JP2001058971A - Production of cyclopropanecarboxylic ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily obtain a cyclopropanecarboxylic ester in an excellent yield by transesterification of a cyclopropanecarboxylic ester with a hydroxy compound in the presence of a hydroxide of an alkali metal. SOLUTION: The objective compound of formula II [e.g. (3-phenoxyphenyl) methyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate] is obtained by transesterification of a compound of formula I [R1 to R5 are each H, a halogen, a (substituted) alkyl or the like; R6 is a 1-10C alkyl or a (substituted) phenyl], e.g. methyl cyclopropanecarboxylate or the like with a compound of the formula: R7OH [R7 is a halogen, a (substituted) alkyl or the like], e.g. methyl alcohol or the like in the presence of a hydroxide of an alkali metal, e.g. LiOH or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing cyclopropanecarboxylic acid esters.

[0002]

2. Description of the Related Art A general method for synthesizing an ester compound of cyclopropane carboxylic acids and various alcohols is as follows.
It is well known that the corresponding lower alcohol ester of cyclopropanecarboxylic acid is once converted into a carboxylic acid by hydrolysis, converted to an acid chloride, and then reacted with the corresponding hydroxy compound to obtain a desired ester compound. . However, this method has a long process and is not always sufficient for an industrial production method. On the other hand, a method has been proposed in which cyclopropanecarboxylic acid esters which are easily available are produced in a short step by a transesterification reaction with a corresponding hydroxy compound.
The transesterification is generally carried out in the presence of an acid or base catalyst. As a method for producing cyclopropanecarboxylic acid esters aimed at by the present invention, a method using a sodium alkoxide catalyst has been disclosed (Japanese Patent Application Laid-Open (JP-A) 52).
-128336). Many reports have also been made on transition metal alkoxide catalysts such as Ti (JP-A-52-128337, German Patent No. 28224).
72, British Patent No. 20052269).

[0003] However, these transesterification catalysts are unstable to moisture, and must be stored, handled and reacted under anhydrous conditions, which is not necessarily sufficient for an industrial production method. Was. Further, when a transition metal alkoxide such as Ti is used as a transesterification catalyst, the resulting ester often has a problem that it is colored.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a method for preparing cyclopropanecarboxylic acid esters in the presence of an alkali metal hydroxide which is inexpensive, industrially easily available, has excellent stability and is easy to handle. And a hydroxy compound. The present invention is intended to provide a production method capable of easily obtaining a desired cyclopropanecarboxylic acid ester in an excellent yield by performing a transesterification reaction with a hydroxy compound.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to the general formula (1) (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an aralkyl group Or an aryl group, and R ⁶ has 1 to 10 carbon atoms.
Represents an alkyl group or a phenyl group which may be substituted. And a general formula (2) R ⁷ OH (2) wherein R ⁷ is a halogen atom, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group or a heterocyclic group An aralkyl group optionally substituted with a phenoxy group, a nitro group, a cyano group, a halogen atom or an alkoxy group; or an alkyl group optionally substituted with an alkyl group, an alkoxy group or a halogen atom. A transesterification reaction with a hydroxy compound represented by the following general formula (3) in the presence of an alkali metal hydroxide: (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁷ have the same meanings as described above).

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, in producing cyclopropanecarboxylic acid ester (3) by transesterification, cyclopropanecarboxylic acid ester (1) is reacted with hydroxy compound (2) in the presence of an alkali metal hydroxide. It is characterized by the following. As the alkali metal hydroxide used as a catalyst in the present invention, Li, N belonging to the alkali metal
At least one selected from the hydroxides of a, K, Rb, Cs, and Fr can be used. Preferred are inexpensive and readily available hydroxides of Li, Na, and K, and more preferred are hydroxides of Li.

As the alkali metal hydroxide, usually,
An anhydride is used, but a hydrate such as LiOH.H ₂ O can also be used. As a charging method, water may be distilled off by an operation such as distillation after charging as an aqueous solution.

The amount of the alkali metal hydroxide used is not particularly limited, but is usually about 0.001 to 200 mol%, preferably about 0.1 to 10 mol%, based on the cyclopropanecarboxylic acid ester (1). It is.

