2006-11-20 2008-05-29 Bayer Cropscience Sa Nouveaux dérivés de benzamide
CN102918029A (zh) * 2011-05-17 2013-02-06 江苏康缘药业股份有限公司 4-苯胺-6-丁烯酰胺-7-烷醚喹唑啉衍生物及其制备方法和用途
US9090588B2 (en) 2011-03-04 2015-07-28 Newgen Therapeutics, Inc. Alkyne substituted quinazoline compound and methods of use

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Publication number Priority date Publication date Assignee Title
US3732307A (en) * 1970-09-24 1973-05-08 Du Pont Benzophenone hydrazones containing perfluoroalkyl,perfluoroalkoxy,and perfluoroalkylthio substituents
JPS54122261A (en) * 1978-03-01 1979-09-21 Boots Co Ltd Noxious living thing expelling agent
JPH093038A (ja) * 1995-04-19 1997-01-07 Kumiai Chem Ind Co Ltd ベンジルスルフィド誘導体、その製造方法及び有害生物防除剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3732307A (en) * 1970-09-24 1973-05-08 Du Pont Benzophenone hydrazones containing perfluoroalkyl,perfluoroalkoxy,and perfluoroalkylthio substituents
JPS54122261A (en) * 1978-03-01 1979-09-21 Boots Co Ltd Noxious living thing expelling agent
JPH093038A (ja) * 1995-04-19 1997-01-07 Kumiai Chem Ind Co Ltd ベンジルスルフィド誘導体、その製造方法及び有害生物防除剤

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6924313B1 (en) 1999-09-23 2005-08-02 Pfizer Inc. Substituted tertiary-heteroalkylamines useful for inhibiting cholesteryl ester transfer protein activity
US7122536B2 (en) 1999-09-23 2006-10-17 Pfizer Inc. (R)-chiral halogenated substituted fused heterocyclic amino compounds useful for inhibiting cholesterol ester transfer protein activity
US7253211B2 (en) 1999-09-23 2007-08-07 Pfizer Inc. (R)-chiral halogenated substituted fused heterocyclic amino compounds useful for inhibiting cholesterol ester transfer protein activity
WO2008061866A1 (fr) * 2006-11-20 2008-05-29 Bayer Cropscience Sa Nouveaux dérivés de benzamide
US9090588B2 (en) 2011-03-04 2015-07-28 Newgen Therapeutics, Inc. Alkyne substituted quinazoline compound and methods of use
US11524956B2 (en) 2011-03-04 2022-12-13 Newgen Therapeutics, Inc. Alkyne substituted quinazoline compound and methods of use
CN102918029A (zh) * 2011-05-17 2013-02-06 江苏康缘药业股份有限公司 4-苯胺-6-丁烯酰胺-7-烷醚喹唑啉衍生物及其制备方法和用途
CN102918029B (zh) * 2011-05-17 2015-06-17 江苏康缘药业股份有限公司 4-苯胺-6-丁烯酰胺-7-烷醚喹唑啉衍生物及其制备方法和用途
US9187459B2 (en) 2011-05-17 2015-11-17 Newgen Therapeutics, Inc. Quinazoline-7-ether compounds and methods of use

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