WO2004052872A1 - Haloalkene compounds, process for their production and pesticides containing them - Google Patents

Haloalkene compounds, process for their production and pesticides containing them Download PDF

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Publication number
WO2004052872A1
WO2004052872A1 PCT/JP2003/015801 JP0315801W WO2004052872A1 WO 2004052872 A1 WO2004052872 A1 WO 2004052872A1 JP 0315801 W JP0315801 W JP 0315801W WO 2004052872 A1 WO2004052872 A1 WO 2004052872A1
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Prior art keywords
substituted
alkyl
atom
heterocyclic group
halogen
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PCT/JP2003/015801
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French (fr)
Inventor
Hiroshi Okada
Masayuki Morita
Tsuyoshi Ueda
Hiromi Takeo
Hidemasa Kominami
Kazuhisa Kiriyama
Kenichi Nakamoto
Yayoi Yoshida
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Ishihara Sangyo Kaisha, Ltd.
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Priority to AU2003288551A priority Critical patent/AU2003288551A1/en
Publication of WO2004052872A1 publication Critical patent/WO2004052872A1/en

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    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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    • A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
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    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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    • C07C233/20—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
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    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a novel haloalkene compound useful as an active ingredient of a pesticide.
  • Haloalkene compounds are disclosed in USP4950666, EP432861, W092/15555, W097/8132 and JP-A-2001-288142 , respectively. However, they are different in the chemical structure from the haloalkene compound represented by the following formula (I) . DISCLOSURE OF THE INVENTION
  • the present inventors have conducted various studies on haloalkene compounds in an effort to find a superior pesticide. As a result, they have found that a novel haloalkene compound has an extremely high pesticidal effect against pests at a low dose and at the same time has safety to crop plants, the natural enemy to pests, or mammals, and have accomplished the present invention.
  • the present invention relates to a haloalkene compound represented by the formula (I) or its salt :
  • each of X 1 and X 2 is halogen
  • Y is a hydrogen atom, halogen, alkyl, haloalkyl or phenyl
  • n is from 0 to 5
  • A is an oxygen atom or a sulfur atom
  • G is a hydrogen atom, alkyl, haloalkyl, phenylalkyl, acyl, alkenyl, haloalkenyl, phenylalkenyl , alkynyl, haloalkynyl or phenylalkynyl, provided that when Y is a hydrogen atom or a halogen atom and A is an oxygen atom, G is alkyl, haloalkyl, phenylalkyl, acyl, alkenyl, haloalkenyl, phenylalkenyl, alkynyl, haloalkynyl or phenylalkynyl, and Q is a 5- to
  • the pesticide containing, as an active ingredient, the novel haloalkene compound represented by the above formula (I) has an extremely high pesticidal effect against pests at a low dose and at the same time has safety to crop plants, the natural enemy to pests, or mammals.
  • each atom of fluorine, chlorine, bromine or iodine may be mentioned.
  • the number of halogens as substituents may be 1 or more, and if more, the respective halogens may be the same or different. Further, the positions for substitution of halogens may be any positions .
  • the alkyl or alkyl moiety for Y, G, Q or W may be linear or branched, and as its specific example, C ⁇ _ ⁇ 2 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl may be mentioned.
  • alkenyl or alkenyl moiety for G or Q may be linear or branched, and as its specific example, C 2 _ ⁇ alkenyl such as vinyl, 1-propenyl, allyl, isopropenyl, 1- butenyl, 1, 3-butadienyl, 1-hexenyl, 1-heptenyl, 4-octenyl, 2-decenyl or 2-dodecenyl may be mentioned.
  • C 2 _ ⁇ alkenyl such as vinyl, 1-propenyl, allyl, isopropenyl, 1- butenyl, 1, 3-butadienyl, 1-hexenyl, 1-heptenyl, 4-octenyl, 2-decenyl or 2-dodecenyl may be mentioned.
  • the alkynyl or alkynyl moiety for G or Q may be linear or branched, and as its specific example, C 2 _ 12 alkynyl such as ethynyl, 2-butynyl, 2-pentynyl, 3-hexynyl, 4, 4-dimethyl-2-pentynyl, 4-octynyl, 2-decynyl or 2- dodecynyl may be mentioned.
  • acyl for G one represented by -COT (wherein T is alkyl, haloalkyl, alkenyl, haloalkenyl or the like) may, for example, be mentioned.
  • T alkyl, haloalkyl, alkenyl, haloalkenyl or the like
  • halogen moiety alkyl, alkyl moiety, alkenyl and alkenyl moiety in the above T, the same ones as contained in the above Y or G may be mentioned.
  • cycloalkyl or cycloalkyl moiety for Q C 3 _ 8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclooctyl may be mentioned.
  • a monocyclic or condensed ring type heterocyclic group containing from 1 to 4 hetero atoms may, for example, be mentioned.
  • Such a heterocyclic group may be saturated or may have an unsaturated moiety, or its methylene moiety may be converted to oxo or thioxo, or may be an N-oxide such as N-oxypyridyl .
  • it may, for example, be 1) a heterocyclic group selected from the group consisting of thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl, triazolyl, tetrazolyl, dithiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, thiazinyl, pyranyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl , benzisoxazolyl, benzimidazolyl, indazolyl, cyclopentapyrazolyl, benzo
  • the above-mentioned heterocyclic group may have several combinations due to the differences in the positions of hetero atoms or the differences of the condensed moieties, and the present invention includes all of them.
  • the thiadiazolyl includes 1, 2 , 3-thiadiazolyl and 1, 3 , 4-thiadiazolyl;
  • the triazolyl includes 1, 2 , 3-triazolyl and 1, 2 , 4-triazolyl;
  • the triazinyl includes, 1, 2 , 4-triazinyl and 1, 3 , 5-triazinyl;
  • the benzothienyl includes benzo [b] thienyl and benzo [c] thienyl;
  • the benzofuranyl includes benzo [b] furanyl and benzo [c] furanyl ;
  • the benzisothiazolyl includes 1, 2-benzisothiazolyl and 2 , 1-benzisothiazolyl ;
  • the benzisoxazolyl includes 1, 2-benzisoxazo
  • the above-mentioned partially saturated heterocyclic group may be one having a part of the above heterocyclic group hydrogenated. It may, for example, be 4,5- dihydrothiazolyl, 4, 5-dihydrooxazolyl, 4,5- dihydroisoxazolyl, 4, 5-dihydro-lH-imidazolyl, 4,5- dihydro-lH-pyrazolyl , 3,4,5, 6-tetrahydropyridinyl , 1, 4, 5, 6-tetrahydropyrimidinyl, 2 , 3-dihydrobenzofuranyl or 4a, 5 , 6 , 7 , 8 , 8a-hexahydroquinoxalinyl .
  • the above-mentioned saturated heterocyclic group may be one having the above heterocyclic group completely hydrogenated. It may, for example, be tetrahydrofuranyl, tetrahydropyranyl, pyrrolidinyl, piperidinyl, piperazinyl or morpholinyl.
  • the above-mentioned oxo or thioxo heterocyclic group may be one having a methylene moiety in the above- mentioned dithiazolyl, oxadinyl, thiadinyl, pyranyl, cyclopentapyrazolyl, benzodioxolyl, partially saturated heterocyclic group or saturated heterocyclic group, converted to oxo or thioxo.
  • the number of substituents in the phenyl which may be substituted in W or in the 5- to 12-membered heterocyclic group (the heterocyclic moiety may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, for Q, may be 1 or more, and if more, such substituents may be the same or different.
  • substituents in the phenyl which may be substituted in W, or in the 5- to 12- membered heterocyclic group (the heterocyclic moiety may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, for Q may be halogen, nitro, cyano, (C ⁇ - 8 ) alkyl, halo (C ⁇ _ 8 ) alkyl, aryl (C ⁇ _ 8 ) alkyl wherein the aryl moiety may be substituted, heteroaryl (C ⁇ _ 8 ) alkyl wherein the heteroaryl moiety may be substituted, (C 3 _ 8 ) cycloalkyl, halo (C 3 _ 8 ) cycloalkyl, (C 2 - 8 ) alkenyl, halo (C_s) alkenyl, (C 2 - 8 ) alkynyl, halo (C- 8 ) alkynyl, ary
  • R 1 and R 2 which are independent of each other, is a hydrogen atom, (C ⁇ _ 8 ) alkyl, halo (Ci-s) alkyl, aryl (C x _ 8 ) alkyl wherein the aryl moiety may be substituted, heteroaryl (C ⁇ _ 8 ) alkyl wherein the heteroaryl moiety may be substituted, (C 3 .
  • R 3 is (C ⁇ _ 8 ) alkyl, halo (C ⁇ _ 8 ) alkyl, aryl (C ⁇ _ 8 ) alkyl wherein the aryl moiety may be substituted, heteroaryl (C ⁇ - 8 ) alkyl wherein the heteroaryl moiety may be substituted, (C 3 _ 8 ) cycloalkyl, halo (C 3 _ 8 ) cycloalkyl , (C 2 _ 8 ) alkenyl, halo (C 2 _ 8 ) alkenyl, (C 2 - 8 ) alkynyl , halo (C 2 - 8 ) alkynyl, aryl which may be substituted, or heteroaryl which may be substituted.
  • the substituent for the aryl which may be substituted or the substituent for the heteroaryl which may be substituted, contained in the 5- to 12-membered heterocyclic group (the heterocyclic moiety may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, for Q, R 1 , R 2 or R 3 , may, for example, be halogen, nitro, cyano, (C ⁇ _ 8 ) alkyl, halo (C ⁇ _ 8 ) alkyl, (C 3 _ 8 ) cycloalkyl, halo (C 3 - 8 ) cycloalkyl, (C 2 _ 8 ) alkenyl, halo (C 2 _ 8 ) alkenyl, (C 2 - 8 ) alkynyl, halo (C 2 - 8 ) alkynyl, -NRR 5 , -OR 4 , -SR 4 , -SOR 4 ,
  • Each of R 4 and R 5 which are independent of each other, is a hydrogen atom, (C ⁇ _ 8 ) alkyl, halo (C ⁇ _ 8 ) alkyl, (C 3 . 8 ) cycloalkyl, halo (C 3 _ 8 ) cycloalkyl, (C 2 _ 8 ) alkenyl, halo (C 2 - 8 ) alkenyl, (C 2 _ 8 ) alkynyl, or halo (C 2 _ 8 ) alkynyl.
  • R 6 is (C 1 _ 8 )alkyl, halo (C ⁇ _ 8 ) alkyl, aryl (d- 8 ) alkyl, heteroaryl (C ⁇ _ 8 ) alkyl, (C 3 -s) cycloalkyl, halo (C 3 _ 8 ) cycloalkyl, (C 2 -s) alkenyl, halo (C 2 _ 8 ) alkenyl, (C 2 - 8 ) alkynyl, halo (C 2 _ 8 ) alkynyl , aryl or heteroaryl.
  • aryl or aryl moiety phenyl, naphthyl, phenanthrenyl , anthracenyl, indenyl or indanyl may be mentioned.
  • heteroaryl or heteroaryl moiety the same one as the heterocyclic group for the above-mentioned Q may be mentioned.
  • the above C ⁇ _ 8 alkyl or alkyl moiety may be linear or branched, and its specific example may be methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl or octyl .
  • C 3 _ 8 cycloalkyl or cycloalkyl moiety cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl may be mentioned.
  • C 2 . 8 alkenyl or alkenyl moiety may be linear or branched, and as its specific example, vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 1,3- butadienyl, 1-hexenyl, 1-heptenyl or 4-octenyl may be mentioned.
  • C 2 - 8 alkynyl or alkynyl moiety may be linear or branched, and as its specific example, ethynyl, 2-butynyl, 2-pentynyl, 3 -hexynyl, 4, 4-dimethyl- 2-pentynyl, or 4-octynyl may be mentioned.
  • each atom of fluorine, chlorine, bromine or iodine may be mentioned.
  • the number of halogens as substituents may be 1 or more, and if more, the respective halogens may be the same or different.
  • the positions for substitution of halogens may be any positions.
  • the salt of the haloalkene compound represented by the above formula (I) includes all kinds so long as they are agriculturally acceptable.
  • an alkali metal salt such as a sodium salt or a potassium salt
  • an alkaline earth metal salt such as a magnesium salt or a calcium salt
  • an ammonium salt such as a dimethylamine salt or a triethylamine salt
  • an inorganic acid salt such as a hydrochloride, a perchlorate, a sulfate or a nitrate
  • an organic acid salt such as an acetate or a methanesulfonate
  • the haloalkene compound represented by the above formula (I) may have geometrical isomers, optical isomers or tautomeric isomers, and such isomers and mixtures thereof are both included in the present invention.
  • the haloalkene compound represented by the above formula (I) or its salt (hereinafter referred to simply as the compound of the present invention) can be produced by the following reactions (A) to (F) and in accordance with a usual method for producing a salt.
  • X 1 , X 2 , Y, n, G and Q are as defined above.
  • a salt with an organic or inorganic acid such as a hydrochloride, a sulfate, an oxalate or a methanesulfonate, may be mentioned.
  • the reaction (A) can be carried out in the presence of a base, as the case requires.
  • a base one or more types may suitably be selected for use from, for example, a tertiary amine such as trimethy1amine, triethylamine, triisopropylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, 2 , 6-dimethylpyridine, 4-pyrrolidinopyridine, N-methylmorpholine, N,N- dimethylaniline, N,N-diethylaniline, N-ethyl-N- methy1aniline, 1, 8-diazabicyclo [5.4.0] -7-undecene or 1,4- diazabicyclo [2.2.2] octane; an alkali metal such as sodium or potassium; an alkali metal carbonate such as sodium carbonate or potassium carbonate; an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an al
  • the base may be used in an amount of from 1 to 5 times by mol, preferably from 1 to 2.5 times by mol, to the compound of the formula (II) .
  • the reaction (A) can be carried out in the presence of a solvent, as the case requires.
  • the solvent may be any solvent so long as it is a solvent inert to the reaction, and one or more types may suitably be selected for use from, for example, an aliphatic hydrocarbon such as pentane, hexane, heptane, octane or cyclohexane; an aromatic hydrocarbon such as benzene, toluene, xylene or pyridine; a halogenated hydrocarbon such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; an ether such as diethyl ether, butyl ethyl ether,
  • the reaction (A) can be carried out in an atmosphere of an inert gas, as the case requires.
  • an inert gas each gas such as nitrogen, helium or argon may be mentioned.
  • the reaction temperature for the reaction (A) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours.
  • reaction (B) X 1 , X 2 , Y, n, G and Q are as defined above. Further, as the salt of the compound represented by the formula (III) , the same one as exemplified in the above-mentioned reaction (A) may be mentioned.
  • the reaction (B) can be carried out by azeotropic dehydration in the presence of a solvent or in the presence of a condensing agent.
  • the solvent to be used for the azeotropic dehydration may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from those exemplified in the above-mentioned reaction (A) .
  • a solvent may be used as the case requires.
  • the solvent to be used here may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from those exemplified in the above reaction (A) .
  • a carbodiimide such as 1, 3-dicyclohexylcarbodiimide, 1, 3-diisopropylcarbodiimide or l-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride; or others such as phenyl dichlorophosphate, diethyl cyanophosphonate, 1,3, 5-triaza-2 , 4, 6-triphosphorin- 2 , 2 , 4, 4, 6, 6-hexachloride, cyanuric chloride, isobutyl chloroformate, chlorosulfonyl isocyanate, N,N' -carbonyl diimidazole, or trifluoroacetic anhydride, may be mentioned.
  • the condensing agent may be used in an amount of from 1 to 5 times by mol, preferably from 1 to 2 times by mol, to the compound of the formula (IV) .
  • the reaction (B) can be carried out in the presence of a base, as the case requires.
  • a base one or more types may suitably be selected for use from, for example, tertiary amines such as trimethylamine, triethylamine, triisopropylamine, diisopropylethylamme, pyridine, 4-dimethylaminopyridine, 2 , 6-dimethylpyridine, 4-pyrrolidinopyridine, N-methylmorpholine, N,N- dimethylaniline, N,N-diethylaniline, and N-ethyl-N- methylaniline.
  • the base may be used in an amount of from 0.1 to 5 times by mol, preferably from 0.1 to 2.5 times by mol, to the compound of the formula (IV) .
  • the reaction (B) can be carried out in an atmosphere of an inert gas, as the case requires.
  • an inert gas one such as nitrogen, helium or argon may be mentioned.
  • the reaction temperature for the reaction (B) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours.
  • the reaction (C) can be carried out in the presence of a base, as the case requires.
  • a base one or more types may suitably be selected for use from, for example, those exemplified in the above reaction (A) , and alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium butoxide; and tertiary amines such as trimethylamine, triethylamine, triisopropylamine, diisopropylethylamme, pyridine, 4-dimethylaminopyridine, 2, 6-dimethylpyridine, 4-pyrrolidinopyridine, N- ethylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, and N-ethyl-N-methylaniline.
  • the base may be used in an amount of from 0.01 to 5 times by mol, preferably from 0.01 to 2.5 times by mol, to the compound of the formula (V) .
  • the reaction (C) can be carried out in the presence of a solvent, as the case requires.
  • the solvent may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from, for example, those exemplified in the above reaction (A) .
  • the reaction (C) can be carried out in an atmosphere of an inert gas, as the case requires.
  • an inert gas each gas such as nitrogen, helium or argon may be mentioned.
  • the reaction temperature for the reaction (C) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours.
  • reaction (I-3) In the reaction (D) , X 1 , X 2 , Y, n and Q are as defined above, and G 1 is alkyl, haloalkyl, phenylalkyl, acyl , alkenyl , haloalkenyl , phenylalkenyl , alkynyl , haloalkynyl or phenylalkynyl, and X 3 is halogen.
  • the reaction (D) can be carried out in the presence of a base, as the case requires.
  • the base one or more types may suitably be selected for use from, for example, those exemplified in the above reaction (A) .
  • the base may be used in an amount of from 0.01 to 10 times by mol, preferably from 0.01 to 5 times by mol, to the compound of the formula (1-2) .
  • the reaction (D) can be carried out in the presence of an N-trialkylsilyl-alkylcarbamate, as the case requires.
  • an N-trialkylsilyl-alkylcarbamate one or more types may suitably be selected for use from, for example, N-trimethylsilyl-ethylcarbamate and N- triethylsilyl-methylcarbamate .
  • the N-trialkylsilyl- alkylcarbamate may be used in an amount of from 0.01 to 10 times by mol, preferably from 0.01 to 5 times by mol, to the compound of the formula (1-2) .
  • the reaction (D) can be carried out in the presence of a solvent, as the case requires.
  • the solvent may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from, for example, those exemplified in the above-mentioned reaction (A) .
  • the reaction (D) can be carried out in an atmosphere of an inert gas, as the case requires.
  • an inert gas one such as nitrogen, helium or argon may be mentioned.
  • the reaction temperature for the reaction (D) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours.
  • X 1 , X 2 , Y, n and Q are as defined above, G 2 is alkyl, and U is alkyl, haloalkyl, alkoxy, phenyl, phenyl substituted by halogen, or phenyl substituted by alkyl.
  • the reaction (E) can be carried out in the presence of a base, as the case requires.
  • a base one or more types may suitably be selected for use from, for example, those exemplified in the above reaction (A) .
  • the base may be used in an amount of from 0.01 to 10 times by mol, preferably from 0.01 to 5 times by mol, to the compound of the formula (1-2).
  • the reaction (E) can be carried out in the presence of a solvent, as the case requires.
  • the solvent may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from, for example, those exemplified in the above-mentioned reaction (A) .
  • the reaction (E) can be carried out in an atmosphere of an inert gas, as the case requires.
  • an inert gas each gas such as nitrogen, helium or argon may be mentioned.
  • the reaction temperature for the reaction (E) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours.
  • X 1 , X 2 , Y, n, G and Q are as defined above.
  • thionizing agent to be used in the reaction (F) phosphorus pentasulfide or Lawesson's reagent may, for example, be mentioned.
  • the thionizing agent may be used in an amount of from 1 to 10 times by mol, preferably from 1 to 2 times by mol, to the compound of the formula (1-1) .
  • the reaction (F) can be carried out in the presence of a solvent, as the case requires.
  • the solvent may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and pyridine; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane and trichloroethane; ethers such as diethyl ether, butyl ethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and anisole; esters such as methyl acetate, ethyl acetate and propyl acetate; and polar aprotic solvents such as acet
  • the reaction (F) can be carried out in an atmosphere of an inert gas, as the case requires.
  • an inert gas each gas such as nitrogen, helium or argon may be mentioned.
  • the reaction temperature for the reaction (F) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours.
  • Each starting materials represented by the formula (II) , (IV) or (V) in the above reaction (A) to (C) is (1) a known compound, or (2) can be produced by or in accordance with the Preparation Examples given hereinafter, or (3) can be produced by or in accordance with the method disclosed in W092/15555, EP661289 or EP432861.
  • the above (3) will be described in more detail a) The method disclosed from p. 15, line 16 to p. 16, line 3 in 092/15555, a method of optionally carrying out usual chlorination or esterification, following such a method, the method disclosed in Preparation Example 16, 22, 28 or 42 in the same publication or a method in accordance therewith. b) The method disclosed from p. 13, line 25 to p.
  • pesticides containing the compounds of the present invention are particularly useful, for example, as agents for controlling various pests which become problematic in the agricultural and horticultural fields, i.e. agricultural and horticultural pesticides, or as agents for controlling pests which are parasitic on animals i.e. pesticides against parasites on animals.