The cyclopropane carboxylate used as a raw material in the present invention is represented by the general formula (1), wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵
Each independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aralkyl group, or an optionally substituted aryl group.

Examples of the alkyl group which may be substituted include an alkyl group having 1 to 10 carbon atoms, which may be linear, branched or cyclic.
Methyl, ethyl, n-propyl, i-propyl, n-butyl,
sec-butyl, tert-butyl, n-pentyl, n-hexyl,
Cyclohexyl, menthyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, 1-chloroethyl, 2-chloroethyl, 1-bromoethyl, 2-bromoethyl, 1,2-dichloroethyl, 1,2-dibromo Ethyl, 2,2,2-trichloroethyl,
2,2,2-tribromoethyl, methoxymethyl, 2-methoxyethyl and the like can be mentioned.

The alkenyl group which may be substituted includes vinyl, 1-methylvinyl, 1-propenyl, 2-methyl-1-propenyl, 2,2-dichlorovinyl, 2,2-dibromovinyl, 2-chloro 2-fluorovinyl, 2-chloro-2-trifluoromethylvinyl, 2-bromo-2-tribromomethylvinyl and the like can be exemplified.

Examples of the aralkyl group which may be substituted include benzyl, diphenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl and the like, and these aromatic rings have the above-mentioned alkyl group, alkoxyl group and / or halogen atom. Can be exemplified.

Examples of the alkoxyl group substituted on the aromatic ring include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t-butoxy, cyclohexoxy and the like.

The optionally substituted aryl group includes, for example, phenyl, 1-naphthyl, 2-naphthyl and the like, and these aromatic rings are formed by the above-mentioned alkyl group, alkoxyl group and / or halogen atom. Substituted ones can be exemplified. In the general formula (1), R ⁶ represents an alkyl group having 1 to 10 carbon atoms or a phenyl group which may be substituted. The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and includes, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, se
c-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, menthyl group and the like, preferably,
Methyl and ethyl groups are exemplified. Examples of the substituent of the optionally substituted phenyl group include the aforementioned alkyl group, alkoxyl group and / or halogen atom.

