WO2013027853A1 - Procédé de production d'ester - Google Patents

Procédé de production d'ester Download PDF

Info

Publication number
WO2013027853A1
WO2013027853A1 PCT/JP2012/071748 JP2012071748W WO2013027853A1 WO 2013027853 A1 WO2013027853 A1 WO 2013027853A1 JP 2012071748 W JP2012071748 W JP 2012071748W WO 2013027853 A1 WO2013027853 A1 WO 2013027853A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
configuration
substituent
cyclopropane ring
Prior art date
Application number
PCT/JP2012/071748
Other languages
English (en)
Japanese (ja)
Inventor
田渕　学典
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2013027853A1 publication Critical patent/WO2013027853A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D209/49—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide and having in the molecule an acyl radical containing a saturated three-membered ring, e.g. chrysanthemumic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/74—Two oxygen atoms, e.g. hydantoin with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • the present invention relates to a method for producing an ester.
  • JP-A-60-16962 discloses certain esters having pest control activity.
  • An object of the present invention is to provide an efficient method for producing a novel ester having an excellent pest control effect.
  • the present inventors have found an efficient production method of an ester represented by the following formula (IV) having an excellent pest control effect, and have reached the present invention. That is, the present invention relates to the following inventions.
  • a heterocyclic compound represented by Formula (III) [Wherein R 4 represents a C1-C5 chain hydrocarbon group, or It represents a phenyl group which may be substituted with a group selected from the group consisting of a C1-C5 chain hydrocarbon group, a C1-C5 alkoxy group, a halogen atom, a trifluoromethyl group and a trifluoromethoxy group. ] And a carboxylic acid represented by formula (IV) [Wherein Q and R 4 represent the same meaning as described above. ] The manufacturing method of ester shown by.
  • a halogen atom means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • R 3 SO 2 Examples of the O group include a methanesulfonyloxy group, a benzenesulfonyloxy group, and a p-toluenesulfonyloxy group.
  • Examples of the C1-C5 chain hydrocarbon group include a C1-C5 alkyl group, a C3-C4 alkenyl group, and a C3-C4 alkynyl group.
  • Examples of the C1-C5 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and a pentyl group.
  • Examples of the C3-C4 alkenyl group include a 2-propenyl group
  • Examples of the C3-C4 alkynyl group include a propargyl group.
  • Examples of the C1-C5 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a pentyloxy group.
  • Examples of the phenyl group optionally substituted with a group selected from the group consisting of a C1-C5 chain hydrocarbon group, a C1-C5 alkoxy group, a halogen atom, a trifluoromethyl group, and a trifluoromethoxy group include a phenyl group, 2,4-dichlorophenyl group, 2-chloro-4-trifluoromethylphenyl group, 4-chlorophenyl group, 4-ethoxyphenyl group, 4-t-butylphenyl group, 4-trifluoromethylphenyl group, 4-fluorophenyl Group and 4-trifluoromethoxyphenyl group.
  • ester (IV) [Wherein Q and R 4 Represents the same meaning as described above. ]
  • a method for producing an ester represented by (hereinafter referred to as ester (IV)) will be described.
  • the ester (IV) has the formula (II) [In formula, Q and X represent the same meaning as the above. ]
  • Formula (III) [In the formula, R 4 Represents the same meaning as described above. ] It can manufacture by making it react with carboxylic acid shown below (it is hereafter described as carboxylic acid (III)).
  • the amount of the heterocyclic compound (II) used in the reaction is usually 0.5 to 10 mol, preferably 1 to 3 mol, relative to 1 mol of the carboxylic acid (III).
  • the reaction is performed in the presence or absence of a solvent.
  • the solvent used in the reaction include saturated hydrocarbons such as hexane, cyclohexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene.
  • the amount of the solvent used in the reaction is usually 0.1 to 100 parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably 1 to 3 parts by weight with respect to 1 part by weight of the carboxylic acid (III). is there.
  • the reaction is usually performed in the presence of a base.
  • the base used in the reaction include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, sodium bicarbonate and potassium bicarbonate.
  • metal bases such as triethylamine, diisopropylethylamine, pyridine, N-methylmorpholine and N, N-dimethylaniline.
  • the amount of the base used in the reaction is usually 0.5 to 10 mol, preferably 1 to 3 mol, per 1 mol of carboxylic acid (III).
  • the reaction time is usually in the range of 5 minutes to 72 hours, preferably 30 minutes to 12 hours.
  • the reaction temperature of the reaction is usually ⁇ 20 to 200 ° C. (provided that the boiling point of the solvent used is less than 200 ° C., ⁇ 20 ° C. to the boiling point of the solvent), preferably ⁇ 10 ° C. to 150 ° C.
  • ° C (provided that the boiling point of the solvent used is less than 150 ° C, -10 ° C to the boiling point of the solvent), particularly preferably 0 to 120 ° C (provided that the boiling point of the solvent used is less than 120 ° C) 0 ° C. to the boiling point of the solvent.
  • a usual analysis means such as high performance liquid chromatography can be used. After confirming the progress of the reaction, the reaction mixture and water can be mixed and extracted with an organic solvent.
  • organic solvent used in the extraction step examples include organic solvents that do not mix freely with water, and specific examples include saturated hydrocarbons such as hexane, cyclohexane and heptane, benzene, toluene and xylene.
  • saturated hydrocarbons such as hexane, cyclohexane and heptane, benzene, toluene and xylene.
  • the organic solvent is preferably an aromatic hydrocarbon.
  • An ester (IV) can be obtained by drying the organic layer thus obtained or concentrating under reduced pressure conditions.
  • the obtained ester (IV) can be further purified by recrystallization, chromatography or the like.
  • esterification is performed by performing extraction after the following stirring step.
  • (IV) can be obtained with high purity.
  • carboxylic acid (III) or heterocyclic compound (II) remains in the extract, it can be removed by adding alkaline water to the extract and stirring.
  • the alkaline water used in the stirring step is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium sulfite, potassium sulfite, sodium hydrogen sulfite, An aqueous solution of an alkaline compound such as potassium hydrogen sulfite or ammonia may be mentioned.
  • the concentration of the alkaline compound in the alkaline water is usually 0.1 to 40% by weight (however, within the solubility range of each alkaline compound).
