TW201033162A - Production method of cyclopropane methanoic acid compound and intermediate thereof - Google Patents

Abstract

A production method of a cyclopropane methanoic acid compound represented by the formula (VI), Formula (VI) ( where R represents an aliphatic alkyl group of 1 to 10 carbon atoms, and so on), characterized by reacting the compound represented by the formula (V) Formula (V) (where R has the same meaning as above, R.sup.1 represents an aliphatic alkyl group of 1 to 10 carbon atoms that can be substituted by halogen atoms, and so on) with an alkali metal borohydride in solvents.

Description

201033162 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a cyclopropanecarboxylic acid compound and an intermediate thereof. [Prior Art] In U.S. Patent Publication No. 2003/0195119, it is disclosed that the formula (VI)

H3c ch3 y cn (VI)

O (wherein R represents an alkoxy group which may be selected from a halogen atom, a fluorenyl group having 2 to 7 carbon atoms, a carbon number of 1 to 7 which may be substituted, a carbon number which may be substituted, and A cyclopropanecarboxylic acid compound represented by at least one of the groups of the phenyl group substituted with a phenyl group substituted with a carbon number of 1 to 10, a cyclic hydrocarbon group having a carbon number of 3 to 1 fluorene or a hydrogen atom) may be used. A pest control agent and an intermediate thereof; as a method for producing the same, it is disclosed that a corresponding propylene acetal compound is reacted with diethyl (1-cyanoethyl) phosphonate. SUMMARY OF THE INVENTION The present invention provides: <1> A method for producing a cyclopropanecarboxylic acid compound represented by formula (VI),

(Π) 139089.doc 201033162 (wherein R represents the same meaning as described below) characterized in that, in the presence of a solvent, the formula (V) h3c ch3

(V) (wherein R represents an alkylthio group which may be selected from a halogen atom, a carbon number of 2 to 7, a substituted alkoxy group having 1 to 7 carbon atoms, a carbon number which may be substituted, and At least one of the group consisting of a substituted phenyl group substituted with a carbon number of 1 to 10, a cyclic hydrocarbon group having a carbon number of 3 to 1 or a hydrogen atom, and R1 represents a carbon which may be substituted by an atom a compound represented by a chain hydrocarbon group or a phenyl group, which is reacted with an alkali metal borohydride; <2> a method for producing a cyclopropanecarboxylic acid compound according to &lt;1&gt;, wherein the alkali metal butterfly hydride is boron A method for producing a cyclopropane decanoic acid compound according to <1> or <2>, wherein the agent is selected from the group consisting of an ether solvent, a guanamine solvent, a heteroaromatic solvent, a sulfur-containing aliphatic agent, and a nitrile solvent. And a method for producing a cyclopropanecarboxylic acid compound according to <1> or <2>, wherein the refrigerant is N, and at least one of the group consisting of a cyclic urea solvent, an alcohol solvent, and an ester solvent; N-dimercaptocarbamide, dimercaptoacetamide, dimercaptoarylene, N-methyl-2-pyrrolidone, acetonitrile or hydrazine, 3 A method for producing a cyclopropanecarboxylic acid compound according to any one of dimethyl-2-imidazoline, wherein the compound represented by the formula (V) is represented by the formula (11) 139089.doc (II) 201033162

(wherein, R represents the same meaning as defined in &lt;1&gt;) and a compound represented by the formula (冚) 冚(冚&gt; X represents a halogenogen (wherein R1 represents &lt;1&gt; The definition of the same meaning sub) is represented by the sulfhydryl dentate or the anhydride represented by the formula (IV) (IV) (wherein 'R1 represents the same meaning as defined in <1>) in the presence of a base &lt;6&gt; The method for producing a cyclopropanecarboxylic acid compound according to &lt;5&gt; wherein the compound represented by the formula (Π) is obtained by the formula (1) h3c ch3 (1)

R ^CHO Ο (wherein, R represents the same meaning as defined in <1>), and a compound obtained by reacting a compound represented by acrylonitrile in the presence of a base; &lt;7&gt; It is of the formula (11) 139089.doc 201033162

(wherein R represents an alkylthio group which may be selected from a halogen atom, a fluorenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms which may be substituted, and a carbon number 可~] which may be substituted and A chain hydrocarbon group having 1 to 10 carbon atoms, a cyclic hydrocarbon group having 3 to 10 carbon atoms or a hydrogen atom substituted with at least an anthracene group in a group consisting of a substituted phenyl group; &lt;8&gt; And a compound of the above formula, wherein R is a chain hydrocarbon group of a carbon number or a carbon number of 丨~(7) substituted by a phenyl group which may be substituted; &lt;9&gt; Or 2,3,5,6 tetrafluoro_4methoxyindenylbenzyl; &lt;1〇&gt; - a compound which is of the formula (V)

(wherein R represents a carbon number i which can be substituted with an alkoxy group selected from a halogen atom and a carbon number of 2 to 7 and substituted with a carbon number of 1 to 7 and can be substituted by the gemming 丄 丄, i a carbaryl group having 2 to 7 carbon atoms, a cyclyl group which may be substituted with at least one of the alkylthio group having 1 to 3 carbon atoms; a hydrogen atom, R1 represents a chain hydrocarbon group of 1 to 10 or a phenyl group; at least a chain hydrocarbon group of the oxime group 10, a cycloalkyl group having 3 to 10 carbon atoms or a hydrogen atom in a group consisting of a phenyl group which may be substituted The atomic number substituted by the carbon number 1;

139089. The compound of <10>, wherein R1 is a carbon number i 201033162 &lt;13&gt; The compound of any one of &lt;10&gt; to &lt;12&gt; wherein R is a carbon number 1~ And a compound of any one of the above-mentioned, wherein the Methyl or 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl; &lt;15&gt; - a method for producing a cyclopropanecarboxylic acid compound represented by formula (IX),

(wherein R2 represents the same meaning as described below) characterized in that in the presence of a solvent, the formula (Va) is used.

(Va) (wherein the ruthenium table can not be selected from a halogen atom, a ruthenium group having 2 to 7 carbon atoms, a silk group of 1 to 7 which can be substituted, a sulfur-burning group having a carbon number of 1 to 3 and a chain of carbon i 110 substituted with at least one group of a group of substituted phenyl groups or a cyclic hydrocarbon group having a carbon number of 3 to 1 G, showing a chain hydrocarbon group having a carbon number of from 10 to 10 which may be substituted by a fang atom Or phenyl) ', 'I, the s species react with the alkali metal borohydride to obtain (Via) ^ 139089.doc 201033162

(wherein R· represents the same meaning as described above) the cyclopropanecarboxylic acid compound represented by the cyclopropanecarboxylic acid compound represented by the formula (VIa) and the formula (VIII) R2-〇H (VIII) (Formula, R2 is a group different from R', and represents an alkoxy group which may be selected from a halogen atom, a carbon number of 2 to 7, a carbon number which may be substituted, and may be substituted = carbon number a compound represented by a chain hydrocarbon group having 1 to 3 carbon atoms and a ring hydrocarbon group having 3 to 1 carbon atoms substituted with at least one group of a group consisting of a substituted alkyl group and a phenyl group which may be substituted &lt;(10) A method for producing a propylene-based carboxylic acid compound according to &lt;15&gt;, wherein the metal hydroxide is lithium hydroxide; &lt;17&gt;15&gt; or &lt;16&gt; propylene propylene burning formic acid compound manufacturing method potted by mystery solvent, amine solvent, heteroaromatic solvent, sulfur-containing agent nitrile (tetra) 'cyclic urea solvent, alcohol solvent money solvent group At least one of the above, &lt;18&gt; a method for producing a cyclopropanedecanoic acid represented by the formula (VII)

Let (V a) be characterized by: in the presence of a solvent 139089.doc 201033162

(Va) ❹

, -4, suction double Z~/I off-label, v4 replaced stone anomaly 1~7 burnt window, its base, the alkylthio group which can be substituted with 1 to 3 carbon atoms and the phenyl group which can be substituted έ日日,*丄丄, at least one base substituted in the group, the carbon number of 1 to 10, or the ring carbon group of 3 carbon atoms, and Ri represents a carbon which can be substituted by a halogen atom. A compound represented by a chain hydrocarbon group of 1 to 10 or a phenyl group is reacted with an alkali metal ruthenium compound to obtain a formula (Via) (Via) (wherein R' represents the same meaning as described above) The cyclic (iv) formic acid compound is represented, and the obtained cyclopropanecarboxylic acid compound represented by the formula (via) is hydrolyzed; (7)&gt; The method for producing a propylene acetonate formic acid according to &lt;18&gt; wherein the solvent is selected from the group consisting of At least one of a group consisting of a solvent of a mystery solvent, a guanamine solvent, a heteroaromatic solvent, a sulfur-containing aliphatic solvent, a nitrile solvent, a cyclic urea (tetra), and an alcohol solvent; and &lt;20&gt; The method for producing a cyclopropane decanoic acid compound represented by 139089.doc 201033162

(wherein R2 represents the same meaning as described below), characterized in that the cyclopropanecarboxylic acid represented by (VII) is obtained by a method for producing a cyclopropanecarboxylic acid compound such as &lt;18&gt; or &lt;19&gt; The obtained propylene cyanate formic acid represented by the formula (VII) and the formula (VHI) R2-OH (VIII) (wherein R2 is a group different from R', which is selected from a halogen atom, a carbon number of 2 At least one of a group consisting of a fluorenyl group of -7, a substituted alkoxy group having a carbon number of 丨7, a substituted alkyl group having 1 to 3 carbon atoms, and a phenyl group which may be substituted The compound represented by the substituted hydrocarbon group having 1 to 10 carbon atoms or the cyclic hydrocarbon group having 3 to 1 carbon atoms is reacted in the presence of a wrong compound; &lt;21&gt; The manufacture of a cyclopropanecarboxylic acid compound such as &lt;20&gt; a method wherein the wrong compound is a zirconium hydride, a zirc〇n〇cene compound or an alkoxy fluorene; &lt;22&gt; a method for producing a cyclopropanecarboxylic acid compound represented by the formula (1) ,