Specific examples of the cyclopropane carboxylate (1) as a raw material include, for example, methyl cyclopropanecarboxylate, methyl 2-fluorocyclopropanecarboxylate, methyl 2,2-dichlorocyclopropanecarboxylate, Methyl 2,2,3,3-tetramethylcyclopropanecarboxylate, methyl 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate, 2,2-dimethyl-3- (2-methyl
(-1-propenyl) methyl cyclopropanecarboxylate, 2,2-
Methyl dimethyl-3- (3-methyl-2-butenyl) cyclopropanecarboxylate, 2,2-dimethyl-3- (2,2-dichlorovinyl)
Methyl cyclopropanecarboxylate, 2,2-dimethyl-3- (2,
Methyl 2,2-trichloroethyl) cyclopropanecarboxylate, methyl 2,2-dimethyl-3- (2-chloro-2-fluorovinyl) cyclopropanecarboxylate, 2,2-dimethyl-3- (2-bromovinyl) Methyl cyclopropanecarboxylate, 2,2-dimethyl-3- (2,2-dibromovinyl) cyclopropanecarboxylate, 2,2-dimethyl-3- (1,2,2,2-tetrabromoethyl) cyclo Methyl propanecarboxylate, 2,2-dimethyl-3-
Methyl (1,2-dibromo-2,2, -dichloroethyl) cyclopropanecarboxylate, 2,2-dimethyl-3- (2-chloro-3,3,3-trifluoro-1-propenyl) cyclopropanecarboxylate Methyl 2,2-dimethyl-3- {3,3,3-trifluoro-2- (trifluoromethyl) -1-propenyl} methyl cyclopropanecarboxylate, 2,2-dimethyl-3- (2- Phenyl-1-propenyl)
Methyl cyclopropanecarboxylate, 2,2-dimethyl-3- (2-
(Phenylvinyl) methyl cyclopropanecarboxylate, 2,2
Methyl 2-dimethyl-3- (2-methyl-3-phenyl-2-butenyl) cyclopropanecarboxylate, methyl 2,2-dimethyl-3-{(2,2-difluorocyclopropylidene) methyl} cyclopropanecarboxylate 2,2-dimethyl-3- {2- (tert-butoxycarbonyl) vinyl} cyclopropanecarboxylate, 2,
Methyl 2-dimethyl-3- {2-fluoro-2- (methoxycarbonyl) vinyl} cyclopropanecarboxylate, 2,2-dimethyl-
Methyl 3- {2-fluoro-2- (ethoxycarbonyl) vinyl} cyclopropanecarboxylate, methyl 2,2-dimethyl-3- {2-fluoro-2- (tert-butoxycarbonyl) vinyl} cyclopropanecarboxylate, 2,2-dimethyl-3- [2- {2,2,2-trifluoro-1- (trifluoromethyl) ethoxycarbonyl}
Vinyl) methyl cyclopropanecarboxylate, 2,2-dimethyl-3- (2-aza-2-methoxyvinyl) methyl cyclopropanecarboxylate, 2,2-dimethyl-3- (4-aza-4-methoxy-3 Methyl-methylbuta-1,3-dienyl) cyclopropanecarboxylate, 2,2-dimethyl-3- [2-{(tert-butyl) sulfonyl} -2
-(tert-butoxycarbonyl) vinyl] methyl cyclopropanecarboxylate, 2,2-dimethyl-3- {2,2,2-tribromo-1
-(Methylsulfonyloxy) ethyl} cyclopropanecarboxylate, 2,2-dimethyl-3- {2,2-dibromo-2- (hydroxysulfinyl) -1- (methoxy) ethyl} cyclopropanecarboxylate, 2 Methyl 2,2-dimethyl-3- (methylsulfonyl) -3- {2- (tert-butylsulfonyl) -2- (tert-butoxycarbonyl) ethyl} cyclopropanecarboxylate, 2,2-dimethyl-3- {2 , 2,2-Tribromo-1- (methylsulfonyloxy) ethyl} methyl cyclopropanecarboxylate, methyl 2-methyl-2-ethyl-3- (1-propenyl) cyclopropanecarboxylate, 2,2-diethyl-3 Methyl 2- (2,2-dichlorovinyl) cyclopropanecarboxylate, methyl 2-methyl-2-phenyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate, and ester sites in these cyclopropanecarboxylates Is a methyl group, an ethyl group, a butyl group, Such as those replaced like pentyl group. Preferably, 2,2-dimethyl-3-
(2,2-dichlorovinyl) cyclopropanecarboxylic acid ester, 2,2-dimethyl-3- (2-methyl-1-
Propenyl) cyclopropanecarboxylate, 2,2-
Dimethyl-3- (1-propenyl) cyclopropanecarboxylate, 2,2-dimethyl-3- (2-aza-2-methoxyvinyl)
Cyclopropane carboxylate is exemplified.

The hydroxy compound represented by the general formula (2) used in the present invention includes optionally substituted alkyl alcohol, aralkyl alcohol and aryl alcohol. Specifically, 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-propargylfurfuryl alcohol, (5-methylisoxazol-3-yl ) Methane-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, 1- {1-prop-2-ynyl-5- (trifluoromethyl) pyrrol-3 -Yl} prop-2-yn-1-ol, (1-prop-2-ynylpyrrol-3-yl) methane-1-ol, 3- (hydroxymethyl) -1-propynyl-imidazolidin-2,4- Dione, 4-hydroxy-3-methyl-2- (2-propenyl) -2-cyclopentene-
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-
Alkyl alcohols such as (hydroxymethyl) -4-methyl- (2-propynyl) -1,3-thiazolin-2-one, 4-methylhept-4-en-1-yn-3-ol, chloromethyl alcohol, dichloro Methyl alcohol, trichloromethyl alcohol, bromomethyl alcohol, dibromomethyl alcohol, tribromomethyl alcohol, fluoromethyl alcohol, difluoromethyl alcohol, trifluoromethyl alcohol,
Fluoroethyl alcohol, difluoroethyl 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, {1- (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-thiazole -4-yl} prop-2-yn-1-ol,
1- {2- (trifluoromethoxy) -1,3-thiazol-4-yl} prop-2-yn-1-ol, 4-
And halogenated alkyl alcohols such as fluorohept-4-en-1-yn-3-ol.