  • the stirring temperature in the stirring step is usually ⁇ 10 to 80 ° C., preferably 0 to 40 ° C.
  • the stirring time in the stirring step is usually 5 minutes to 24 hours, preferably 10 minutes to 5 hours.
  • the base can be removed by adding acidic water to the extract and stirring.
  • the acidic water used in the stirring step include aqueous solutions of acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, formic acid, oxalic acid, and citric acid.
  • the concentration of the acidic compound in the acidic water is usually 0.1 to 40% by weight (however, within the solubility range of each acidic compound).
  • the stirring temperature in the stirring step is usually ⁇ 10 to 80 ° C., preferably 0 to 40 ° C.
  • the stirring time in the stirring step is usually 5 minutes to 5 hours, preferably 10 minutes to 2 hours.
  • ester (IV) can be easily obtained with high purity.
  • ester (IV) manufactured in this way the following compounds are mentioned, for example.
  • Q is NR 1 -CH 2 -C * A compound which is ( ⁇ O), ie the formula (a) [In the formula, R 1 And R 4 Represents the same meaning as described above. ]
  • a compound in which the relative configuration of the double bond at the 1 ′ position is the E configuration;
  • the relative configuration of the 1'-position double bond present in the substituent at the 3-position of the cyclopropane ring is the E configuration;
  • ester (IV) isomers derived from the two asymmetric carbon atoms present at the 1-position and the 3-position on the cyclopropane ring, and the 1 ′ present in the substituent at the 3-position of the cyclopropane ring are included.
  • the present invention includes each isomer having pesticidal activity and any ratio of isomer mixtures.
  • the heterocyclic compound (II) has the formula (I) [Wherein Q represents the same meaning as described above. ] Is a halogenating agent or a compound represented by the formula (X) R 3 SO 2 Cl [In the formula, R 3 Represents the same meaning as described above.
  • halogenating agent used in the reaction include thionyl halides such as thionyl chloride and thionyl bromide, and phosphorus-containing compounds such as phosphorus trichloride, phosphorus pentachloride and phosphorus oxychloride.
  • Thionyl chloride is particularly preferable.
  • the compound (X) include sulfonyl halide compounds such as methanesulfonyl chloride, benzenesulfonyl chloride, and p-toluenesulfonyl chloride.
  • the halogenating agent or compound (X) used in the reaction is preferably a halogenating agent, more preferably thionyl halide, and still more preferably thionyl chloride.
  • the amount of the halogenating agent or compound (X) used in the reaction is usually 0.5 to 100 mol, preferably 0.7 to 10 mol, particularly preferably 1 to 1 mol of the heterocyclic methanol (I). ⁇ 3 moles.
  • the reaction is performed in the presence or absence of a solvent.
  • solvent used in the reaction examples include saturated hydrocarbons such as hexane, cyclohexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene.
  • the amount of the solvent used in the reaction is 0.1 to 100 times by weight, preferably 0.5 to 10 times by weight, particularly preferably 1 to 3 times by weight with respect to the heterocyclic methanol represented by the formula (I). A triple weight is preferred.
  • This reaction can also be performed in presence of a catalyst as needed.
  • Examples of the catalyst used in the reaction include acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, lithium chloride, lithium bromide, magnesium chloride, zinc chloride, iron chloride (III ), Metal halides such as titanium tetrachloride and tin tetrachloride, phosphorus compounds such as triphenylphosphine, triphenylphosphine dichloride and triphenylphosphine dibromide, trimethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride and benzyltriethylammonium Examples include quaternary ammonium salts such as chloride, hydrogen chloride, and hydrogen bromide.
  • acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone
  • lithium chloride lithium bromide
  • the amount of the catalyst used in the reaction is usually 0.001 to 100 mol%, preferably 0.1 to 10 mol%, relative to 1 mol of the heterocyclic methanol (1).
  • This reaction can also be performed in presence of a base as needed.
  • the base used in the reaction include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate And an organic base such as triethylamine, diisopropylethylamine, pyridine, N-methylmorpholine and N, N-dimethylaniline.
  • the amount of the base used in the reaction is usually 0.1 to 100 mol, preferably 0.5 to 10 mol, particularly preferably 1 to 3 mol, per 1 mol of heterocyclic methanol (I).
  • the reaction time is usually 5 minutes to 72 hours, preferably 30 minutes to 12 hours.
  • the reaction temperature of the reaction is usually -30 to 150 ° C (provided that the boiling point of the solvent used is less than 150 ° C, -30 ° C to the boiling point of the solvent), preferably -20 to 100 ° C ( However, when the boiling point of the solvent used is less than 100 ° C., ⁇ 20 ° C. to the boiling point of the solvent), particularly preferably ⁇ 10 to 50 ° C.
  • a crude product containing the heterocyclic compound (II) can be obtained by concentrating the reaction mixture under reduced pressure.
  • the crude product can also be used as a raw material for producing ester (IV) as it is.
  • the crude product containing the heterocyclic compound (II) thus obtained may contain a plurality of impurities, and when used in the reaction with the carboxylic acid (III) as it is, the ester (IV containing a large amount of impurities) ) May be obtained.
  • Q is NR 1 -CH 2 -C *
  • the post-treatment of the compound ( ⁇ O) and X being a chlorine atom, that is, the compound represented by formula (Va) will be described. This post-treatment is accomplished by including a water washing treatment in which the reaction mixture is stirred with water.
  • the reaction mixture containing the heterocyclic compound (Va) may be used as it is, but when it contains a substance that reacts violently with acid gas such as hydrogen chloride or water such as thionyl chloride or phosphorus oxychloride. It is preferable to remove these substances by distillation under reduced pressure or the like before the post-treatment.
  • the solvent used for the synthesis reaction of the heterocyclic compound (Va) can be used continuously, but the solvent can be removed and the reaction can be performed in the absence of the solvent. Further, when the solvent is mixed uniformly with water, it is possible to remove the solvent once and replace it with another solvent.
  • the solvent in the case of using a solvent in the water washing treatment include a solvent used in the reaction for synthesizing the heterocyclic compound (Va) from the heterocyclic methanol (I) described above.
  • Examples of the solvent in the case of replacing with another solvent include organic solvents that do not freely mix with water, specifically, saturated hydrocarbons such as hexane, cyclohexane and heptane, benzene, toluene and xylene.