  • the agricultural and horticultural pesticides containing the compounds of the present invention are useful as an insecticide, a iticide, a nematicide and a soil pesticide, and they are effective for controlling plant parasitic mites such as two-spotted spider mite (Tetranychus urticae) , carmine spider mite (Tetranychus cinnabarinus) , kanzawa spider mite (Tetranychus kanzawai) , citrus red mite (Panonychus citri) , European red mite (Panonychus ulmi) , broad mite (Polyphagotarsonemus latus) , pink citrus rust mite (Aculops pelekassi) and bulb mite (Rhizoglyphus echinopus) ; aphids such as green peach aphid (Myzus persicae) and cotton aphid (Aphis gossypii) ; agricultural insect pests such as diamondback
  • Colorado potato beetle (Leptinotarsa decemlineata) , cucurbit leaf beetle (Aulacophora femoralis) , boll weevil (Anthonomus grandis) , planthoppers, leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiid flies, scarabs, black cutworm (Agrotis ipsilon) , cutworm (Agrotis segetum) and ants; plant parasitic nematodes such as root-knot nematodes, cyst nematodes, root-lesion nematodes, rice white-tip nematode (Aphelenchoides besseyi) , strawberry bud nematode (Nothotylenchus acris) , pine wood nematode (Bursaphelenchus lignicolus) ; gastropods such as slugs and snails
  • the agricultural and horticultural pesticides containing the compounds of the present invention are particularly effective for controlling plant parasitic mites, agricultural insect pests, plant parasitic nematodes or the like. Further, they are effective against insect pests having acquired resistance to organophosphorus , carbamate and/or synthetic pyrethroid insecticides. Moreover, the compounds of the present invention have excellent systemic properties, and by the application of the compounds of the present invention to soil treatment, not only noxious insects, noxious mites, noxious nematodes, noxious gastropods and noxious isopods in soil but also foliage pests can be controlled.
  • pesticides containing compounds of the present invention may be agricultural and horticultural pesticides which collectively control the above-mentioned plant parasitic mites, agricultural insect pests, plant parasitic nematodes, gastropods and soil pests.
  • the agricultural and horticultural pesticide containing the compound of the present invention is usually formulated by mixing the compound with various agricultural adjuvants and used in the form of a formulation such as a dust, granules, water-dispersible granules, a wettable powder, a water-based suspension concentrate, an oil-based suspension concentrate, water soluble granules, an emulsifiable concentrate, a soluble concentrate, a paste, an aerosol or an ultra low-volume formulation.
  • a formulation such as a dust, granules, water-dispersible granules, a wettable powder, a water-based suspension concentrate, an oil-based suspension concentrate, water soluble granules, an emulsifiable concentrate, a soluble concentrate, a paste, an aerosol or an ultra low-volume formulation.
  • a formulation such as a dust, granules, water-dispersible granules, a wettable powder, a water
  • Such agricultural adjuvants include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaoline, bentonite, a mixture of kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, mirabilite, zeolite and starch; solvents such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethylsulfoxide, N,N- dimethylformamide, di ethylacetamide, N-methyl-2- pyrrolidone, and alcohol; anionic surfactants and spreaders such as a salt of fatty acid, a benzoate, an alkylsulfosuccinate, a dialkylsulfosuccinate, a polycarboxylate, a salt of alkylsulfuric acid este
  • each of the components as such adjuvants may be one or more suitably selected for use, so long as the purpose of the present invention can thereby be accomplished.
  • various additives which are commonly used, such as a filler, a thickener, an anti-settling agent, an anti-freezing agent, a dispersion stabilizer, a phytotoxicity reducing agent, and an anti-mold agent, may also be employed.
  • the weight ratio of the compound of the present invention to the various agricultural adjuvants is usually from 0.001:99.999 to 95:5, preferably from 0.005:99.995 to 90:10.
  • the agricultural and horticultural pesticide containing the compound of the present invention can not generally be defined, as it varies depending upon the weather conditions, the type of the formulation, the application season, the application site or the types or degree of outbreak of the pest insects.
  • the active ingredient being from 0.05 to 800,000 ppm, preferably from 0.5 to 500,000 ppm, and the dose per unit area is such that the compound of the present invention is from 0.05 to 50,000 g, preferably from 1 to 30,000 g, per hectare.
  • agricultural and horticultural pesticides as another preferred embodiment of pesticides containing the compounds of the present invention may be applied in accordance with the above-described application of pesticides.
  • the present invention includes such a method for controlling pests, particularly for controlling plant parasitic mites, agricultural insect pests or plant parasitic nematodes by such applications.
  • compositions of agricultural and horticultural pesticides containing the compounds of the present invention or their diluted compositions may be applied by conventional methods for application which are commonly employed, such as spraying (e.g. spraying, jetting, misting, atomizing, powder or grain scattering or dispersing in water), soil application (e.g. mixing or drenching), surface application (e.g. coating, powdering or covering) or impregnation to obtain poisonous feed.
  • spraying e.g. spraying, jetting, misting, atomizing, powder or grain scattering or dispersing in water
  • soil application e.g. mixing or drenching
  • surface application e.g. coating, powdering or covering
  • impregnation to obtain poisonous feed.
  • the active ingredient may also be applied by a so-called ultra low-volume application method. In this method, the composition may be composed of 100% of the active ingredient .
  • the agricultural and horticultural pesticides containing compounds of the present invention may be mixed with or may be used in combination with other agricultural chemicals, fertilizers or phytotoxicity-reducing agents, whereby synergistic effects or activities may sometimes be obtained.
  • Such other agricultural chemicals include, for example, a herbicide, an insecticide, a miticide, a nematicide, a soil pesticide, a fungicide, an antivirus agent, an attractant, an antibiotic, a plant hormone and a plant growth regulating agent.
  • the application range, the application time, the pesticidal activities, etc. may be improved to preferred directions.
  • the compound of the present invention and the active compounds of other agricultural chemicals may separately be formulated so that they may be mixed for use at the time of application, or they may be formulated together.
  • the present invention includes such a mixed pesticidal composition.
  • the mixing ratio of the compound of the present invention to the active compounds of other agricultural chemicals can not generally be defined, since it varies depending upon the weather conditions, the types of formulations, the application time, the application site, the types or degree of outbreak of insect pests, etc., but it is usually within a range of from 1:300 to 300:1, preferably from 1:100 to 100:1, by weight. Further, the dose for the application is such that the total amount of the active compounds is from 0.1 to 50,000 g, preferably from 1 to 30,000 g, per hectare.
  • the present invention includes a method for controlling pests by an application of such a mixed pesticide composition.
  • insects pest control agents such as insecticides, miticides, nematicides or soil pesticides in the above-mentioned other agricultural chemicals, include, for example, (by common names, some of them are still in an application stage) organic phosphate compounds such as Profenofos, Dichlorvos,
  • Fenamiphos Fenitrothion, EPN, Diazinon, Chlorpyrifos- methyl, Acephate, Prothiofos, Fosthiazate, Phosphocarb, Cadusafos, Disulfoton, Chlorpyrifos, Demeton-S-methyl, Dimethoate, and Methamidophos; carbamate compounds such as Carbaryl, Propoxur, Aldicarb, Carbofuran, Thiodicarb, Methomyl, Oxa yl , Ethiofencarb, Pirimicarb, Fenobucarb, Carbosulfan, and Benfuracarb; nereistoxin derivatives such as Cartap, and Thiocyclam, and Bensultap; organic chlorine compounds such as Dicofol, and Tetradifon; organometallic compounds such as Fenbutatin Oxide; pyrethroid compounds such as Fenvalerate, Per ethrin, Cypermethr
  • Triazamate Pymetrozine, Pyrimidifen, Chlorfenapyr, Indoxacarb, Acequinocyl , Etoxazole, Cyromazin, 1,3- dichloropropene, Diafenthiuron, Benclothiaz, Flufenerim, Pyridalyl, Spirodiclofen, Bifenazate, Spiromesifen, Propargite, Clofentezine, Etoxazole, and Fluacrypyrim.
  • BT agents microbial agricultural chemicals such as insect viruses, entomopathogenic fungi, and nematophagous fungi, or antibiotics such as Avermectin, Emamectin-Benzoate, Milbemectin, Spinosad, and Ivermectin, may be used in admixture or in combination.
  • the active compounds of fungicides among the above- mentioned other agricultural chemicals include, for example, (by common names, some of which are still in an application stage) pyrimidinamine compounds such as Mepanipyri , Pyrimethanil, and Cyprodinil; azole compounds such as Triadimefon, Bitertanol, Triflumizole, Etaconazole, Propiconazole, Penconazole, Flusilazole,
  • Cyproconazole Terbuconazole, Hexaconazole, Furconazole-cis, Prochloraz , Metconazole, Epoxiconazole, Tetraconazole, Oxpoconazole, and Sipconazole; quinoxaline compounds such as Quinomethionate; dithiocarbamate compounds such as Maneb, Zineb, Mancozeb, Polycarbamate, Propineb; organic chlorine compounds such as Fthalide, Chlorothalonil , and Quintozene; imidazole compounds such as Benomyl, Thiophanate-Methyl, Carbendazim, and Cyazofamid; pyridinamine compounds such as Fluazinam; cyanoacetamide compounds such as Cymoxanil; phenylamide compounds such as Metalaxyl , Oxadixyl, Ofurace, Benalaxyl, Furalaxyl, and Cyprofuram; sulfenic acid
  • Trifloxystrobin, Picoxystrobin, and Pyraclostrobin oxazolidinedione compounds such as Famoxadone; thiazole carboxamide compounds such as Ethaboxam; silyl amide compounds such as Silthiopham; aminoacid amidecarbamate compounds such as Iprovalicarb; i idazolidine compound such as Fenamidone; hydroxyanilide compounds such as Fenhexamid; benzene sulfonamide compounds such as Flusulfamide; anthraquinone compounds; crotonic acid compounds; antibiotics; and other compounds, such as Isoprothiolane, Tricyclazole, Pyroquilon, Diclomezine, Pro.
  • oxazolidinedione compounds such as Famoxadone
  • thiazole carboxamide compounds such as Ethaboxam
  • silyl amide compounds such as Silthiopham
  • aminoacid amidecarbamate compounds such as I
  • agricultural chemicals which may be used in admixture with or in combination with the compounds of the present invention, may, for example, be the active ingredient compounds in the herbicides as disclosed in Farm Chemicals Handbook (2000 edition) , particularly those of soil treatment type.
  • the pesticides against parasites on animals are effective for controlling e.g. external parasites which are parasitic on the body surface of host animals (such as the back, the axilla, the lower abdomen or inside of the thigh) or internal parasites which are parasitic in the body of host animals (such as the stomach, the intestinal tract, the lung, the heart, the liver, the blood vessels, the subcutis or lymphatic tissues), but they are particularly effective for controlling the external parasites.
  • external parasites which are parasitic on the body surface of host animals (such as the back, the axilla, the lower abdomen or inside of the thigh) or internal parasites which are parasitic in the body of host animals (such as the stomach, the intestinal tract, the lung, the heart, the liver, the blood vessels, the subcutis or lymphatic tissues), but they are particularly effective for controlling the external parasites.
  • the external parasites may, for example, be animal parasitic acarus or fleas .
  • Their species are so many that it is difficult to list all of them, and therefore, their typical examples will be given.
  • the animal parasitic acarus may, for example, be ticks such as Boophilus microplus, Rhipicephalus sanguineus, Haemaphysalis longicornis, Haemaphysa1is flava, Haemaphysalis campanulata, Haemaphysalis concinna, Haemaphysalis japonica, Haemaphysa1is kitaokai, ticks such as Boophilus microplus, Rhipicephalus sanguineus, Haemaphysalis longicornis, Haemaphysa1is flava, Haemaphysalis campanulata, Haemaphysalis concinna, Haemaphysalis japonica, Haemaphysa1is kitaokai,
  • the fleas may, for example, be externally parasitic wingless insects belonging to Siphonaptera, more specifically, fleas belonging to Pulicidae, Ceratephyllus , etc.
  • Fleas belonging to Pulicidae may for example, be Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Echidnophaga gallinacea, Xenopsylla cheopis, Leptopsylla segnis, Nosopsyllus fasciatus, and Monopsyllus anisus .
  • the pesticides against parasites on animals, containing the compounds of the present invention are particularly effective for the control of fleas belonging to Pulicidae, particularly Ctenocephalides canis and Ctenocephalides felis, among them.
  • Other external parasites may, for example, be sucking lice (Anoplura) such as shortnosed cattle louse (Haematopinus eurysternus) , horse sucking louse
  • the internal parasites may, for example, be nematodes such as lung worms , whipworms (Trichuris) , tuberous worms , gastric parasites, ascaris, and filarioidea; tapeworms; flukes; and protozoa such as coccidia, malaria parasites (Plasmodium malariae) , intestinal sarcocyst, toxoplasma, and cryptosporidium.
  • nematodes such as lung worms , whipworms (Trichuris) , tuberous worms , gastric parasites, ascaris, and filarioidea; tapeworms; flukes; and protozoa such as coccidia, malaria parasites (Plasmodium malariae) , intestinal sarcocyst, toxoplasma, and cryptosporidium.
  • the host animals may, for example, be pet animals such as dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (such as pigeons, parrots, hill mynas, Java sparrows, honey parrots, lovebirds and canaries); domestic animals such as cows, horses, pigs and sheep; and poultry such as ducks and chickens.
  • pet animals such as dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (such as pigeons, parrots, hill mynas, Java sparrows, honey parrots, lovebirds and canaries); domestic animals such as cows, horses, pigs and sheep; and poultry such as ducks and chickens.
  • the pesticides against parasites on animals, containing the compounds of the present invention are particularly effective for the control of pests parasitic on pet animals or domestic animals, especially for the control of external parasite
  • the compound of the present invention when used as a pesticide against parasites on animals, it may be used as it is or may be used together with suitable adjuvants, as formulated into various formulations such as a dust, granules, tablets, a powder, capsules, a soluble concentrate, an emulsifiable concentrate, a water-based suspension concentrate and an oil-based suspension concentrate. In addition to such formulations, it may be formulated into any type of formulation which is commonly used in this field, so long as it is suitable for the purpose of the present invention.
  • the adjuvants to be used for formulations may, for example, be anionic surfactants or nonionic surfactants exemplified above as adjuvants for formulation of agricultural and horticultural pesticides; a cationic surfactant such as cetyl trimethylammonium bromide; a solvent such as water, acetone, acetonitrile, monomethylacetamide, dimethylacetamide, dimethylformamide, 2-pyrrolidone, N- methyl-2-pyrrolidone, kerosene, triacetin, methanol, ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, liquid polyoxyethylene glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol n- butyl ether, dipropylene glycol monomethyl ether, or dipropylene glycol
  • one or more of the respective components of these adjuvants may be suitably selected for use, so long as such will not depart from the purpose of the present invention. Further, other than the above-mentioned adjuvants, some among those known in this field may suitably be selected for use, and still further, some among the above- mentioned various adjuvants to be used in the agricultural and horticultural field may suitably be selected for use.
  • the blend ratio of the compound of the present invention to various adjuvants is usually from 0.1:99.9 to 90:10. In the actual use of such a formulation, it may be used as it is, or may be diluted to a predetermined concentration with a diluent such as water, and various spreaders (e.g. surfactants, vegetable oils or mineral oils) may be added thereto, as the case requires .
  • Administration of the compound of the present invention to a host animal is carried out orally or parenterally.
  • a method of administering a tablet, a liquid agent, a capsule, a wafer, a biscuit, a minced meat or other feed, containing the compound of the present invention may be mentioned.
  • a parenteral administration method there may, for example, be mentioned a method wherein the compound of the present invention is formulated into a suitable formulation and then taken into the body by e.g. intravenous administration, intramuscular administration, intradermal administration, hypodermic administration, etc.; a method wherein it is administered on the body surface by spot-on treatment, pour-on treatment or spray treatment; or a method of embedding a resin fragment or the like containing the compound of the present invention under the skin of the host animal .
  • the dose of the compound of the present invention to a host animal varies depending upon the administration method, the purpose of administration, the deceased symptom, etc., but it is usually administered in a proportion of from 0.01 mg to 100 g, preferably from 0.1 mg to 10 g, per 1 kg of the body weight of the host animal .
  • the present invention also includes a method for controlling a pest by the above-mentioned administration method or by the above-mentioned dose, particularly a method for controlling external parasites or internal parasites .
  • the compound of the present invention When the compound of the present invention is used as a pesticide against parasites on animals, various vitamins, minerals, amino acids, nutrients, enzymes, antipyretics, sedatives, antiphlogistics, fungicides, colorants, aromatic substances, preservatives, etc., may be used in admixture with or in combination with the adjuvants. Further, as the case requires, other animal drugs or agricultural chemicals, such as vermicides, anti-coccidium agents, insecticides, miticides, pulicides, nematocides, bactericides or antibacterial agents, may be mixed or combined for use, whereby improved effects may sometimes be obtained.
  • the present invention includes such a mixed pesticidal composition having the above- mentioned various components mixed or combined for use, and further a method for controlling a pest by using it, particularly a method for controlling external parasites or internal parasites.
  • Q is a 5- to 12-membered heterocyclic group (the heterocyclic group may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom.
  • Q is a heterocyclic group selected from the group consisting of thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl
  • the mixture was stirred at the same temperature for 1 hour, and a mixed solution comprising 3.00 g of methyl 9-oxodecanoate and 10 ml of diethylene glycol dimethyl ether was gradually dropwise added thereto.
  • the mixture was reacted at room temperature for 2 hours, and then further reacted at 30°C for 20 hours.
  • the reaction mixture was filtered, and the filtrate was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure.
  • a mixed solution comprising 20.64 g of benzoyl chloride and 10 ml of anhydrous diethyl ether, was dropwise added to a mixed solution comprising 25.0 g of 10-undecen-l-ol, 17.79 g of N,N-dimethylaniline and 60 ml of anhydrous diethyl ether and reacted for 3 hours and 10 minutes under reflux. After completion of the reaction, the mixture was cooled to room temperature, and the reaction mixture was filtered. The crystals were washed with a mixed solution of diethyl ether and hexane.
  • the NMR spectrum data thereof are as follows .
  • the NMR spectrum data thereof are as follows. 1 H-NMR ppm (Solvent : CDC1 3 /400MHz)
  • the mixture was reacted at the same temperature for 1 hour, and a mixed solution comprising 2.776 g of ethyl 11-oxododecanoate and 16 ml of diethylene glycol dimethyl ether, was dropwise added thereto over a period of 10 minutes. After completion of the dropwise addition, the mixture was returned to room temperature and reacted for 1 hour, and then further reacted at 40°C for 4 hours. After completion of the reaction, the reaction mixture was filtered, and crystals were washed with hexane. To the filtrate, water was added, followed by liquid separation.
  • the NMR spectrum data thereof are as follows.
  • a mixed solution comprising 14.8 ml of a tetrahydrofuran solution of 1M ethyl magnesium bromide and 10 ml of tetrahydrofuran, was cooled to -60°C under nitrogen atmosphere.
  • a mixed solution comprising the above concentrate and 10 ml of tetrahydrofuran, was dropwise added thereto at a temperature of from -60 to -50°C. After completion of the dropwise addition, the mixture was reacted at the same temperature for 1 hour. After completion of the reaction, water was added to the reaction mixture, followed by extraction with ethyl acetate . The organic layer was dried over anhydrous sodium sulfate to obtain 2.43 g of oily methyl 9- oxoundecanoate .
  • the NMR spectrum data thereof are as follows .
  • reaction mixture was concentrated under reduced pressure, and a mixed solution comprising the crude 10, 10-difluoro-9-ethyl-9- decenyl chloride thereby obtained and 3 ml of toluene, was gradually dropwise added to a mixture comprising 0.145 g of 2-amino-5-methylpyridine, 0.27 ml of triethylamine, 0.246 g of 4-dimethylaminopyridine and 2 ml of toluene. After completion of the dropwise addition, the mixture was reacted at room temperature for 30 minutes and then reacted for 1 hour under reflux.
  • reaction mixture was poured into a saturated sodium chloride aqueous solution and extracted with ethyl acetate.
  • the organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure.
  • the organic layer was dried over anhydrous sodium sulfate, and diethyl ether was distilled off under reduced pressure to obtain an oily substance, to which 1470 ml of 10% sulfuric acid was added. After refluxing for 1 hour, it was cooled to room temperature and extracted with 200 ml of diethyl ether. The diethyl ether layer was dried over anhydrous sodium sulfate, and diethyl ether was distilled off under reduced pressure to obtain 64.8 g of crude 7- oxononanoic acid.
  • the mixture was reacted at 45°C for 13.5 hours and then reacted at 100°C for 5 hours.
  • the reaction mixture was poured into 250 ml of water and extracted twice with 250 ml and 150 ml of hexane.
  • the hexane layer was washed six times with 100 ml of water and dried over anhydrous sodium sulfate, and hexane was distilled off under reduced pressure to obtain 21.98 g of oily crude ethyl 7-ethyl-8 , 8-difluoro-7-octenoate.
  • the NMR spectrum data thereof are as follows .
  • reaction mixture was concentrated under reduced pressure, and a mixed solution comprising a crude 7-ethyl-8 , 8-difluoro-7-octenyl chloride thereby obtained and 2.6 ml of toluene, was gradually dropwise added under cooling with ice to a mixture comprising 0.184 g of 2-amino-6-methylpyridine, 0.257 g of triethylamine, 0.311 g of 4-dimethylaminopyridine and 6 ml of toluene. After completion of the dropwise addition, the mixture was reacted at room temperature for 1 hour and 20 minutes and then reacted for 2 hours under reflux and left to stand overnight.
  • reaction mixture was poured into a saturated sodium chloride aqueous solution and extracted with ethyl acetate.
  • the organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure.
  • N- (5-methyl-2-pyridyl) -6 , 6-difluoro-7- hexenethioamide (after-mentioned Compound No. 426)
  • a mixture comprising 1.685 g of N- (5-methyl-2- pyridyl) -6, 6-difluoro-7-hexenamide, 3.84 g of phosphorus pentasulfide and 18 ml of toluene, was reacted at 40°C for 2 hours, then reacted at 60°C for 11 hours and further reacted at room temperature for 5.5 hours.