The optionally substituted aralkyl alcohol includes, for example, benzyl alcohol, 2-methyl-3-
Phenylbenzyl alcohol, 2,3,5,6-tetrafluorobenzyl alcohol, 2,3,5,6-tetrafluoro-4-methylbenzyl alcohol, 2,3,5,6-tetrafluoro-4-methoxybenzyl alcohol , 2,3,5,6-tetrafluoro-4
-(Methoxymethyl) benzyl alcohol, 2,3,5,6-tetrafluoro-4-propargylbenzyl alcohol, 2,3,
5,6-tetrafluoro-4- (difluoromethyl) benzyl alcohol, 2,3,5,6-tetrafluoro-4- (difluoromethoxy) benzyl alcohol, 2,3,5,6-tetrafluoro-4-
(2,2,2-trifluoroacetyloxy) methylbenzyl alcohol, 6-chloro-2,3,4-trifluorobenzyl alcohol, 2-chloro-3,6-difluorobenzyl alcohol, 4- (trifluoromethyl) Benzyl alcohol, 2,3,
4,5-tetrafluoro-6-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-tetrafluorophenyl) -2-hydroxyethanenitrile, 2- (4-fluoro-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, anthracenyl methyl 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) methane-1-ol, (1
-Prop-2-ynyl-2-methylindol-3-yl) methan-1-ol, {1-prop-2-ynyl-
2- (trifluoromethyl) 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-trifluoro-4-pyridyl) methane-1-ol and these are fluorine, chlorine, bromine atoms Haloaralkyl alcohol substituted with halogen, such as
And the halogen atom in the haloaralkyl alcohol is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-
Alkoxy aralkyl alcohol arbitrarily changed to butoxy and the like, cyano aralkyl alcohol, nitro aralkyl alcohol and the like.

Examples of the optionally substituted aryl alcohol 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 alkoxyl group, a halogen atom, or the like can be given.

Preferred examples of the hydroxy compound (2) include primary alcohols and benzyl alcohols, more preferably 3-phenoxybenzyl alcohol.

The amount of the hydroxy compound (2) used is usually 1 equivalent or more relative to the cyclopropane carboxylic acid ester (1), and may be used in excess if necessary, or used as a solvent. Generally, after the reaction is completed, unreacted raw materials can be recovered by an operation such as distillation.

The reaction of the cyclopropanecarboxylic acid ester (1) with the hydroxy compound (2) in the presence of an alkali metal hydroxide is usually carried out in an atmosphere of an inert gas such as argon or nitrogen. The reaction can be carried out under normal pressure, increased pressure or reduced pressure. The reaction is preferably carried out under normal pressure or reduced pressure, and since the transesterification reaction is usually biased toward the raw material, alcohols derived from the cyclopropanecarboxylic acid ester (1), which is generally a raw material having a low boiling point, can be used. It is preferable to carry out the reaction while continuously removing it outside the reaction system by distillation or the like.

The reaction can be carried out without a solvent or in a solvent.
Halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, aliphatic hydrocarbons such as hexane, heptane, octane and nonane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, diethyl ether and tetrahydrofuran And the like. Further, by adding a solvent that causes azeotropic distillation with the alcohol derived from the cyclopropanecarboxylic acid ester (1) as a raw material, only the alcohol can be continuously removed.

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

The cyclopropane carboxylate (3) produced by the above reaction can remove the catalyst by washing or the like with water or acidic water and, if necessary, by performing an operation such as distillation. It can be easily separated from the reaction mixture.

[0025]

According to the present invention, the desired cyclopropanecarboxylic acid ester (3) is obtained by reacting the ester (1) with the hydroxy compound (2) in the presence of an alkali metal hydroxide. ) Can be easily obtained with excellent yield and selectivity, which is advantageous as an industrial production method.