  • saturated hydrocarbons such as hexane, cyclohexane and heptane
  • benzene toluene and xylene.
  • Aromatic hydrocarbons, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene
  • ethers such as diethyl ether, diisopropyl ether and t-butyl methyl ether
  • esters such as ethyl acetate, isopropyl acetate and butyl acetate
  • aromatic hydrocarbons are particularly preferable.
  • the amount of water used in the water washing treatment is usually 0.1 to 100 parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably based on 1 part by weight of the heterocyclic methanol (I) used in the reaction. 1 to 3 parts by weight.
  • the water washing treatment can also be performed in the presence of an additive.
  • the additive used for the water washing treatment include acidic substances such as ammonium chloride, formic acid and acetic acid, and neutral substances such as sodium chloride, sodium bromide, sodium sulfate and magnesium sulfate.
  • the concentration of the additive is usually 0.001 to 10% by weight, preferably 0.1 to 5% by weight, based on water.
  • the water washing treatment can be usually carried out while confirming the purity (area%) improvement of the heterocyclic compound (II) using an analytical means such as gas chromatography or high performance liquid chromatography.
  • the stirring time is usually 5 minutes to 24 hours, preferably 30 minutes to 7 hours.
  • the stirring temperature is usually ⁇ 20 to 80 ° C., preferably ⁇ 10 to 40 ° C.
  • the aqueous layer obtained after the water washing treatment can be removed from the organic layer containing the heterocyclic compound (Va) by liquid separation.
  • the post-treatment for example, when an insoluble substance is present, more impurities can be removed by performing filtration or decantation in addition to the water washing treatment.
  • the purified heterocyclic compound (Va) thus obtained can be used in the next step (for example, reaction with carboxylic acid (III)) as it is or by distilling off the solvent under reduced pressure. it can.
  • the heterocyclic compound (II) include the following compounds.
  • Q is NR 1 -CH 2 -C * A compound which is ( ⁇ O), ie Formula (IIa) [In the formula, R 1 And X represent the same meaning as described above. ]
  • heterocyclic methanol (I) examples include the following compounds.
  • Q is NR 1 -CH 2 -C *
  • Heterocyclic methanol (I) is a commercially available product or a compound described in JP-A No. 05-255271, JP-A No. 57-158765, and US Pat. No. 3,345,379. It can be produced by the method described in the publication and the patent.
  • carboxylic acid (III) will be described.
  • carboxylic acid (III) isomers derived from the two asymmetric carbon atoms present at the 1-position and the 3-position on the cyclopropane ring, and 1 present in the substituent at the 3-position of the cyclopropane ring.
  • the raw materials for the production method of the present invention include each isomer and an isomer mixture in an arbitrary ratio.
  • the carboxylic acids (III) the carboxylic acid represented by the formula (III-1) in which the relative configuration of the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration is, for example, It can be manufactured by the method shown in 1. That is, the formula (V) [Wherein, R represents a C1-C5 alkyl group.
  • a caronaldehyde ester represented by Formula (VI) [In the formula, R 4 Represents the same meaning as described above.
  • Formula (VII) [Wherein R and R 4 Represents the same meaning as described above.
  • Formula (III-1) [In the formula, R 4 Represents the same meaning as described above. ] Can be produced.
  • the reaction is usually performed at a ratio of 1.0 to 1.5 mol of the nitrile represented by the formula (VI) and a ratio of 1 to 10 mol of the base with respect to 1 mol of the caronaldehyde ester represented by the formula (V).
  • the compound represented by the formula (VII) can be produced by reacting at 0 to 100 ° C, preferably 0 to 80 ° C.
  • Examples of the base include carbonates such as potassium carbonate and sodium carbonate, metal hydroxides such as sodium hydroxide and potassium hydroxide, metal alkoxides such as sodium methoxide and sodium ethoxide, and metal hydrides such as sodium hydride. Is mentioned.
  • the reaction can be carried out without solvent or in a solvent.
  • the solvent used in the solvent examples include aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, acetonitrile, Examples include nitriles such as propionitrile, acid amides such as N, N-dimethylformamide, and sulfoxides such as dimethyl sulfoxide, and two or more of these solvents can be mixed and used in an arbitrary ratio.
  • the compound represented by the formula (VII) can be obtained by performing post-treatment operations such as adding the reaction mixture to water, extracting with an organic solvent, and drying and concentrating the organic layer. .
  • the base is usually used at a ratio of 1 to 10 mol with respect to 1 mol of the compound represented by the formula (VII).
  • Carboxylic acid represented by formula (III) can be produced by reacting in a solvent at 0 ° C., preferably 0 ° C. to 30 ° C.
  • the base include alkali metal carbonates such as potassium carbonate and sodium carbonate, and alkali metal compounds such as sodium hydride.
  • the solvent include ethers such as tetrahydrofuran, alcohols such as methanol, water, and mixtures thereof.
  • the reaction solution is acidified and then extracted with an organic solvent, and post-treatment operations such as drying and concentration of the organic layer are performed to obtain the carboxylic acid represented by the formula (III).
  • the caronaldehyde ester represented by the formula (V) can be produced according to the method described in Tetrahedron 45, 3039-3052 (1989).
  • the relative configuration of the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a cis configuration, and R 4 Is R 5
  • the carboxylic acid represented by the formula (III-2) can be produced, for example, by the method shown below.
  • R 5 Represents a phenyl group which may be substituted with a group selected from the group consisting of a C1-C5 chain hydrocarbon group, a C1-C5 alkoxy group, a halogen atom, a trifluoromethyl group and a trifluoromethoxy group.
  • Formula (III-2) [In the formula, R 5 Represents the same meaning as described above. ] Can be obtained.
  • the nitrile represented by the formula (IX) is usually used in a proportion of 1.0 to 1.5 mol and the base is used in a proportion of 1 to 10 mol with respect to 1 mol of the lactol represented by the formula (VIII).
  • the carboxylic acid represented by the formula (III-2) can be produced by reacting in a polar solvent at 0 ° C. to 100 ° C., preferably 0 ° C. to 80 ° C.
  • the base include carbonates such as potassium carbonate and sodium carbonate, and alkali metal compounds such as sodium hydride.
  • the polar solvent include acid amides such as N, N-dimethylformamide and sulfoxides such as dimethyl sulfoxide.