(wherein R3 represents the same meaning as described below) characterized in that, in the presence of a solvent, the formula (Vb) 139089.doc 201033162

Or a compound represented by phenyl) is reacted with an alkali metal borohydride to obtain a cyclopropanecarboxylic acid compound represented by the formula (VIb) h3c ch3 h^〇y^Cx _ ,, such that the obtained formula (VIb) And the propylene group which is represented by the formula (VIIIa) r3-〇h (Villa) (wherein R represents a carbon number which may be selected from a halogen atom, a carbon number of 2 to 7 and a carbon number which may be substituted Alkyloxy group of 1 to 7 or a carbon group of 1 to 10 or substituted with at least an anthracene group of a group of a carbon group which may be substituted and substituted with a stupid group The compound represented by the cyclic hydrocarbon group of 3 to 1 fluorene is reacted in the presence of a knot compound; &lt;23&gt; The process for producing a cyclopropanecarboxylic acid compound of &lt;22&gt; wherein the ruthenium compound is zirconium tetrachloride, ferrocene A method for producing a cyclopropane decanoic acid compound, such as 22> or <23>, wherein the solvent is selected from the group consisting of a pharmaceutically active agent, a sulphuric solvent, a sulfur-containing aliphatic solvent, and a nitrile. At least one of a group consisting of a solvent, a cyclic urea solvent, and an alcohol (iv) money solvent. 139089.doc (V) (V) 201033162 [Embodiment] The present invention is based on equation (v)

The compound represented (hereinafter abbreviated as compound (V)) is a compound of the formula, wherein R represents a carbon number which can be substituted with a carbon number of 2 to 7 which can be substituted by a halogen atom, and can be substituted. Alkyloxy group of ～7, alkoxy group of 1 to 3 carbon atoms which may be substituted, and a chain hydrocarbon group of 1 to 10 substituted by at least i groups of a group which may be substituted with a stupid group, carbon number a cyclic hydrocarbon group of 3 to 10 or a chlorine atom, and R1 represents a hydrocarbon group or a stupid group having a carbon number of 丨~... which may be substituted by a halogen atom. &quot; Examples of the smoky group having a carbon number of 1 to 10 include fluorenyl group, acetaminophen, propyl butyl butyl group, tert-butyl group, 2-propylene group, propargyl group and the like. Examples of the dentate atom include a fluorine atom, a bromine atom, and a gas atom. Examples of the fluorenyl group having 2 to 7 carbon atoms which may be substituted include an unsubstituted fluorenyl group having 2 to 7 carbon atoms such as an ethyl fluorenyl group, a propyl fluorenyl group and a benzoinyl group. A thiol group having a carbon number of 2 to 7 substituted by a halogen atom. Examples of the alkoxy group having a carbon number of -7 to 7 which may be substituted include a carbon number of 1 to 7 such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group. An alkoxy group having an unsubstituted alkoxy group, a benzyloxy group or the like which has been substituted with a carbon number. Examples of the alkylthio group of the carbon number which may be substituted include a methylthio group, an unsubstituted sulfothio group having 1 to 3 carbon atoms such as an ethylthio group, I39089.doc 201033162, and an ethylthio group. Examples of the phenyl group which may be substituted include a phenyl group; a 4-bromobenzyl group, a 'methoxyphenyl group, a 2,3-difluorophenyl group, a 2,3,5-trifluorophenyl group, and 2, 3,5,6-tetraqi- 4-methoxymethylphenyl, 2-nitrophenyl, nitrophenyl, fluoren-2-yl, etc. selected from dentate atoms, carbon number 7 At least one of the group consisting of an alkoxy group, an alkoxyalkyl group having 2 to 7 carbon atoms, a nitro group and a fluorenyl group having 2 to 1 carbon atoms is substituted with a phenyl group or the like. φ is an alkoxy group having a carbon number of from 1 to 7 which may be substituted by a halogen atom which may be substituted with a carbon atom of 2 to 7, and an alkylthio group which may be substituted with a carbon number of 丨3 to 3 The chain hydrocarbon group having a carbon number of 1 to ί, which is substituted with at least an anthracene group in the group consisting of substituted phenyl groups, may be exemplified by 2-chloroethyl, 2,2,2-trieethyl, benzamidine Methyl, p-bromobenzhydrylmethyl, methoxymethyl, methoxymethoxymethyl, ethoxymethyl, thio-thiocarbamidine, 2-methylidylethylbenzyl, phenylethyl , 4-bromobenzyl, 4_foxybenzyl, 2,3-difluorobenzyl, 2,3,5-trisole, 2,3,5,6-tetrafluoro-4-yloxy Methylbenzyl, 2-nitro-benzyl, 4-nitrobenzyl, bis(o-nitrophenyl)methyl, (indol-2-yl)indenyl, and the like. Examples of the cyclic hydrocarbon group having a slave number of 3 to 10 include a cyclopropyl group, a cyclopentyl ring, a hexyl group and the like. Among the groups represented by κ, a chain hydrocarbon group having 1 to 10 carbon atoms or a carbon number 丨 丨 which is substituted by a phenyl group which may be substituted is preferred. More preferably, the chain hydrocarbon group is a methyl group or a 2,3,5,6-tetraqi_4_methoxyindenyl group. Examples of the bond smoky group having a carbon number of 1 to 10 which may be substituted by a halogen atom represented by R1 in the above formula (V) include methyl group, ethyl group, propyl group, allyl group, and 139089.doc 201033162 alkyne. a chain hydrocarbon group having a carbon number of 1 to 10 such as a propyl group; a chain hydrocarbon group having a carbon number substituted by a halogen atom such as a 2-ethyl group, a 2,2,2-trisethane group, or the like. Among them, a chain hydrocarbon group having 1 to 10 carbon atoms is preferred, and a mercapto group is more preferred. Examples of the compound (V) include 3-(1-ethoxycarbonyl cyanyl 2 propenyl)-2,2-didecylcyclopropanecarboxylic acid decyl ester and 3-(1-ethyloxy-cyanide). Its 2-propenyl)-2,2-dimethylcyclopropane decanoic acid ethyl ester, 3_(1_acetoxycyano-2-propenyl)-2,2-dimethylcyclopropane decanoic acid Ester, 3 〇m % keto-2-cyano-2-propenyl) 2,2-dimethylcyclopropanecarboxylic acid 2-propenyl, 3-(1-acetoxy-2-cyano-2-propene Methyl-2,2-dimethylcyclopropanecarboxylic acid methoxymethyl ester, 3-(1-ethoxycarbonyl-2-cyano-2-propenyl)-2,2-dimethylcyclopropanecarboxylic acid Benzoylmethyl ester, benzyl 3-(1-acetoxy-2-cyano-2-propenyl)_2,2-dimethylcyclopropanecarboxylate, 3-(1-ethyloxyl-2_ Cyano-2-propenyl)-2,2-dimercaptocyclopropanecarboxylic acid 2,3,5,6-tetrafluoro-4-decyloxymethyl, S, 3-(1-ethyloxy) -2 -Cyano-2-propanyl)-2,2-dimethylcyclopropane p-nitrobenzyl phthalate, 3-(ethylidene-2-cyano-2-propenyl) _2,2-Dimercaptocyclopropanecarboxylic acid bis(o-nitrophenyl) decyl ester, 3-(1-acetoethoxycarbonyl-2-cyano-2-propenyl)-2,2-dimethyl Base ring propyl acetate formic acid 3-(1-trisethoxyethyl-2-oxo-2-propenyl)-2,2-dimercaptocyclopropanecarboxylate, 3-(1-butoxy-2-cyanide Methyl 2-propenyl)-2,2-dimethylcyclopropanecarboxylate, 3-(1-propenyloxy-2-cyano-2-propanyl)-2,2-dimethyl Methyl formate, methyl 3-(1-trimethylacetoxy-2-cyano-2-propenyl)_2,2-dimethylcyclopropanecarboxylate, 3-(1-phenylene) Methyl methoxy-2-cyano-2-propenyl)-2,2-dimercaptocyclopropanecarboxylate, 3-(1-propenyloxy-2-cyano-2-propenyl)-2 ,2-Dimethylcyclopropane decanoic acid 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl ester, 3- 139089.doc • 14- 201033162 (1-trimethylethenyloxy) 2-cyano-2-propenyl) 2,2-dimercaptocyclopropanecarboxylic acid 2,3,5,6-tetrafluoro-4-decyloxymethylbenzyl ester, 3_g_benzylideneoxy group 2Cyano-2-propenyl)-2,2-dimethylcyclopropanecarboxylic acid 2,3,5,6-tetrafluoro-4-ylmethoxybenzyl ester and the like. By reacting the compound (V) with an alkali metal borohydride in the presence of a solvent, the formula (VI) can be produced.