[0026]

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

Example 1 0.021 g of LiOH.H ₂ O was placed in a 20 ml three-necked flask.
After charging 2.26 g of methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate and 6.17 g of 3-phenoxybenzyl alcohol, the mixture was heated at 110 ° C. for 1 hour.
Stir for 2 hours. The reaction mixture was analyzed by gas chromatography to find that (3-phenoxyphenyl) methyl
The yield of 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate is 98% based on the starting ester.
Met.

Example 2 0.084 g of LiOH.H ₂ O was placed in a 50 ml three-necked flask.
4.48 g of methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate, 8.03 g of 3-phenoxybenzyl alcohol, 9.00 g of n-heptane
I charged. The mixture was stirred at a heptane reflux temperature for 6 hours while removing by-produced methanol from the reaction system under an azeotropic condition of heptane. When this reaction mixture was analyzed by gas chromatography, the yield of (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate was 98% based on the starting ester. Met.

Example 3 0.084 g of LiOH.H ₂ O was placed in a 50 ml three-necked flask.
8.93 g of methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate, 10.03 g of 3-phenoxybenzyl alcohol, and 18.0 of n-heptane.
g. The mixture was stirred at a heptane reflux temperature for 6 hours while removing by-produced methanol from the reaction system under an azeotropic condition of heptane. The reaction mixture was analyzed by gas chromatography to find that (3-phenoxyphenyl) methyl 2,2-
The yield of dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate was 98% based on the starting ester.

Example 4 In Example 3, instead of 0.084 g of LiOH.H ₂ O, 1
The reaction was carried out in the same manner using 0.48 g of a 0% LiOH aqueous solution. When this reaction mixture was analyzed by gas chromatography, the yield of (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate was 98% based on the starting ester. Met.

Example 5 In a 100 ml three-necked flask, 0.096 g of LiOH was added.
17.85 g of methyl 2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate, 16.04 g of 3-phenoxybenzyl alcohol, and 17.9 of n-heptane.
g. The mixture was stirred at a heptane reflux temperature for 22 hours while removing by-produced methanol from the reaction system under heptane azeotropic conditions. The reaction mixture was analyzed by gas chromatography to find that (3-phenoxyphenyl) methyl 2,2
The yield of -dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate was 97% based on the starting ester.

Example 6 In a 100 ml three-necked flask, 0.096 g of LiOH was added.
17.89 g of methyl 2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate, 16.09 g of 3-phenoxybenzyl alcohol, and 17.9 g of xylene were charged. The mixture was stirred at the xylene reflux temperature for 12 hours. The reaction mixture was analyzed by gas chromatography to find that (3-phenoxyphenyl) methyl 2,2-dimethyl-3-
The yield of (2,2-dichlorovinyl) cyclopropanecarboxylate was 95% based on the starting ester.

Example 7 In Example 1, instead of 0.021 g of LiOH.H ₂ O, NaO was used.
Using 0.020 g of H, the reaction was carried out similarly. The reaction mixture was analyzed by gas chromatography to find that (3-phenoxyphenyl) methyl 2,2-dimethyl-3-
The yield of (2,2-dichlorovinyl) cyclopropanecarboxylate was 93% based on the starting ester.

EXAMPLE 8 0.007 g of LiOH.H ₂ O was placed in a 30 ml two-necked flask.
0.30 g of methyl 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate, 0.36 g of 3-phenoxybenzyl alcohol, and 2.0 g of toluene were charged. The mixture was stirred at the reflux temperature of toluene for 8 hours. When the reaction mixture was analyzed by gas chromatography, (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (1-propenyl)
The yield of cyclopropanecarboxylate was 99% based on the starting ester.

Example 9 In a 30 ml two-necked flask, 0.007 g of LiOH.H ₂ O was added.
0.33 g of methyl 2,2-dimethyl-3- (2-aza-2-methoxyvinyl) cyclopropanecarboxylate, 0.36 g of 3-phenoxybenzyl alcohol, and 2.0 g of toluene were charged. The mixture was stirred at the reflux temperature of toluene for 8 hours. When this reaction mixture was analyzed by gas chromatography,
The yield of (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2-aza-2-methoxyvinyl) cyclopropanecarboxylate was 83% based on the raw material ester.