  • the reaction solution is acidified, extracted with an organic solvent, and post-treatment operations such as drying and concentration of the organic layer are performed to obtain the carboxylic acid represented by the formula (III-2).
  • Can do examples of pests for which ester (IV) is effective include harmful arthropods such as harmful insects and harmful mites, and specifically include the following.
  • Hemiptera small brown planthopper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), Sejirounka (Sogatella furcifera) planthoppers such as, green rice leafhopper (Nephotettix cincticeps), Taiwan green rice leafhopper (Nephotettix virescens) leafhoppers such as, cotton aphid (Aphis gossypii) , Aphids such as the peach aphid (Myzus persicae), Nezoara tenta (Nezara antennata), Riptortus clavetus (Riptortus clavetus), Eysarcoris worms ris parvus, Chabaen's stink bug (Platia stale), scallop stink bug (Halyomorpha mista) and other stink bugs, i.e.
  • Hriga cues such as Hyphantria cunea, Hirosukoga such as iga (Tinea bisselliella), etc .
  • Diptera Culex pipiens pallens, Culex tritaenorhyes phys (Cedus quasi es), Culex quasius ed (E), Aedes moth Anopheles genus such as Anopheles gambae), chironomids, houseflies (Musca domestica), house flies such as house flies (Muscina stabulans), fly flies, fly flies, moth flies, , Fruit flies, Drosophila acids, Nomibae such as Oki Mont Nomibae (Megaselia spiracularis), giant flies (Clogmia albipunctata) flies include, blackfly acids, Abu acids, biting flies such, leafminers, and the like; Coleopter
  • Weevil such as Sitophilus zeamais, Rice worm weevil (Lissohoprus oryzophilus), Azuki beetle (Callosobrchuchus Kunststoffsis), Chilobole moss, Tenebrio molit m) etc.
  • Epilacunas such as Epilachna vigintioctopuncta, Soleoptera, Nagashimushimushi, Leopard beetle, Longicorn beetle, Paederus fuscipes, etc .
  • Cockroach pests German cockroaches (Blatella germanica), Black cockroaches (Periplaneta furiginosa), American cockroaches (Periplaneta americana), Japanese cockroaches (Peripraneta brunet) Thrips of the order: Thrips palmi, Trips tabaci, Franklinella occidentalis, Franklin, etc.
  • Hymenoptera Monomorium phalaosis, Black ants (Formica fusca japonica), Luritari (Ochetellus glamen), Phitomy (Phitomymex pungens) (Polistes chinensis antennalis), scallion wasp (Polistes jadwigae), wasp (Polistes rothneyi), etc., Vespa mandarinia japonica (Vespa mandaria), Data hornet (Vespa analis insularis), Mont hornet (Vespa crabro flavofasciata), wasps such as Anthrenus hornet (Vespa ducalis), Arigatabachi acids, carpenter bees, Bekkoubachi, wasps, Dorobachi like; Straight-eyed pests: keratoids, grasshoppers, etc .; Lepidoptera: Cat fleas (Ctenocephalides felis), dog fleas (Ctenocephalides canis),
  • Lice insect pests Japanese white lice (Pediculus humanus corporis), white lice (Phythrus pubis), cattle lice (Haematopinus eurysternus), sheep lice (Dalmalinia ovis), etc .;
  • Termite pests Yamato termites (Reticulites spertermus), Western termites (Cantopterites teremite) (Reticulitermes tibias), Subteranian termites such as dessert Subteranian termite (Heterotermes aureus), Dora such as American termite minor (Incitermes minor) Wood terpolymers mites such, and Nevada dump wood coater termite (Zootermopsis nevadensis) Dump Wood terpolymers mitogen such as such; Acarid pests: Taninychus urticae, Kanzawa spider mite (Tetranychus kanzawai), citrus spider mite (Pananychus citri), mite spider mite (Penonych
  • Spiders Birch spider, red spider spider, wolf spider, trash spider, striped spider, long-tailed spider, spider, spider, long-tailed spider, yellow spider, spider spider, giant spider spider, spider spider, etc
  • Lippods Centipedes such as Geese (Thereunema hilgendorfi), Tobismukade (Scolopedra subspinipes), Aoskade, Sesdiakamkade, Issunmukade, etc .
  • Double-legged class Millipedes such as Oxidus gracilis, Nedyopus tambanus, Obibabayasude, Kishayasude, Nikuirobabayasude, Higasiobiyasude, etc .
  • Isopods Bark beetles, such as scallops and walnuts, Scarabs such as Okadamushi, Funabs such as Funabushi
  • the ester (IV) can be a pest control agent containing the ester (IV) as an active ingredient (hereinafter referred to as the present pest control agent).
  • the pest control agent may be ester (IV) itself, but is usually used as a preparation as described below. Examples of the preparation include oils, emulsions, wettable powders, flowables (suspensions in water, emulsions in water, etc.), microcapsules, powders, granules, tablets, aerosols, carbon dioxide preparations, and heat evaporation agents.
  • the formulation method include the following methods.
  • ester (IV) is mixed with a solid carrier, liquid carrier, gaseous carrier, bait, etc., and a surfactant or other formulation adjuvant is added and processed as necessary.
  • These preparations usually contain 0.001 to 98% by weight of ester (IV) depending on the form of preparation.
  • solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, bentonite, fusami clay, acidic clay), synthetic hydrous silicon oxide, talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur).
  • Activated carbon calcium carbonate, hydrated silica, etc.
  • fine powders and particulates such as chemical fertilizers (ammonium sulfate, phosphorous acid, ammonium nitrate, ammonium chloride, urea, etc.), substances that are solid at room temperature (2,4,6-triisopropyl) -1,3,5-trioxane, naphthalene, p-dichlorobenzene, camphor, adamantane, etc.), wool, silk, cotton, hemp, pulp, synthetic resin (for example, low density polyethylene, linear low density polyethylene, high Polyethylene resins such as density polyethylene; ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymers; ethylene-methacrylic acid Copolymer, ethylene-methacrylic acid ester copolymer such as ethylene-ethyl methacrylate copolymer; ethylene-acrylic acid ester copolymer such as
  • liquid carrier examples include aromatic or aliphatic hydrocarbons (xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosene, light oil, hexane, cyclohexane, etc.), halogenated hydrocarbons (chlorobenzene, dichloromethane, dichloroethane, trichloroethane).
  • Etc. alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, etc.), ethers (diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran) , Dioxane, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (aceto , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, N -Methyl-
  • gaseous carrier examples include butane gas, freon gas, liquefied petroleum gas (LPG), dimethyl ether, and carbon dioxide gas.
  • surfactants include, for example, alkyl sulfate esters, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, polyarylethylenes of alkyl aryl ethers, polyethylene glycol ethers, polyhydric alcohol esters and sugars. Examples include alcohol derivatives.
  • formulation adjuvants include fixing agents, dispersants and stabilizers, such as casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone), polyacrylic acid, etc., BHT (2,6-di-tert-butyl-4-methylphenol), and BHA (2-tert-butyl-4-methoxyphenol) 3-tert-butyl-4-methoxyphenol).
