JP2003002866A - Method for producing trans-cyclopropane carboxylic esters each substituted with vinyl group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing trans-cyclopropane carboxylic esters each substituted with a vinyl group. SOLUTION: The method for producing the trans-cyclopropane carboxylic esters each substituted with the vinyl group represented by formula (3) (wherein, R<1> , R<2> , R<3> , R<4> and R<5> are each independently hydrogen atom, a halogen atom, a 1-4C alkyl group that may be substituted, an aryl group that may be substituted, or an alkoxy carbonyl group that may be substituted; R<1> and R<2> may combine to form a ring) is characterized by reacting cyclopropane carboxylic acid substituted with the vinyl group comprising cis/trans isomers represented by formula (1) (wherein, R<1> , R<2> , R<3> and R<4> are the same as defined above) and a monohydroxy compound in the presence of a compound of an element belonging to the IV group of the periodic table.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing trans-vinyl-substituted cyclopropanecarboxylic acid esters.

[0002]

2. Description of the Related Art Vinyl-substituted cyclopropanecarboxylic acid esters are important compounds as synthetic pyrethroid insecticides for household and epidemic protection as well as agricultural or forest pests or intermediates thereof. Although vinyl-substituted cyclopropanecarboxylic acid esters have geometric isomers of cis and trans based on a three-membered ring, generally the synthetic pyrethroid insecticide has a stronger insecticidal effect in the trans form than in the cis form. Are known. Furthermore, it is known that the trans form is less toxic to warm-blooded animals than the cis form (Nature, 244 , 456 (1973)). From the above viewpoints, development of a method for industrially producing trans-vinyl-substituted cyclopropanecarboxylic acid esters has been desired.

As a method for producing vinyl-substituted cyclopropanecarboxylic acid esters, a desired ester compound is obtained by converting a corresponding vinyl-substituted cyclopropanecarboxylic acid into an acid chloride and then reacting it with a corresponding alcohol. A method is known in which a corresponding ester is obtained by reacting a corresponding methyl- or ethyl ester of vinyl-substituted cyclopropanecarboxylic acid with a corresponding alcohol in the presence of a catalyst. However, vinyl-substituted cyclopropanecarboxylic acid esters obtained by these production methods are
Since the cis / trans form depends on the raw material vinyl-substituted cyclopropanecarboxylic acid or methyl- or ethyl ester of vinyl-substituted cyclopropanecarboxylic acid,
In order to produce the trans isomer, it was necessary to remove the cis isomer from the raw material in advance and improve the trans isomer abundance ratio to a target value before use. Therefore, a resolution method by acting a resolving agent to form a diastereomeric salt, a biochemical synthesis or resolution by an enzyme is used, but the operation is complicated and the control of cis / trans form is not sufficient. For these reasons, it was not always a method that is industrially sufficiently satisfactory.

[0004]

DISCLOSURE OF THE INVENTION According to the present invention, the trans-form ratio is improved as compared with the raw material even when the vinyl-substituted cyclopropanecarboxylic acid containing cis / trans form is not separated in advance and used in the reaction as it is. -Providing a method capable of industrially producing vinyl-substituted cyclopropanecarboxylic acid esters.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and as a result, have achieved the present invention. That is, the present invention provides a compound represented by the general formula (1) (In the formula, R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom, or an optionally substituted carbon number 1 to
4 represents an alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxycarbonyl group. Further, R ¹ and R ² may be combined to form a ring. ) Cis / trans-containing vinyl-substituted cyclopropanecarboxylic acid represented by the general formula (2) R ⁵ OH (2) (In the formula, R ⁵ represents a halogen atom, an alkenyl group, an alkynyl group, a cycloalkyl group, or a cycloalkenyl group. A group or an alkyl group which may be substituted with a heterocyclic group; a phenoxy group, a nitro group, a cyano group, an aralkyl group which may be substituted with a halogen atom or an alkoxy group; or an alkyl group, an alkoxy group or a halogen atom A general formula (3), which comprises reacting a monohydroxy compound represented by an optionally substituted aryl group) in the presence of a compound of an element belonging to Group 4 of the periodic table. (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above.) A method for producing a trans-vinyl-substituted cyclopropanecarboxylic acid ester is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The present invention, when producing trans-vinyl substituted cyclopropanecarboxylic acid esters by dehydration condensation reaction,
Cis / trans-containing vinyl-substituted cyclopropanecarboxylic acid (1) and monohydroxy compound (2)
It is characterized by reacting in the presence of a group element compound.