  • 0.295 g of l-ethyl-3-(3- dimethylaminopropyl) carbodiimide hydrochloride was added to a mixture comprising 0.300 g of 9-ethyl-10 , 10- difluoro-9-decenoic acid, 0.105 g of ethylamine hydrochloride, 0.18 ml of triethylamine, 3 ml of tetrahydrofuran and 3 ml of dichloromethane, and the mixture was reacted at room temperature for 22 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate.
  • Me represents a methyl group
  • Et an ethyl group n-Pr a n-propyl group
  • c-Pr a cyclopropyl group n-Bu a n-butyl group
  • i-Bu an isobutyl group s-Bu a sec-butyl group
  • t-Bu a tert-butyl group a phenyl group.
  • 3-CN-4,5- (Me) 2 -2-furyl represents a 2-furyl group having a cyano group substituted at the 3-position and having methyl groups substituted at both the 4- and 5-positions
  • - CH 2 CH 2 - (4-N0 2 -Ph) represents an ethyl group substituted by phenyl having a nitro group at the 4-position.
  • the compounds represented by the above formula (IV) to be used for the preparation of the compounds of the present invention include some which show pesticidal activities .
  • Typical examples of the compounds represented by the above formula (IV) will be given in Table 3
  • the NMR spectrum data thereof will be given in Table 4.
  • No . represents Compound No.
  • Me represents a methyl group
  • Et an ethyl group n-Pr a n-propyl group
  • i-Pr an isopropyl group
  • n-Bu a n-butyl group i-Bu an isobutyl group
  • s-Bu a sec-butyl group t-Bu a tert-butyl group
  • Ph a phenyl group
  • a miticidal solution was prepared to bring the concentration of a compound of the present invention to 200 ppm.
  • Kidney bean Phaseolus vulgaris
  • a pot diameter: 8 cm, height: 7 cm
  • 20 adults of two- spotted spider mite Tetranychus urticae
  • the adult mites were immersed together with the kidney bean leaf in the above miticidal solution, then dried in air and left in a constant temperature chamber at 25°C with lightening.
  • dead adult mites were counted, and the mortality was calculated by the following equation.
  • Rice seedling was dipped in an insecticidal solution prepared to bring the concentration of a compound of the present invention to 200 ppm and then dried in air. Then, the seedling with its root wrapped with a wet absorbent cotton, was put into a test tube. Then, 10 larvae of small brown planthopper (Laodelphax striatellus) were released therein, and the test tube was covered with a gauze and left in a constant temperature chamber at 25°C with lightening. On the 5th day after the release, dead larvae were counted, and the mortality was calculated by the following equation.
  • the mortality was obtained with respect to the above-mentioned Compound Nos. 8, 9, 22, 24 to 26, 28, 38, 40, 41, 58, 76, 98, 101, 103, 121, 124, 127, 132, 170, 201, 205, 275, 288, 290, 292, 294, 322, 337, 348, 353, 360, 363, 365, 370, 371, 373 to 375, 383 to 385, 399, 400, 402, 408, 426, 473 and 513, whereby all compounds showed high controlling effects with a mortality of at least 80%. Further, the mortality was obtained with respect to the above-mentioned Compound Nos. IV-8, IV-10, IV-14 and IV- 20, whereby all compounds showed high controlling effects with a mortality of at least 80%.
  • An insecticidal solution was prepared to bring the concentration of a compound of the present invention to 200 pm.
  • the petiole of each of eggplants with only one foliage leaf left (planted in a pot having a diameter of 8 cm and a height of 7 cm) was coated with a sticker, and about 2-3 apterous viviparous female of green peach aphid (Myzus persicae) were infested and incubated on the foliage leaf of the eggplant. After two days from the infestation, the adult insects were removed, and the number of larvae was counted. Then, the foliage leaf of the eggplant infested with the larvae was dipped in the above insecticidal solution, then dried in air and left in a constant temperature chamber at 25°C with lightening.
  • a Petri dish having a diameter of 9 cm 1 ml of an acetone solution of the compound of the present invention (concentration: 10 ⁇ mg/ml) is dropped by a micropipette. After the internal surface of the Petri dish dries up, from 60 to 180 infant mites are put, and the Petri dish is covered with a polyethylene sheet and sealed by an elastic band. The number of knocked down mites after contact with the pesticide is observed, whereby the compound of the present invention knocks down the majority of New Zealand cattle mite.
  • Pesticidal test against New Zealand cattle mite (Haemaphysalis longicornis) , employing a dog
  • N,N' -dimethylaceta ide 20 parts by weight
  • Fine silica powder 25 parts by weight A mixture of the above components is mixed with compound of the present invention in a weight ratio of 4:1 to obtain a wettable powder.
  • the above components are uniformly mixed and pulverized to obtain a base liquid, and

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Abstract

ABSTRACT A novel haloalkene compound represented by the formula (I), useful as an active ingredient of a pesticide, is presented: wherein each of X1 and X2 is halogen, Y is a hydrogen atom, halogen, alkyl or the like, n is from 0 to 5, A is an oxygen atom or a sulfur atom, G is a hydrogen atom, alkyl, acyl or the like, and Q is a 5- to 12-membered heterocyclic group (the heterocyclic group may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, alkyl which may be substituted by W, alkenyl which may be substituted by W, alkynyl which may be substituted by W, or cycloalkyl which may be substituted by W, wherein W is halogen, alkoxy, alkylthio, hydroxyl, cyano, nitro or phenyl which may be substituted.

Description

DESCRIPTION HA OALKENE COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND PESTICIDES CONTAINING THEM TECHNICAL FIELD The present invention relates to a novel haloalkene compound useful as an active ingredient of a pesticide. BACKGROUND ART
Haloalkene compounds are disclosed in USP4950666, EP432861, W092/15555, W097/8132 and JP-A-2001-288142 , respectively. However, they are different in the chemical structure from the haloalkene compound represented by the following formula (I) . DISCLOSURE OF THE INVENTION
For many years, many pesticides have been used, but many of them have various problems such that the effects are inadequate, their use is restricted as pests have acquired resistance, etc. Accordingly, it is desired to develop a novel pesticide substantially free from such problems, for example, a pesticide capable of controlling various pests which create problems in agricultural and horticultural fields or a pesticide which is capable of controlling pests parasitic on animals .
The present inventors have conducted various studies on haloalkene compounds in an effort to find a superior pesticide. As a result, they have found that a novel haloalkene compound has an extremely high pesticidal effect against pests at a low dose and at the same time has safety to crop plants, the natural enemy to pests, or mammals, and have accomplished the present invention.
Namely, the present invention relates to a haloalkene compound represented by the formula (I) or its salt :
Figure imgf000003_0001
wherein each of X1 and X2 is halogen, Y is a hydrogen atom, halogen, alkyl, haloalkyl or phenyl, n is from 0 to 5, A is an oxygen atom or a sulfur atom, G is a hydrogen atom, alkyl, haloalkyl, phenylalkyl, acyl, alkenyl, haloalkenyl, phenylalkenyl , alkynyl, haloalkynyl or phenylalkynyl, provided that when Y is a hydrogen atom or a halogen atom and A is an oxygen atom, G is alkyl, haloalkyl, phenylalkyl, acyl, alkenyl, haloalkenyl, phenylalkenyl, alkynyl, haloalkynyl or phenylalkynyl, and Q is a 5- to 12-membered heterocyclic group (the heterocyclic group may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, alkyl which may be substituted by W, alkenyl which may be substituted by W, alkynyl which may be substituted by W, or cycloalkyl which may be substituted by W, wherein W is halogen, alkoxy, alkylthio, hydroxy, cyano, nitro or phenyl which may be substituted, provided that (1) a case where X1 and X2 are simultaneously fluorine atoms, Y is a hydrogen atom, a chlorine atom or a bromine atom, n is from 1 to 5, A is an oxygen atom, G is alkyl, and Q is pyridyl which may be substituted by halogen, 2, 2-dimethyl-2 , 3- dihydrobenzofuranyl, alkyl which may be substituted by W, alkenyl which may be substituted by W, alkynyl which may be substituted by W, or cycloalkyl which may be substituted by W, (2) a case where X1 and X2 are simultaneously fluorine atoms, Y is a hydrogen atom or halogen, n is 0, A is an oxygen atom, G is alkyl, and Q is pyridyl, benzothiazolyl (both may be substituted by halogen, alkyl or haloalkyl) , alkyl substituted by phenyl which may be substituted, or cycloalkyl which may be substituted by , (3) a case where X1, X2 and Y are simultaneously fluorine atoms, and A is an oxygen atom, and (4) a case where X1 and X2 are simultaneously fluorine atoms, Y is a methyl group, n is 1, A is an oxygen atom, G is a hydrogen atom, and Q is a 2-propynyl group, are excluded; a process for its production; and a pesticide containing it. The pesticide containing, as an active ingredient, the novel haloalkene compound represented by the above formula (I) , has an extremely high pesticidal effect against pests at a low dose and at the same time has safety to crop plants, the natural enemy to pests, or mammals.
BEST MODE FOR CARRYING OUT THE INVENTION
As the halogen or halogen as a substituent in X1, X2, Y, G or W, each atom of fluorine, chlorine, bromine or iodine may be mentioned. The number of halogens as substituents may be 1 or more, and if more, the respective halogens may be the same or different. Further, the positions for substitution of halogens may be any positions .
The alkyl or alkyl moiety for Y, G, Q or W may be linear or branched, and as its specific example, Cι_ι2 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl may be mentioned.
The alkenyl or alkenyl moiety for G or Q may be linear or branched, and as its specific example, C2_ι alkenyl such as vinyl, 1-propenyl, allyl, isopropenyl, 1- butenyl, 1, 3-butadienyl, 1-hexenyl, 1-heptenyl, 4-octenyl, 2-decenyl or 2-dodecenyl may be mentioned.
The alkynyl or alkynyl moiety for G or Q may be linear or branched, and as its specific example, C2_12 alkynyl such as ethynyl, 2-butynyl, 2-pentynyl, 3-hexynyl, 4, 4-dimethyl-2-pentynyl, 4-octynyl, 2-decynyl or 2- dodecynyl may be mentioned.
As the acyl for G, one represented by -COT (wherein T is alkyl, haloalkyl, alkenyl, haloalkenyl or the like) may, for example, be mentioned. As the halogen moiety, alkyl, alkyl moiety, alkenyl and alkenyl moiety in the above T, the same ones as contained in the above Y or G may be mentioned. As the cycloalkyl or cycloalkyl moiety for Q, C3_8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclooctyl may be mentioned.
As the 5- to 12-membered heterocyclic group containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, for Q, a monocyclic or condensed ring type heterocyclic group containing from 1 to 4 hetero atoms, may, for example, be mentioned. Such a heterocyclic group may be saturated or may have an unsaturated moiety, or its methylene moiety may be converted to oxo or thioxo, or may be an N-oxide such as N-oxypyridyl . Preferably, it may, for example, be 1) a heterocyclic group selected from the group consisting of thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl, triazolyl, tetrazolyl, dithiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, thiazinyl, pyranyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl , benzisoxazolyl, benzimidazolyl, indazolyl, cyclopentapyrazolyl, benzothiadiazolyl, benzotriazolyl, quinolyl, isoquinolyl, phthalazinyl, cinnolinyl, quinazolinyl, quinoxalinyl, benzotriazinyl, naphthyridinyl , thiazolopyridyl, benzodioxolyl, benzodioxynyl, pyrazolopyrimidinyl, triazolopyrimidinyl and purinyl, 2) a partially saturated heterocyclic group having a part of such a heterocyclic group hydrogenated, 3) a saturated heterocyclic group having such a heterocyclic group completely hydrogenated, or 4) an oxo or thioxo heterocyclic group having a methylene moiety in the above-mentioned dithiazolyl, oxadinyl, thiadinyl, pyranyl, cyclopentapyrazolyl, benzodioxolyl, partially saturated heterocyclic group or saturated heterocyclic group, converted to oxo or thioxo.
The above-mentioned heterocyclic group may have several combinations due to the differences in the positions of hetero atoms or the differences of the condensed moieties, and the present invention includes all of them. For example, the thiadiazolyl includes 1, 2 , 3-thiadiazolyl and 1, 3 , 4-thiadiazolyl; the triazolyl includes 1, 2 , 3-triazolyl and 1, 2 , 4-triazolyl; the triazinyl includes, 1, 2 , 4-triazinyl and 1, 3 , 5-triazinyl; the benzothienyl includes benzo [b] thienyl and benzo [c] thienyl; the benzofuranyl includes benzo [b] furanyl and benzo [c] furanyl ; the benzisothiazolyl includes 1, 2-benzisothiazolyl and 2 , 1-benzisothiazolyl ; the benzisoxazolyl includes 1, 2-benzisoxazolyl and 2,1- benzisoxazolyl; and the benzothiadiazolyl includes 1,2,3- benzothiadiazolyl and 2 , 1, 3-benzothiadiazolyl . Further, the same applies to the partially saturated heterocyclic group, the saturated heterocyclic group or the oxo or thioxo heterocyclic group.
The above-mentioned partially saturated heterocyclic group may be one having a part of the above heterocyclic group hydrogenated. It may, for example, be 4,5- dihydrothiazolyl, 4, 5-dihydrooxazolyl, 4,5- dihydroisoxazolyl, 4, 5-dihydro-lH-imidazolyl, 4,5- dihydro-lH-pyrazolyl , 3,4,5, 6-tetrahydropyridinyl , 1, 4, 5, 6-tetrahydropyrimidinyl, 2 , 3-dihydrobenzofuranyl or 4a, 5 , 6 , 7 , 8 , 8a-hexahydroquinoxalinyl .
The above-mentioned saturated heterocyclic group may be one having the above heterocyclic group completely hydrogenated. It may, for example, be tetrahydrofuranyl, tetrahydropyranyl, pyrrolidinyl, piperidinyl, piperazinyl or morpholinyl.
The above-mentioned oxo or thioxo heterocyclic group may be one having a methylene moiety in the above- mentioned dithiazolyl, oxadinyl, thiadinyl, pyranyl, cyclopentapyrazolyl, benzodioxolyl, partially saturated heterocyclic group or saturated heterocyclic group, converted to oxo or thioxo. It may, for example, be 2- oxotetrahydrothienyl, 2-thioxotetrahydrothienyl, 2- oxotetrahydrofuranyl, 2-thioxotetrahydrofuranyl, 2- oxopyrrolidinyl, 2 , 5-dioxopyrrolidinyl, 2,4- dioxothiazolidinyl, 4-oxo-4, 5-dihydrooxazolyl, 4-oxo-4,5- dihydro-lH-imidazol-2-yl, 5-oxo-4, 5-dihydro-lH-pyrazolyl, 3-OXO-2 , 3-dihydro-lH-pyrazolyl, 5-thioxo-5H- [1, 2 , 4] dithiazolyl, 6-oxo-l, 6-dihydropyridinyl, 6-oxo- 1, 6-dihydropyridazinyl, 2 , 6-dioxo-l, 2 , 3 , 6- tetrahydropyrimidinyl , 3-oxo-3H- [1, 2 , 4] triazinyl, 2-oxo- 1, 2-dihydroquinolinyl, or 1, 3-dioxo-l, 3-dihydroisoindol- 2-yl.
The number of substituents in the phenyl which may be substituted in W or in the 5- to 12-membered heterocyclic group (the heterocyclic moiety may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, for Q, may be 1 or more, and if more, such substituents may be the same or different.
Specific examples of the substituents in the phenyl which may be substituted in W, or in the 5- to 12- membered heterocyclic group (the heterocyclic moiety may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, for Q, may be halogen, nitro, cyano, (Cι-8) alkyl, halo (Cι_8) alkyl, aryl (Cι_8) alkyl wherein the aryl moiety may be substituted, heteroaryl (Cι_8) alkyl wherein the heteroaryl moiety may be substituted, (C3_8) cycloalkyl, halo (C3_8) cycloalkyl, (C2-8) alkenyl, halo (C_s) alkenyl, (C2-8) alkynyl, halo (C-8) alkynyl, aryl which may be substituted, heteroaryl which may be substituted, -NR , -OR1, -SR1, -SOR1, -SO-^R1, -SO^R^Ε2, -COR1,
Figure imgf000009_0001
-COSR1, -CSOR1, -OCOR3 and -CH2CN.
Each of R1 and R2 which are independent of each other, is a hydrogen atom, (Cι_8) alkyl, halo (Ci-s) alkyl, aryl (Cx_8) alkyl wherein the aryl moiety may be substituted, heteroaryl (Cι_8) alkyl wherein the heteroaryl moiety may be substituted, (C3.8) cycloalkyl, halo (C3_8) cycloalkyl, (C2-8) alkenyl, halo (C_8) alkenyl, (C2_8) alkynyl, halo (C_8) alkynyl, aryl which may be substituted, or heteroaryl which may be substituted.
R3 is (Cι_8) alkyl, halo (Cι_8) alkyl, aryl (Cι_8) alkyl wherein the aryl moiety may be substituted, heteroaryl (Cι-8) alkyl wherein the heteroaryl moiety may be substituted, (C3_8) cycloalkyl, halo (C3_8) cycloalkyl , (C2_8) alkenyl, halo (C2_8) alkenyl, (C2-8) alkynyl , halo (C2-8) alkynyl, aryl which may be substituted, or heteroaryl which may be substituted.
The substituent for the aryl which may be substituted or the substituent for the heteroaryl which may be substituted, contained in the 5- to 12-membered heterocyclic group (the heterocyclic moiety may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, for Q, R1, R2 or R3, may, for example, be halogen, nitro, cyano, (Cι_8) alkyl, halo (Cι_8) alkyl, (C3_8) cycloalkyl, halo (C3-8) cycloalkyl, (C2_8) alkenyl, halo (C2_8) alkenyl, (C2-8) alkynyl, halo (C2-8) alkynyl, -NRR5, -OR4, -SR4, -SOR4, -S02R4, -S02NR4 R5, -COR4, -C02R4, -COSR4, -CSOR4 or -OCOR6.
Each of R4 and R5 which are independent of each other, is a hydrogen atom, (Cι_8) alkyl, halo (Cι_8) alkyl, (C3.8) cycloalkyl, halo (C3_8) cycloalkyl, (C2_8) alkenyl, halo (C2-8) alkenyl, (C2_8) alkynyl, or halo (C2_8) alkynyl. R6 is (C1_8)alkyl, halo (Cι_8) alkyl, aryl (d-8) alkyl, heteroaryl (Cι_8) alkyl, (C3-s) cycloalkyl, halo (C3_8) cycloalkyl, (C2-s) alkenyl, halo (C2_8) alkenyl, (C2-8) alkynyl, halo (C2_8) alkynyl , aryl or heteroaryl.
As a specific example for the above-mentioned aryl or aryl moiety, phenyl, naphthyl, phenanthrenyl , anthracenyl, indenyl or indanyl may be mentioned. As a specific example for the above-mentioned heteroaryl or heteroaryl moiety, the same one as the heterocyclic group for the above-mentioned Q may be mentioned.
The above Cι_8 alkyl or alkyl moiety may be linear or branched, and its specific example may be methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl or octyl . As a specific example for the above-mentioned C3_8 cycloalkyl or cycloalkyl moiety, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl may be mentioned.
The above-mentioned C2.8 alkenyl or alkenyl moiety may be linear or branched, and as its specific example, vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 1,3- butadienyl, 1-hexenyl, 1-heptenyl or 4-octenyl may be mentioned.
The above-mentioned C2-8 alkynyl or alkynyl moiety may be linear or branched, and as its specific example, ethynyl, 2-butynyl, 2-pentynyl, 3 -hexynyl, 4, 4-dimethyl- 2-pentynyl, or 4-octynyl may be mentioned.
As a specific example for the above-mentioned halogen or the halogen as a substituent, each atom of fluorine, chlorine, bromine or iodine may be mentioned. The number of halogens as substituents, may be 1 or more, and if more, the respective halogens may be the same or different. Further, the positions for substitution of halogens may be any positions.
The salt of the haloalkene compound represented by the above formula (I) includes all kinds so long as they are agriculturally acceptable. For example, an alkali metal salt such as a sodium salt or a potassium salt; an alkaline earth metal salt such as a magnesium salt or a calcium salt; an ammonium salt such as a dimethylamine salt or a triethylamine salt; an inorganic acid salt such as a hydrochloride, a perchlorate, a sulfate or a nitrate; or an organic acid salt such as an acetate or a methanesulfonate, may be mentioned.
The haloalkene compound represented by the above formula (I) may have geometrical isomers, optical isomers or tautomeric isomers, and such isomers and mixtures thereof are both included in the present invention. The haloalkene compound represented by the above formula (I) or its salt (hereinafter referred to simply as the compound of the present invention) can be produced by the following reactions (A) to (F) and in accordance with a usual method for producing a salt.
Figure imgf000013_0001
(1-1 )
In the reaction (A) , X1, X2, Y, n, G and Q are as defined above. Further, as the salt of the compound represented by the formula (III), a salt with an organic or inorganic acid, such as a hydrochloride, a sulfate, an oxalate or a methanesulfonate, may be mentioned.