  • fixing agents such as casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, saccharides, Synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone), polyacrylic acid, etc., BHT (2,6-di-tert-but
  • Examples of the insecticidal incense base material include a mixture of a vegetable powder such as wood powder and straw powder and a binder such as tab powder, starch and gluten.
  • Examples of the base material for the insecticidal electric mat include those obtained by solidifying a cotton linter into a plate shape and those obtained by solidifying a fillable of a mixture of cotton linter and pulp into a plate shape.
  • Examples of the base material of the self-combustion type smoke agent include nitrate, nitrite, guanidine salt, potassium chlorate, nitrocellulose, ethyl cellulose, wood powder and other combustion exothermic agents, alkali metal salts, alkaline earth metal salts, heavy metals.
  • Examples thereof include pyrolysis stimulants such as chromate and chromate, oxygen supply agents such as potassium nitrate, flame retardants such as melamine and wheat starch, extenders such as diatomaceous earth, and binders such as synthetic glue.
  • Examples of the base material for the chemical reaction type smoke agent include exothermic agents such as alkali metal sulfides, polysulfides, hydrosulfides and calcium oxide, catalyst materials such as carbonaceous materials, iron carbide and activated clay, azo Examples thereof include organic foaming agents such as dicarbonamide, benzenesulfonyl hydrazide, dinitropentamethylenetetramine, polystyrene and polyurethane, and fillers such as natural fiber pieces and synthetic fiber pieces.
  • the resin used for the substrate such as a resin transpiration agent
  • polyethylene resins such as low density polyethylene, linear low density polyethylene, and high density polyethylene
  • ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer.
  • Ethylene-acrylic acid ester copolymer ethylene-vinyl carboxylic acid copolymer such as ethylene-acrylic acid copolymer; ethylene-tetracyclododecene copolymer; propylene copolymer, propylene-ethylene copolymer, etc.
  • Polypropylene resin poly-4-methylpentene-1, polybutene-1, poly Butadiene, polystyrene, acrylonitrile-styrene resin; styrene-based elastomers such as acrylonitrile-butadiene-styrene resin, styrene-conjugated diene copolymer, styrene-conjugated diene block copolymer hydrogenated product; fluororesin; polymethyl methacrylate, etc.
  • Acrylic acid resin Polyamide resin such as nylon 6 and nylon 66; Polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polybutylene butarate, polycyclohexylene dimethylene terephthalate; Polycarbonate, polyacetal, polyacrylsulfone, polyarylate , Hydroxybenzoic acid polyester, Polyetherimide, Polyester carbonate, Polyphenylene ether resin, Polyvinyl chloride, Polyvinyl chloride These base materials may be used alone or as a mixture of two or more. These base materials may contain phthalates (dimethyl phthalate, dioctyl phthalate, etc.) as necessary. Further, a plasticizer such as adipic acid esters and stearic acid may be added.
  • phthalates dimethyl phthalate, dioctyl phthalate, etc.
  • a plasticizer such as adipic acid esters and stearic acid may be added.
  • the resin transpiration agent can be obtained by kneading the ester (IV) into the substrate and then molding it by injection molding, extrusion molding, press molding or the like.
  • the obtained resin preparation can be further processed into a plate shape, a film shape, a tape shape, a net shape, a string shape or the like through steps such as molding and cutting if necessary.
  • These resin preparations are processed, for example, as animal collars, animal ear tags, sheet preparations, attracting strings, or gardening supports.
  • poison bait base materials include bait ingredients such as cereal flour, vegetable oil, sugar, crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, and pepper powder.
  • Ester (IV) is an effective amount of ester (IV), usually in the form of the pest control agent, in the pest or pest habitat (plant, soil, house, animal, vehicle, Pests can be controlled by applying to open spaces in the open air.
  • Examples of the application method of the pest control agent include the following methods, which can be appropriately selected depending on the form, use place, and the like of the pest control agent. (1) A method of treating this pest control agent as it is in a pest or a pest habitat. (2) A method in which the pest control agent is diluted with a solvent such as water and then sprayed to the pest or the habitat of the pest.
  • the present pest control agent usually formulated into an emulsion, wettable powder, flowable agent, microcapsule formulation or the like is diluted so that the concentration of ester (IV) is 0.1 to 10,000 ppm.
  • the application amount and application concentration of the ester (IV) can be appropriately determined according to the form of the pest control agent, the application time, the application place, the application method, the type of the pest, the damage situation, and the like.
  • the application rate is usually 0.0001 to 1000 mg / m as the amount of ester (IV) when applied to space.
  • Insecticidal incense sticks, electric insecticidal mats, and the like are applied by volatilizing active ingredients by heating in accordance with the formulation form.
  • Resin transpiration agents, paper transpiration agents, non-woven fabric transpiration agents, knitted fabric transpiration agents, sublimable tablets and the like can be used, for example, by leaving them in the space to be applied as they are and by placing them in the preparation under ventilation. Examples of the space where this pest control agent is applied for prevention of epidemics include closets, closets, Japanese dance, cupboards, toilets, bathhouses, storerooms, living rooms, canteens, warehouses, car interiors, etc. It can also be applied.
  • this pest control agent When this pest control agent is used to control ectoparasites of domestic animals such as cattle, horses, pigs, sheep, goats and chickens, and small animals such as dogs, cats, rats and mice, Can be used for As a specific usage method, for the purpose of systemic control, for example, it is administered by tablet, feed mixing, suppository, injection (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.)
  • injection intramuscular, subcutaneous, intravenous, intraperitoneal, etc.
  • non-systemic control for example, spraying an oil or aqueous solution, pour-on or spot-on, washing animals with shampoo formulations or It is used by a method such as attaching a resin transpiration agent to an animal using a collar or ear tag.
  • the amount of ester (IV) when administered to an animal body is usually in the range of 0.01 to 1000 mg per kg of animal body weight.