(wherein, R represents the same meaning as described above) is a propylene cyanate compound (hereinafter abbreviated as compound (VI)). The alkali metal borohydride may, for example, be lithium borohydride, sodium borohydride, potassium borohydride, tris(t-butyl) potassium borohydride or sodium cyanoborohydride, and more preferably sodium borohydride. The amount of the alkali metal borohydride used is not limited to the amount of the hydrogen atom bonded to the boron atom in the alkali metal borohydride relative to the compound (乂" molar, and is not limited. Relative to the compound (v W mole, 1 to 20 moles based on the hydrogen atom bonded to the hydrogen atom in the metal borohydride). Hydrogenation using 4 hydrogen atoms bonded to the boron atom When sodium is used as the metal borohydride, it is practically 0.3 to 5 moles relative to the compound (v) 1 mole. The hydrogen atom bonded to the boron atom is one. When the (t-butyl) potassium is used as a barrier of the boron hydride compound, it is used in an amount of 1 to 20 mol per gram of the compound (V). 139089.doc -15- 201033162 compound (v) The reaction of the metal borohydride (hereinafter abbreviated as a reduction reaction) is carried out in the presence of a solvent. Examples of the solvent include an ether solvent, a guanamine solvent, a heteroaromatic solvent, a sulfur-containing aliphatic solvent, and a nitrile solvent. Cyclic urea solvent, alcohol solvent, ester solvent, aromatic hydrocarbon The solvent may be used singly or in combination of two or more. In addition to the solvent, the reduction reaction may also be a solvent of jW·AA l human lJ Hf, which may be τ 7 witch T, Field ::: 虱 furan, 1,4_dioxane, 2,3_dihydrofuran, etc.; as a brewing amine solution: Ν, Ν-dimercaptomethylamine, hydrazine, Ν_dimethyl乙乙醯=比分烧_, etc.; as a heteroaromatic solvent, dimethyl hydrazine, sulfolane propionitrile, 3-hydroxypropionitrile, and gas 1,3- dimethyl _2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ And etc., as an ester solvent, ester, etc. are mentioned. Methanol, ethanol, 2-propanol, polyethylene glycol, methyl acetate, ethyl acetate, and butyl acetate: 乍 is an aromatic-smoke solvent, and it is mentioned. The compound (VI), the ^ a ^ yield, and the Z body/E body ratio are selected from the group consisting of the ether solvent to the stomach ratio, the group solvent, the nitrile solvent heteroaromatic solvent, and the The composition of at least one solvent·alcohol>alcohol and ester solvent in the lipid group is more preferably selected from the group consisting of a guanamine solvent, a sulfur-containing month 1 139089.doc 201033162 an aliphatic/treasure agent, a nitrile solvent, a cyclic urea solvent. And at least one solvent selected from the group consisting of an alcohol solvent and a vinegar solvent; particularly preferably at least one solvent selected from the group consisting of a guanamine solvent, a sulfur-containing aliphatic solvent, and a cyclic urea solvent. Is N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, N-methyl-2-pyrrolidone, acetonitrile and hydrazine, 3_dimercapto-2 - Imidazolinone, more preferably N-methyl-2-pyrrolidone and -dimethyl -2-pyrimidine. _ In the present specification, a compound in which a cyano group and a cyclopropane ring are on the same side in a carbon-carbon double bond moiety bonded to a cyclopropane ring of a compound (VI) is referred to as a "Z body", and The compound in which the cyano group and the cyclopropane ring are on the opposite side of the carbon double bond moiety is referred to as r E body. The solvent is usually used in an amount of from 5 to 10 parts by weight based on 1 part by weight of the compound (V). The reduction reaction is carried out by mixing a solvent, a compound (v) and an alkali metal boron chloride. There is no limitation on the order in which they are mixed, but in terms of the aspect of the preparation and the reaction control, it is preferred to add the compound (V) to the mixture of the alkali metal borohydride and the solvent. The reaction temperature of the reduction reaction is usually _5 〇 ~ just. c, it is better to pay attention. The reaction time of the reduction reaction is usually from 5 minutes to 72 hours. ' _ reverse, can be borrowed money (four) analysis method 'W assisted chromatography method and other common methods to confirm. After the completion of the reduction reaction, a mixture containing the compound (VI) is obtained, and the mixture is subjected to neutralization, extraction, water washing, and the like, and then subjected to usual post-treatment, followed by usual isolation treatment such as hydrazine or crystallization, whereby the compound (VI) can be taken out. 139089.doc 17 201033162 The obtained compound (5) can also be purified by recrystallization, extraction and purification, steaming, activated carbon, oxygen cutting, oxidation treatment, and (iv) tube method. m As the compound (VI) thus obtained, n-cyano-bu(tetra)yl-2,2-dimethylcyclopropanecarboxylic acid, arsenic-based propylene) 2,2-dimethylcyclopropane Hyunmic acid methyl vinegar, 3-(2-cyanopropionyl) 2,2 dimethylcyclopropanecarboxylate formic acid, 3_(2·cyanopropenyl)·2,2-dimethyl(10)propane carboxylic acid Vinegar, 3-(2-cyanopropenyl)_2,2. dimethylcyclopropanecarboxylic acid 2_propylene vinegar, 3-(2-cyano-1-propionyl)·2,2•dimethyl Base ring propyl &quot; acid methoxymethyl hydrazine, 3-(2 cyano-i-propyl) 2,2-dimethyl propyl propyl benzoate methyl ester, 3-(2-cyanide 1,-1-propenyl)_2,2-dimethylcyclopropane decanoate, %(2-cyano-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid 2,3,5, 6_tetrafluoro_4_methoxymethyl vinegar, 3-(2-cyano)-propanyl)_2,2-dimethylcyclopropanecarboxylic acid p-nitrobenzyl SI, 3-(2-cyanide Base + propenyl) 2,2-dimercaptocyclopropanecarboxylic acid bis(o-nitrophenyl)methyl ester and the like. Compound (V), which can be made by formula (II)

(II) (wherein, R represents the same meaning as above), the compound (hereinafter abbreviated as compound (H)) and the formula (II)t) S (III) X human R1 (wherein R1 represents The same meaning as above, X represents a halogen atom) fluorenyl halide (hereinafter abbreviated as fluorenyl halide (ΙΠ)) represented by B9089.doc -18- 201033162 or by formula (IV)

R1A〇ARl (IV) (wherein 'R1 represents the same meaning as above) is produced by reacting an acid anhydride (hereinafter abbreviated as an acid anhydride (IV)) in the presence of a base. Further, a mercapto halide (ΠΙ) and an acid anhydride (IV) are sometimes combined as a "deuteration agent". Further, the reaction of the compound with a deuteration agent is hereinafter referred to as "deuteration reaction". As the compound (II), 3-(2-cyanohydroxy-2-propenyl)-2,2-dimercaptocyclopropanecarboxylic acid, 3-(2-cyano-1-hydroxy-2-propene) Ethyl phthalate, 2-(2-cyanohydroxy-2-propenyl) 2,2-diindenylcyclopropane decanoate, 3-(2-cyano- Hydroxy-2-propenyl)_2,2-dimethylcyclopropane decanoate, 3-(2-cyano-1-hydroxy-2-propenyl)-2,2-dimercaptocyclopropanoic acid 2- Propylene ester, 3-(2-cyano-1-hydroxy-2-propenyl)· 2,2·dimercaptocyclopropane decanoate decyloxy ester, 3-(2-cyano-1-hydroxy-2) -B-propyl)-2,2-dimercaptocyclopropane phthalate, 3_(2-cyano-indolyl-2-propenyl)-2,2-dimercaptocyclopropane Benzyl methacrylate, 3-(2-cyano-1-hydroxy-2-propenyl) 2,2-dimercaptocyclopropanoic acid 2,3,5,6-tetrafluoro-4-decyloxymethyl Benzyl ester, 3-(2-cyano-1-hydroxy-2-propenyl)-2,2-dimercaptocyclopropanecarboxylic acid p-nitrobenzyl ester, 3-(2-cyano-1-hydroxy-2 -propenyl)-2,2-dimethylwang propanecarboxylic acid bis(o-nitrophenyl)decyl ester. The halogen atom represented by X in the formula (III) may, for example, be a chlorine atom, a bromine atom or an iodine atom. 139089.doc •19· 201033162 As the sulfhydryl halide (III), there are mentioned: ethyl chloroform, acetamidine bromine, chloroethane oxime, triethylene ethane oxime, propylene bromide, propylene chloride, n-butyl fluorene Butanoyl chloride, trimethyl ethane oxime, benzamidine gas, stupid guanidine bromine, etc. Examples of the acid oxime (IV) include acetic anhydride, propionic acid needle, butyric acid, isobutyric anhydride, hexanoic anhydride, valeric anhydride, chloroacetic anhydride, trifluoroacetic anhydride, and benzoic anhydride. These oximes may be those which are commercially available, and may be produced by a known method such as a method of derivatizing a corresponding carboxylic acid or a method of dehydrating a corresponding carboxylic acid. The deuteration agent is usually used in an amount of from 1 to 5 mols per mol of the compound (11). As a test, it is possible to extract the diethylamine, pyridine, N,N-diethylaniline and 4-methylamino. ratio. Hydrazine, diisopropylethylamine, tetradecylethylenediamine, etc., including gasification mouth, sodium methoxide and other metal oxides; sodium acetate and other tickrate; ^ sodium oxide potassium hydroxide and other alkali Metal hydroxide; alkali metal slave I salt such as potassium carbonate. Preferred are basic nitrogen-containing compounds, more preferably triethylamine, biting, N,N-diethylaniline or dimethylamino. ratio. Di-diisopropylethylamine. These tests may be used singly or in combination of two or more. The amount of the base to be used is not limited to 'the amount of the catalyst, and may be an excess amount relative to the compound (II).眚 I used 'mole' relative to compound (II), and the amount of base used was 0.01 to 3 moles. The brewing reaction can also be carried out in the presence of a hexahydrate &gt; + 丄 A w agent. Examples of the solvent include a stupid, a stupid, a dimethyl bromide &amp; beta &amp; Τ 导 导 aromatic hydrocarbon solvent; a fat hydrazine hydrocarbon solvent such as hexane or heptane; diethyl ether, a first butyl group, a ring戊基甲谜,四氢0夫139089.doc •20- 201033162 Ether, 1,4·2, etc. Ether solvent; dioxo, ^dichloroethane, chlorobenzene and other halogenated hydrocarbon solvents; methyl isobutyl Ketone solvent such as ketone; Jingjing solvent such as nitromethane or nitrobenzene; nitrile solvent such as acetonitrile, propionitrile or benzonitrile; guanamine solvent such as dimethylformamide or dimethylacetamide. These solvents may be used singly or in combination of two or more. The solvent is usually used in an amount of 〇 2 to 2 parts by weight based on the weight of the compound (1). Deuteration reaction by compounding in the presence of a solvent as needed