The reaction (A) can be carried out in the presence of a base, as the case requires. As the base, one or more types may suitably be selected for use from, for example, a tertiary amine such as trimethy1amine, triethylamine, triisopropylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, 2 , 6-dimethylpyridine, 4-pyrrolidinopyridine, N-methylmorpholine, N,N- dimethylaniline, N,N-diethylaniline, N-ethyl-N- methy1aniline, 1, 8-diazabicyclo [5.4.0] -7-undecene or 1,4- diazabicyclo [2.2.2] octane; an alkali metal such as sodium or potassium; an alkali metal carbonate such as sodium carbonate or potassium carbonate; an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an alkali metal hydride such as sodium hydride or potassium hydride; an alkali metal bicarbonate such as sodium bicarbonate or potassium bicarbonate; and an alkyl lithium such as butyl lithium. The base may be used in an amount of from 1 to 5 times by mol, preferably from 1 to 2.5 times by mol, to the compound of the formula (II) . The reaction (A) can be carried out in the presence of a solvent, as the case requires. The solvent may be any solvent so long as it is a solvent inert to the reaction, and one or more types may suitably be selected for use from, for example, an aliphatic hydrocarbon such as pentane, hexane, heptane, octane or cyclohexane; an aromatic hydrocarbon such as benzene, toluene, xylene or pyridine; a halogenated hydrocarbon such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; an ether such as diethyl ether, butyl ethyl ether, tetrahydrofuran, dioxane, dimethoxyethane or anisole; an ester such as methyl acetate, ethyl acetate or propyl acetate; a ketone such as acetone, diethyl ketone, methyl ethyl ketone or methyl isobutyl ketone; and a polar aprotic solvent such as acetonitrile, propionitrile, N,N- dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, sulfolane, dimethylacetamide or N-methylpyrrolidone.
The reaction (A) can be carried out in an atmosphere of an inert gas, as the case requires. As such an inert gas, each gas such as nitrogen, helium or argon may be mentioned. The reaction temperature for the reaction (A) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours.
Figure imgf000015_0001
(1-1 )
In the reaction (B) , X1, X2, Y, n, G and Q are as defined above. Further, as the salt of the compound represented by the formula (III) , the same one as exemplified in the above-mentioned reaction (A) may be mentioned. The reaction (B) can be carried out by azeotropic dehydration in the presence of a solvent or in the presence of a condensing agent.
The solvent to be used for the azeotropic dehydration may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from those exemplified in the above-mentioned reaction (A) . Further, in a case where the reaction is carried out in the presence of a condensing agent, a solvent may be used as the case requires. The solvent to be used here may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from those exemplified in the above reaction (A) . As the condensing agent to be used in the reaction (B) , a carbodiimide such as 1, 3-dicyclohexylcarbodiimide, 1, 3-diisopropylcarbodiimide or l-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride; or others such as phenyl dichlorophosphate, diethyl cyanophosphonate, 1,3, 5-triaza-2 , 4, 6-triphosphorin- 2 , 2 , 4, 4, 6, 6-hexachloride, cyanuric chloride, isobutyl chloroformate, chlorosulfonyl isocyanate, N,N' -carbonyl diimidazole, or trifluoroacetic anhydride, may be mentioned. The condensing agent may be used in an amount of from 1 to 5 times by mol, preferably from 1 to 2 times by mol, to the compound of the formula (IV) .
The reaction (B) can be carried out in the presence of a base, as the case requires. As the base, one or more types may suitably be selected for use from, for example, tertiary amines such as trimethylamine, triethylamine, triisopropylamine, diisopropylethylamme, pyridine, 4-dimethylaminopyridine, 2 , 6-dimethylpyridine, 4-pyrrolidinopyridine, N-methylmorpholine, N,N- dimethylaniline, N,N-diethylaniline, and N-ethyl-N- methylaniline. The base may be used in an amount of from 0.1 to 5 times by mol, preferably from 0.1 to 2.5 times by mol, to the compound of the formula (IV) .
The reaction (B) can be carried out in an atmosphere of an inert gas, as the case requires. As such an inert gas, one such as nitrogen, helium or argon may be mentioned.
The reaction temperature for the reaction (B) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours.
Figure imgf000017_0001
( )
In the reaction (C) , X1, X2, Y, n, G and Q are as defined above, and Z is C1-4 alkyl. Further, as the salt of the compound represented by the formula (III) , the same one as exemplified in the above reaction (A) may, for example, be mentioned.
The reaction (C) can be carried out in the presence of a base, as the case requires. As the base, one or more types may suitably be selected for use from, for example, those exemplified in the above reaction (A) , and alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium butoxide; and tertiary amines such as trimethylamine, triethylamine, triisopropylamine, diisopropylethylamme, pyridine, 4-dimethylaminopyridine, 2, 6-dimethylpyridine, 4-pyrrolidinopyridine, N- ethylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, and N-ethyl-N-methylaniline. The base may be used in an amount of from 0.01 to 5 times by mol, preferably from 0.01 to 2.5 times by mol, to the compound of the formula (V) .
The reaction (C) can be carried out in the presence of a solvent, as the case requires. The solvent may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from, for example, those exemplified in the above reaction (A) .
The reaction (C) can be carried out in an atmosphere of an inert gas, as the case requires. As the inert gas, each gas such as nitrogen, helium or argon may be mentioned.
The reaction temperature for the reaction (C) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours.
Figure imgf000018_0001
(I-3) In the reaction (D) , X1, X2, Y, n and Q are as defined above, and G1 is alkyl, haloalkyl, phenylalkyl, acyl , alkenyl , haloalkenyl , phenylalkenyl , alkynyl , haloalkynyl or phenylalkynyl, and X3 is halogen. The reaction (D) can be carried out in the presence of a base, as the case requires. As the base, one or more types may suitably be selected for use from, for example, those exemplified in the above reaction (A) . The base may be used in an amount of from 0.01 to 10 times by mol, preferably from 0.01 to 5 times by mol, to the compound of the formula (1-2) .
The reaction (D) can be carried out in the presence of an N-trialkylsilyl-alkylcarbamate, as the case requires. As such an N-trialkylsilyl-alkylcarbamate, one or more types may suitably be selected for use from, for example, N-trimethylsilyl-ethylcarbamate and N- triethylsilyl-methylcarbamate . The N-trialkylsilyl- alkylcarbamate may be used in an amount of from 0.01 to 10 times by mol, preferably from 0.01 to 5 times by mol, to the compound of the formula (1-2) .
The reaction (D) can be carried out in the presence of a solvent, as the case requires. The solvent may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from, for example, those exemplified in the above-mentioned reaction (A) .
The reaction (D) can be carried out in an atmosphere of an inert gas, as the case requires. As such an inert gas, one such as nitrogen, helium or argon may be mentioned.
The reaction temperature for the reaction (D) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours. [E]
Figure imgf000020_0001
(I-4)
In the reaction (E) , X1, X2, Y, n and Q are as defined above, G2 is alkyl, and U is alkyl, haloalkyl, alkoxy, phenyl, phenyl substituted by halogen, or phenyl substituted by alkyl.
The reaction (E) can be carried out in the presence of a base, as the case requires. As the base, one or more types may suitably be selected for use from, for example, those exemplified in the above reaction (A) . The base may be used in an amount of from 0.01 to 10 times by mol, preferably from 0.01 to 5 times by mol, to the compound of the formula (1-2).
The reaction (E) can be carried out in the presence of a solvent, as the case requires. The solvent may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from, for example, those exemplified in the above-mentioned reaction (A) . The reaction (E) can be carried out in an atmosphere of an inert gas, as the case requires. As such an inert gas, each gas such as nitrogen, helium or argon may be mentioned.
The reaction temperature for the reaction (E) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours. [F]
Figure imgf000021_0001
(1-5)
In the reaction (F) , X1, X2, Y, n, G and Q are as defined above. As the thionizing agent to be used in the reaction (F) , phosphorus pentasulfide or Lawesson's reagent may, for example, be mentioned. The thionizing agent may be used in an amount of from 1 to 10 times by mol, preferably from 1 to 2 times by mol, to the compound of the formula (1-1) . The reaction (F) can be carried out in the presence of a solvent, as the case requires. The solvent may be any solvent so long as it is a solvent inert to the reaction, and for example, one or more types may suitably be selected for use from, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and pyridine; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane and trichloroethane; ethers such as diethyl ether, butyl ethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and anisole; esters such as methyl acetate, ethyl acetate and propyl acetate; and polar aprotic solvents such as acetonitrile, propionitrile, dimethylsulfoxide and sulfolane.
The reaction (F) can be carried out in an atmosphere of an inert gas, as the case requires. As such an inert gas, each gas such as nitrogen, helium or argon may be mentioned. The reaction temperature for the reaction (F) is usually from -78 to +250°C, preferably from 0 to 150°C, and the reaction time is usually from 0.1 to 72 hours, preferably from 0.1 to 24 hours.
Each starting materials represented by the formula (II) , (IV) or (V) in the above reaction (A) to (C) is (1) a known compound, or (2) can be produced by or in accordance with the Preparation Examples given hereinafter, or (3) can be produced by or in accordance with the method disclosed in W092/15555, EP661289 or EP432861. The above (3) will be described in more detail a) The method disclosed from p. 15, line 16 to p. 16, line 3 in 092/15555, a method of optionally carrying out usual chlorination or esterification, following such a method, the method disclosed in Preparation Example 16, 22, 28 or 42 in the same publication or a method in accordance therewith. b) The method disclosed from p. 13, line 25 to p. 14, line 37 in EP661289, the method disclosed in Preparation Example Zl, Z2 or Z3 in the same publication or a method in accordance therewith. c) The method disclosed from p. 4, line 22 to p . 8, line 45 in EP432861, the method disclosed in Preparation Example 3, 4, 8, 9, 10 or 16 in the same publication or a method in accordance therewith.
Preferred embodiments of pesticides containing the compounds of the present invention will be described below. The pesticides containing the compounds of the present invention are particularly useful, for example, as agents for controlling various pests which become problematic in the agricultural and horticultural fields, i.e. agricultural and horticultural pesticides, or as agents for controlling pests which are parasitic on animals i.e. pesticides against parasites on animals. The agricultural and horticultural pesticides containing the compounds of the present invention are useful as an insecticide, a iticide, a nematicide and a soil pesticide, and they are effective for controlling plant parasitic mites such as two-spotted spider mite (Tetranychus urticae) , carmine spider mite (Tetranychus cinnabarinus) , kanzawa spider mite (Tetranychus kanzawai) , citrus red mite (Panonychus citri) , European red mite (Panonychus ulmi) , broad mite (Polyphagotarsonemus latus) , pink citrus rust mite (Aculops pelekassi) and bulb mite (Rhizoglyphus echinopus) ; aphids such as green peach aphid (Myzus persicae) and cotton aphid (Aphis gossypii) ; agricultural insect pests such as diamondback moth (Plutella xylostella) , cabbage armyworm (Mamestra brassicae) , common cutworm ( Spodoptera litura) , codling moth (Laspeyresia pomonella) , bollworm (Heliothis zea) , tobacco budworm (Heliothis virescens) , gypsy moth (Lymantria dispar) , rice leafroller (Cnaphalocrocis medinalis) , Adoxophyes sp. , Colorado potato beetle (Leptinotarsa decemlineata) , cucurbit leaf beetle (Aulacophora femoralis) , boll weevil (Anthonomus grandis) , planthoppers, leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiid flies, scarabs, black cutworm (Agrotis ipsilon) , cutworm (Agrotis segetum) and ants; plant parasitic nematodes such as root-knot nematodes, cyst nematodes, root-lesion nematodes, rice white-tip nematode (Aphelenchoides besseyi) , strawberry bud nematode (Nothotylenchus acris) , pine wood nematode (Bursaphelenchus lignicolus) ; gastropods such as slugs and snails; soil pests such as isopods such as pillbugs (Armadilidium vulgare) and pillbugs (Porcellio scaber) ; hygienic insect pests such as tropical rat mite (Ornithonyssus bacoti) , cockroachs, housefly (Musca domestica) and house mosquito (Culex pipiens) ; stored grain insect pests such as angoumois grai moth (Sitotroga cerealella) , adzuki bean weevil (Callosobruchus chinensis) , red flour beetle (Tribolium castaneum) and mealworms; household goods insect pests such as casemaking clothes moth (Tinea pellionella) , black carpet beetle (Anthrenus scrophularidae) and subterranean termites; domestic mites such as mold mite (Tyrophagus putrescentiae) , Dermatophagoides farinae and Chelacaropsis moorei . Among them, the agricultural and horticultural pesticides containing the compounds of the present invention are particularly effective for controlling plant parasitic mites, agricultural insect pests, plant parasitic nematodes or the like. Further, they are effective against insect pests having acquired resistance to organophosphorus , carbamate and/or synthetic pyrethroid insecticides. Moreover, the compounds of the present invention have excellent systemic properties, and by the application of the compounds of the present invention to soil treatment, not only noxious insects, noxious mites, noxious nematodes, noxious gastropods and noxious isopods in soil but also foliage pests can be controlled.
Another preferred embodiments of the pesticides containing compounds of the present invention may be agricultural and horticultural pesticides which collectively control the above-mentioned plant parasitic mites, agricultural insect pests, plant parasitic nematodes, gastropods and soil pests.
The agricultural and horticultural pesticide containing the compound of the present invention, is usually formulated by mixing the compound with various agricultural adjuvants and used in the form of a formulation such as a dust, granules, water-dispersible granules, a wettable powder, a water-based suspension concentrate, an oil-based suspension concentrate, water soluble granules, an emulsifiable concentrate, a soluble concentrate, a paste, an aerosol or an ultra low-volume formulation. However, so long as it is suitable for the purpose of the present invention, it may be formulated into any type of formulation which is commonly used in this field. Such agricultural adjuvants include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaoline, bentonite, a mixture of kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, mirabilite, zeolite and starch; solvents such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethylsulfoxide, N,N- dimethylformamide, di ethylacetamide, N-methyl-2- pyrrolidone, and alcohol; anionic surfactants and spreaders such as a salt of fatty acid, a benzoate, an alkylsulfosuccinate, a dialkylsulfosuccinate, a polycarboxylate, a salt of alkylsulfuric acid ester, an alkyl sulfate, an alkylaryl sulfate, an alkyl diglycol ether sulfate, a salt of alcohol sulfuric acid ester, an alkyl sulfonate, an alkylaryl sulfonate, an aryl sulfonate, a lignin sulfonate, an alkyldiphenyl ether disulfonate, a polystyrene sulfonate, a salt of alkylphosphoric acid ester, an alkylaryl phosphate, a styrylaryl phosphate, a salt of polyoxyethylene alkyl ether sulfuric acid ester, a polyoxyethylene alkylaryl ether sulfate, a salt of polyoxyethylene alkylaryl ether sulfuric acid ester, a polyoxyethylene alkyl ether phosphate, a salt of polyoxyethylene alkylaryl phosphoric acid ester, and a salt of a condensate of naphthalene sulfonate with formalin; nonionic surfactants and spreaders such as a sorbitan fatty acid ester, a glycerin fatty acid ester, a fatty acid polyglyceride, a fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, an oxyalkylene block polymer, a polyoxyethylene alkyl ether, a polyoxyethylene alkylaryl ether, a polyoxyethylene styrylaryl ether, a polyoxyethylene glycol alkyl ether, a polyethylene glycol, a polyoxyethylene fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene glycerin fatty acid ester, a polyoxyethylene hydrogenated castor oil, and a polyoxypropylene fatty acid ester; and vegetable and mineral oils such as olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, and liquid paraffins. Each of the components as such adjuvants may be one or more suitably selected for use, so long as the purpose of the present invention can thereby be accomplished. Further, various additives which are commonly used, such as a filler, a thickener, an anti-settling agent, an anti-freezing agent, a dispersion stabilizer, a phytotoxicity reducing agent, and an anti-mold agent, may also be employed. The weight ratio of the compound of the present invention to the various agricultural adjuvants is usually from 0.001:99.999 to 95:5, preferably from 0.005:99.995 to 90:10.
In the actual application of such a formulation, it may be used as it is, or may be diluted to a predetermined concentration with a diluent such as water, and various spreaders e.g. surfactants, vegetable oils or mineral oils may be added thereto, as the case requires. The application of the agricultural and horticultural pesticide containing the compound of the present invention can not generally be defined, as it varies depending upon the weather conditions, the type of the formulation, the application season, the application site or the types or degree of outbreak of the pest insects. However, it is usually applied in a concentration of the active ingredient being from 0.05 to 800,000 ppm, preferably from 0.5 to 500,000 ppm, and the dose per unit area is such that the compound of the present invention is from 0.05 to 50,000 g, preferably from 1 to 30,000 g, per hectare. Further, agricultural and horticultural pesticides as another preferred embodiment of pesticides containing the compounds of the present invention may be applied in accordance with the above-described application of pesticides. The present invention includes such a method for controlling pests, particularly for controlling plant parasitic mites, agricultural insect pests or plant parasitic nematodes by such applications.
Various formulations of agricultural and horticultural pesticides containing the compounds of the present invention or their diluted compositions may be applied by conventional methods for application which are commonly employed, such as spraying (e.g. spraying, jetting, misting, atomizing, powder or grain scattering or dispersing in water), soil application (e.g. mixing or drenching), surface application (e.g. coating, powdering or covering) or impregnation to obtain poisonous feed. Further, it is possible to feed domestic animals with a food containing the above active ingredient and to control the outbreak or growth of pests, particularly insect pests, with their excrements. Furthermore, the active ingredient may also be applied by a so-called ultra low-volume application method. In this method, the composition may be composed of 100% of the active ingredient .
Further, the agricultural and horticultural pesticides containing compounds of the present invention may be mixed with or may be used in combination with other agricultural chemicals, fertilizers or phytotoxicity-reducing agents, whereby synergistic effects or activities may sometimes be obtained. Such other agricultural chemicals include, for example, a herbicide, an insecticide, a miticide, a nematicide, a soil pesticide, a fungicide, an antivirus agent, an attractant, an antibiotic, a plant hormone and a plant growth regulating agent. Especially, with a mixed pesticide having a compound of the present invention mixed with or used in combination with one or more active compounds of other agricultural chemicals, the application range, the application time, the pesticidal activities, etc. may be improved to preferred directions. The compound of the present invention and the active compounds of other agricultural chemicals may separately be formulated so that they may be mixed for use at the time of application, or they may be formulated together. The present invention includes such a mixed pesticidal composition.
The mixing ratio of the compound of the present invention to the active compounds of other agricultural chemicals can not generally be defined, since it varies depending upon the weather conditions, the types of formulations, the application time, the application site, the types or degree of outbreak of insect pests, etc., but it is usually within a range of from 1:300 to 300:1, preferably from 1:100 to 100:1, by weight. Further, the dose for the application is such that the total amount of the active compounds is from 0.1 to 50,000 g, preferably from 1 to 30,000 g, per hectare. The present invention includes a method for controlling pests by an application of such a mixed pesticide composition. The active compounds of insect pest control agents such as insecticides, miticides, nematicides or soil pesticides in the above-mentioned other agricultural chemicals, include, for example, (by common names, some of them are still in an application stage) organic phosphate compounds such as Profenofos, Dichlorvos,
Fenamiphos, Fenitrothion, EPN, Diazinon, Chlorpyrifos- methyl, Acephate, Prothiofos, Fosthiazate, Phosphocarb, Cadusafos, Disulfoton, Chlorpyrifos, Demeton-S-methyl, Dimethoate, and Methamidophos; carbamate compounds such as Carbaryl, Propoxur, Aldicarb, Carbofuran, Thiodicarb, Methomyl, Oxa yl , Ethiofencarb, Pirimicarb, Fenobucarb, Carbosulfan, and Benfuracarb; nereistoxin derivatives such as Cartap, and Thiocyclam, and Bensultap; organic chlorine compounds such as Dicofol, and Tetradifon; organometallic compounds such as Fenbutatin Oxide; pyrethroid compounds such as Fenvalerate, Per ethrin, Cypermethrin, Deltamethrin, Cyhalothrin, Tefluthrin, Ethofenprox, Fenpropathrin and Bifenthrin; benzoylurea compounds such as Diflubenzuron, Chlorfluazuron, Teflubenzuron, Flufenoxuron, Lufenuron, and Novaluron; juvenile hormone-like compounds such as Methoprene, Pyriproxyfen, and Fenoxycarb; pyridazinone compounds such as Pyridaben; pyrazole compounds such as Fenpyroximate, Fipronil, Tebufenpyrad, Ethiprole, Tolfenpyrad, and Acetoprole; neonicotinoids such as Imidacloprid, Nitenpyram, Acetamiprid, Thiacloprid, Thiamethoxam, Clothianidin, and Dinotefuran; hydrazine compounds such as Tebufenozide, Methoxyfenozide, and Chromafenozide; dinitro compounds; organic sulfur compounds; urea compounds; triazine compounds; hydrazone compounds; and other compounds, such as Flonicamid, Buprofezin, Hexythiazox, Amitraz, Chlordimeform, Silafluofen,
Triazamate, Pymetrozine, Pyrimidifen, Chlorfenapyr, Indoxacarb, Acequinocyl , Etoxazole, Cyromazin, 1,3- dichloropropene, Diafenthiuron, Benclothiaz, Flufenerim, Pyridalyl, Spirodiclofen, Bifenazate, Spiromesifen, Propargite, Clofentezine, Etoxazole, and Fluacrypyrim.
Further, BT agents, microbial agricultural chemicals such as insect viruses, entomopathogenic fungi, and nematophagous fungi, or antibiotics such as Avermectin, Emamectin-Benzoate, Milbemectin, Spinosad, and Ivermectin, may be used in admixture or in combination.