  • this pest control agent When this pest control agent is used for pest control in the agricultural field, its application rate can be varied widely depending on the application time, application location, application method, etc., but generally 10,000 m 2
  • the amount of ester (IV) per unit is 1 to 10,000 g.
  • the pest control agent When the pest control agent is formulated into an emulsion, wettable powder, flowable agent, etc., it is usually diluted with water so that the active ingredient concentration is 0.01 to 10,000 ppm. Powders and the like are usually applied as they are.
  • esters (IV) can be used as a pest control agent for agricultural land such as fields, paddy fields, lawns, orchards, or non-agricultural land. Esters (IV) can control pests on the farmland in the farmland where the following “crop” and the like are cultivated.
  • Agricultural crops corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, sugarcane, tobacco, etc.
  • Vegetables Solanum vegetables (eggplants, tomatoes, peppers, peppers, potatoes, etc.), Cucurbitaceae vegetables (cucumbers, pumpkins, zucchini, watermelons, melons, etc.), Brassicaceae vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage) , Mustard, broccoli, cauliflower, etc.), asteraceae vegetables (burdock, shungiku, artichoke, lettuce, etc.), lily family vegetables (eg, leek, onion, garlic, asparagus, etc.), celery family vegetables (carrot, parsley, celery, American redfish) Etc.), red crustacean vegetables (spinach, chard, etc.), persimmon vegetables (perilla, mint, basil,
  • Fruit trees berries (apples, pears, Japanese pears, quince, quince, etc.), nuclear fruits (peaches, plums, nectarines, ume, sweet cherry, apricots, prunes, etc.), citrus (satsuma mandarin, orange, lemon, lime, grapefruit) ), Nuts (chestnut, walnut, hazel, almond, pistachio, cashew nut, macadamia nut, etc.), berries (blueberry, cranberry, blackberry, raspberry, etc.), grape, oyster, olive, loquat, banana, coffee, Date palm, coconut palm, oil palm etc.
  • Trees other than fruit trees tea, mulberry, flowering trees (Satsuki, camellia, hydrangea, sasanqua, shikimi, sakura, yurinoki, crape myrtle, snapdragon, etc.), roadside trees (ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak) , Poplar, redwood, fu, sycamore, zelkova, blackfish, Japanese amberjack, moths, pine, pine, spruce, yew, elm, Japanese cypress, etc.), coral jug, dogwood, cedar, cypress, croton, masaki, kanamochi, etc.
  • Lawn Shiba (Nasis, Pleurotus, etc.), Bermudagrass (Neurodonidae, etc.), Bentgrass (Oleoptera, Hykonukagusa, Odonoptera, etc.), Bluegrass (Nagahagusa, Oosuzunokatabira, etc.), Fescue (Oonishi nokegusa, Drosophila, etc.) , Grass, etc.), ryegrass (rat, wheat, etc.), anemonefish, and blue whale.
  • “Crop” also includes genetically modified crops. Esters (IV) are mixed with other insecticides, acaricides, nematicides, soil pesticides, fungicides, herbicides, plant growth regulators, repellents, synergists, fertilizers, soil conditioners, or It can also be used in combination.
  • Synthetic pyrethroid compounds Acrinathrin, allethrin, beta-cyfluthrin, bifenthrin, cycloprothrin, cyfluthrin, cyhalothrin, cyhalothrin, cyhalothrin, cyhalothrin, cyhalothrin ), Deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, flucytrinate Flufenprox, flumethrin, fluvalinate, halfenprox, imiprothrin, permethrin, rethrethrin, praretrin, sylmethrin Sigma-cypermethrin, silafluofen, tefluthrin, tralomethrin, transfluthrin, tetramethrin (tetramethrin (tetramethr
  • Phenylpyrazole compound Acetoprole, ethiprole, fipronil (fiproni1), vaniliprole (vaniliprole), pyriprole, pyrafluprole, etc .; (8) Bt toxin insecticide Live spores and produced crystal toxins from Bacillus thuringiensis, and mixtures thereof; (9) Hydrazine compounds Chromafenozide, halofenozide, methoxyphenozide, tebufenozide and the like; (10) Organochlorine compounds Aldrin, dieldrin, dienochlor, endosulfan, methoxychlor and the like; (11) Natural insecticide Machine oil, nicotine-sulfate; (12) Other insecticides Avermectin (vermectin-B), bromopropyrate, buprofezin, chlorphenapyr, cyromazine, D-D (1,3-Dichloropropene, D-D (1,3
  • the repellent for example, N, N-diethyl-m-toluamide, limonene, linalool, citronellal, menthol, menthone, hinokitiol, geraniol, eucalyptol, indoxacarb, caran-3,4-diol, MGK -R-326, MGK-R-874 and BAY-KBR-3023.
  • synergist for example, 5- [2- (2-butoxyethoxy) ethoxymethyl] -6-propyl-1,3-benzodioxole, N- (2-ethylhexyl) bicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, octachlorodipropyl ether, isobornyl thiocyanoacetate, N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo [2.2.2] Oct-5-ene-2,3-dicarboximide is mentioned.
  • Production Example 8 1.67 g (10.0 mmol) of 2-hydroxymethyl-5-methyl-3-oxo-4- (2-propynyl) -3,4-dihydro-1,2,4-triazole and 15 mg of N, N-dimethylformamide While cooling a mixture of (0.21 mmol) suspended in 8.5 g of toluene with ice cooling and stirring, 2.41 g (20.3 mmol) of thionyl chloride was added dropwise. After stirring for 40 minutes under ice cooling and 1.5 hours at room temperature, 5.0 ml of acetonitrile was added and the mixture was further stirred for 1 hour.
  • the mixture was stirred at 80 ° C. for 3 hours, then cooled to room temperature and washed with water. After adding 2.0 g of toluene to the organic layer, 790 mg of 10% aqueous ammonia was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was separated, and the organic layer was washed successively with 10% hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 1.31 g of a pale reddish brown crude oil.
  • reaction solution was added to 60 ml of ice water and extracted with 50 ml of ethyl acetate. Hydrochloric acid was added to the obtained aqueous layer until the pH reached 2, and then extracted twice with 50 ml of ethyl acetate. The obtained ethyl acetate layers were combined, washed twice with 50 ml of saturated brine, and dried over magnesium sulfate. Concentration under reduced pressure yielded 8.98 g of (1R) -trans-3-[(1EZ) -2-cyano-2- (ethylthio) ethenyl] -2,2-dimethylcyclopropanecarboxylic acid.
  • reaction solution was added to 30 mL of ice water and extracted with 20 mL of ethyl acetate. Hydrochloric acid was added to the obtained aqueous layer until the pH reached 2, and then extracted twice with 30 mL of ethyl acetate. The obtained ethyl acetate layers were combined, washed twice with 30 mL of saturated brine, and dried over magnesium sulfate. Concentration under reduced pressure yielded 2.08 g of (1R) -trans-3-[(1EZ) -2-cyano-2- (methylthio) ethenyl] -2,2-dimethylcyclopropanecarboxylic acid.
  • reaction solution was cooled to room temperature, poured into 560 mL of ice water and acidified to pH 2 with 10% hydrochloric acid. The mixture was extracted 3 times with 100 mL of ethyl acetate, and then the ethyl acetate layers were combined and washed once with 200 mL of saturated brine. The obtained organic layer was dried over magnesium sulfate and then concentrated under reduced pressure to obtain 12.14 g of a tan oil.