(II) It is carried out by mixing with a deuterating agent and a base. There is no limitation on the order in which they are mixed. The reaction temperature of the deuteration reaction is usually _2 〇 to 1 〇 {^c, preferably -5 to 100 °C. The reaction time of the deuteration reaction is usually from 5 minutes to 72 hours. The progress of the deuteration reaction can be confirmed by a usual method such as gas chromatography or high performance liquid chromatography. After the completion of the deuteration reaction, a reaction mixture containing the compound (v) is obtained, and the obtained reaction mixture is subjected to neutralization, extraction, water washing, etc., usually after treatment, and then subjected to usual isolation treatment such as distillation or crystallization, whereby the CT product can be taken out. (V). The compound (V) taken out may be further purified by recrystallization, extraction, distillation, adsorption treatment of activated carbon 'cerium oxide, aluminum oxide, etc., and chromatography such as ruthenium column chromatography. . The removed compound (v) can be used for the reduction reaction, and the purified compound (V) can also be used for the reduction reaction. Further, the obtained reaction mixture containing the substance (V) may be directly used in the above reduction reaction, or the reaction mixture may be subjected to neutralization, extraction, water washing or the like, usually after the treatment, and then used for the reduction reaction. 139089.doc •21 - 201033162 Compound (II), by formula (I)

The compound represented by the formula (wherein 'R represents the same meaning as defined above) is produced by reacting a compound (hereinafter abbreviated as the compound (1)) with acrylonitrile in the presence of a base. Hereinafter, the reaction of the compound (1) with acrylonitrile is referred to as "coupling reaction". As the compound (I) ', 3-methylmercapto-2,2-dimethylcyclopropanecarboxylic acid, methyl 3-carbamimido-2,2-dimethylcyclopropanecarboxylate, and 3, formazan are mentioned. Base 2,2_dimethylcyclopropane decanoate, 3_mercapto-2,2-dimethylcyclopropane decanoate, 3-mercapto-2,2-dimercaptopropane 2,propenyl phthalate, methoxymethyl 3-methylglycolyl-2,2-dimethylcyclopropanecarboxylate, benzamidine methyl 3-methylcarbazide-2,2-dimethylcyclopropanecarboxylate , 3_methylmercapto-2,2-dimethylcyclopropanecarboxylate, 3-methylindenyl 2,2-dimethylcyclopropanecarboxylic acid 2,3,5,6-tetrafluoro_4_methoxy Methylbenzyl g曰, 3-methylmercapto-2,2-dimethylcyclopropane decanoic acid p-nitrodecyl ester, 3-methylindenyl, 2,2-dimethylcyclopropanecarboxylic acid bis (neighbor) Nitrophenyl) methyl vinegar and the like. The compound (I) can be produced by a known method described in JP-A-2002-89427, and JP-A-2006-89427. Acrylonitrile is usually used commercially. The amount of acrylonitrile used is usually 〇8 to 5 mol, preferably 1 to 3 mol, based on 1 mol of the compound (1). Triethyl as a base used in the coupling reaction, 舆- 139089.doc 201033162 Amine, pyridine, 4-dimethylaminopyridine, phenanthiadicycloundecene, * Diazabicyclo[2.2.2] Xinxuan, quinuclidine, 3•pyridinium, ndndolizine), tetramethylguanidine, imidazole, guanidine methylimidazole, etc. [2.2.2 ] octyl basic nitrogen compounds. Among them, trimethylamine and triethylamine are preferred! 8_ Diazabicyclo[5.4.0M-de-olefin, M_diazepine]. These tests are usually performed using a commercial person. There is no limit to the amount of alkali to be used, which may be the amount of catalyst or relative to

The compound (I) is in an excess amount, but practically, relative to the compound (1) 1 molar base, the base is used in an amount of from 0 to 1 to 3 moles. The coupling reaction is usually carried out in the presence of a solvent. Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; and aliphatic hydrocarbon solvents such as hexane and heptane; diethyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, and hydrogen furan. An ether solvent such as 4-dioxane; a hydrocarbon solvent such as dichloromethane, hydrazine, 2_dioxaethane or chlorobenzene; a solvent such as acetone, methyl isobutyl ketone or cyclohexanone; Ester solvent such as ethyl acetate or butyl acetate; nitro solvent such as nitromethane or nitrobenzene; nitrile solvent such as acetonitrile, propionitrile or benzonitrile; dimethylformamide, dimercaptoacetamide, etc. Amine solvent; alcohol solvent such as methanol, ethanol, 1-propanol or 2-propanol; water, etc. These solvents may be used singly or in combination of two or more. The solvent is usually used in an amount of from 〇 to 3 parts by weight based on 1 part by weight of the compound (I). The coupling reaction is carried out by mixing the compound (I) with acrylonitrile and a base in the presence of a solvent as needed, and the mixing order for these is not 139089.doc. 23-201033162 The reaction temperature of the coupling reaction is usually _20~1〇(rc, preferably -5~l〇〇°C. The reaction time of the coupling reaction is usually from 5 minutes to 72 hours. The coupling reaction can be carried out by gas chromatography, high-efficiency liquid It is confirmed by a usual method such as phase chromatography. After the completion of the reaction, a reaction mixture containing the compound (11) is obtained, and the obtained reaction mixture is subjected to neutralization, extraction, water washing, etc., usually after treatment, and then subjected to usual isolation treatment such as distillation or crystallization. Therefore, the compound (II) can be taken out. For the compound (11) taken out, the adsorption treatment of the 'steamed' activated carbon, the sulphur dioxide, the oxidized knot, etc. can be extracted and purified by recrystallization, and the stone stalk tube column can be extracted. Further purification is carried out by a usual purification method such as chromatography or the like, and the extracted compound („) can be used for the deuteration reaction, or the purified compound (II) can be used for the deuteration reaction. The reaction mixture containing the obtained compound (9) is directly used in the above-mentioned brewing reaction, and the reaction mixture may be neutralized, extracted, washed with water (iv) and then used for the brewing reaction. The following formula (Va) H3C ch3 ( Va)

(wherein R· represents an alkoxy group which may be selected from a functional group atom, a fluorenyl group having 2 to 7 carbon atoms, a substituted number 1 to 7 of a slave, a carbon number of 3 to 7 which may be substituted, and a chain hydrocarbon group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms substituted with at least an anthracene group in a group consisting of a substituted phenyl group, which means the same as the above 139089.doc -24- 201033162 The compound represented by the compound (v) is subjected to the above reduction reaction, whereby the formula (Via) is obtained.

(Via) (wherein R' represents the same meaning as above)

The cyclopropanecarboxylic acid compound (hereinafter abbreviated as compound (Via)) is represented, and the obtained compound (Via) is represented by the formula (νπΐ) R2-OH (VIII) (wherein R2 is a group different from RI, Selecting a halogen atom, a fluorenyl group having 2 to 7 carbon atoms, an alkoxy group of a carbon number which may be substituted, an alkylthio group which may be substituted with 1 to 3 carbon atoms, and a phenyl group which may be substituted a compound represented by at least t groups substituted with at least t groups of carbon atoms of 1 to 10 or a cyclic hydrocarbon group having 3 to 1 carbon atoms (hereinafter abbreviated as compound (vm)) in the presence of an alkali metal hydroxide The reaction occurs, which can be manufactured by the formula (Ιχ)

(wherein R2 represents the same meaning as described above) (cyclo) The cyclopropanecarboxylic acid compound (hereinafter abbreviated as a compound). The R in the compound (Via) is the same as the above-mentioned ruler. The metal hydroxide may, for example, be a hydrogen peroxide, sodium hydroxide, potassium hydroxide, hydrogen (IV), barium hydroxide or hydroxide; preferably 139089.doc -25· 201033162 More preferably hydroxide Lithium. However, lithium hydroxide lithium hydroxide, sodium hydroxide and potassium hydroxide can also be used. The alkali metal hydroxide is usually a hydrate such as an anhydrous metal monohydrate. VIa) 1 mole, which is _~ mole relative to mole %. Ear/〇, preferably 0.W0 as R2 in compound (VIII), different from R'. The same, R2 is Examples of the compound (viii) include: 2-air ethanol, 2,2,2-trisethanol, benzamidine methanol, parabenzamide methanol, methoxymethyl fermentation, and:::methoxy group Methanol, oxy-methanol, methylthiocarbazide, 2-methylthioethanol: benzyl alcohol, phenylethyl alcohol, 4-indiyl benzyl alcohol, 4 Methoxybenzyl alcohol, 23-difluorobenzyl alcohol, 2,3,5-trifluorobenzophenone, 2,3,5,6.tetrafluoro-4-indolyloxybenzyl alcohol, 2-nitro Benzyl alcohol, 4-nitro benzyl alcohol, bis(o-nitrophenyl sterol, (indol-2-yl) decyl alcohol, etc. The amount of the compound (VIII) used is not limited, usually relative to the compound (Vla l mol is 0.5 to 3 moles, and can be used in a large amount as needed, and can also be used as a solvent. The reaction of the compound (Via) with the compound (vm) is usually carried out under an inert gas atmosphere such as argon or nitrogen. The reaction can be carried out under normal pressure, under pressure or under reduced pressure. It is preferably carried out under normal pressure or reduced pressure. The reaction is an equilibrium reaction, preferably one side. The reaction is carried out by removing the by-produced alcohol derived from the compound (Via) to the outside of the reaction system by a method such as steaming. 139089.doc -26· 201033162 The reaction can be carried out in the absence of τ or in a solvent. Out: Dichlorohydrazine, 翕/, 1,2 - Windy Hyun and other halogenated hydrocarbons dissolve the sword; hex, &quot;&quot; '- Xinxing simmering and other aliphatic hydrocarbons Agent; aromatic hydrocarbon solvent such as benzene, γ benzene, xylene, chlorobenzene, etc., acetamidine, methyl butyl hydride, cyclopentyl guanidine tetrahydronethane, l4-di sigma, etc. X may also be carried out by using a solvent which can form a mixture with a by-produced alcohol derived from a compound (νι) to exclude the by-produced alcohol as a mixture of the mixture to the outside of the reaction system.