The active compounds of fungicides among the above- mentioned other agricultural chemicals include, for example, (by common names, some of which are still in an application stage) pyrimidinamine compounds such as Mepanipyri , Pyrimethanil, and Cyprodinil; azole compounds such as Triadimefon, Bitertanol, Triflumizole, Etaconazole, Propiconazole, Penconazole, Flusilazole,
Myclobutanil, Cyproconazole, Terbuconazole, Hexaconazole, Furconazole-cis, Prochloraz , Metconazole, Epoxiconazole, Tetraconazole, Oxpoconazole, and Sipconazole; quinoxaline compounds such as Quinomethionate; dithiocarbamate compounds such as Maneb, Zineb, Mancozeb, Polycarbamate, Propineb; organic chlorine compounds such as Fthalide, Chlorothalonil , and Quintozene; imidazole compounds such as Benomyl, Thiophanate-Methyl, Carbendazim, and Cyazofamid; pyridinamine compounds such as Fluazinam; cyanoacetamide compounds such as Cymoxanil; phenylamide compounds such as Metalaxyl , Oxadixyl, Ofurace, Benalaxyl, Furalaxyl, and Cyprofuram; sulfenic acid compounds such as Dichlofluanid; copper compounds such as cupric hydroxide, and Oxine Copper; isoxazole compounds such as Hydroxyisoxazole; organophosphorus compounds such as Fosetyl-Al, Tolclofos-Methyl, S-benzyl 0,0- diisopropylphosphorothioate, 0-ethyl S,S- diphenylphosphorodithioate, and aluminumethylhydrogen phosphonate; N-halogenothioalkyl compounds such as Captan, Captafol, and Folpet; dicarboximide compounds such as Procymidone, Iprodione, and Vinclozolin; benzanilide compounds such as Flutolanil, Mepronil, and Zoxamide; piperazine compounds such as Triforine; pyrizine compounds such as Pyrifenox; carbinol compounds such as Fenarimol; and Flu.triafol ; piperidine compounds such as Fenpropidine; morpholine compounds such as Fenpropimorph; organotin compounds such as Fentin Hydroxide, and Fentin Acetate; urea compounds such as Pencycuron; cinnamic acid compounds such as Dimetho orph; phenylcarbamate compounds such as Diethofencarb; cyanopyrrole compounds such as Fludioxonil, and Fenpiclonil; Strobilurin compounds such as Azoxystrobin, Kresoxim-Methyl, Metominofen,
Trifloxystrobin, Picoxystrobin, and Pyraclostrobin; oxazolidinedione compounds such as Famoxadone; thiazole carboxamide compounds such as Ethaboxam; silyl amide compounds such as Silthiopham; aminoacid amidecarbamate compounds such as Iprovalicarb; i idazolidine compound such as Fenamidone; hydroxyanilide compounds such as Fenhexamid; benzene sulfonamide compounds such as Flusulfamide; anthraquinone compounds; crotonic acid compounds; antibiotics; and other compounds, such as Isoprothiolane, Tricyclazole, Pyroquilon, Diclomezine, Pro. benazole, Quinoxyfen, Propamocarb Hydrochloride, Spiroxamine, Chloropicrin, Dazomet. and Metam-Sodium. Further, agricultural chemicals which may be used in admixture with or in combination with the compounds of the present invention, may, for example, be the active ingredient compounds in the herbicides as disclosed in Farm Chemicals Handbook (2000 edition) , particularly those of soil treatment type.
The pesticides against parasites on animals are effective for controlling e.g. external parasites which are parasitic on the body surface of host animals (such as the back, the axilla, the lower abdomen or inside of the thigh) or internal parasites which are parasitic in the body of host animals (such as the stomach, the intestinal tract, the lung, the heart, the liver, the blood vessels, the subcutis or lymphatic tissues), but they are particularly effective for controlling the external parasites.
The external parasites may, for example, be animal parasitic acarus or fleas . Their species are so many that it is difficult to list all of them, and therefore, their typical examples will be given.
The animal parasitic acarus may, for example, be ticks such as Boophilus microplus, Rhipicephalus sanguineus, Haemaphysalis longicornis, Haemaphysa1is flava, Haemaphysalis campanulata, Haemaphysalis concinna, Haemaphysalis japonica, Haemaphysa1is kitaokai,
Haemaphysalis ias, Ixodes ovatus , Ixodes nipponensis, Ixodes persulcatus, Amblyomma testudinarium, Haemaphysalis megaspinosa, Dermacentor reticulates, and Dermacentor taiwanesis; common red mite (Dermanyssus gallinae) ; northern fowl mites such as Ornithonyssus sylviarum, and Ornithonyssus bursa; trombidioids such as Eutrombicula wichmanni , Leptotrombidium akamushi, Leptotrombidium pallidum, Leptotrombidium fuji , Leptotrombidium tosa, Neotrombicula autumnalis, Eutrombicula alfreddugesi , and Helenicula miyagawai ; cheyletidae such as Cheyletiella yasguri, Cheyletiella parasitivorax, and Cheyletiella blakei ; sarcoptic mange mites such as Psoroptes cuniculi, Chorioptes bovis, Otodectes cynotis, Sarcoptes scabiei, and Notoedres cati; and Demodicidae such as Demodex canis . The pesticides against parasites on animals, containing the compounds of the present invention, are particularly effective for the control of ticks among them.
The fleas may, for example, be externally parasitic wingless insects belonging to Siphonaptera, more specifically, fleas belonging to Pulicidae, Ceratephyllus , etc. Fleas belonging to Pulicidae may for example, be Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Echidnophaga gallinacea, Xenopsylla cheopis, Leptopsylla segnis, Nosopsyllus fasciatus, and Monopsyllus anisus . The pesticides against parasites on animals, containing the compounds of the present invention, are particularly effective for the control of fleas belonging to Pulicidae, particularly Ctenocephalides canis and Ctenocephalides felis, among them.
Other external parasites may, for example, be sucking lice (Anoplura) such as shortnosed cattle louse (Haematopinus eurysternus) , horse sucking louse
(Haematopinus asini) , sheep louse, longnosed cattle louse (Linognathus vituli) , and head louse (Pediculus capitis) ; biting lice such as dog biting louse (Trichodectes canis) ; and blood-sucking dipterous insects such as horsefly (Tabanus trigonus ) , biting midges (Culicoides schultzei) , and blackfly (Simulium ornatum) . Further, the internal parasites may, for example, be nematodes such as lung worms , whipworms (Trichuris) , tuberous worms , gastric parasites, ascaris, and filarioidea; tapeworms; flukes; and protozoa such as coccidia, malaria parasites (Plasmodium malariae) , intestinal sarcocyst, toxoplasma, and cryptosporidium.
The host animals may, for example, be pet animals such as dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (such as pigeons, parrots, hill mynas, Java sparrows, honey parrots, lovebirds and canaries); domestic animals such as cows, horses, pigs and sheep; and poultry such as ducks and chickens. The pesticides against parasites on animals, containing the compounds of the present invention, are particularly effective for the control of pests parasitic on pet animals or domestic animals, especially for the control of external parasites, among them. Among pet animals, they are effective particularly for dogs and cats, and among domestic animals, they are particularly effective for cows and horses. When the compound of the present invention is used as a pesticide against parasites on animals, it may be used as it is or may be used together with suitable adjuvants, as formulated into various formulations such as a dust, granules, tablets, a powder, capsules, a soluble concentrate, an emulsifiable concentrate, a water-based suspension concentrate and an oil-based suspension concentrate. In addition to such formulations, it may be formulated into any type of formulation which is commonly used in this field, so long as it is suitable for the purpose of the present invention. The adjuvants to be used for formulations may, for example, be anionic surfactants or nonionic surfactants exemplified above as adjuvants for formulation of agricultural and horticultural pesticides; a cationic surfactant such as cetyl trimethylammonium bromide; a solvent such as water, acetone, acetonitrile, monomethylacetamide, dimethylacetamide, dimethylformamide, 2-pyrrolidone, N- methyl-2-pyrrolidone, kerosene, triacetin, methanol, ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, liquid polyoxyethylene glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol n- butyl ether, dipropylene glycol monomethyl ether, or dipropylene glycol n-butyl ether; an antioxidant such as butylhydroxyanisole, butylhydroxytoluene, ascorbic acid, sodium hydrogenmetasulfite, propyl gallate or sodium thiosulfate; a coating film-forming agent such as polyvinylpyrrolidone, polyvinyl alcohol, or a copolymer of vinyl acetate and vinyl pyrrolidone; the vegetable oils and mineral oils as exemplified above as adjuvants for formulation of agricultural and horticultural pesticides; and a carrier such as lactose, sucrose, glucose, starch, wheat flour, corn powder, soybean cake and meal, defatted rice bran, calcium carbonate or other commercially available feed materials. One or more of the respective components of these adjuvants may be suitably selected for use, so long as such will not depart from the purpose of the present invention. Further, other than the above-mentioned adjuvants, some among those known in this field may suitably be selected for use, and still further, some among the above- mentioned various adjuvants to be used in the agricultural and horticultural field may suitably be selected for use.
The blend ratio of the compound of the present invention to various adjuvants is usually from 0.1:99.9 to 90:10. In the actual use of such a formulation, it may be used as it is, or may be diluted to a predetermined concentration with a diluent such as water, and various spreaders (e.g. surfactants, vegetable oils or mineral oils) may be added thereto, as the case requires . Administration of the compound of the present invention to a host animal is carried out orally or parenterally. As an oral administration method, a method of administering a tablet, a liquid agent, a capsule, a wafer, a biscuit, a minced meat or other feed, containing the compound of the present invention, may be mentioned. As a parenteral administration method, there may, for example, be mentioned a method wherein the compound of the present invention is formulated into a suitable formulation and then taken into the body by e.g. intravenous administration, intramuscular administration, intradermal administration, hypodermic administration, etc.; a method wherein it is administered on the body surface by spot-on treatment, pour-on treatment or spray treatment; or a method of embedding a resin fragment or the like containing the compound of the present invention under the skin of the host animal .
The dose of the compound of the present invention to a host animal varies depending upon the administration method, the purpose of administration, the deceased symptom, etc., but it is usually administered in a proportion of from 0.01 mg to 100 g, preferably from 0.1 mg to 10 g, per 1 kg of the body weight of the host animal .
The present invention also includes a method for controlling a pest by the above-mentioned administration method or by the above-mentioned dose, particularly a method for controlling external parasites or internal parasites .
When the compound of the present invention is used as a pesticide against parasites on animals, various vitamins, minerals, amino acids, nutrients, enzymes, antipyretics, sedatives, antiphlogistics, fungicides, colorants, aromatic substances, preservatives, etc., may be used in admixture with or in combination with the adjuvants. Further, as the case requires, other animal drugs or agricultural chemicals, such as vermicides, anti-coccidium agents, insecticides, miticides, pulicides, nematocides, bactericides or antibacterial agents, may be mixed or combined for use, whereby improved effects may sometimes be obtained. The present invention includes such a mixed pesticidal composition having the above- mentioned various components mixed or combined for use, and further a method for controlling a pest by using it, particularly a method for controlling external parasites or internal parasites.
Now, some of preferred embodiments of the compounds of the present invention will be shown. However, the present invention is by no means thereby restricted.
(1) A compound of the above formula (I) wherein each of X1 and X2 is a fluorine atom.
(2) A compound of the above formula (I) wherein Y is alkyl, haloalkyl or phenyl.
(3) A compound of the above formula (I) wherein Y is alkyl .
(4) A compound of the above formula (I) wherein A is an oxygen atom.
(5) A compound of the above formula (I) wherein G is a hydrogen atom. (6) A compound of the above formula (I) wherein Q is a 5- to 12-membered heterocyclic group (the heterocyclic group may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom. (7) A compound of the above formula (I) wherein Q is 1) a heterocyclic group selected from the group consisting of thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl, triazolyl, tetrazolyl, dithiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, thiazinyl, pyranyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, indazolyl, cyclopentapyrazolyl, benzothiadiazolyl, benzotriazolyl, quinolyl, isoquinolyl, phthalazinyl, cinnolyl, quinazolinyl, quinoxalinyl, benzotriazinyl, naphthylidinyl, thiazolopyridyl, benzodioxolyl, benzodioxynyl , pyrazolopyrimidinyl, triazolopyrimidinyl and purinyl, 2) a partially saturated heterocyclic group having a part of such a heterocyclic group hydrogenated, 3) a saturated heterocyclic group having such a heterocyclic group completely hydrogenated, or 4) an oxo or thioxo heterocyclic group having a methylene moiety in the above-mentioned dithiazolyl, oxadinyl, thiadinyl, pyranyl, cyclopentapyrazolyl, benzodioxolyl, partially saturated heterocyclic group or saturated heterocyclic group, converted to oxo or thioxo.
(8) A compound of the above formula (I) wherein Q is a heterocyclic group selected from the group consisting of thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl, triazolyl, tetrazolyl, dithiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, thiazinyl, pyranyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, indazolyl, cyclopentapyrazolyl, benzothiadiazolyl, benzotriazolyl, quinolyl, isoquinolyl, phthalazinyl, cinnolyl, quinazolinyl, quinoxalinyl, benzotriazinyl, naphthylidinyl, thiazolopyridyl, benzodioxolyl, benzodioxynyl, pyrazolopyrimidinyl, triazolopyrimidinyl and purinyl.
(9) The compound of the above formula (I) wherein Q is a 5- to 6-membered heterocyclic group (the heterocyclic group may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom.
(10) A compound of the above formula (I) wherein Q is a heterocyclic group selected from the group consisting of thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl, triazolyl, tetrazolyl, dithiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, thiazinyl and pyranyl.
(11) A compound wherein X1, X2, Y, A, G and Q in the above (1) to (10) are suitably combined.
Now, Examples of the present invention will be given, but the present invention is by no means thereby restricted. Firstly, Preparation Examples of the compounds of the present invention will be described. PREPARATION EXAMPLE 1
Preparation of N- (4-methyl-2-thiazolyl) -6, 6-difluoro-5- methyl-5-hexamide (after-mentioned Compound No. 8) 0.203 g of l-ethyl-3-(3- dimethylaminopropyl) carbodiimide hydrochloride was added to a mixture comprising 0.173 g of 6, 6-difluoro-5-methyl- 5-hexenoic acid, 0.100 g of 2-amino-4-methylthiazole and 2 ml of dichloromethane. Then, the mixture was reacted at room temperature for 19 hours. After completion of the reaction, the reaction mixture was poured into a water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=8/2 ) to obtain 0.12 g of the desired product having a melting point of from 82 to 83°C.
PREPARATION EXAMPLE 2
Preparation of N- (4-methyl-2-thiazolyl) -6, 6-difluoro-5- propyl-5-hexenamide (after-mentioned Compound No. 12) 1) 0.50 ml of concentrated sulfuric acid was added to a mixture comprising 25.5 g of δ -octanolactone and 210 ml of dehydrated methanol, and then the mixture was reacted for 5 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with sodium bicarbonate and further reacted at room temperature for 30 minutes. After completion of the reaction, the reaction mixture was filtered, and from the filtrate, methanol was distilled off under reduced pressure to obtain 35.0 g of an oily substance containing methyl 5-hydroxyoctanoate .
2) A mixture comprising 35.0 g of the oily substance containing methyl 5-hydroxyoctanoate obtained in the above step 1) and 70 ml of dichloromethane, was added to a mixture comprising 60 g of pyridinium chlorochromate, 60 g of silica gel and 250 ml of dichloromethane. Then, the mixture started to gradually generate heat and to reflux. After completion of the refluxing, the mixture was further reacted at room temperature for 3 hours. After completion of the reaction, the reaction mixture was filtered, and the filtrate was combined with an organic layer obtained by extracting the solid with ethyl acetate. Then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=95/5) to obtain 23.5 g of oily methyl 5- oxooctanoate. The NMR spectrum data of this product are as follows.
XH-NMR δppm (Solvent : CDC13./400MHz)
3.64(3H,s) ,2.44(2H, t, J=7.6Hz) , 2.29-2.37 (4H,m) , 1.82-
1.90 (2H,m) ,1.52-1.63 (2H,m) , 0.88 (3H, t , J=7.6Hz)
3) A mixture comprising 2.00 g of methyl 5-oxooctanoate, 2.60 ml of N,N-dimethylformamide and 2.58 ml of tributylphosphine, was heated to 150°C, and a mixture comprising 3.52 g of sodium chlorodifluoroacetate and 7.56 ml of N,N-dimethylformamide, was gradually dropwise added thereto. After completion of the dropwise addition, the mixture was reacted at the same temperature for 16 hours. After completion of the reaction, N,N- dimethylformamide was distilled off under reduced pressure from the reaction mixture. The residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=95/5) to obtain 0.260 g of oily methyl 6, 6-difluoro-5-propyl-5-hexenoate . The NMR spectrum data thereof are as follows. XH-NMR δppm (Solvent : CDC13 /400MHz) 3.63 (3H,s) ,2.28(2H,t,J=7.6Hz) , 1.95-2.01 (2H,m) , 1.89- 1.95 (2H,m) , 1.66-1.75 (2H,m) ,1.34- 1.44(2H,m) , 0.87 (3H, t , J=7.6Hz) 4) 0.260 g of methyl 6, 6-difluoro-5-propyl-5-hexenoate, 0.4 g of potassium hydroxide and 4 ml of methanol were mixed and reacted at room temperature for 14 hours . After completion of the reaction, methanol was distilled off under reduced pressure from the reaction mixture. Water was added to the residue, followed by washing with dichloromethane. Concentrated hydrochloric acid was added thereto for acidification, followed by extraction with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, and dichloromethane was distilled off under reduced pressure to obtain 0.160 g of oily 6, 6-difluoro-5-propyl-5-hexenoic acid. The NMR spectrum data thereof are as follows . 1H-NMR ppm (Solvent : CDC13 /400MHz) 2.33(2H,t,J=7.6Hz) , 1.97-2.03 (2H,m) , 1.89-1.95 (2H,m) ,1.67- 1.76(2H,m) , 1.34-1.44 (2H,m) ,0.87 (3H, t , J=7.6Hz) 5) 0.240 g of l-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride was added to a mixture comprising 0.200 g of 6 , 6-difluoro-5-propyl- 5-hexanoic acid, 0.237 g of 2-amino-4-methylthiazole and 2 ml of dichloromethane. Then, the mixture was reacted at room temperature for 19 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=8/2 ) to obtain 0.15 g of the oily desired product. PREPARATION EXAMPLE 3
Preparation of N- (4-methyl-2-thiazolyl) -6, 6-difluoro-5- phenyl-5-hexenamide (after-mentioned Compound No. 17) 1) 0.5 ml of concentrated hydrochloric acid was added to a mixture comprising 0.416 g of benzyl 6 , 6-difluoro-5- phenyl-5-hexenoate, 3 ml of acetic acid and 0.5 ml of water. Then, the mixture was reacted at room temperature for 15 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=8/2) to obtain 0.220 g of oily 6,6- difluoro-5-phenyl-5-hexenoic acid. The NMR spectrum data thereof are as follows.
XH-NMR δppm (Solvent : CDCl3 /400MHz) 7.18-7.37 (5H,m) , 2.37-2.43 (2H,m) , 2.28 (2H, t , =7.6Hz) ,1.60- 1.68(2H,m)
2) 0.144 g of l-ethyl-3- (3- dimethylaminopropyl ) carbodiimide hydrochloride was added to a mixture comprising 0.226 g of 6 , 6-difluoro-5-phenyl- 5-hexenoic acid, 0.114 g of 2-amino-4-methylthiazole and 2 ml of dichloromethane. Then, the mixture was reacted at room temperature for 7 hours . After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=7/3) to obtain 0.085 g of the oily desired product. PREPARATION EXAMPLE 4
Preparation of N- (4-methyl-2-thiazolyl) -10, 10-difluoro-9- methyl-9-decenamide (after-mentioned Compound No. 25) 1) A mixture comprising 2.32 ml of dibromodifluoromethane and 80 ml of diethylene glycol dimethyl ether, was cooled to 0°C, and a mixed solution comprising 10.9 ml of tris (dimethylamino)phosphine and 10 ml of diethylene glycol dimethyl ether, was gradually dropwise added thereto. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour, and a mixed solution comprising 3.00 g of methyl 9-oxodecanoate and 10 ml of diethylene glycol dimethyl ether was gradually dropwise added thereto. After completion of the dropwise addition, the mixture was reacted at room temperature for 2 hours, and then further reacted at 30°C for 20 hours. After completion of the reaction, the reaction mixture was filtered, and the filtrate was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=95/5) to obtain 2.00 g of oily methyl 10 , 10-difluoro-9-methyl-9-decenoate. The NMR spectrum data thereof are as follows. 1H-NMR δppm (Solvent : CDC13 /400MHz)
3.64(3H,s) ,2.28(2H,t, J=7.6Hz) , 1.89-1. 4 (2H,m) ,1.54- 1.62 (2H,m) , 1.51 (3H, t , J=3.2Hz) ,1.25-1.39 (8H,m) 2) 1.12 g of methyl 10 , 10-difluoro-9-methyl-9-decenoate, 1.2 g of potassium hydroxide and 12 ml of methanol were mixed and reacted at room temperature for 15 hours .
After completion of the reaction, methanol was distilled off from the reaction mixture under reduced pressure. To the residue, water was added, followed by washing with ethyl acetate. Then, it was acidified by an addition of concentrated hydrochloric acid and extracted with ethyl acetate . The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure, to obtain 1.08 g of oily 10, 10- difluoro-9-methyl-9-decenoic acid. The NMR spectrum data thereof are as follows .