  • Formulation Example 1 20 parts of each of compounds 1 to 25 are dissolved in 65 parts of xylene, 15 parts of Solpol 3005X (Toho Chemical Registration) is added, and the mixture is stirred well to obtain an emulsion.
  • Formulation Example 2 Add 5 parts of Solpol 3005X to 40 parts of each of compounds 1 to 25, mix well, add 32 parts of Carplex # 80 (synthetic hydrous silicon oxide, Shionogi Pharmaceutical registered trademark) and 23 parts of 300 mesh diatomaceous earth. Stir and mix to obtain a wettable powder.
  • Formulation Example 3 1.5 parts of each of compounds 1 to 25, 1 part of Toxeal GUN (synthetic hydrous hydrous, manufactured by Tokuyama Corporation), 2 parts of Liax 85A (sodium lignin sulfonate, manufactured by West vaco chemicals), bentonite Fuji (bentonite, Hojun) 30 parts and 65.5 parts of Katsuyama A clay (Kaolin clay, manufactured by Katsuyama Mining Co., Ltd.) are thoroughly pulverized and mixed, mixed well with water, granulated with an extrusion granulator, and dried. Thus, 1.5% granules are obtained.
  • Formulation Example 4 After mixing 10 parts of each of compounds 1 to 25, 10 parts of phenylxylylethane and 0.5 part of Sumidur L-75 (tolylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.), in 20 parts of 10% aqueous solution of gum arabic In addition, the mixture is stirred with a homomixer to obtain an emulsion having an average particle size of 20 ⁇ m. 2 parts of ethylene glycol is added thereto, and the mixture is further stirred in a warm bath at 60 ° C. for 24 hours to obtain a microcapsule slurry.
  • Sumidur L-75 tolylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd.
  • xanthan gum and 1.0 part of bee gum R aluminum magnesium silicate, manufactured by Sanyo Kasei
  • bee gum R aluminum magnesium silicate, manufactured by Sanyo Kasei
  • Formulation Example 5 After mixing 10 parts of each of compounds 1 to 25 and 10 parts of phenylxylylethane, the mixture is added to 20 parts of a 10% aqueous solution of polyethylene glycol and stirred with a homomixer to obtain an emulsion having an average particle size of 3 ⁇ m.
  • xanthan gum and 1.0 part of bee gum R are dispersed in 58.8 parts of ion-exchanged water to obtain a thickener solution.
  • a flowable agent is obtained by mixing 40 parts of the emulsion solution and 60 parts of the thickener solution.
  • Formulation Example 6 5 parts of each of compounds 1 to 25 was added 3 parts of Carplex # 80 (synthetic hydrous hydrous powder, Shionogi Pharmaceutical), 0.3 parts of PAP (mixture of monoisopropyl phosphate and diisopropyl phosphate) and talc (300 Add 91.7 parts of mesh) and stir and mix with a juice mixer to obtain a powder.
  • Formulation Example 7 0.1 part of each of compounds 1 to 25 is dissolved in 10 parts of dichloromethane and mixed with 89.9 parts of deodorized kerosene to obtain an oil.
  • Formulation Example 8 Each 0.1 part of compounds 1 to 25 and 39.9 parts of deodorized kerosene are mixed and dissolved, filled into an aerosol container, and after attaching a valve part, 60 parts of propellant (liquefied petroleum gas) is added through the valve part. Pressurized to obtain an oily aerosol.
  • propellant liquefied petroleum gas
  • Formulation Example 9 A mixture of 0.6 parts of each compound 1 to 25, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of Rhedol MO-60 (emulsifier, registered trademark of Kao Corporation) and 50 parts of water are aerosolized. The container is filled, and 40 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve portion to obtain an aqueous aerosol.
  • propellant liquefied petroleum gas
  • Formulation Example 12 A solution obtained by dissolving 3 parts of each of compounds 1 to 25 in 97 parts of deodorized kerosene is placed in a container made of vinyl chloride, and the upper part can be heated with a heater (inorganic powder is hardened with a binder and sintered) The parts used for the liquid absorption core type heat transpiration apparatus are obtained by inserting the tie.
  • Formulation Example 13 100 mg of each of compounds 1 to 25 is dissolved in an appropriate amount of acetone and impregnated into a porous ceramic plate having a size of 4.0 cm ⁇ 4.0 cm and a thickness of 1.2 cm to obtain a heated smoke.
  • Formulation Example 14 100 ⁇ g of each of compounds 1 to 25 is dissolved in an appropriate amount of acetone, uniformly applied to a filter paper having a size of 2 cm ⁇ 2 cm and a thickness of 0.3 mm, and then acetone is air-dried to obtain a room temperature volatilizer.
  • Formulation Example 15 10 parts of each of compounds 1 to 25, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt, and 55 parts of water are mixed and pulverized by a wet pulverization method to obtain a 10% flowable agent. .
  • ester (IV) is effective as an active ingredient of a pest control agent.
  • Test example 1 0.1 part of each of compounds 1 to 3, 5 to 9, 13, 15 and 19 to 23 is dissolved in 10 parts of isopropyl alcohol and mixed with 89.9 parts of deodorized kerosene to obtain 0.1% (w / V) An oil was prepared.
  • Six American cockroaches (3 males and 2 females) are placed in a test container with a buttered inner wall (diameter 12.5 cm, height 10 cm, bottom 16 mesh wire mesh) and the container is placed in a test chamber ( (Bottom: 46 cm ⁇ 46 cm, height: 70 cm).
  • Knockdown rate (%) (number of knockdown insects / number of test insects) ⁇ 100
  • the following formula 2,5-dioxo-3- (2-propynyl) imidazolidinylmethyl (1R) -trans-3- (2-methyl-1-propenyl) -2,2-dimethylcyclopropanecarboxylate (Pesticide) Science, 10, p.291 (1979), hereinafter referred to as comparative compound (1).
  • the following formula 2,5-dioxo-3- (2-propynyl) imidazolidinylmethyl (1R) -cis-3-((Z) -2-cyano-2-methoxyethenyl) -2,2-dimethyl Cyclopropanecarboxylate (compound described in JP-A-60-16962, hereinafter referred to as comparative compound (2))
  • Test example 2 0.1 parts of each of compounds 4, 10 to 12 and 19 to 23 are dissolved in 10 parts of isopropyl alcohol and mixed with 89.9 parts of deodorized kerosene to prepare a 0.1% (w / v) oil. did. 10 German cockroaches (5 males and 5 females) are placed in a test container with a buttered inner wall (diameter 8.75 cm, height 7.5 cm, bottom 16 mesh wire mesh) and the container is used for testing. It was installed at the bottom of the chamber (bottom: 46 cm ⁇ 46 cm, height: 70 cm).
  • Knockdown rate (%) (number of knockdown insects / number of test insects) ⁇ 100 The results after 2 minutes are shown in Table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pyrrole Compounds (AREA)
  • Indole Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Procédé de production d'ester permettant d'obtenir un ester qui est représenté par la formule (IV) et a un effet supérieur en termes de lutte contre les ravageurs, ledit procédé de production étant caractérisé par la réaction d'un composé hétérocyclique représenté par la formule (II) avec un acide carboxylique représenté par la formule (III).
PCT/JP2012/071748 2011-08-24 2012-08-22 Procédé de production d'ester WO2013027853A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-182316 2011-08-24
JP2011182316 2011-08-24