The reaction temperature is not limited, and is preferably 20 to 2 Torr (TC. After the completion of the reaction, for example, the obtained reaction mixture is varnished with an acidic aqueous solution such as water or a sulfuric acid aqueous solution, and the key is removed, the slag is taken, and the koji/month is washed, and then The compound (IX) can be taken out by concentration, and the extracted compound (ΙΧ) can be further purified by a purification method such as distillation, recrystallization, column chromatography or the like. By subjecting the obtained compound (VIa) to hydrolysis, it can be produced by the formula (VII) ^

The hydrolysis reaction of the compound (VIa) can be carried out in the presence of an acid, and can be carried out in the presence of an acid. An alkali metal hydroxide such as sodium oxide or potassium oxyhydroxide, etc., is usually used in an amount of from 0.5 to 20 mol, preferably from 1 to 10 mol, based on the compound (νι &amp;). The inorganic acid such as sulfuric acid or hydrochloric acid is used. The phase is relative to the compound 〇/1&amp;)1 139089.doc • 27- 201033162 ear, the acid is usually used in an amount of 0.5 to 20 moles, preferably 1 〇1〇 ear. In the hydrolysis reaction of the compound (Via), water of 1 mol or more is usually used with respect to the compound (νι &amp;). Water can also be used as a solvent. Further, a solvent other than water may be used, and examples of the solvent include alcohol solvents such as methanol, ethanol, isopropanol, butanol, second butanol, and third butanol; tetrahydrofuran, 1,4-two An ether solvent such as decane; a ketone solvent such as acetone; a nitro solvent such as nitromethane: a nitrile solvent such as acetonitrile; and a second-strength amine solvent. 1 part by weight of the solvent (Vla) of the solvent is practically 0.5 to 20 parts by weight. The methylmethamine and dimethylacetamide are not limited to 1, and the reaction temperature of the hydrolysis reaction is usually ot 10 (rc), preferably 0.001 to 50 parts by weight. 20 ° C ~ 8 (TC. There is no limitation on the reaction time, the time point at which the compound disappears or the time at which the decrease of the compound (VIa) is stopped is taken as the reaction end point. After the reaction is finished, the reaction mixture is neutralized. The carboxylic acid (νπ) can be taken out by extraction, extraction, washing, concentration, etc., and the carboxylic acid (νπ) can be taken out. The extracted acid (VH) can be further purified by a usual purification method such as recrystallization or tube chromatography. The compound (Ιχ) can also be produced by reacting the obtained carboxylic acid (νπ) with the compound (VIII) in the presence of a hammer compound. As the zirconium compound, a Lewis acid compound which exhibits Lewis acidity is usually used. It is better to use formula (X)

Zr(〇)m(XI)„(Y1)4-2.m-„ (X) (wherein, X1 and Y1 independently represent a dentate atom, an alkoxy group, a decyloxy group, an acetoacetone group, and two Alkylamino, cyclopentadienyl or pentamethylcyclopentane 139089.doc -28- 201033162 Dienyl, m represents 0 or 1, and η represents the wrong compound represented by 0, 1 or 2). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and examples of the alkoxy group include a decyloxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. An alkylene group having 1 to 4 carbon atoms such as isobutoxy group or tert-butoxy group. Examples of the decyloxy group include a fluorenyloxy group having 2 to 6 carbon atoms such as an ethoxylated group; and the dialkylamino group includes a dimethylamino group, a diethylamino group, and a mercaptoethylamine. An amine group substituted by two alkyl groups having 1 to 6 carbon atoms. Examples of the ruthenium compound represented by the formula (X) include a tetrahalogenated hammer such as ruthenium tetrafluoride, zirconium tetrachloride, ruthenium tetrabromide or a tetraiodide hammer; a carboxylic acid knot such as zirconium acetate; and acetic acid pyruvic acid. Miscellaneous; zirconium ethoxide, zirconium isopropoxide, zirconium butoxide, zirconium alkoxide such as zirconium titanate; halogen oxidation of gas oxidized knots; tetrakis Amine, tetrakis(diethylamine), and the like; zirconocene dichloride, zirconocene dimethoxide, bis(pentamethylcyclopentadienyl) A dioxin compound such as decamethylzirconocene dichloride; preferably a zirconium tetrachloride, a hafnocene compound, and an alkoxy zirconium. The wrong compound is usually used by a commercial person. Further, an anhydrate may be used, and a hydrate may also be used. Further, a complex formed by a compound having a coordinating property such as tetrahydrofuran or tetradecylethylenediamine may also be used. The amount of the zirconium compound used is not limited, and is practically 0.001 to 200 mol%, preferably 0.1 to 10 mol%, based on the carboxylic acid (VII) 1 mol. The amount of the compound (VIII) to be used is not limited, and is usually 0.5 to 3 moles per mole of the carboxylic acid (VII). It may be used in a large amount as needed to make 139089.doc -29-201033162, or Used as a solvent. The reaction of the carboxylic acid (VII) with the compound (VIII) is usually carried out under an inert gas atmosphere such as argon or nitrogen. The reaction can be carried out under normal conditions, under pressure, or under reduced pressure. It is preferably at normal pressure or reduced pressure; Further, it is preferred that the reaction is carried out while removing water as a by-product from the outside of the reaction system by distillation or the like.

The reaction can be carried out without a solvent or in a solvent. Examples of the solvent include a hydrocarbon solvent such as dioxane, gas, and 1,2-dichloroethane, and an aliphatic hydrocarbon solvent such as hexane, heptane, octane or decane; An aromatic hydrocarbon solvent such as benzene, xylene or benzene; an ether solvent such as diethyl ether, methyl tert-butyl ether, cyclopentyl oxime ether, tetrahydrofuran, or the like. &amp;, the reaction can be carried out while using a solvent which forms a mixture with water and excluding water as an azeotrope outside the reaction system. The reaction temperature is not limited, but is usually 20 to 2 Torr. (: After the reaction is completed, for example, the resulting reaction mixture is dissolved in water or sulfuric acid

The acidic aqueous solution is washed, and then concentrated, whereby the servant (IX) can be taken out. The extracted compound (ΙΧ) can also be further purified by a usual purification method such as distillation, recrystallization or column chromatography. Use the following formula (Vb)

(Vb) (wherein R1 represents the same meaning as described above) 139089.doc -30- 201033162 The compound represented as the compound (v), the above reduction reaction is carried out, whereby the formula (VIb) is obtained.

The cyclopropane decanoic acid compound represented by the cyclopropanecarboxylic acid compound represented by the formula (VIb) and the formula (Villa) R3-〇H (Villa)

(wherein R3 represents an alkoxy group which may be selected from a halogen atom, a carbon number of 2 to 7, a carbon number of 1 to 7 which may be substituted, a carbon number which may be substituted, and an alkylthio group which may be substituted a compound having at least an anthracene group substituted with a substituted phenyl group and having a carbon number of 1 to 10 or a cyclic hydrocarbon group having a carbon number of 3 to 10) is reacted in the presence of a zirconium compound, This can also be made by the formula (IXa)

(IXa) (wherein R3 represents the same meaning as described above) The cyclopropanecarboxylic acid compound represented by the above. The reaction of the cyanoic acid compound represented by the formula (4)) with the compound represented by the formula (V?Ia) can be carried out in the same manner as the reaction of the above retardation (VIII). ^ ° ^ Example ' The present invention is not limited to the following, and the embodiment of the invention is described in more detail. (IV) The present invention 139089.doc • 31 - 201033162 is limited to the embodiments. Example 1 (10), 3R)-3-cartosyl.2,2_2 Methylcyclopropanecarboxylic acid 2,3,5,6-tetra- 4 4-methoxymethyl group S is intended to be 26.44 g mixed with acrylonitrile 8 () 6 g, 3 () weight % aqueous solution of trimethylamine 7.48 3 After the mixture was mixed at room temperature, 9 mL of methanol was added, and the mixture was stirred at room temperature for 3 hours. After adding diluted hydrochloric acid to the obtained reaction mixture, it was subjected to acetic acid. The organic layer (4) and the aqueous solution of the money and the saturated water are washed, and dried with anhydrous sodium sulfate. After removing the sodium sulfate by shouting, the residue is concentrated under reduced pressure to obtain the formula (1). The compound represented by the compound (hereinafter abbreviated as the compound (1)) is a light yellow oil of 30.5 g as a main component. (1) Pure method 11.0 g of the obtained oil was obtained as a ruthenium tube column compound (1) 10.1 g.] H-NMR (CDC13, TMS) δ (ppm): δ ι 'Ζ/ (s, 3/2Η), 1.27 (s 3/2Η), 1.28 (s, 3/2Η), 1.32 (s, 3/2Η,, ' }, 1-60-1.72 (m, 2H) 2.06 (br. d, 1/2H), 2.16 (br. d, 1/2H,, ' J,3·40 (s,3/2H), 3.41 (s, 3/2H), 3.92 (br.,1H), 4.59 (q,2U, u), 5.25-26 (m, 2H) 6.00 (d, 1/2H), 6.05 (d, 1H), 6.10 (d, 1/2H). Example 2 The oil obtained in Example 1 was 19.55 g. 3.76 g of sibipyridine, 0.42 g of 4-(two 139089.doc -32-201033162 methylamino)pyridine, and 80 mL of toluene were mixed. The mixture was cooled in an ice bath, and acetic anhydride was added dropwise under a nitrogen atmosphere. After the dropwise addition of the toluene 2 I I was added, the resulting mixture was stirred under ice cooling for an hour. Water and dilute hydrochloric acid were added to the obtained reaction mixture, stirred, and then allowed to stand to separate into an organic layer and an aqueous layer. The obtained organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After removing sodium sulfate by filtration, the obtained residue was concentrated under reduced pressure to give There is a pale yellow oil having a compound represented by the following formula (7) (hereinafter abbreviated as compound (2)) as a main component