1H-N R δppm (Solvent : CDC13 /400MHz) 2.33 (2H,t, J=7.6Hz) , 1.89-1.95 (2H,m) , 1.57- 1.67(2H,m) , 1.52 (3H, t , J=3.2Hz) , 1.20-1.40 (8H,m) 3) 0.559 g of l-ethyl-3- (3-dimethylaminopropyl) - carbodiimide hydrochloride was added to a mixture comprising 0.493 g of 10 , 10-difluoro-9-methyl-9-decenoic acid, 0.511 g of 2-amino-4-methylthiazole and 3 ml of dichloromethane. Then, the mixture was reacted at room temperature for 18 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent : hexane/ethyl acetate=8/2) to obtain 0.33 g of the desired product having a melting point of from 56 to 57°C. PREPARATION EXAMPLE 5
Preparation of N-methyl-N- (4-methyl-2-thiazolyl) -10, 10- difluoro-9-decenamide (after-mentioned Compound No. 26) 1) 6.0 ml of oxalyl chloride was added to 4.33 g of 10 , 10-difluoro-9-decenoic acid under cooling with ice and reacted for 20 minutes and then further reacted at room temperature for 40 minutes. From the reaction mixture, excess oxalyl chloride was distilled off under reduced pressure, and crude 10 , 10-difluoro-9-decenoic acid chloride thereby obtained was added to a mixture comprising 2.517 g of 2-amino-4-methylthiazole, 4.4 ml of triethylamine, 70 ml of tetrahydrofuran and a small amount of 4-dimethylaminopyridine under cooling with ice. Then, the mixture was reacted at room temperature for 18 hours. After completion of the reaction, water was added to the reaction mixture, followed by extraction with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, and diethyl ether was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=8/l) to obtain 3.425 g of N- (4-methyl-2-thiazolyl) -10 , 10-difluoro-9-decenamide having a melting point of 59.6°C. The NMR spectrum data thereof are as follows.
^•H-NMR δppm (Solvent : CDC13 /400MHz) 6.52(lH,s) ,4.02- 4.13 (lH,m) ,2.39(2H,t, J=7.2Hz) ,2.33 (3H,s) ,1.88- 1.94 (2H,m) ,1.63-1.70 (2H,m) , 1.26-1.30 (8H,m)
2) A mixture comprising 3.220 g of N- (4-methyl-2- thiazolyl) -10, 10-difluoro-9-decenamide, 30 ml of tetrahydrofuran and 30 ml of N,N-dimethylformamide, was cooled to 0°C, and 0.451 g of 68% sodium hydride was added thereto. Then, the mixture was reacted at room temperature for 0.5 hour. Then, 0.8 ml of methyl iodide was added, and the mixture was further reacted at room temperature for 20 hours. After completion of the reaction, water was added to the reaction mixture, followed by extraction with diethyl ether. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and then diethyl ether was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent : hexane/ethyl acetate=20/l) to obtain 2.37 g of the desired product having a melting point of 44.0°C. PREPARATION EXAMPLE 6
Preparation of N- (4-methyl-2-thiazolyl) -12 , 12-difluoro- 11-methyl-ll-dodecenamide (after-mentioned Compound No. 28)
1) A mixed solution comprising 20.64 g of benzoyl chloride and 10 ml of anhydrous diethyl ether, was dropwise added to a mixed solution comprising 25.0 g of 10-undecen-l-ol, 17.79 g of N,N-dimethylaniline and 60 ml of anhydrous diethyl ether and reacted for 3 hours and 10 minutes under reflux. After completion of the reaction, the mixture was cooled to room temperature, and the reaction mixture was filtered. The crystals were washed with a mixed solution of diethyl ether and hexane. The filtrate was distilled off under reduced pressure, and then residue was purified by silica gel column chromatography (developing solvent :hexane/ethyl acetate=95/5) to obtain 30.42 g of oily 10-undecenyl benzoate. The NMR spectrum data thereof are as follows. ^•H-NMR δppm (Solvent : CDC13 /400MHz) 8.03 (2H,d,J=8.4Hz) ,7.53 (1H, t, J=7.6Hz) , 7.42 (2H, t , J=7.6Hz) , 5.74-5.84 (lH,m) , 4.90-5.00 (2H,m) , 4.29 (2H, t , J=6.6Hz) ,1.99- 2.05(2H,m) , 1.71-1.78 (2H,m) , 1.24-1.45 (14H,m)
2) 48.3 ml of a borane-tetrahydrofuran complex (a tetrahydrofuran solution, 1.15 mol/L) was gradually dropwise added to a mixed solution comprising 30.42 g of 10-undecenyl benzoate and 120 ml of tetrahydrofuran under cooling with ice. After completion of the dropwise addition, the mixture was reacted at room temperature for 1 hour and 50 minutes. After completion of the reaction, 5.5 ml of water was added to the reaction mixture, and 18.4 ml of a 3M sodium hydroxide aqueous solution was added thereto under cooling with ice. Then, 12.1 ml of a 30% hydrogen peroxide aqueous solution was dropwise added, and the mixture was reacted at 50°C for 1 hour. After completion of the reaction, a small amount of sodium chloride was added to the reaction mixture, for liquid separation. The aqueous layer was extracted with ethyl acetate, and the tetrahydrofuran layer and the ethyl acetate layer were put together and dried over anhydrous sodium sulfate. Then, the solvent was distilled off to obtain 32.37 g of oily crude 11-hydroxyundecyl benzoate. The NMR spectrum data thereof is as follows. XH-NMR δppm (Solvent : CDCl3 /400MHz)
8.02 (2H,d, J=8.6Hz) ,7.53 (1H, t , J=7.2Hz) ,7.42 (2H, t , J=7.8Hz) ,
4.29(2H,t,J=6.6Hz) ,3.62 (2H, t , J=6.8Hz) ,1.71-
1.78 (2H,m) , 1.51-1.58 (2H,m) , 1.24-1.44 (14H,m)
3) 31.02 g of pyridinium chlorochromate and 25 g of silica gel were thoroughly mixed by a mortar and then transferred to flask, and 150 ml of dry dichloromethane was added thereto. Then, a mixed solution comprising 32.37 g of the crude 11-hydroxyundecyl benzoate obtained in the above-mentioned step 2) and 80 ml of dichloromethane, was dropwise added with stirring. After completion of the dropwise addition, the mixture was reacted at room temperature for 1 hour and 40 minutes. After completion of the reaction, the reaction mixture was filtered, and crystals were sufficiently washed with ethyl acetate. The filtrate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent : hexane/ethyl acetate=9/l) to obtain 14.51 g of oily 11-oxoundecyl benzoate. The NMR spectrum data thereof are as follows . 1H-NMR δppm (Solvent : CDCl3 /400MHz) 9.74(1H, t, J=1.8Hz) ,8.02 (2H, d, J=7.6Hz) ,7.53 ( 1H, t , J=7.2Hz ) , 7.42 (2H,t, J=7.6Hz) , 4.29 (2H, t , J=6.6Hz) ,2.40 (2H, td, J=7.6 , 1. 6Hz) ,1.71-1.78 (2H,m) , 1.57-1.64 (2H,m) , 1.26-1.45 (12H,m) 4) To a mixed solution comprising 10.188 g of 11- oxoundecyl benzoate and 240 ml of anhydrous tetrahydrofuran, 92.5 ml of a 1.14M methyllithium-diethyl ether solution was dropwise added at 0°C in a nitrogen atmosphere. After completion of the dropwise addition, the mixture was reacted at room temperature for 6 hours . After completion of the reaction, a small amount of ice was added to the reaction mixture, and further, 200 ml of a saturated ammonium chloride aqueous solution was added, followed by extraction three times with diethyl ether. The extract solution was dried over anhydrous sodium sulfate and then purified by silica gel column chromatography (developing solvent : hexane/ethyl acetate=7/3) to obtain 3.75 g of oily 1, 11-dodecanediol . 5) A mixed solution comprising 3.96 g of chromium (VI) oxide, 3.48 ml of concentrated sulfuric acid and 11.67 ml of water, was gradually dropwise added and reacted at room temperature to a mixed solution comprising 3.75 g of 1, 11-dodecanediol and 52 ml of acetone. When the color of the reaction mixture turned red, the dropwise addition was stopped, and the mixture was extracted twice with dichloromethane and once with diethyl ether. The extract solution was dried over anhydrous sodium sulfate, and then, the solvent was distilled off under reduced pressure to obtain 3.932 g of oily 11-oxododecanoic acid. The NMR spectrum data thereof are as follows. 1H-NMR δppm (Solvent : CDC13 /400MHz)
8.29(lH,brs) ,2.39 (2H, t, J=7.4Hz) ,2.31 (2H, t , J=7.6Hz) ,1.51- 1.63(4H,m) , 1.16-1.38 (10H,m) 6) 25 Drops of concentrated sulfuric acid was added to a mixed solution comprising 3.93 g of 11-oxododecanoic acid and 82 ml of ethanol, and the mixture was reacted under reflux overnight. After completion of the reaction, ethanol was distilled off from the reaction mixture. The residue was dissolved in diethyl ether and washed with a saturated sodium chloride aqueous solution. The diethyl ether layer was dried over anhydrous sodium sulfate and then purified by silica gel column chromatography (developing solvent :hexane/ethyl acetate=7/3) to obtain 2.776 g of oily ethyl 11-oxododecanoate . The NMR spectrum data thereof are as follows. 1H-NMR ppm (Solvent : CDC13 /400MHz)
4.10 (2H, quartet, J=7.lHz) ,2.3 (2H, t , J=7.4Hz) , 2.26 (2H, t, J=7 .6Hz) ,2.11 (3H,s) ,1.52-1.60 (4H,m) , 1.21-1.25 (13H,m) 7) A mixed solution comprising 8.85 ml of hexamethylphosphorous triamide and 36 ml of diethylene glycol dimethyl ether, was dropwise added at 0°C over a period of 20 minutes to a mixed solution comprising 2.23 ml of dibromodifluoromethane and 38 ml of diethylene glycol dimethyl ether. After completion of the dropwise addition, the mixture was reacted at the same temperature for 1 hour, and a mixed solution comprising 2.776 g of ethyl 11-oxododecanoate and 16 ml of diethylene glycol dimethyl ether, was dropwise added thereto over a period of 10 minutes. After completion of the dropwise addition, the mixture was returned to room temperature and reacted for 1 hour, and then further reacted at 40°C for 4 hours. After completion of the reaction, the reaction mixture was filtered, and crystals were washed with hexane. To the filtrate, water was added, followed by liquid separation. The hexane layer was dried over anhydrous sodium sulfate, and then purified by silica gel column chromatography (developing solvent :hexane/diethyl ether=9/l) to obtain 2.75 g of oily ethyl 12 , 12-difluoro- 11-methyl-ll-dodecenoate. The NMR spectrum data thereof are as follows.
XH-NMR ppm (Solvent : CDC13 /400MHz) 4.06 (2H, quartet, J=7.2Hz) ,2.22 (2H, t, J=7.6Hz) ,1.85- 1.89 (2H, m) ,1.46-1.64 (5H,m) , 1.17-1.36 (15H,m)
8) 2.6 g of ethyl 12 , 12-difluoro-11-methyl-ll- dodecenoate was added to a mixed solution comprising 0.56 g of potassium hydroxide and 10 ml of methanol, and the mixture was reacted at room temperature for 24 hours. After completion of the reaction, water was added to the reaction mixture, and further concentrated hydrochloric acid was added thereto for acidification. The obtained mixture was extracted three times with dichloromethane and dried over anhydrous sodium sulfate. Dichloromethane was distilled off under reduced pressure to obtain 2.29 g of an oily substance containing about 64% of 12, 12- difluoro-11-methyl-ll-dodecenoic acid .
9) A mixed solution comprising 0.374 g of the oily substance containing 12 , 12-difluoro-11-methyl-11- dodecenoic acid obtained in the above step 8), 0.171 g of 2-amino-4-methylthiazole, 0.444 g of l-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride and 4 ml of dichloromethane, was reacted for 6.5 hours under reflux. After completion of the reaction, the reaction mixture was purified by silica gel column chromatography (developing solvent :hexane/ethyl acetate=7/3) to obtain 0.144 g of the desired product having a melting point of from 54 to 55°C. PREPARATION EXAMPLE 7
Preparation of N-acetyl-N- (4-methyl-2-thiaolyl) -6, 6- difluoro-5-hexenamide (after-mentioned Compound No. 41) 1) 0.282 g of l-ethyl-3- (3-dimethylaminopropyl) - carbodiimide hydrochloride was added to a mixture comprising 0.200 g of 6, 6-difluoro-5-hexenoic acid, 0.076 g of 2-amino-4-methylthiazole and 2 ml of dichloromethane, and the mixture was reacted at room temperature for 24 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate . The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent : hexane/ethyl acetate=8/2) to obtain 0.13 g of N- (4-methyl-2- thiazolyl) -6, 6-difluoro-5-hexenamide having a melting point of from 49 to 52°C. The NMR spectrum data thereof are as follows. XH-NMR δppm (Solvent : CDCl3 /400MHz) 9.44(lH,brs) , 6.51 (1H, s) , 4.06-
4.17 (lH,m) ,2.41(2H,t, J=7.2Hz) , 2.32 (3H, s) , 2.03- 2.06(2H,m) , 1.76-1.84 (2H,m) 2) 0.177 g of N- (4-methyl-2-thiaolyl) -6, 6-difluoro-5- hexenamide, 0.58 g of N-trimethylsilyl-ethyl carbamate, 0.282 g of acetyl chloride and 5 ml of dichloromethane were mixed and reacted for 18 hours under reflux. After completion of the reaction, water was added to the reaction mixture, followed by liquid separation. The organic layer was dried over anhydrous sodium sulfate. Then, dichloromethane was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent : hexane/ethyl acetate=80/20) to obtain 0.073 g of the oily desired product. PREPARATION EXAMPLE 8 Preparation of N- (5-methyl-2-pyridyl) -9-ethyl-10 , 10- difluoro-9-decenamide (after-mentioned Compound No. 286) 1) 2.1 ml of thionyl chloride was added to 3.00 g of monomethyl azelate, and the mixture was reacted at room temperature for 22 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. A mixed solution comprising 14.8 ml of a tetrahydrofuran solution of 1M ethyl magnesium bromide and 10 ml of tetrahydrofuran, was cooled to -60°C under nitrogen atmosphere. A mixed solution comprising the above concentrate and 10 ml of tetrahydrofuran, was dropwise added thereto at a temperature of from -60 to -50°C. After completion of the dropwise addition, the mixture was reacted at the same temperature for 1 hour. After completion of the reaction, water was added to the reaction mixture, followed by extraction with ethyl acetate . The organic layer was dried over anhydrous sodium sulfate to obtain 2.43 g of oily methyl 9- oxoundecanoate . The NMR spectrum data thereof are as follows .
1H-NMR ppm (Solvent : CDC13 /400MHz) 3.66(3H,s) ,2.34-2.42 (4H,m) , 2.27 (2H, t, J=7.6Hz) ,1.49- 1.63 (4H,m) ,1.15-1.30 (6H,m) , 1.02 (3H, t, J=7.2Hz) 2) A mixture comprising 1.50 ml of dibromodifluoromethane and 60 ml of diethylene glycol dimethyl ether, was cooled with ice, and a mixed solution comprising 7.05 ml of tris (dimethylamino)phosphine and 10 ml of diethylene glycol dimethyl ether, was gradually dropwise added thereto. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour, and then, a mixed solution comprising 2.08 g of methyl 9-oxoundecanoate and 10 ml of diethylene glycol dimethyl ether, was gradually dropwise added thereto. After completion of the dropwise addition, the mixture was reacted at 30°C for 15 hours. After completion of the reaction, the reaction mixture was filtered, and the filtrate was poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent :hexane/ethyl acetate=95/5) to obtain 1.03 g of oily methyl 9-ethyl- 10, 10-difluoro-9-decenoate . The NMR spectrum data thereof are as follows. 1H-NMR ppm (Solvent : CDC13 /400MHz) 3 . 57 (3H , s ) , 2 . 24 (2H, t , J=7 . 6Hz ) , 1 . 85-1 . 94 ( 4H, m) , 1 . 51- 1 . 59 (2H, m) , 1 . 22-1 .34 ( 8H, m) , 0 . 92 ( 3H, t , J=7 . 6Hz )
3) 0.948 g of methyl 9-ethyl-10, 10-difluoro-9-decenoate, 1.03 g of potassium hydroxide and 10 ml of methanol were mixed and reacted at room temperature for 18 hours .
After completion of the reaction, methanol was distilled off under reduced pressure from the reaction mixture. Water was added to the residue, followed by washing with ethyl acetate. Then, concentrated hydrochloric acid was added for acidification, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain 0.747 g of oily 9- ethyl-10 , 10-difluoro-9-decenoic acid. The NMR spectrum data thereof are as follows.
^•H-NMR δppm (Solvent : CDC13 /400MHz)
2.33 (2H,t, J=7.2Hz) , 1.90-1.99 (4H,m) , 1.57-1.66 (2H,m) , 1.27-
1.39 (8H,m) , 0.97 (3H, t, J=7.2Hz)
4) 1 ml of oxalyl chloride was dropwise added under cooling with ice to 0.314 g of 9-ethyl-10, 10-difluoro-9- decenoic acid. After completion of the dropwise addition, the mixture was reacted at the same temperature for 30 minutes and then reacted at room temperature for 1 hour. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and a mixed solution comprising the crude 10, 10-difluoro-9-ethyl-9- decenyl chloride thereby obtained and 3 ml of toluene, was gradually dropwise added to a mixture comprising 0.145 g of 2-amino-5-methylpyridine, 0.27 ml of triethylamine, 0.246 g of 4-dimethylaminopyridine and 2 ml of toluene. After completion of the dropwise addition, the mixture was reacted at room temperature for 30 minutes and then reacted for 1 hour under reflux. After completion of the reaction, the reaction mixture was poured into a saturated sodium chloride aqueous solution and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent :hexane/ethyl acetate=8/2) to obtain 0.424 g of the desired product having a melting point of from 38 to 39°C.
PREPARATION EXAMPLE 9
Preparation of N- (6-methyl-2-pyridyl) -7-ethyl-8, 8- difluoro-7-octenamide (after-mentioned Compound No. 353)
1) 10.91 g of sodium was added to 444 ml of dry ethanol and dissolved with stirring at room temperature, and to this solution, 61.75 g of methyl 3-oxopentanoate and then 99.2 g of ethyl 5-bromopentanoate were added, whereupon the mixture was reacted for 8 hours under reflux and then reacted at room temperature overnight. After completion of the reaction, ethanol was distilled off under reduced pressure, and water was added to such an extent that the solid was dissolved, and the mixture was poured into a saturated sodium chloride aqueous solution. It was extracted three times with ethyl acetate and dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain 125.0 g of oily crude diethyl 2- (propionyl)heptanedioate.
2) A solution having 60.55 g of 85% potassium hydroxide dissolved in 900 ml of water, was added to 125.0 g of the crude diethyl 2- (propionyl)heptanedioate, and the mixture was reacted at room temperature for 3 days . After completion of the reaction, it was washed three times with 200 ml of diethyl ether, and the aqueous layer was acidified with concentrated hydrochloric acid. Sodium chloride was added to saturation, followed by extraction three times with 200 ml of diethyl ether. The organic layer was dried over anhydrous sodium sulfate, and diethyl ether was distilled off under reduced pressure to obtain an oily substance, to which 1470 ml of 10% sulfuric acid was added. After refluxing for 1 hour, it was cooled to room temperature and extracted with 200 ml of diethyl ether. The diethyl ether layer was dried over anhydrous sodium sulfate, and diethyl ether was distilled off under reduced pressure to obtain 64.8 g of crude 7- oxononanoic acid.
3) A mixture comprising 500 ml of ethanol and 5.5 ml of concentrated sulfuric acid, was added to 43.1 g of the crude 7-oxononanoic acid, and the mixture was reacted for 15 hours under reflux. After completion of the reaction, ethanol was distilled off under reduced pressure, and diethyl ether was added, followed by washing three times with water and once with a saturated sodium chloride aqueous solution. It was dried over anhydrous sodium sulfate, and diethyl ether was distilled off under reduced pressure to obtain 47.8 g of crude ethyl 7- oxononanate .
4) A mixture comprising 20 ml of dibromodifluoromethane and 340 ml of diethylene glycol dimethyl ether, was cooled with ice, and a mixed solution comprising 79.68 ml of tris (dimethylamino)phosphine and 165 ml of diethylene glycol dimethyl ether, was gradually dropwise added thereto. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hour and then a mixed solution comprising 20.78 g of the crude ethyl 7-oxononanate and 10 ml of diethylene glycol dimethyl ether, was gradually dropwise added. After completion of the dropwise addition, the mixture was reacted at 45°C for 13.5 hours and then reacted at 100°C for 5 hours. After completion of the reaction, the reaction mixture was poured into 250 ml of water and extracted twice with 250 ml and 150 ml of hexane. The hexane layer was washed six times with 100 ml of water and dried over anhydrous sodium sulfate, and hexane was distilled off under reduced pressure to obtain 21.98 g of oily crude ethyl 7-ethyl-8 , 8-difluoro-7-octenoate. The NMR spectrum data thereof are as follows . XH-NMR δppm (Solvent : CDC13 /400MHz) 4.10 (2H, quartet , J=7.1Hz ) , 2.27 (2H, t , J=7.4Hz ) , 1.92- 1.99 (4H,m) , 1.61 (2H, quintet ,J=7.4Hz) ,1.26- 1.41(4H,m) ,1.23(3H,t,J=7.2Hz) , 0.96 (3H, J=7.4Hz) 5) 5.0 g of the crude ethyl 7-ethyl-8 , 8-difluoro-7- octenoate, 1.69 g of 85% potassium hydroxide and 20 ml of methanol were mixed and reacted at 40°C for 1 hour and then reacted at room temperature for 13.5 hours. After completion of the reaction, methanol was distilled off under reduced pressure from the reaction mixture. Water was added to the residue, followed by washing three times with dichloromethane. The aqueous layer was acidified by an addition of concentrated hydrochloric acid and extracted three times with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, and dichloromethane was distilled off under reduced pressure to obtain 3.72 g of oily crude 7-ethyl-8 , 8-difluoro-7- octenoic acid. The NMR spectrum data thereof are as follows . 1H-NMR δppm (Solvent : CDC13 /400MHz) 2.34 (2H, t, J=7.6Hz) ,1.92-
1.99 (4H,m) ,1.63 (2H, quintet ,J=7.5Hz) ,1.28- 1.42 (4H,m) ,0.97(3H,t, J=7.4Hz) 6) 1.4 ml of oxalyl chloride was dropwise added under cooling with ice to 0.35 g of the crude 7-ethyl-8,8- difluoro-7-octenoic acid. After completion of the dropwise addition, the mixture was reacted at room temperature for 3 hours and 10 minutes. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and a mixed solution comprising a crude 7-ethyl-8 , 8-difluoro-7-octenyl chloride thereby obtained and 2.6 ml of toluene, was gradually dropwise added under cooling with ice to a mixture comprising 0.184 g of 2-amino-6-methylpyridine, 0.257 g of triethylamine, 0.311 g of 4-dimethylaminopyridine and 6 ml of toluene. After completion of the dropwise addition, the mixture was reacted at room temperature for 1 hour and 20 minutes and then reacted for 2 hours under reflux and left to stand overnight. Thereafter, the reaction mixture was poured into a saturated sodium chloride aqueous solution and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent :hexane/ethyl acetate=8/2) to obtain 0.334 g of the oily desired product.