Publications (1)

Publication Number Publication Date
WO2013027853A1 true WO2013027853A1 (fr) 2013-02-28

Family

ID=47746585

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/071748 WO2013027853A1 (fr) 2011-08-24 2012-08-22 Procédé de production d'ester

Country Status (2)

Country Link
JP (1) JP2013060437A (fr)
WO (1) WO2013027853A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5111171B1 (fr) * 1971-06-28 1976-04-09 Sumitomo Chemical Co
US4053625A (en) * 1974-12-05 1977-10-11 Sumitomo Chemical Company, Limited Insecticides
JPS5412348A (en) * 1977-06-17 1979-01-30 Sumitomo Chem Co Ltd Cyclopropane carboxylic acid esters, their preparation, and insecticides and acaricides comprising them as active constituents
JPS54109950A (en) * 1978-01-26 1979-08-29 Fmc Corp Arylthiovinyl cyclopropane carboxilate insecticide and its intermediates
US4176189A (en) * 1977-06-20 1979-11-27 Sumitomo Chemical Company, Limited Insecticidal and acaricidal hydantoin N-methylol esters
JPS57158765A (en) * 1981-03-24 1982-09-30 Sumitomo Chem Co Ltd Carboxylic acid ester, its preparation, and insecticide containing said ester as active component
JPS6016962A (ja) * 1983-06-14 1985-01-28 ルセル−ユクラフ シアノ基を有するシクロプロパンカルボン酸のエステル，その製造法及びその殺虫殺ダニ剤としての使用
JP2011195576A (ja) * 2010-02-25 2011-10-06 Sumitomo Chemical Co Ltd エステル化合物及びその用途

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5111171B1 (fr) * 1971-06-28 1976-04-09 Sumitomo Chemical Co
US4053625A (en) * 1974-12-05 1977-10-11 Sumitomo Chemical Company, Limited Insecticides
JPS5412348A (en) * 1977-06-17 1979-01-30 Sumitomo Chem Co Ltd Cyclopropane carboxylic acid esters, their preparation, and insecticides and acaricides comprising them as active constituents
US4176189A (en) * 1977-06-20 1979-11-27 Sumitomo Chemical Company, Limited Insecticidal and acaricidal hydantoin N-methylol esters
JPS54109950A (en) * 1978-01-26 1979-08-29 Fmc Corp Arylthiovinyl cyclopropane carboxilate insecticide and its intermediates
JPS57158765A (en) * 1981-03-24 1982-09-30 Sumitomo Chem Co Ltd Carboxylic acid ester, its preparation, and insecticide containing said ester as active component
JPS6016962A (ja) * 1983-06-14 1985-01-28 ルセル−ユクラフ シアノ基を有するシクロプロパンカルボン酸のエステル，その製造法及びその殺虫殺ダニ剤としての使用
JP2011195576A (ja) * 2010-02-25 2011-10-06 Sumitomo Chemical Co Ltd エステル化合物及びその用途

Also Published As

Publication number Publication date
JP2013060437A (ja) 2013-04-04

Similar Documents

Publication Publication Date Title
KR101810701B1 (ko) 해충 방제 조성물
JP5326424B2 (ja) 含フッ素有機硫黄化合物およびその有害節足動物防除剤
JP5287033B2 (ja) 含フッ素有機硫黄化合物およびその有害節足動物防除剤
JP2011225542A (ja) エステル化合物とその有害生物防除用途
JP5760577B2 (ja) エステル化合物とその用途
JP2011195576A (ja) エステル化合物及びその用途
JP2011225539A (ja) エステル化合物及びその用途
JP5423011B2 (ja) ニトリル化合物ならびにその有害節足動物防除用途
WO2013027853A1 (fr) Procédé de production d'ester
JP2011195578A (ja) エステル化合物及びその用途
JP2011195577A (ja) エステル化合物及びその用途
KR20100110333A (ko) 시클로프로판카르복실레이트 및 이를 함유하는 유해 생물 방제 조성물
JP2011195579A (ja) エステル化合物及びその用途
JP2013060435A (ja) エステル化合物及びその用途
JP2013060436A (ja) エステル化合物及びその用途
JP2011225541A (ja) エステル化合物及びその有害生物防除用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12825267

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12825267

Country of ref document: EP

Kind code of ref document: A1