5.0 g of the obtained oil was purified by silica gel column chromatography to obtain Compound (2) 4.1 g. JH-NMR (CDC13, TMS) δ (ppm): 1.21 (Sj 3/2n)} j 26 (Sj • 3/2H), L28 (S, 3H), i.55 (d, 1/2H), 1.71 (d, 1/2H), uo (dd, 1/2H), 1.89 (dd, 1/2H), 2.12 (s, 3/2H), 2.13 (s, 3/2H), 3.40 (s, 3/ 2H), 3.41 (s, 3/2H), 4.58-4.60 (m, 2H), 5.〇〇' 1/2H), 5.11 (d, 1/2H), 5.22-5.29 (m, 2H), 5.96 (d5 1/2H), 6·00 (d, 1/2H), 6. 〇3 (d, 1/2H), 6.08 (d, 1/2H). Example 3 0.66 g of sodium hydride sodium hydride was mixed with 5 mL of hexidine and N mL of N,N-dimethylamine. The resulting mixture was cooled in an ice-bath, and a mixture of the pale yellow oil of &lt;RTI ID=0.0&gt;&gt; The obtained compound was stirred under ice cooling for 1.5 hours. The obtained reaction mixture was added to 8 to dilute hydrochloric acid and mixed, and then extracted with ethyl acetate. The resulting scary organic layer was washed with dilute hydrochloric acid, 3% by weight aqueous sodium hydrogencarbonate solution, and 20% by weight of water, and then dried with anhydrous sodium sulfate. The liquid was concentrated under reduced pressure to give a white crystals (yield: white crystals) containing a compound represented by the following formula (3) (hereinafter abbreviated as compound (3)) as a main component.

曰曰· S

The NMR spectrum of the crystal was measured, and the triad steroid ratio was about 8/1. h-NMR (CDCl3, TMS) δ (ppm): i 21 &amp; 3Η, 乙^), i 32 (s, 3H, Z+E), i.73 (m, 1H, Z+E) , i % (s, 3h, exosome), 2.20 (m, 1/9H, E body), 2.47 (m, 8/9H, z body), 3 4i (s, 3H, z+e body), 4.59 (s, 2H, Z+E body), 5.26 (s, 2H, Z+E body), 5 78 (m, 8/9H, Z body), 6.01 (m, 1/9H, E body). Example 4 31 〇g of (lR,3R)-3-carbamimido-2,2-dimethylcyclopropanecarboxylate and 15.8 g of acrylonitrile and 30% by weight of an aqueous solution of triammonium 195 8 were mixed. The resulting mixture was stirred overnight at room temperature. The resulting mixture was cooled in an ice bath, and then diluted with hydrochloric acid and mixed. After the resulting mixture was adjusted to room temperature, it was extracted with ethyl acetate. The resulting organic layer was dried over anhydrous sodium sulfate. After the sodium sulfate was removed by filtration, the obtained filtrate was concentrated under reduced pressure to give a pale yellow oil containing a compound represented by the following formula (4) (hereinafter abbreviated as compound 139089.doc • 34 - 201033162 (4)) as a main component. 40.8 g

CH3 CHS (4) ,00

T L 1.02 g of the obtained oil was purified by silica gel column chromatography to afford compound (4): 0.96 g. The yield was 94%. ^-NMR (CDC13, TMS) δ (ppm): 1.27 (s, 3/2H), i 28 (s, 3/2H), 1_28 (s, 3/2H), 1, 33 (s, 3/2H ),1.61] 7()'(m 2H)| 2.06 (d, 1/2H), 2.21 (d, 1/2H), 3.70 (s, 3/^^ 3/2H), 3.89-3.96 (m, 1H), 6.00 (d, 1/2H), 6.〇5 \^ 6.07 (d, 1/2H), 6.10 (d, 1/2H). Example 5 39 8 g of the pale yellow oil obtained in Example 4 was combined with pyridine g, 4-(dimethylamino) hydrazine 2 g, toluene. The obtained mixture was cooled in an ice bath, and acetic anhydride was added dropwise under a nitrogen atmosphere, and the mixture was added dropwise, and the resulting mixture was stirred under ice-cooling, and water and 6 N were added to the mixture. Hydrochloric acid and mix. After standing, the eight', organic layer and water layer. The obtained organic layer was washed with 2N of a solution of a mixture of 4 N male and 1 N air-gasified sodium chloride and saturated brine, and dried over anhydrous sodium sulfate. The sulfuric acid (4) is removed by filtration, and the obtained line is concentrated under reduced pressure to form a pale oil of the knife. 4 〇 2 g 〇 139089.doc • 35- 201033162

The obtained oil (1 g) was purified by silica gel column chromatography to give the compound (5): 0.87 g. H-NMR (CDC13, TMS) δ (ppm): 1.21 (s, 5/4H), 1.26 (s, 5/4H), 1.26 (s, 7/4H), 1.28 (s, 7/4H), 1.55 (d,5/12H), 1.71 (d,7/12H), 1.79 (dd,7/12H),1_87 (dd, 5/12H), 2.13 (s, 7/4H), 2.14 (s, 5/) 4H), 3.70 (s, 7/4H), 3.7〇 (s, 5/4H), 5.01 (d, 5/12H), 5.12 (d, 7/12H), 5.97 (d, 5/12H), 6.00 (d, 7/12H), 6.03 (d, 5/12H), 6.08 (d, 7/12H). Example 6 50.9 g of the compound (4) and 4-(diguanylamino) π pyridine i 6 §, toluene Μ g were combined. The obtained mixture was cooled in an ice bath, and acetic acid (iv) was added dropwise under a gas atmosphere. After the completion of the dropwise addition, the resulting mixture was allowed to stand under ice cooling for an hour. The obtained reaction mixture was sequentially dried with i weight% sulfuric acid water, 8 parts of hydrazine/hydrazine sodium hydroxide aqueous solution, water, and dried. #彳纟&amp;Into the order / successively, concentrated under reduced pressure, to obtain 66.9 g of the inflammatory oil-colored oil containing the compound (5) as the main component. By gas chromatography internal standard method The yield of the compound (5) was 88%, and the yield of the compound (5) was 88%. Example 7 Under a nitrogen atmosphere, the orientation A 榀μ, ! η Λ ^ φ h ^ , 。. (5) 1. 〇 § mixed with methanol 20 ml

The amount of 乂 & 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Further, a small amount of the U substance is added to a weight of 〇·15 g of sodium borohydride, 139089.doc -36 - 201033162, and the resulting mixture is stirred at room temperature for a small L, and the reaction mixture is added to the reaction mixture. After 1 N hydrochloric acid was added and mixed, 1 was subjected to extraction with ethyl acetate. The obtained organic layer was washed with fresh food, and dried with anhydrous sulfuric acid. After the magnesium sulfate was removed by hydrazine, the obtained filtrate was concentrated under reduced pressure to give a crude product of the compound (6)), which is represented by the following formula (6).

(6) The lH_NMR of the obtained crude product was measured, and the obtained body ratio was 8 ΐ/ΐ9. The crude product was purified by silica gel column chromatography to obtain (10) 〇·55 g and steroid 0.12 g°Z and the total yield of the steroid was 87% (ζ body ratio = 82/18) . Steroid: 咕-NMR (CDCl3, TMS) δ (ppm)·"2〇 (s, 3h), i 32 (s,

3H), 1.71 (d, 1H), 1.96 (d, 3H), 2.45 (dd, 1H), 3.70 (s, 3H), 5.80 (dd, 1H). E. H. NMR (CDC13, TMS) δ (ppm): 1.22 (s, 3H), 1.30 (s, 3H), 1.73 (d, 1H), 1.97 (d, 3H), 2.17 (dd, 1H) 3.70 (s, 3H), 6.02 (dd, 1H) ° Example 8 A mixed solution of sodium borohydride 37 mg and acetonitrile 4 mL was cooled to -5 ° C under a nitrogen atmosphere. To the resulting mixture, a mixed solution of the compound (5) 25 g and 1 mL of acetonitrile was added dropwise. The resulting mixture was stirred at _5 〇c for 3 hours. Water and 1 N hydrochloric acid were added to the obtained reaction mixture and mixed, and then extracted with 139089.doc 37-201033162 ethyl acetate. The obtained organic layer was washed with saturated brine and dried with anhydrous sulfuric acid. After removing the sulfuric acid by using hydrazine, the obtained filtrate and liquid are concentrated and concentrated to obtain a crude product of the compound (6). The 1H_NMR of the obtained crude product was measured, and the Z-body/E-body ratio was 87/13. The crude product was purified by Shih Hil column chromatography to obtain a mixture of z and e. The yield was 72%. Example 9 A crude product of the compound ruthenium (6) was obtained in the same manner as in Example 8 except that N,N-dimethylamine was used in the same manner as in Example 8. The lH_NMR was measured, and the obtained 2 body/body ratio was 92/8, and the obtained crude product was purified by a ruthenium column chromatography to obtain a mixture of z and E. The yield was 78%. Example 10 混合 A mixed solution of compound (7) 0.38 gm, 3· dimethyl group such as imipenemone 1.16 g was cooled to a generation under a nitrogen atmosphere. The mixture was added little by little to the obtained Kunming: 58 mg of side hydrogenation was added at the same temperature. To: Transfer the reaction mixture to human water and 6 _ acid and wash. The organic layer was concentrated under reduced pressure to give a crude product of compound (6). The crude product obtained by the gas phase two method area percentage was analyzed and the result was obtained.