PREPARATION EXAMPLE 10
Preparation of N- (5-methyl-2-pyridyl) -6 , 6-difluoro-7- hexenethioamide (after-mentioned Compound No. 426) A mixture comprising 1.685 g of N- (5-methyl-2- pyridyl) -6, 6-difluoro-7-hexenamide, 3.84 g of phosphorus pentasulfide and 18 ml of toluene, was reacted at 40°C for 2 hours, then reacted at 60°C for 11 hours and further reacted at room temperature for 5.5 hours. After completion of the reaction, a saturated sodium hydrogencarbonate aqueous solution and diethyl ether were added to the reaction mixture, followed by stirring, and the mixture was separated. The organic layer was washed with a saturated sodium hydrogencarbonate aqueous solution and then further washed with a saturated sodium chloride aqueous solution. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent :hexane/ethyl acetate=9/l) to obtain 0.68 g of the oily desired product. PREPARATION EXAMPLE 11 Preparation of N-ethyl-9-ethyl-10 , 10-difluoro-9- decenamide (after-mentioned Compound No. 468)
0.295 g of l-ethyl-3-(3- dimethylaminopropyl) carbodiimide hydrochloride was added to a mixture comprising 0.300 g of 9-ethyl-10 , 10- difluoro-9-decenoic acid, 0.105 g of ethylamine hydrochloride, 0.18 ml of triethylamine, 3 ml of tetrahydrofuran and 3 ml of dichloromethane, and the mixture was reacted at room temperature for 22 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate.
The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent :hexane/ethyl acetate=2/l) to obtain 0.259 g of the oily desired product . Now, typical examples of the compounds of the present invention represented by the above formula (I) will be given in Table 1, and the NMR spectrum data thereof will be given in Table 2. These compounds can be prepared by the above-described Preparation Examples or by the above-mentioned various processes for the production of the compounds of the present invention. In Tables 1 and 2 , No . represents Compound No . Further , in Table 1, Me represents a methyl group, Et an ethyl group, n-Pr a n-propyl group, i-Pr an isopropyl group, c-Pr a cyclopropyl group, n-Bu a n-butyl group, i-Bu an isobutyl group, s-Bu a sec-butyl group, t-Bu a tert-butyl group, and Ph a phenyl group. Further, in Table 1, 3-CN-4,5- (Me)2-2-furyl represents a 2-furyl group having a cyano group substituted at the 3-position and having methyl groups substituted at both the 4- and 5-positions, and - CH2CH2- (4-N02-Ph) represents an ethyl group substituted by phenyl having a nitro group at the 4-position. The same applies to other similar descriptions. Table 1
Figure imgf000070_0001
Figure imgf000070_0002
Table 1 (continued)
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
77
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Table 1 (continued)
Figure imgf000082_0001
Table 1 (continued)
Figure imgf000083_0001
Table 2
Figure imgf000084_0001
Table 2 (continued)
Figure imgf000085_0001
Table 2 (continued)
Figure imgf000086_0001
86
Table 2 (continued)
No . ^-NMR δ ppm (Solvent : CDCl3/400MHz )
287 8.30 ( IH, d, J=2. OHz ) , 7.54 (IH, dd, J=8.0 , 2. OHz ) , .13 (IH, d, J=i OHz ),3.31(3H,s),2.34(3H,s) ,2.14-2.29 (2H,m) ,1.86- 1.97 (4H,m) , 1.55-1.69 (2H,m) , 1.22-1.32 (2H,m) ,1.17- 1.24 (6H,m) , 0.95 (3H, t , J=7.2Hz)
288 8.66 (IH, brs) , 8.22-8.27 (2H,m) , 7.74 (IH, td, J=7.0, 1.8Hz) , 7.05(lH,t,J=6.4Hz) , 2.40 (2H, t , J=7.6Hz) , 1.92-1.96 (2H,m) ,1.67- 1.76 (2H,m) , 1.51 (3H, t , J=3.0Hz) , 1.31-1.44 (4H,m)
289 8.48(lH,dd,J=4.8,2.0Hz) , 7.73 (IH, td, J=7.2,2. OHz) , 7.27 (IH, d, = 7.2Hz) ,7.18 (lH,dd,J=7.6, 5.2Hz) ,3.35 (3H,s) , 2.27(2H,t,J=7.4Hz) , 1.86-1.91 (2H,m) , 1.57-1.65 (2H,m) , 1.48(3H,t,J=3.2Hz) , 1.28-1.36 (2H,m) , 1.18-1.24 (2H,m)
290 8.34 (IH, brs) , 8.22-8.24 (2H,m) , 7.70 (IH, td, J*=7.2 , 1.6Hz) , 7.02 (lH,td,J=6.2,1. OHz) , 2.37 (2H, t , =7.6Hz) , 1.89-1.93 (2H,m) 1.66-1.74 (2H,m) , 1.51 (3H, t, =3. OHz) , 1.22-1.38 (12H,m)
292 8.85(lH,s) ,8.69 (lH,brs) , 8.66 (IH, d, =8. OHz) ,8.27 (IH, d, J=8.4Hz ) ,7.45 (lH,dd,J=8.4, 4.8Hz) , 2.47 (2H, t, J=7.4Hz) ,1.92-1.97 (2H,m) , 1.66-1.78 (2H,m),l.52 (3H,t,J=3.2Hz) , 1.32-1.43 (4H,m)
294 8.56(lH,s) , 8.29 (lH,d,J=4. OHz) , 8.21 (IH, d, J=8.4Hz) ,8.10 (lH,brs ) , 7.25 (lH,dd,J-=8.4,5.2Hz) , 2.37 (2H, t, J=7.6Hz) ,1.88-1.93 (2H,m) ,1.66-1.73 (2H,m) , 1.50 (3H, t , J=3.2Hz) , 1.20-1.37 (12H,m)
296 8.50(lH,d,J=0.8Hz) , 8.34 (IH, d, =8.8Hz) ,8.32 (lH,brs) ,7.90 (lH,d d,J=8.8,2.4Hz) ,2.41(2H,t, =7.4Hz) , 1.91-1.97 (4H,m) ,
1.73 ( 2H, uintet, J=7.4Hz) , 1.30-1.44 (4H,m) , 0.95 (3H, t, J=7.4Hz)
302 8.54 (lH,s) ,7.96(lH,brs) ,7.91(lH,s) , 2.78 (2H, t, J=7.6Hz) ,1.93- 1.99 (4H,m) , 1.74 (2H, quintet ,J=7.4Hz) ,1.33- 1.46 (4H,m) , 0.97 (3H, t , J*=7.6Hz)
305 8.55 (lH,s) ,7.96(lH,brs) , 7.91 (IH, d, J=l .6Hz) , 2.77(2H,t,J=7.6Hz) , 1.91-2.00 (4H,m) , 1.68-1.79 (2H,m) ,1.26- 1.43 (8H,m) , 0.97 (3H, t, J=7.6Hz)
315 6.53 (lH,s) ,4.98 (2H,s) ,4.04-4.15 (lH, ) , 2.71-2.74 (2H,m) ,2.37 (3H,s) ,1.92-1.95 (2H,m) ,1.72-1.79 (5H,m) ,1.32-1.38 (8H,m)
316 8.44 (IH, brs) , 8.18-8.25 (2H,m) , 7.70 (IH, td, =7.8, 1.5Hz) , 7.04(lH,t, J=6.0Hz) , 3.10 (2H, t , J=2. OHz) ,2.09- 2.15 (2H,m) ,1.02 (3H, t, J=7.6Hz)
318 8.22 (IH, brs) , 8.21-8.24 (2H,m) .7.71 (IH, td, J=8.0 , 2. OHz) , 7.03 (lH,td, J=6.1,1.0Hz) ,2.37 (2H, t , J=7.6Hz) ,1.93- 2.06(4H,m) ,1.77-1.84 (2H, ) , 0.97 (3H, t , J=7.6Hz)
320 8.46 (IH, brs) , 8.21-8.24 (2H, ) , 7.71 (IH, td, J=8.0 , 1.8Hz) ,7.01-
7.04(lH,m) ,2.38(2H,t,J=8.0Hz) , 1.91-1.97 (4H,m) ,1.72
(2H, quintet, J=7.4Hz) , 1.29-1.43 (4H,m) , 0.96 (3H, t, J=7.2Hz)
322 8.62 (lH,brs) , 8.28 (lH,d, J=8.8Hz) , 8.20-8.23 (lH,m) ,7.74-7.79 (lH,m) ,7.04-7.09(lH,m) , 2.41 (2H, t, J=7.6Hz) , 1.90-1.99 (4H,m) , 1.67-1.76 (2H,m) , 1.18-1.38 (8H,m) , 0.96 (3H, t, J=7.6Hz)
330 8.54(lH,d, J=2.0Hz) , 8.36 (lH,brs) , 8.28 (IH, d, J=4. OHz) ,8.17 (lH,d,J=7.6Hz) ,7.24(lH,dd,J=8.0,5.2Hz) , 2.36 (2H, t, J=7.4Hz) , 1.90-1.96 (4H,m) , 1.70 (2H, quintet, J=7.5Hz) , 1.27-1.41 (4H,m) , 0.94(3H,t,J=7.6Hz) 87
Table 2 (continued)
Figure imgf000088_0001
Table 2 (continued)
Figure imgf000089_0001
Table 2 (continued)
Figure imgf000090_0001
Table 2 (continued)
Figure imgf000091_0001
Table 2 (continued)
Figure imgf000092_0001
Table 2 (continued)
No. H-NMR δppm (Solvent : CDCl3/400MHz)
490 5.65 (IH,brs) ,3.86-3.95 (2H,qd,J=8.6, 6.4Hz) , 2.23(2H,t,J=7.6Hz) , 1.90-1.99 (4H,m) ,1.59-1.66 (2H,m) ,1.24- 1.40 (8H,m) , 0.96(3H,t, J=7.2Hz)
491 5.77 (IH,brs) ,3.43 (2H,s) ,3.42(2H,s) ,3.34(3H,s) , 2.16 (2H, t, J=8 .OHz) ,1.91-1.99 (4H,m) , 1.56-1.67 (2H,m) ,1.31-1.42 (2H,m) ,1.21- 1.31 (2H,m) ,0.96(3H,t,J=7.6Hz)
492 5.77 (IH, brs) , 3.40-3.44 (4H,m) ,3.34(3H,s) , 2.15 (2H, t , =7.6Hz) , 1.90-2.01 (4H,m) ,1.53-1.63 (2H,m) , 1.27-1.38 (8H,m) ,0.96 (3H,t, J=7.6Hz)
493 6.11 (IH, brs) , 3.50 (2H, t , J=5.6Hz) , 3.46 (2H, q, J=6.8Hz) ,3.35 (2H,q, =6.0Hz) ,2.12 (2H, t, J=7.6Hz) , 1.91-1.99 (4H,m) ,1.71-1.78 (2H,m) , 1.56-1.65 (2H,m) ,1.31-1.42 (2H,m) , 1.21-1.30 (2H,m) ,1.19 (3H,t, J=6.8Hz) , 0.96 (3H,t, J=7.6Hz)
494 6.10 (IH, brs) , 3.43-3.56 (4H,m) , 3.29-
3.38(2H,m) ,2.12 (2H, t, J=7.6Hz) , 1.90-2.00 (4H,m) ,1.71-
1.78 (2H,m) , 1.54-1.60 (2H,m) , 1.21-1.38 (8H,m) ,
1.19 (3H,t,J=7.2Hz) , 0.96 (3H, t, J=7.6Hz)
496 5.63 (lH,brs) , 4.47 (IH, t , =5.2Hz) , 3.64-3.73 (2H,m) , 3.48- 3.56(2H,m) ,3.37 (2H,m) , 2.16 (2H, t , J=7.6Hz) ,1.89- 2.01(4H,m) ,1.53-1.62 (2H,m) ,1.25- 1.36 (8H,m) , 1.20 (3H, t, J=7.2Hz) , 0.96 (3H, t , J=7.6Hz)
498 5.89 (lH,brs) , 3.69-3.73 (2H,m) , 3 ,38-
3.43 (2H,m) , 2.60 (lH,brs) ,2.19 (2H, t , J-=7.6Hz) , 1.90-1.99 (4H,m) ,
1.54-1.64 (2H,m) , 1 ■ 22-1.39 (8H,m) , 0.96 (3H, t , J=7.6Hz)
499 5.82 (lH,brs) , 4.16 (2H, d, J*=4.4Hz) , 2.24 (2H, t , J*=8. OHz) ,1.91- 2.05 (4H,m) ,1.60-1.69 (2H, ) , 1.34-1.43 (2H,m) ,1.25- 1.33 (2H,m) , 0.96 (3H, t, =7.6Hz)
504 5.82 (lH,brs) ,3.54-3.63 (4H,m) , 2.18 (2H, t , J=7.6Hz) ,1.89-2.13 (4H,m) ,1.53-1.65 (2H,m) ,1.19-1.39 (8H,m) , 0.96 (3H, t , J=7.6Hz)
507 5.77-5.87 (lH,m) ,5.45 (IH, brs) ,5.09-5.19 (2H,m) ,3.84- 3.89 (2H,m) , 2.17 (2H, t, J=7.6Hz) , 1.90-1.99 (4H,m) ,1.57- 1.66(2H,m) , 1.21-1.38 (8H,m) , 0.96 (3H, t , *J-=7.6Hz)
512 5.58 (lH,brs) , 4.02-4.05 (2H,m) ,2.15-2.22 (3H,m) ,1.92- 2.03 (4H,m) , 1.58-1.67 (2H,m) , 1.30-1.42 (2H,m) ,1.23- 1.29 (2H,m) , 0.96 (3H, t , J=7.6Hz)
513 5.84 (IH, brs) , 4.04 (2H, q, J=3.2Hz) , 2.15-2.22(3H,m) ,1.90- 1.99(4H,m) , 1.57-1.64 (2H,m) ,1.19- 1.41 (8H,m) , 0.96(3H,t, J=7.6Hz)
520 5.53 (IH, brs) ,2.65-2.70 (lH, ) , 2.09 (2H, t, =7.6Hz) ,1.90-1.98 (4H,m) , 1.55-1.65 (2H,m) , 1.27-1.40 (2H,m) ,1.21-1.27 (2H,m) ,0.95 (3H,t, J=7.6Hz) , 0.72-0.75 (2H,m) ,0.42-0.47 (2H,m)
540 9.18 (IH,brs) ,7.66(lH,s) , 4.03-4.14 (lH,m) , 2.55 (3H, s) , 2.36 (2H,t,J=7.2Hz) , 1.90-1.94 (2H,m) , 1.66-1.71 (2H,m) ,1.30- 1.41(8H,m) Table 2 (continued) o. ^-NMR ppm (Solvent : CDCl3/400MHz)
541 7.22-7.32 (5H,m) , 5.80 (lH,brs) ,4.39 (2H, d, J=5.6Hz) ,2.17 (2H,t, =7.6Hz) , 1.89-1.96 (4H,m) , 1.67 (2H, quintet, J=7.6Hz) , 1.22-1.39 (4H,m) , 0.9 (3H, t, J=7.6Hz)
542 7.16-7.31 (5H,m) , 5.41 (lH,brs) , 3.51 (2H, q, J=6.7Hz) ,2.80 (2H,t, J=6.8Hz) ,2.10(2H,t,J=7.4Hz) , 1.90-1.98 (4H,m) , 1.58 (2H, quintet, J=7.6Hz) ,1.21- 1.39 (4H,m) , 0.96 (3H, t, J=7.4Hz)
543 8.12 (2H,d,J=8.8Hz) ,7.33 (2H, d, J=8.8Hz) , 5.59 (lH,brs) ,3.52 (2H,q,J-=6.7Hz) , 2.91 (2H, t, J=7. OHz) , 2.11 (2H, t, J=7.6Hz) , 1.90-1.97 (4H,m) , 1.58 (2H, quintet , =7.6Hz) , 1.20-1.39 (4H,m) , 0.95 (3H,t, J=7.6Hz)
544 7.09(2H,d,J=-7.6Hz) , 7.05 (2H, d, J=7.6Hz) ,5.51 (IH, brs) ,3.47 (2H,q, J=6.5Hz) , 2.75 (2H, t, J=6.8Hz) , 2.30 (3H, s) , 2.09 (2H,t, J=7 .4Hz) ,1.90-1.97 (4H,m) ,1.58 (2H, quintet,J=7.6Hz) ,1.21- 1.39 (4H,m) , 0.96 (3H, t, J=7.6Hz)
545 8.58 (IH, brs) , 8.43 (2H,d, J=5.2Hz) , 7.51 (2H, d, =6.4Hz) ,2.37 (2H, t, =7.6Hz) ,1.89-1.96 (4H,m) , 1.70 (2H, quintet ,J=7.4Hz) 1.26-1.41 (4H,m) , 0.94 (3H, t , J=7.6Hz)
The compounds represented by the above formula (IV) to be used for the preparation of the compounds of the present invention, include some which show pesticidal activities . Typical examples of the compounds represented by the above formula (IV) will be given in Table 3 , and the NMR spectrum data thereof will be given in Table 4. In Tables 3 and , No . represents Compound No. Further, in Table 3, Me represents a methyl group, Et an ethyl group, n-Pr a n-propyl group, i-Pr an isopropyl group, n-Bu a n-butyl group, i-Bu an isobutyl group, s-Bu a sec-butyl group, t-Bu a tert-butyl group, and Ph a phenyl group . Table
Figure imgf000095_0001
Figure imgf000095_0002
Table 4
No . ^-N R δ ppm (Solvent : CDCl3/400MHz )
IV- 1 10 . 68 (lH, brs ) , 4 .21-4 . 45 ( lH, m) , 3 . 07-3 . 11 (2H, d, J=7 . 6Hz ]
IV-2 11 . 07 ( IH, brs ) , 4 . 06-4 .17 ( lH , m) , 2 .36 (2H, t , J=7 . 6Hz ) , 2 . 03 ( 2H, quartet , J=7 . 7Hz ) , 1 . 70 (2H, quintet , J=7 . 4Hz )
IV-3 4.05-4.15(lH,m) ,2.33( 2H,t,J=7.6Hz) ,1.93-1.99 (2H,m) , 1.58-1.66 (2H,m) ,1.30-1.37(4H,m)
IV-4 4.04-4.11(lH,m) ,3.46 2H, quartet , J=7.2Hz ) , 2.33 (2H,t,J=7.4Hz) ,1.94 (2H, quartet, J=7.2Hz) ,1.61(2H,qu intet, J=6.8Hz) ,1.23-1 37 (6H,m)
IV-8 2.33 (2H,t,J=8.0Hz) ,1. 98-2.04(2H,m) , 1.66-1.77 (2H,m) , 1.55 (3H,t,J=2.8Hz)
IV-9 2.29 (2H,t,J=7.4Hz) ,1. 87-1.92 (2H,m) ,1.54-1.62 (2H,m) 1.47(3H,t,J=3.0Hz) ,1.21-1.38(4H,m)
IV-10 2.33 (2H,t, J=7.6Hz) ,1. 89-1.95 (2H,m) , 1.57-1.67 (2H,m) 1.52 (3H,t, J=3.2Hz) ,1.20-1.40(8H,m)
IV-13 3.04(2H,t, J=2.0Hz) ,2.06-2.13 (2H,m) , 1.00 (3H, t , J=7.6Hz)
IV-14 2.36(2H,t, J=8.0Hz) ,1. 90-2.16(4H,m) ,1.68-1.76 (2H,m) , 0.98 (3H,t,J=7.6Hz)
IV-15 2.34(2H,t, J-=7.6Hz) ,1.92-1 99(4H,m) ,1.63 (2H, quintet, J=7.5Hz) ,1.28 1.42 (4H,m) , 0.97 (3H,t, J=7. 4Hz)
IV-16 2.33 (2H,t,J=7.2Hz) ,1.90-1 .99(4H,m) , 1.57-1.66 (2H,m) , 1.27-1.39 (8H,m) ,0.97 (3H,t ,J=7.2Hz)
IV-20 2.33 (2H,t, J=7.6Hz) ,1.97-2 .03 (2H,m) ,1.89-1.95 (2H,m) , 1.67-1.76 (2H,m) ,1.34-1.'44 (2H,m) ,0.87(3H,t, J=7.6Hz)
IV-22 2.42-2.50 (lH,m) ,2.34 (2H,t ,J=7.6Hz) ,1.84-1.90 (2H,m) , 1.58-1.66 (2H,m) ,1.28-1.41 (8H,m) ,0.85(6H,d,J=7.6Hz)
IV-34 7.18-7.37(5H,m) ,2.37 -2.43 (2H,m) , 2.28 (2H, t, J=7.6Hz) , 1.60-1.68 (2H,m)
IV-37 2.29-2.45(4H,m) ,1.84-1.93 (2H,m)
Now, Test Examples will be described. TEST EXAMPLE 1 Test on southern root-knot nematode (Meloidgyne incognita)
To 200 ml of the soil contaminated by southern root- knot nematode, 10 ml of a chemical solution having the concentration of the compound of the present invention adjusted to be 800 ppm, was poured, followed by mixing so that the compound was uniformly dispersed. The treated soil was put into a pot (diameter: 8 cm, height: 9 cm), and then a tomato seedling in 2-leaf stage was transplanted and placed in a greenhouse. After six weeks from the transplantation of the tomato, the root knot index was determined based on the following standards. Such determination was made with respect to the above- mentioned Compound Nos. 8, 9, 23 to 25, 27 to 29, 34, 35, 38 to 41, 58, 76, 82, 98, 101, 103, 121, 124 to 128, 131, 132, 170, 201, 205, 235, 284, 286, 288 to 290, 292, 294, 302, 315, 316, 337, 348, 349, 353, 360, 363, 365, 370, 371, 373, 375, 376, 382 to 386, 393, 394, 400, 401, 461, 486, 487, 491, 493, 496, 498, 504, 507, 513 and 520, whereby all compounds showed high controlling effects at a level of a root knot index of not more than 1. Further, determination was made with respect to the above- mentioned Compound Nos. IV-2, IV-8, IV-10, IV-15, IV-16 and IV-37, whereby all compounds showed high controlling effects at a level of a root knot index of not more than 1. 00
97
Figure imgf000098_0001
TEST EXAMPLE 2
Miticidal test against two-spotted spider mite (Tetranychus urticae)
A miticidal solution was prepared to bring the concentration of a compound of the present invention to 200 ppm. Kidney bean (Phaseolus vulgaris) seedling with only one primary leaf left, was transplanted in a pot (diameter: 8 cm, height: 7 cm) and 20 adults of two- spotted spider mite (Tetranychus urticae) were inoculated thereto. The adult mites were immersed together with the kidney bean leaf in the above miticidal solution, then dried in air and left in a constant temperature chamber at 25°C with lightening. On the second or third day after the treatment, dead adult mites were counted, and the mortality was calculated by the following equation. The adult mites dropped off the leaf were counted as dead adult mites. The mortality was obtained with respect to the above-mentioned Compound Nos. 8, 9, 12, 22 to 29, 34, 35, 37 to 41, 46, 55, 58, 59, 65, 76, 81, 82, 98, 101, 103, 111, 119, 121, 122, 124 to 128, 131, 132, 170, 201, 202, 205, 235, 275, 284 to 290, 292, 294, 296, 302, 305, 315, 316, 318, 320, 322, 330, 336 to 338, 348, 349, 351 to 354, 360 to 377, 379, 380, 382 to 405, 407 to 412, 419, 420, 426, 460, 461, 467, 468, 470, 473, 474, 477, 480, 483, 484, 486, 487, 489 to 494, 496, 498, 499, 504, 507, 512, 513, 520 and 543 to 545, whereby all compounds showed high controlling effects with a mortality of at least 80%. Further, the mortality was obtained with respect to the above-mentioned Compound Nos. IV-2, IV-8, IV-10, IV-13 to 16 and IV-20, whereby all compounds showed high controlling effects with a mortality of at least 80%.