The cis / trans isomer-containing vinyl-substituted cyclopropanecarboxylic acid used as a raw material in the present invention is represented by the general formula (1).
¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom, an aryl group, an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted aryl group, or a substituted group. Represents an optionally substituted alkoxycarbonyl group. Further, R ¹ and R ² may be combined to form a ring.

Examples of the optionally substituted alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl and tert-butyl. Substituents for substituting these alkyl groups include halogen atoms such as fluorine, chlorine, bromine and iodine; alkoxy groups such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy and tert-butoxy. Etc. Examples of the aryl group which may be substituted include a phenyl group, and examples of the substituent include an alkyl group and a halogen atom.

Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl and the like. Further, these alkoxycarbonyl groups may be substituted with a halogen atom such as fluorine, chlorine, bromine and iodine.

Specific examples of the cis / trans-containing vinyl-substituted cyclopropanecarboxylic acid (1) as a raw material include, for example, 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylic acid and 2,2 -Dimethyl-3- (2-methyl-1-
Propenyl) cyclopropanecarboxylic acid, 2,2-dimethyl-
3- (2,2-dichlorovinyl) cyclopropanecarboxylic acid, 2,
2-dimethyl-3- (2-chloro-2-fluorovinyl) cyclopropanecarboxylic acid, 2,2-dimethyl-3- (2-bromovinyl) cyclopropanecarboxylic acid, 2,2-dimethyl-3- (2, 2-dibromovinyl) cyclopropanecarboxylic acid, 2,2-dimethyl-3-
(2-chloro-3,3,3-trifluoro-1-propenyl) cyclopropanecarboxylic acid, 2,2-dimethyl-3- {3,3,3-trifluoro-2- (trifluoromethyl) -1 -Propenyl} cyclopropanecarboxylic acid, 2,2-dimethyl-3- (2-phenyl-1-propenyl) cyclopropanecarboxylic acid, 2,2-dimethyl-3- (2
-Phenylvinyl) cyclopropanecarboxylic acid, 2,2-dimethyl-3-{(2,2-difluorocyclopropylidene) methyl}
Cyclopropanecarboxylic acid, 2,2-dimethyl-3- {2- (tert-
Butoxycarbonyl) vinyl} cyclopropanecarboxylic acid, 2,2-dimethyl-3- {2-fluoro-2- (methoxycarbonyl) vinyl} cyclopropanecarboxylic acid, 2,2-dimethyl-3
-{2-Fluoro-2- (ethoxycarbonyl) vinyl} cyclopropanecarboxylic acid, 2,2-dimethyl-3- {2-fluoro-2- (te
rt-butoxycarbonyl) vinyl} cyclopropanecarboxylic acid, 2,2-dimethyl-3- [2- {2,2,2-trifluoro-1- (trifluoromethyl) ethoxycarbonyl} vinyl] cyclopropanecarboxylic acid, 2-Methyl-2-ethyl-3- (1-propenyl) cyclopropanecarboxylic acid, 2,2-diethyl-3- (2,2
-Dichlorovinyl) cyclopropanecarboxylic acid, 2-methyl
-2-Phenyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid and the like can be mentioned. Preferred are 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylic acid and 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid.

The cis / trans isomer-containing vinyl-substituted cyclopropanecarboxylic acid (1) used in the present invention has a steric configuration of a vinyl group and a carbonyl group which substitute the three-membered ring.
In addition to the cis / trans isomers, there are four types of stereoisomers (+) and (−) isomers. The cis / trans mixing ratio is not particularly limited, but since the production efficiency becomes poor if the cis isomer is too much, the cis / trans content ratio of the vinyl-substituted cyclopropanecarboxylic acid is
Usually 0/100 to 99/1, preferably 0/100 to 5
It is 0/50. The (+)-form / (-)-form ratio in the (±) -cis / (±) -trans containing form is not particularly limited, and the (+) form / (-) form ratio can be used.
In the present invention, the (+)-form / (-)-form ratio of the vinyl-substituted cyclopropanecarboxylic acid (1) is maintained as it is, and the trans-vinyl-substituted cyclopropanecarboxylic acid ester having a similar steric structure in the carboxylic acid-derived part. Are manufactured.

Examples of the monohydroxy compound represented by the general formula (2) used in the present invention include optionally substituted alkyl alcohol, aralkyl alcohol, aryl alcohol and the like.