= cut. The analysis was carried out by the internal standard method of gas chromatography, and as a result, the total yield of the body was 88 〇. . X, E Examples 11 to 20 Except that the solvent shown in Example 9 was used instead of 丄^2·imidazolidinone in Example 9, the reaction was carried out in the same manner as in the monomethyl-J^ method. 38- 201033162 The crude product of the compound (6) is obtained. The results are shown in Table 1. In the table, the yield is the total yield of the Z body and the E body. [Table 1] Example Solvent steroid/steroidal yield (%) 11 Ν, Ν-dimethyl decylamine 90/10 90 12 Dimercapto yttrium 89/11 80 13 Polyethylene glycol (PEG 200) 85/15 89 14 Cyclobutane 84/16 79 15 Propionitrile 83/17 64 16 Ethyl acetate 82/18 83 17 Isopropyl alcohol 82/18 83 18 0 ratio bite 81/19 70 19 Tetrahydrogen 11 Furan 79 /21 86 20 ° ratio 0 70/30 92 Example 21 A mixed solution of 1.91 g of sodium borohydride and 41.0 g of N-mercapto-2-pyrrolidone and 6.8 g of heptane was cooled to 0 ° C under a nitrogen atmosphere. A mixed solution of 20.0 g of the compound (5) and 20.5 g of N-mercapto-2-pyrrolidone was added dropwise thereto, and the mixture was stirred at the same temperature for 1 hour. Thereafter, the reaction mixture was added dropwise to a 3 wt% aqueous hydrochloric acid solution, and then the resulting mixture was neutralized with a 23 wt% sodium hydroxide water solution, and extracted with heptane. The obtained organic layer was washed with a 3% by weight aqueous sodium hydrogencarbonate solution and water, and the obtained organic layer was concentrated under reduced pressure to obtain a crude product of compound (6). The crude product was analyzed by gas chromatography to give an area ratio of 92/8. The analysis was carried out by the internal standard method of gas chromatography, and the total amount of the Z body and the E body was 13.5 g, and the total yield of the Z body and the E body was 90%. Example 22 139089.doc -39- 201033162 Compound (4) 2.0 g was mixed with pyridinium 83 g, tetrahydrofuran 2 〇 mL, and the denture mixture was cooled in an ice bath, and trimethyl acetamidine was added dropwise under a nitrogen atmosphere. Chlorine 1.27 g. After the end of the dropwise addition, the resulting mixture was stirred under ice cooling for about 3 hours. To the obtained mixture, 76 g of pyridinium chloride and 1 · 1.5 g of trimethylhydrazine chloride were added, and the resulting mixture was further stirred under ice-cooling for about 4 hours to add water to the known reaction mixture and mixed to acetic acid. Extraction with ethyl vinegar. The obtained organic layer was washed with dilute hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution and brine, and dried over anhydrous sodium sulfate. After the sodium sulfate was removed by filtration, the obtained filtrate was concentrated under reduced pressure. The residue obtained was purified by silica gel column chromatography to give the compound of the formula (5-2) 〇. 7 6 g.

HsCO CH3 ch, J /CH3 , ch3 (5-2) ^-NMR (CDC135 TMS) δ (ppm): !.15H)? 1 59„ 1.68 (m,1H),m (dd,5/6H), i 88 (10), i/6h), /π (s, 5/2H), 3.70 (S, 1/2H), 4.98 (d, 1/6H), 5.15 (d, 5/6H), 5.95 (d, W6H), 5·98 (d, 5/6H), 6.02 (d, 1/6H), 6 〇7 (4) 5/6h). Example 23 In place of the use of benzamidine chloride 148 g in Example 22 In the same manner as in Example 22, the compound 1 represented by the following formula (5-3) was obtained in the same manner as in Example 22 except that the base two gas was used in the same manner as in Example 22 except that the benzamidine gas was used instead of the trimethylethene chloride. 63 g. 139089.doc •40- 201033162 Ο CHS pi3 (5-3) o h-NMR (CDC13, TMS) δ (ppm): 1.24 (s, 1H), 1.28 (s, 1H), 1.30 (s , 2H), 1.35 (s, 2H), 1.66 (d, 1/3H), 1.88 (d, 2/3H), 1.95 (dd, 2/3H), 2.03 (dd, 1/3H), 3.66 (s , 2H), 3.72 (s, 1H), 5.28 (d, 1/2H), 5.39 (d, 2/3H), 6.05 (d, 1/3H), 6.06 (d, 1/3H), 6.09 (d , 2/3H), 6.12 (d, 2/3H), 7.45-7.51 (m, 2H), 7.58-7.63 (m, 1H), 8.06-8.10 (m, 2H). Example 24 ❿ 2,3 ,5,6-tetrafluoro-4-methoxymethyl-benzofuran 913 g and compound (6) 7.50 g And a mixture of 74 mg of lithium decoxide and 74 mL of heptane, and the resulting mixture was refluxed for 9 hours while azeotroping methanol and heptane were azeotroped to the outside of the reaction system. Heptane 2 was refluxed. 〇mL was added to the reaction system, and the mixture of sterol and heptane which was excluded from the reaction system was 5 〇mL. The obtained reaction mixture was cooled to room temperature, and then toluene and brine were added and mixed to obtain a liquid. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. (4) After the transition was removed by sodium sulfate, the solution was subjected to reduced pressure and condensed. The obtained residue was purified by Shixi gum column chromatography. Compound (3) 142 g 〇 Example 25 19.3 g of the compound (6) was mixed with 6.0 g of sodium hydroxide, 20 mL of water and 18 mL of methanol. The resulting mixture was refluxed for 1 hour. After cooling the resulting reaction mixture to room temperature, the mixture was evaporated under reduced pressure to remove methanol. To the resulting residue, J 50 89.doc 201033162 was added water 250 ml, and the resulting mixture was cooled in an ice bath. Concentrated hydrochloric acid was added to the mixture to adjust the pH to 1 or less, followed by extraction with ethyl acetate. The resulting organic layer was dried with magnesium sulfate. After the magnesium sulfate was removed by filtration, the obtained filtrate was concentrated under reduced pressure to give 16.9 g (yield compound (7)). The Z body/E body ratio of the product was about 8/1 as a result of 1H-NMR measurement. Ch3 ch3

</ RTI> </ RTI> <RTIgt; (d, 8/9H), 1.74 (d, 1/9H), 1.97 (d, 8/9H), 1.97 (d, 1/9H), 2.20 (dd, 1/9H), 2.48 (dd, 8/ 9H), 5.82 (dq, 8/9H), 6.03 (dq, 1/9H). Example 26 2.24 g of 2,3,5,6-tetrafluoro-4-methoxymethyl-benzyl alcohol was mixed with zirconium chloride 70 mg and xylene 20 mL. After the resulting mixture was refluxed for about 10 minutes, xylene 1 〇 mL was distilled off. After the resulting mixture was cooled to 80 ° C, 1.97 g of the compound (7) obtained in the above Example 25 was added. The resulting mixture was stirred at reflux temperature of xylene for 7 hours. This operation is carried out while azeotropy water is azeotroped with diphenylbenzene and is excluded from the reaction system. After the resulting mixture was cooled to room temperature, it was washed twice with a 5 wt% aqueous sulfuric acid solution. The obtained solution was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to afford compound 3. According to the results of 1H-NMR measurement, the Z body/E body ratio of the product was about 8/1. 139089.doc • 42· 201033162 Example 27 2,3,5,6-tetrafluoro-4-methoxymethyl-benzyl alcohol 8.0 g and 70% by weight tetraisopropoxy /2-propanol solution 〇·3 g, 55 g of xylene were mixed. After the resulting mixture was heated to reflux, 39 g of a distillate was removed. After cooling the resulting mixture to 8 ° C, compound (7)_/E body ratio = 96 M) 74 L was added. The resulting mixture was stirred at reflux temperature of xylene for 13 hours. This operation is carried out by azeotroping the by-product water and xylene to the outside of the reaction system.

get on. After the resulting mixture was cooled to room temperature, xylene Ηg was added. The obtained mixture was washed successively with 5 wt% sulfuric acid, 5 wt% sodium hydroxide water and water, and then concentrated under reduced pressure to obtain a compound (3) 13·4 ^ which was analyzed by a gas chromatography area percentage method. z body (four) is more than coffee. Example 28 A reaction was carried out in the same manner as in Example 9 except that gas benzene was used instead of dimethyl-2-yt(tetra) ketone in Example 9, to obtain a crude product of Compound W. The body ratio is 65/35, and the total yield of z-body and e-body is 27%. [Industrial Applicability] The compound represented by the formula (7) of the present invention is a novel compound which can be produced in a high yield by reacting the compound represented by the formula (7) with a metal borohydride. The compound which is a control agent for a pest and an intermediate thereof is a propylene-based carboxylic acid compound represented by the formula (5). 139089.doc -43-

Claims (1)