Number of dead adult mites
Mortality (%) = X 100
Number of treated adult mites
TEST EXAMPLE 3 Insecticidal test against small brown planthopper (Laodelphax striatellus)
Rice seedling was dipped in an insecticidal solution prepared to bring the concentration of a compound of the present invention to 200 ppm and then dried in air. Then, the seedling with its root wrapped with a wet absorbent cotton, was put into a test tube. Then, 10 larvae of small brown planthopper (Laodelphax striatellus) were released therein, and the test tube was covered with a gauze and left in a constant temperature chamber at 25°C with lightening. On the 5th day after the release, dead larvae were counted, and the mortality was calculated by the following equation.
The mortality was obtained with respect to the above-mentioned Compound Nos. 8, 9, 22, 24 to 26, 28, 38, 40, 41, 58, 76, 98, 101, 103, 121, 124, 127, 132, 170, 201, 205, 275, 288, 290, 292, 294, 322, 337, 348, 353, 360, 363, 365, 370, 371, 373 to 375, 383 to 385, 399, 400, 402, 408, 426, 473 and 513, whereby all compounds showed high controlling effects with a mortality of at least 80%. Further, the mortality was obtained with respect to the above-mentioned Compound Nos. IV-8, IV-10, IV-14 and IV- 20, whereby all compounds showed high controlling effects with a mortality of at least 80%.
Number of dead insects
Mortality (%)= X 100
Number of released insects
TEST EXAMPLE 4
Insecticidal test against green peach aphid (Myzus persicae)
An insecticidal solution was prepared to bring the concentration of a compound of the present invention to 200 pm. The petiole of each of eggplants with only one foliage leaf left (planted in a pot having a diameter of 8 cm and a height of 7 cm) was coated with a sticker, and about 2-3 apterous viviparous female of green peach aphid (Myzus persicae) were infested and incubated on the foliage leaf of the eggplant. After two days from the infestation, the adult insects were removed, and the number of larvae was counted. Then, the foliage leaf of the eggplant infested with the larvae was dipped in the above insecticidal solution, then dried in air and left in a constant temperature chamber at 25°C with lightening. On the 5th day after the treatment, dead insects were counted, and the mortality was calculated by the following equation. The insects dropped off the leaf were counted as dead insects . The mortality was obtained with respect to the above-mentioned Compound Nos. 9, 22, 26, 29, 34, 35, 38 to 41, 98, 275, 408 and 426, whereby all compounds showed high controlling effects with a mortality of at least 80%. Further, the mortality was obtained with respect to the above-mentioned Compound No. IV-2, whereby this compound showed a high controlling effect with a mortality of at least 80%.
Number of dead insects
Mortality (%)= x 100
Number of treated insects
TEST EXAMPLE 5 Pesticidal test against New Zealand cattle mite (Haemaphysalis longicornis)
In a Petri dish having a diameter of 9 cm, 1 ml of an acetone solution of the compound of the present invention (concentration: 10 μmg/ml) is dropped by a micropipette. After the internal surface of the Petri dish dries up, from 60 to 180 infant mites are put, and the Petri dish is covered with a polyethylene sheet and sealed by an elastic band. The number of knocked down mites after contact with the pesticide is observed, whereby the compound of the present invention knocks down the majority of New Zealand cattle mite.
TEST EXAMPLE 6
Pesticidal test against New Zealand cattle mite (Haemaphysalis longicornis) , employing a dog
50 Young mites of New Zealand cattle mite are released on the auricle of a dog (beagle, 8 months old) and artificially parasitized. Upon expiration of two days from parasitizing, the number of parasitized mites is counted, and then the compound of the present invention formulated is spotted on at a dose of 10 mg/kg at the dorsal cervical region. Up to five days after administration of the pesticide, observation is carried out to insect the parasitic number, the fallen number and the mortality of the fallen New Zealand cattle mite. Here, the dog is individually raised in a cage and permitted to drink tap water freely, and a predetermined amount of a dog food is given once a day. As a result, the compound of the present invention is effective to have the parasitized New Zealand cattle mite fallen or dead. TEST EXAMPLE 7 Pesticidal test against cat flea, employing a dog
100 non-bloodsucked adults of cat flea (Ctenocephalides felis) within three days after adult emergence are released on the dorsal fur of a dog (beagle, 8 months old) and artificially parasitized, and the compound of the present invention formulated is spotted on at a dose of 10 mg/kg on the dorsal cervical region. On the third day after administration of the pesticide, the cat flea is recovered by means of a flea catching comb, and the parasitized number is counted. Here, the dog is individually raised in a cage and permitted to drink tap water freely, and a predetermined amount of a dog food is given once a day. As a result, the compound of the present invention is effective to control the parasitizing of cat flea. FORMULATION EXAMPLE 1
(1) Compound of the present invention
20 parts by weight
(2) Clay 72 parts by weight (3) Sodium lignin sulfonate 8 parts by weight
The above components are uniformly mixed to obtain a wettable powder. FORMULATION EXAMPLE 2
(1) Compound of the present invention 5 parts by weight
(2) Talc 95 parts by weight
The above components are uniformly mixed to obtain a dust. FORMULATION EXAMPLE 3
(1) Compound of the present invention
20 parts by weight (2) N,N' -dimethylaceta ide 20 parts by weight
(3) Polyoxyethylenealkylphenyl ether
10 parts by weight
(4) Xylene 50 parts by weight The above components are uniformly mixed and dissolved to obtain an emulsifiable concentrate. FORMULATION EXAMPLE 4
(1) Clay 68 parts by weight
(2) Sodium lignin sulfonate 2 parts by weight
(3) Polyoxyethylenealkylaryl sulfate 5 parts by weight
(4) Fine silica powder 25 parts by weight A mixture of the above components is mixed with compound of the present invention in a weight ratio of 4:1 to obtain a wettable powder. FORMULATION EXAMPLE 5
"(1) Compound of the present invention
50 parts by weight (2) Oxylated polyalkylpheny1 phosphate-triethanolamine 2 parts by weight (3) Silicone 0.2 part by weight
(4) Water 47.8 parts by weight
The above components are uniformly mixed and pulverized to obtain a base liquid, and
(5) Sodium polycarboxylate 5 parts by weight
(6) Anhydrous sodium sulfate 42.8 parts by weight are added, and the mixture is uniformly mixed and dried to obtain water-dispersible granules. FORMULATION EXAMPLE 6
(1) Compound of the present invention
5 parts by weight
(2) Polyoxyethyleneoctylphenyl ether 1 part by weight
(3) polyoxyethylene phosphoric acid ester 0.1 part by weight
(4) Granular calcium carbonate 93.9 parts by weight The above components (1) to (3) are preliminarily uniformly mixed and diluted with a proper amount of acetone, and then the mixture is sprayed onto the component (4), and acetone is removed to obtain granules. FORMULATION EXAMPLE 7
(1) Compound of the present invention 2.5 parts by weight
(2) N-methyl-2-pyrrolidone 2.5 parts by weight
(3) Soybean oil 95.0 parts by weight The above components are uniformly mixed and dissolved to obtain an ultra low volume formulation. FORMULATION EXAMPLE 8
(1) Compound of the present invention
40 parts by weight (2) Oxylated polyalkylphenylphosphate- triethanolamine 2 parts by weight
(3) Silicone 0.2 part by weight
(4) Zanthan gum 0.1 part by weight (5) Ethylene glycol 5 parts by weight
(6) Water 52.7 parts by weight
The above components are uniformly mixed and pulverized to obtain a water-based suspension concentrate. FORMULATION EXAMPLE 9 (1) Compound of the present invention
10 parts by weight (2) Diethylene glycol monoethyl ether 90 parts by weight
The above components are uniformly mixed to obtain a soluble concentrate.

Claims

CLAIMS : 1. A haloalkene compound represented by the formula (I ) or its salt :
Figure imgf000107_0001
wherein each of X1 and X2 is halogen, Y is a hydrogen atom, halogen, alkyl, haloalkyl or phenyl, n is from 0 to 5, A is an oxygen atom or a sulfur atom, G is a hydrogen atom, alkyl, haloalkyl, phenylalkyl, acyl, alkenyl, haloalkenyl, phenylalkenyl, alkynyl, haloalkynyl or phenylalkynyl, provided that when Y is a hydrogen atom or a halogen atom and A is an oxygen atom, G is alkyl, haloalkyl, phenylalkyl, acyl, alkenyl, haloalkenyl, phenylalkenyl, alkynyl, haloalkynyl or phenylalkynyl, and Q is a 5- to 12-membered heterocyclic group (the heterocyclic group may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, alkyl which may be substituted by W, alkenyl which may be substituted by W, alkynyl which may be substituted by W, or cycloalkyl which may be substituted by W, wherein W is halogen, alkoxy, alkylthio, hydroxy, cyano, nitro or phenyl which may be substituted, provided that (1) a case where X1 and X2 are simultaneously fluorine atoms, Y is a hydrogen atom, a chlorine atom or a bromine atom, n is from 1 to 5, A is an oxygen atom, G is alkyl, and Q is pyridyl which may be substituted by halogen, 2 , 2-dimethyl-2 , 3- dihydrobenzofuranyl, alkyl which may be substituted by W, alkenyl which may be substituted by W, alkynyl which may be substituted by W, or cycloalkyl which may be substituted by W, (2) a case where X1 and X2 are simultaneously fluorine atoms, Y is a hydrogen atom or halogen, n is 0, A is an oxygen atom, G is alkyl, and Q is pyridyl, benzothiazolyl (both may be substituted by halogen, alkyl or haloalkyl) , alkyl substituted by phenyl which may be substituted, or cycloalkyl which may be substituted by W, (3) a case where X1, X2 and Y are simultaneously fluorine atoms, and A is an oxygen atom, and (4) a case where X1 and X2 are simultaneously fluorine atoms, Y is a methyl group, n is 1, A is an oxygen atom, G is a hydrogen atom, and Q is a .2-propynyl group, are excluded.
2. The haloalkene compound or its salt according to Claim 1, wherein Y is alkyl, haloalkyl or phenyl.
3. The haloalkene compound or its salt according to Claim 2, wherein Y is alkyl.
4. The haloalkene compound or its salt according to Claim 1, wherein Q is a 5- to 12-membered heterocyclic group containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom.
5. The haloalkene compound or its salt according to Claim 4, wherein the heterocyclic group for Q is 1) a heterocyclic group selected from the group consisting of thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl, triazolyl, tetrazolyl, dithiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, thiazinyl, pyranyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, indazolyl, cyclopentapyrazolyl, benzothiadiazolyl, benzotriazolyl, quinolyl, isoquinolyl, phthalazinyl, cinnolinyl, quinazolinyl, quinoxalinyl, benzotriazinyl, naphthyridinyl , thiazolopyridyl, benzodioxolyl, benzodioxynyl, pyrazolopyrimidinyl, triazolopyrimidinyl and purinyl, 2) a partially saturated heterocyclic group having a part of such a heterocyclic group hydrogenated, 3 ) a saturated heterocyclic group having such a heterocyclic group completely hydrogenated, or 4) an oxo or thioxo heterocyclic group having a methylene moiety in the above-mentioned dithiazolyl, oxadinyl, thiadinyl, pyranyl, cyclopentapyrazolyl, benzodioxolyl, partially saturated heterocyclic group or saturated heterocyclic group, converted to oxo or thioxo.
6. The haloalkene compound or its salt according to Claim 1, wherein Q is a 5- or 6-membered heterocyclic group containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom.
7. The haloalkene compound or its salt according to Claim 6, wherein the heterocyclic group for Q is a heterocyclic group selected from the group consisting of thienyl, furyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiadiazolyl, oxadiazolyl, triazolyl, tetrazolyl, dithiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, oxazinyl, thiazinyl and pyranyl .
8. A process for producing a' haloalkene compound represented by the formula (I) or its salt:
Figure imgf000110_0001
wherein each of X1 and X2 is halogen, Y is a hydrogen atom, halogen, alkyl, haloalkyl or phenyl, n is from 0 to 5, A is an oxygen atom or a sulfur atom, G is a hydrogen atom, alkyl, haloalkyl, phenylalkyl, acyl, alkenyl, haloalkenyl, phenylalkenyl, alkynyl, haloalkynyl or phenylalkynyl, provided that when Y is a hydrogen atom or a halogen atom and A is an oxygen atom, G is alkyl, haloalkyl, phenylalkyl, acyl, alkenyl, haloalkenyl, phenylalkenyl, alkynyl, haloalkynyl or phenylalkynyl, and Q is a 5- to 12-membered heterocyclic group (the heterocyclic group may be substituted) containing an optional hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom, alkyl which may be substituted by W, alkenyl which may be substituted by W, alkynyl which may be substituted by W, or cycloalkyl which may be substituted by W, wherein W is halogen, alkoxy, alkylthio, hydroxy, cyano, nitro or phenyl which may be substituted, provided that (1) a case where X1 and X2 are simultaneously fluorine atoms, Y is a hydrogen atom, a chlorine atom or a bromine atom, n is from 1 to 5, A is an oxygen atom, G is alkyl, and Q is pyridyl which may be substituted by halogen, 2 , 2-dimethyl-2 , 3- dihydrobenzofuranyl, alkyl which may be substituted by W, alkenyl which may be substituted by W, alkynyl which may be substituted by W, or cycloalkyl which may be substituted by W, (2) a case where X1 and X2 are simultaneously fluorine atoms, Y is a hydrogen atom or halogen, n is 0, A is an oxygen atom, G is alkyl, and Q is pyridyl, benzothiazolyl (both may be substituted by halogen, alkyl or haloalkyl), alkyl substituted by phenyl which may be substituted, or cycloalkyl which may be substituted by W, (3) a case where X1, X2 and Y are simultaneously fluorine atoms, and A is an oxygen atom, and (4) a case where X1 and X2 are simultaneously fluorine atoms, Y is a methyl group, n is 1, A is an oxygen atom, G is a hydrogen atom, and Q is a 2-propynyl group, are excluded, which comprises (1) reacting a compound represented by the formula (II) :
Figure imgf000111_0001
wherein X1, X2, Y and n are as defined above, with a compound represented by the formula (III) or its salt: G HN-Q (HI) wherein G and Q are as defined above; or (2) reacting a compound represented by the formula (IV) :
Figure imgf000112_0001
wherein X1, X2, Y and n are as defined above, with a compound represented by the formula (III) or its salt:
G HN-Q (III) wherein G and Q are as defined above; or (3) reacting a compound represented by the formula (V) :
Figure imgf000112_0002
wherein X1, X2, Y and n are as defined above, and Z is Cι_4 alkyl, with a compound represented by the formula (III) or its salt:
G HN-Q (III) wherein G and Q are as defined above; or (4) reacting a compound represented by the formula (1-2) :
Figure imgf000112_0003
wherein X1, X2, Y, n and Q are defined above, with a compound represented by the formula (VI) :
G1-X3 (VI)
wherein G1 is alkyl, haloalkyl, phenylalkyl, acyl, alkenyl, haloalkenyl, phenylalkenyl, alkynyl, haloalkynyl or phenylalkynyl, and X3 is halogen; or (5) reacting a compound represented by the formula (1-2) :
Figure imgf000113_0001
wherein X1, X2, Y, n and Q are as defined above, with a compound represented by the formula (VII) : G2-OS02-U (VII) wherein G2 is alkyl, and U is alkyl, haloalkyl, alkoxy, phenyl, phenyl substituted by halogen, or phenyl substituted by alkyl; or (6) reacting a compound represented by the formula (1-1) :
Figure imgf000113_0002
wherein X1, X2, Y, n, G and Q are as defined above, with a thionizing agent.
9. A pesticide containing the haloalkene compound or its salt as defined in Claim 1, as an active ingredient.
10. An insecticide, iticide or nematicide containing the haloalkene compound or its salt as defined in Claim 1, as an active in ingredient.
11. A method for controlling a pest, which applies an effective amount of the haloalkene compound or its salt as defined in Claim 1.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104163792A (en) * 2013-05-20 2014-11-26 湖南化工研究院 N-picolinamide compound, preparation method and application thereof
CN111909031A (en) * 2020-08-14 2020-11-10 华东师范大学 Gem difluoroalkenyl substituted alkyl carboxylic acid compound and synthesis method thereof
CN112694436A (en) * 2020-12-30 2021-04-23 济南周行医药科技有限公司 Method for synthesizing arecoline

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4950666A (en) * 1989-03-30 1990-08-21 Fmc Corporation Difluoroalkane and difluoroalkenylalkane pesticides
EP0432861A1 (en) * 1989-12-15 1991-06-19 Schering Aktiengesellschaft Halogenated olefines, process for the preparation thereof and their use as pesticides
WO1992015555A2 (en) * 1991-03-01 1992-09-17 Monsanto Company Fluoroalkenyl compounds and their use as pest repellents
WO1997008132A1 (en) * 1995-08-25 1997-03-06 Bayer Aktiengesellschaft Fluorobutene acid amides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4950666A (en) * 1989-03-30 1990-08-21 Fmc Corporation Difluoroalkane and difluoroalkenylalkane pesticides
EP0432861A1 (en) * 1989-12-15 1991-06-19 Schering Aktiengesellschaft Halogenated olefines, process for the preparation thereof and their use as pesticides
WO1992015555A2 (en) * 1991-03-01 1992-09-17 Monsanto Company Fluoroalkenyl compounds and their use as pest repellents
WO1997008132A1 (en) * 1995-08-25 1997-03-06 Bayer Aktiengesellschaft Fluorobutene acid amides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HASSNER A ET AL: "Photochemical generation of vinylketenes by electrocyclic opening of cyclobutenones", TETRAHEDRON LETTERS, vol. 27, no. 52, 1986, pages 6389 - 6392, XP002272784 *
ROEDIG A ET AL: "Eninamine aus Perchlorbutenin und sek. aliphatischen Aminen", CHEMISCHE BERICHTE, vol. 109, no. 6, 11 June 1976 (1976-06-11), pages 2159 - 2163, XP002272783 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104163792A (en) * 2013-05-20 2014-11-26 湖南化工研究院 N-picolinamide compound, preparation method and application thereof
WO2014187298A1 (en) * 2013-05-20 2014-11-27 湖南化工研究院有限公司 N-pyridine amide compound, preparation method therefor, and application thereof
CN111909031A (en) * 2020-08-14 2020-11-10 华东师范大学 Gem difluoroalkenyl substituted alkyl carboxylic acid compound and synthesis method thereof
CN112694436A (en) * 2020-12-30 2021-04-23 济南周行医药科技有限公司 Method for synthesizing arecoline
CN112694436B (en) * 2020-12-30 2022-07-08 济南周行医药科技有限公司 Method for synthesizing arecoline

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