Example 10 0.004 g of LiOH.H ₂ O was placed in a 30 ml two-necked flask.
0.31 g of methyl 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate, 1.00 g of (2,3,4,5,6-pentafluorophenyl) methyl alcohol, toluene Was charged in an amount of 0.6 g. The mixture was stirred at the reflux temperature of toluene for 8 hours. The reaction mixture was analyzed by gas chromatography to find that (2,3,4,5,6-pentafluorophenyl) methyl 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate The yield was 92% based on the starting ester.

Example 11 0.004 g of LiOH.H ₂ O was placed in a 30 ml two-necked flask.
0.40 g of methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate, 1.00 g of (2,3,4,5,6-pentafluorophenyl) methyl alcohol, and toluene 0.8 g was charged. The mixture was stirred at the reflux temperature of toluene for 8 hours. The reaction mixture was analyzed by gas chromatography to find (2,3,4,5,6-pentafluorophenyl)
The yield of methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate is based on the starting ester,
84%.

Example 12 In a 30 ml two-necked flask, 0.004 g of LiOH.H ₂ O was added.
0.40 g of methyl 2,2-dimethyl-3- (2-aza-2-methoxyvinyl) cyclopropanecarboxylate, 1.00 g of (2,3,4,5,6-pentafluorophenyl) methyl alcohol,
0.8 g of toluene was charged. 8 at the reflux temperature of toluene
Stirred for hours. The reaction mixture was analyzed by gas chromatography to find that (2,3,4,5,6-pentafluorophenyl) methyl 2,2-dimethyl-3- (2-aza-2-methoxyvinyl) cyclopropanecarboxylate Was 88% based on the starting ester.

Example 13 In Example 12, NaOH was replaced with 0.00 in place of LiOH.H ₂ O.
Using 4 g, a similar reaction was carried out. The reaction mixture was analyzed by gas chromatography to find (2,3,4,
5,6-pentafluorophenyl) methyl 2,2-dimethyl-3-
The yield of (2-aza-2-methoxyvinyl) cyclopropanecarboxylate was 78% based on the starting ester.

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Claims (8)

[Claims] 1. The general formula (1) (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an aralkyl group Or an aryl group, and R ⁶ has 1 to 10 carbon atoms.
Represents an alkyl group or a phenyl group which may be substituted. )) And a compound represented by the general formula (2) R ⁷ OH (2)
(Wherein, R ⁷ is an alkyl group optionally substituted with a halogen atom, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group or a heterocyclic group; a phenoxy group, a nitro group, a cyano group, a halogen atom or An aralkyl group optionally substituted by an alkoxy group; or an alkyl group, an alkoxy group or an aryl group optionally substituted by a halogen atom) in the presence of an alkali metal hydroxide. General formula (3) characterized in that transesterification is carried out on (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁷ have the same meanings as described above). 2. The method according to claim 1, wherein the alkali metal is Li or Na.
The manufacturing method as described. 3. The method according to claim 1, wherein the alkali metal hydroxide is LiOH or LiOH.
_2. The production method according to claim 1, wherein the production method is OH.H ₂ O. 4. The process according to claim 1, wherein R ^{6 of the} cyclopropanecarboxylic acid ester represented by the general formula (1) is methyl or ethyl. 5. The cyclopropanecarboxylic acid ester represented by the general formula (1) is 2,2-dimethyl-3- (2,2
-Dichlorovinyl) cyclopropanecarboxylic acid ester, 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid ester, 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylic acid The method according to any one of claims 1 to 4, which is an ester or 2,2-dimethyl-3- (2-aza-2-methoxyvinyl) cyclopropanecarboxylic acid ester. 6. The method according to claim 1, wherein the hydroxy compound represented by the general formula (2) is a primary alcohol. 7. The production method according to claim 1, wherein the hydroxy compound represented by the general formula (2) is a benzyl alcohol. 8. The method according to claim 1, wherein the hydroxy compound represented by the general formula (2) is 3-phenoxybenzyl alcohol.
6. The production method according to any one of items 1 to 5,