201033162 VII. Patent application scope: 1 · A method for producing a cyclopropanecarboxylic acid compound represented by formula (VI), (wherein R represents a thiol group which may be selected from a halogen atom, a carbon number of 2 to 7 and a carbon number of 1 to 7 which may be substituted, and a carbon number of 1 to 3 which may be substituted and a chain hydrocarbon group having 1 to 10 carbon atoms, a cyclic hydrocarbon group having 3 to 1 fluorene or a hydrogen atom substituted with at least one group of the group consisting of a substituted phenyl group, characterized by: in the presence of a solvent, Let formula (V) The atom-substituted compound having a carbon number of 1 to 10 or a stupid group is reacted with an alkali metal borohydride. A method for producing a cyclopropane acid compound which can be obtained by halogen, such as β, wherein the borohydride is sodium borohydride. A method for producing a cyclopropanoid compound according to item 1, wherein the solvent is an ether solvent, a guanamine solvent, a heteroaromatic solvent, a sulfur-containing aliphatic solvent, a clear solvent, a cyclic urea solvent, or an alcohol solvent. And at least one of the group consisting of ester solvents. , ' 4. For example, the method for the manufacture of citric acid compounds of Cyclohexane rs, 1 and propylene, wherein the solvent 139089.doc 201033162 is 'N_methylformamide, dimethylacetamidine, 1 methacrylate Sub-grinding, N-T-based-2-. Pyrrolidine, acetonitrile or j 3_ di-main η &, T U-imidazoline. • For example, if the compound of the cyclopropane decanoic acid compound of the above formula 1 is produced - the method of the method is as follows: (V) is not a compound of the formula (II) H3c ch3 (8) 〇 OH (wherein R represents The meaning of the definition in the claim 1 is the same) ❿ The compound represented by the formula (III) 0 X person Rl (10) (wherein the R table does not have the same meaning as defined in the claim X, X represents a halogen atom) a compound obtained by reacting a mercapto halide or an acid anhydride represented by the formula (IV) R and R1 &lt;IV) (wherein R1 represents the same meaning as defined in claim 1) in the presence of a base . 6) A method for producing a cyclopropanecarboxylic acid compound according to claim 5, wherein the compound represented by the formula (H) is a formula (I) (I) (wherein, R represents the same meaning as defined in the claim 1) 139089.doc 201033162 A compound obtained by reacting a compound represented by acrylonitrile with a base in the presence of a base. 7. a compound of the formula (Π) h3c ch3 'wherein 'R represents a sulphuric acid group which may be selected from a halogen atom, a carbon number of 2 to 7, a carbon number of 1 to 7 which may be substituted, and a carbon number of 1 to 3 which may be substituted. The group represented by at least one of the group consisting of a phenyl group which may be substituted and substituted with a hydrocarbon group having 1 to 10 carbon atoms, a cyclic hydrocarbon group having 3 to 10 carbon atoms or a hydrogen atom). 8. The compound of claim 7, wherein R is a chain hydrocarbon group having a carbon number of 丨~1〇 or a chain hydrocarbon group having a carbon number of 丨~(7) substituted with a phenyl group which may be substituted. 9. The compound of claim 7, wherein R is methyl or 2,3,5,6-tetrafluoro-4-methylmethoxybenzyl. Φ 10 · a compound which is of the formula (v) (wherein R represents an alkoxy group which may be selected from a halogen atom, a fluorenyl group having 2 to 7 carbon atoms, a carbon number of 1 to 7 which may be substituted, a carbon number of 1 to 3 which may be substituted, and The at least one group of the group of the phenyl groups which may be substituted is substituted with a chain hydrocarbon group of 1 to 10, a cyclic hydrocarbon group having a carbon number of 3 to 1 fluorene or a hydrogen atom, 139089.doc 201033162 R1 represents a halogen atom Represented by a substituted hydrocarbon group or a phenyl group. 11. 12. 13. 14. 15. The compound of claim 10, wherein R1 is a chain hydrocarbon group having from 1 to 10 carbon atoms. The compound of claim 10, wherein R1 is methyl. The compound according to any one of claims 10 to 12, wherein R is a chain hydrocarbon group having a carbon number of 丨~1〇 or a chain hydrocarbon group having a carbon number of 丨~(7) substituted with a phenyl group which may be substituted. The compound of any one of claims 10 to 12, wherein R is methyl or 2,3,5,6-tetrafluoro-4-decyloxymethylbenzyl. A method for producing a cyclopropanecarboxylic acid compound represented by formula (IX), (wherein R2 is a group different from R1, and represents an alkoxy group which may be selected from a halogen atom, a fluorenyl group having 2 to 7 carbon atoms, a carbon number 丨7 which may be substituted, and a carbon number which may be substituted 1 a hydrocarbon group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 1 carbon atoms substituted with at least one of a group consisting of a thio group and a phenyl group which may be substituted at the end of ～3 is characterized by a solvent In the presence of the formula (va) 139089.doc •4· 201033162 At least one of the group consisting of alkoxy groups having 1 to 7 carbon atoms, a carbon atom which may be substituted, and an alkyl group which may be substituted may be substituted. a compound represented by a substituted hydrocarbon group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 3 to 10 carbon atoms, and R1 represents a hydrocarbon group having 1 to 10 carbon atoms or a phenyl group which may be substituted by a halogen atom, and an alkali metal borohydride. Reacts, and gets the formula (Via) (Via) Ο (wherein, R1 represents the same meaning as above), the cyclopropane decanoic acid compound is represented, and the obtained propylene sulfonate compound represented by the formula (via) is obtained by the formula (VHI) R2. -OH (VIII) (wherein R2 represents the same meaning as above) The compound represented by the reaction in the presence of an alkali metal hydroxide. 16. The process for producing a cyclopropanecarboxylic acid compound according to claim 15, wherein the alkali metal hydroxide is lithium hydroxide. 17. The method for producing a cyclopropanecarboxylic acid compound according to claim 15, wherein the solvent is a free (tetra) agent, a stilbene solvent, a heteroaromatic solvent, a sulfur-containing fat hydrazine/mixture, a nitrile solvent, a cyclic urea solvent, an alcohol solvent. And at least one of the group consisting of ester solvents. 18's method for producing cyclopropane decanoic acid represented by formula (VII), 139089.doc 201033162 It is characterized in that: in the presence of a solvent, the formula R· HaC CH3 Y CN (Va) (wherein the R table can not be selected from a halogen atom, a carbon number of 2 to 7, a carbon number which can be substituted Alkoxy group of 7 or a carbon group of 1 to 10 substituted with at least an anthracene group of a group of a carbon group which may be substituted and a group of a group which may be substituted, or a carbon number of 3 to A compound represented by a cyclic hydrocarbon group of 1 ,, R1 represents a chain hydrocarbon group of a carbon number 丨~(7) or a phenyl group which may be substituted by an atom of an atom, and an alkali metal borohydride is reacted to obtain a formula (Via). 0 (wherein R' represents the same meaning as above) is a cyclopropanecarboxylic acid compound, and the obtained propylene cyanate compound represented by (Vh) is hydrolyzed. 19. The method for producing ciprofloxacin formic acid according to claim 18, wherein the solvent is selected from the group consisting of a 2-ether solvent, a guanamine solvent, a heteroaromatic solvent, a sulfur-containing aliphatic solvent, a nitrile solvent, a cyclic urea solvent, an alcohol solvent, and At least one of the components of the ester solvent. 139089.doc 201033162 20. A method for producing a cyclopropanecarboxylic acid compound represented by the formula (ΐχ), 0 (IX) (wherein R2 is a group different from R', and may be selected from alkoxy groups selected from a halogen atom, a carbon number of 2 to 7, and a carbon number of 1 to 7 which may be substituted, and may be a substituted alkyl group having 1 to 3 carbon atoms and a substituted carbon group substituted with at least one group of carbon atoms, or a cyclic hydrocarbon group having a carbon number of 3 to 1 fluorene) The cyclopropane decanoic acid represented by the formula (vii) is obtained by the production method of the claim 18 or 19, and the obtained ciprofidolcarboxylic acid represented by the formula (νπ) is obtained by the formula (VHI). The compound represented by r2-°H (VIII) (wherein R2 represents the same meaning as above) is reacted in the presence of a knot compound. A method for producing a cyclopropanecarboxylic acid compound according to claim 20, wherein the hammer compound is a tetra-functional zirconium, a hafnocene compound or an alkoxy hammer. 22. A method for producing a propylene-based carboxylic acid compound represented by formula (ixa), (wherein R3 may be selected from the group consisting of a halogen atom, a fluorenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms which may be substituted, a carbon number of 可~3 which may be substituted, and At least i group-substituted stone in the group consisting of substituted phenyl groups * 139089.doc 201033162 Number 1 to 10 chain hydrocarbon group or carbon number 3 to 1 ring ring hydrocarbon group) characterized by: π 仔, let the formula (Vb) h3c ch3 (Vb) a charcoal number of 1 to 10 or a hydrocarbon group (wherein R1 represents a phenyl group which may be substituted by a halogen atom) The compound represented reacts with the metal (tetra) compound to obtain (Vib) The cyclopropane-burning formic acid compound is represented by the cyclopropanecarboxylic acid compound obtained by the formula (VIb) and the formula (VIIIa) r3-°H (Villa) (wherein the 'R table is not the same as above Meaning) The compound represented reacts in the presence of a ruthenium compound. 23. 24. A process for producing a cyclopropanecarboxylic acid compound according to claim 22, wherein the ruthenium compound is a tetra-imprinted compound, a dioxin compound or an alkoxy condensate. The method for producing a ciprofloxacin compound according to claim 22, wherein the solvent is selected from the group consisting of an ether solvent, a guanamine solvent, a heteroaromatic solvent, a ruthenium solvent, a nitrile solvent, a cyclic gland solvent, an alcohol solvent, and an vinegar solvent: : At least one of the group. 139089.doc 4 201033162 r IV. Designation of representative drawings: (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 139089.doc -2-