Examples of the alkyl group of the optionally substituted alkyl alcohol include an alkyl group having 1 to 10 carbon atoms, which may be linear, branched or cyclic, and have a double bond or a triple bond. It may have a bond. As the substituent, for example, a halogen atom such as fluorine, chlorine, bromine, iodine, a furyl group, a phenoxyfuryl group, a benzylfuryl group, a difluoromethyl unit, a propargylfuryl group, a methylisoxazolyl group, a trifluoro group. Methyl thiazolyl group, trifluoromethoxy thiazolyl group, propynyl trifluoromethyl euroylyl group,
Examples thereof include a propynylpyrrolyl group, a propynyldioxoimidazolidinyl group, an oxo group, a propenyl group, a propynyl group, a dioxotetrahydroisoindolyl group, and an oxothiazolyl group.

Specific examples of the alkyl alcohol which may be substituted include, for example, methyl alcohol,
Ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, neopentyl alcohol, amyl alcohol, n-hexyl alcohol, n-octyl alcohol, n- Decyl alcohol, 2-furylmethyl alcohol, 3-furylmethyl alcohol, (5-phenoxy-3-furyl) methyl alcohol, (5-benzyl-3-furyl) methane-1-ol, {5- (difluoromethyl)- 3-furyl} methane-1-ol, 5-propargylfurfuri
Alcohol, (5-methylisoxazol-3-yl) methan-1-ol, 1- {2- (trifluoromethyl) -1,3-thiazol-4-yl} prop-2-yn-1- All, 1- {2- (trifluoromethoxy) -1,3-thiazol-4-yl} prop-2-yn-1-ol, 1- {1-prop-2-ynyl-5- (trifluoromethyl )
Pyrrol-3-yl} prop-2-yn-1-ol, (1-prop-2
-Inylpyrrol-3-yl) methan-1-ol, 3- (hydroxymethyl) -1-propynyl-imidazolidine-
2,4-dione, 4-hydroxy-3-methyl-2-
(2-propenyl) -2-cyclopenten-1-one,
4-hydroxy-3-methyl-2- (2-propynyl)
2-Cyclopenten-1-one, 2- (hydroxymethyl) -4,5,6,7-tetrahydroisoindole-1,3-dione, {1- (2-propynyl) pyrrol-3-yl} methane- 1-ol, 5- (hydroxymethyl) -4-methyl- (2-propynyl) -1,3-thiazolin-2-one, 4-methylhept-4-en-1
-In-3-ol, chloromethyl alcohol, dichloromethyl alcohol, trichloromethyl alcohol, bromomethyl alcohol, dibromomethyl alcohol, tribromomethyl alcohol, fluoromethyl alcohol, difluoromethyl alcohol, trifluoromethyl alcohol, fluoroethyl alcohol, difluoro Ethyl alcohol, trifluoroethyl alcohol, tetrafluoroethyl alcohol, pentafluoroethyl alcohol, 3,3-dibromo-2-propen-1-ol, perfluoropropyl alcohol, hexafluoroisopropyl alcohol, perfluorobutyl alcohol, perfluoropentyl Alcohol, perfluorohexyl alcohol, perfluorooctyl alcohol, perfluorodecyl alcohol, - (2-propynyl) -5-
(Trifluoromethyl) -4-pyrazolyl} methane-1
-Ol, 1- {1- (2-propynyl) -5- (trifluoromethyl) pyrrol-3-yl} prop-2-yn-1-ol, 1- {2- (trifluoromethyl)-
1,3-thiazol-4-yl} prop-2-yn-1
-Ol, 1- {2- (trifluoromethoxy) -1,
3-thiazol-4-yl} prop-2-yn-1-ol, 4-fluorohepto-4-en-1-yn-3-
Examples include oars.

Examples of the aralkyl of the aralkyl alcohol which may be substituted include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, anthracenyl and indolylmethyl. As the substituent, an alkyl group, a halogen atom, an alkoxyalkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a haloalkoxy group, a haloalkylacetyloxy group, a phenoxy group, a phenyl group, a cyano group, a halophenoxy group, an amino group, Examples thereof include a pyridyl group and a thienyl group.

Specific examples of the aralkyl alcohol which may be substituted include, for example, benzyl alcohol, 2-methyl-3-phenylbenzyl alcohol, 2,3,5,6-tetrachlorobenzyl alcohol, 2,3,5, 6-tetrachloro-4-
Methylbenzyl alcohol, 2,3,5,6-tetrachloro-4-
Methoxybenzyl alcohol, 2,3,5,6-tetrachloro-4
-(Methoxymethyl) benzyl alcohol, 2,3,5,6-tetrachloro-4-propargylbenzyl alcohol, 2,3,5,6
-Tetrachloro-4- (dichloromethyl) benzyl alcohol, 2,3,5,6-tetrachloro-4- (dichloromethoxy) benzyl alcohol, 2,3,5,6-tetrachloro-4- (2,2 , 2-Trichloroacetyloxy) methylbenzyl alcohol, 4-
(Trichloromethyl) benzyl alcohol, 2,3,4,5-tetrachloro6-methylbenzyl alcohol, 3-phenylbenzyl alcohol, 2,6-dichlorobenzyl alcohol, 3
-Phenoxybenzyl alcohol, 2-hydroxy-2
-(3-phenoxyphenyl) ethanenitrile, 2-hydroxy-2- {4- (methoxymethyl) phenyl} ethanenitrile, 2- {3- (4-chlorophenoxy) phenyl} -2-hydroxyethanenitrile, 2- (4-amino-2,
3,5,6-Tetrachlorophenyl) -2-hydroxyethanenitrile, 2- (4-chloro-3-phenoxyphenyl) -2-hydroxyethanenitrile, (2-methylphenyl) methyl alcohol, (3-methylphenyl) methyl alcohol,
(4-methylphenyl) methyl alcohol, (2,3-
Dimethylphenyl) methyl alcohol, (2,4-dimethylphenyl) methyl alcohol, (2,5-dimethylphenyl) methyl alcohol, (2,6-dimethylphenyl) methyl alcohol, (3,4-dimethylphenyl) methyl alcohol, (2,3,4-trimethylphenyl) methyl alcohol, (2,3,5-trimethylphenyl) methyl alcohol, (2,3,6-trimethylphenyl) methyl alcohol, (3,4,5-trimethylphenyl) methyl Alcohol, (2,4,6-trimethylphenyl) methyl alcohol, (2,3,4,5-
Tetramethylphenyl) methyl alcohol, (2,3,
4,6-tetramethylphenyl) methyl alcohol,
(2,3,5,6-tetramethylphenyl) methyl alcohol, (pentamethylphenyl) methyl alcohol,
(Ethylphenyl) methyl alcohol, (n-propylphenyl) methyl alcohol, (isopropylphenyl) methyl alcohol, (n-butylphenyl) methyl alcohol, (sec-butylphenyl) methyl alcohol, (tert-butylphenyl) methyl alcohol, (N-pentylphenyl) methyl alcohol, (neopentylphenyl) methyl alcohol, (n-hexylphenyl) methyl alcohol, (n-octylphenyl) methyl alcohol, (n-decylphenyl) methyl alcohol, (n-dodecylphenyl) Methyl alcohol, (n-tetradecylphenyl) methyl alcohol,
Naphthylmethyl alcohol, anthracenylmethyl alcohol, 1-phenylethyl alcohol, 1- (1-naphthyl) ethyl alcohol, 1- (2-naphthyl) ethyl alcohol, 4-prop-2-ynylphenyl) methan-1-ol, 3-prop-2-ynylphenyl) methan-1-ol, (1-prop-2-ynyl-2-methylindol-3-yl) methan-1-ol, {1-
Prop-2-ynyl-2- (trichloromethyl) indol-3-yl} methan-1-ol, 4-prop-2-enylindan-1-ol, 4-phenylindan-2-ol, 4- (2
-Thienyl) indan-2-ol, (2,3,6-trichloro-4-pyridyl) methan-1-ol and the halogen atom in the haloaralkyl alcohol, methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, se
Examples thereof include alkoxyaralkyl alcohols arbitrarily changed to c-butoxy, tert-butoxy and the like, cyanoaralkyl alcohols, nitroaralkyl alcohols and the like.

Examples of the aryl alcohol which may be substituted include phenol, 1-naphthol, 2-naphthol, 4-prop-2-ynylphenol, 3-prop-2-ynylphenol, 4-hydroxyacetophenone, 4-hydroxybenzaldehyde and those in which these aromatic rings are substituted with an alkyl group, an alkoxy group, a halogen atom or the like can be mentioned.

Preferred monohydroxy compounds (2) are primary alcohols, benzyl alcohols,
Hydroxycyclopentenones are mentioned, and more preferably, 3-phenoxybenzyl alcohol, 4-hydroxy-3-methyl-2- (2-propenyl) -2-cyclopenten-1-one, 4-hydroxy-3-methyl. −
2- (2-propynyl) -2-cyclopenten-1-one may be mentioned.

The monohydroxy compound (2) used in the present invention may have an asymmetric carbon and may have two or more kinds of stereoisomers, and the present invention includes any of them. In the present invention, the three-dimensional structure of the monohydroxy compound (2) is maintained as it is, and trans-vinyl-substituted cyclopropanecarboxylic acid esters (3) having the same three-dimensional structure in the alcohol-derived part are produced.

The amount of the monohydroxy compound (2) used is usually 1 equivalent or less with respect to the trans isomer contained in the cis / trans isomer-containing vinyl-substituted cyclopropanecarboxylic acid (1), but even if used in a small excess. Good. Generally, after the completion of the reaction, the unreacted raw material can be recovered by operations such as distillation, extraction and liquid separation.

Examples of the compound of the periodic table group 4 element used as the catalyst in the present invention include titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium acetate, titanium acetylacetonate, titanium ethoxide, Titanium i
-Propoxide, titanium n-butoxide, titanium t-butoxide, titanium nitrate, titanium oxychloride, tetrakis (dimethylamino) titanium, tetrakis (diethylamino) titanium, titanocene dichloride, titanocene dimethoxide, decamethyltitanocene dichloride, etc. From zirconium to hafnium. Preferably titanium tetrachloride,
Titanium i-propoxide, titanocene dichloride,
Zirconium tetrachloride, zirconium i-propoxide,
Zirconocene dichloride, hafnium tetrachloride, hafnium t-butoxide, hafnocene dichloride and the like can be mentioned.

As the compound of the Group 4 element of the periodic table, a commercially available anhydride or hydrate can be used as it is. Also,
A complex with a compound having a coordination property such as tetrahydrofuran or tetramethylethylenediamine can also be used.

The amount of the Group 4 element compound of the periodic table used is not particularly limited, but is usually 0.001 to 200 moles relative to the cis / trans-containing vinyl-substituted cyclopropanecarboxylic acid (1).
%, And preferably in the range of about 0.1 to 10 mol%.

When the cis / trans-containing vinyl-substituted cyclopropanecarboxylic acid (1) and the monohydroxy compound (2) are reacted in the presence of a compound of the periodic table group 4 element, an atmosphere of an inert gas such as argon or nitrogen is usually used. It is carried out below. The reaction can be carried out under normal pressure, increased pressure and reduced pressure. The reaction is preferably carried out under normal pressure or reduced pressure. Further, it is preferable that water, which is a by-product of the dehydration condensation reaction, is continuously removed outside the reaction system by a method such as distillation.

The reaction can be carried out without solvent or in a solvent. As the solvent used, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, aliphatic hydrocarbons such as hexane, heptane, octane and nonane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene. Examples thereof include hydrocarbons, ether solvents such as diethyl ether and tetrahydrofuran. Further, by adding a solvent that is azeotropic with water, it is possible to continuously remove only water as a by-product.

The reaction temperature is not particularly limited, but is preferably in the range of about 20 to 200 ° C.

The trans-vinyl-substituted cyclopropanecarboxylic acid ester produced by such a reaction is, for example, washed with water or acidic water to give a catalyst, and washed with alkaline water to give an unreacted carboxylic acid. Can be removed. Further, if necessary, it can be easily separated from the reaction mixture by carrying out ordinary operations such as distillation, recrystallization and column chromatography.

[0028]

INDUSTRIAL APPLICABILITY According to the present invention, a vinyl-substituted cyclopropanecarboxylic acid containing a cis / trans isomer (1) and a monohydroxy compound (2) are reacted in the presence of an element compound of Group 4 of the periodic table. The trans-vinyl-substituted cyclopropanecarboxylic acid esters (3) can be easily obtained with excellent yield and selectivity, which is advantageous as an industrial production method thereof.

[0029]

The present invention will be described in more detail by the following examples, but the present invention is not limited to these examples.

Example 1 210 mg of 2,2-dimethyl-3 in a 10 ml reactor.
152 mg of-(2-methyl-1-propenyl) cyclopropanecarboxylic acid (trans isomer ratio: E / Z = 4/1)
4-Hydroxy-3-methyl-2- (2-propenyl) -2-cyclopenten-1-one, 93 mg of hafnium tetrachloride / tetrahydrofuran complex, and 2 ml of toluene were charged. The mixture was heated under reflux and stirred under reflux for 24 hours while removing water by-produced during the reaction with calcium hydride. The reaction mixture was analyzed by gas chromatography to find that it was 3- (2-propenyl) -2-methyl-4-
Oxo-2-cyclopentenyl 2,2-dimethyl-3
The yield of-(2-methyl-1-propenyl) cyclopropanecarboxylate was 90% with respect to the raw material alcohol, and the stereoisomer of the cyclopropane moiety was only the trans isomer.

Example 2 A reaction was carried out in the same manner as in Example 1 except that 188 mg of hafnium tetra-t-butoxide was used in place of 93 mg of the hafnium tetrachloride / tetrahydrofuran complex in Example 1 and the reaction time was 28 hours. . Obtained 3-
The yield of (2-propenyl) -2-methyl-4-oxo-2-cyclopentenyl 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate was 92% with respect to the raw material alcohol. And the cyclopropane moiety was the trans form only.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C07C 69/747 C07C 69/747 Y

Claims (13)

[Claims] 1. A general formula (1) (In the formula, R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a halogen atom, or an optionally substituted carbon number 1 to
4 represents an alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxycarbonyl group. Further, R ¹ and R ² may be combined to form a ring. ) Cis / trans-containing vinyl-substituted cyclopropanecarboxylic acid represented by the general formula (2) R ⁵ OH (2) (In the formula, R ⁵ represents a halogen atom, an alkenyl group, an alkynyl group, a cycloalkyl group, or a cycloalkenyl group. A group or an alkyl group which may be substituted with a heterocyclic group; a phenoxy group, a nitro group, a cyano group, an aralkyl group which may be substituted with a halogen atom or an alkoxy group; or an alkyl group, an alkoxy group or a halogen atom A general formula (3), which comprises reacting a monohydroxy compound represented by an optionally substituted aryl group) in the presence of a compound of an element belonging to Group 4 of the periodic table. (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above.) A process for producing a trans-vinyl-substituted cyclopropanecarboxylic acid ester. 2. The production method according to claim 1, wherein the trans ratio of the trans-vinyl substituted cyclopropanecarboxylic acid ester is improved as compared with the trans ratio of the raw material cis / trans-containing vinyl substituted cyclopropanecarboxylic acid. 3. The method according to claim 1, wherein the group 4 element compound of the periodic table is a Lewis acidic compound. 4. A compound of Group 4 element of the periodic table represented by the general formula (4) M (O) _m (X) _n (Y) _4-2m-n (4) (wherein X and Y are independently halogens). Atom, alkoxy group, acyloxy group, cyclopentadienyl group,
Or an amino group, M is an element of Group 4 of the periodic table, and m
Represents 0 or 1, and n represents 0, 1 or 2. The manufacturing method of Claim 1 or 2 which is a compound shown by these. 5. The compound of Group 4 element of the periodic table is a halide, an alkoxide compound, or an amide compound.
Or the manufacturing method according to 2. 6. The cis / trans isomer-containing vinyl-substituted cyclopropanecarboxylic acid represented by the general formula (1) is 2,2-
Dimethyl-3- (1-propenyl) cyclopropanecarboxylic acid is a manufacturing method in any one of Claims 1-5. 7. A cis / trans-containing vinyl-substituted cyclopropanecarboxylic acid represented by the general formula (1) is 2,2-
Dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid is the process according to any one of claims 1 to 5. 8. The production method according to claim 1, wherein the monohydroxy compound represented by the general formula (2) is a primary alcohol. 9. The production method according to claim 1, wherein the monohydroxy compound represented by the general formula (2) is benzyl alcohol. 10. The production method according to claim 1, wherein the monohydroxy compound represented by the general formula (2) is 3-phenoxybenzyl alcohol. 11. The monohydroxy compound represented by the general formula (2) is a hydroxycyclopentenone.
7. The manufacturing method according to any one of to 7. 12. The monohydroxy compound represented by the general formula (2) is 4-hydroxy-3-methyl-2- (2-propenyl) -2-cyclopenten-1-one. The manufacturing method described in. 13. The monohydroxy compound represented by the general formula (2) is 4-hydroxy-3-methyl-2- (2-propynyl) -2-cyclopenten-1-one. The manufacturing method described in.