JP2000178232A - Method for producing cyclopropanecarboxylic acid esters - Google Patents

Abstract

(57) [Problem] To provide a method for producing cyclopropanecarboxylic acid esters. SOLUTION: General formula (1) (R ¹ , R ² , R ³ , R ⁴ and R ⁵ are hydrogen, halogen, good alkyl, alkenyl, aralkyl, aryl group, R ⁶
Is alkyl or phenyl. ) And a monohydroxy compound represented by the general formula (2) R ⁷ OH (2) (R ⁷ is alkyl, aralkyl, aryl) in the presence of a lanthanoid group metal alkoxide compound. General formula (3) for transesterification A method for producing cyclopropanecarboxylic acid esters represented by the formula:

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 a method of obtaining a desired ester compound by converting an ester of the corresponding cyclopropanecarboxylic acid with a lower alcohol to a carboxylic acid by hydrolysis once, converting the ester into an acid chloride, and then reacting the ester with the corresponding monohydroxy compound is well known. ing. 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 monohydroxy compound. The transesterification is generally carried out in the presence of an acid or base catalyst. British Patent No. 15581/76 discloses a sodium alkoxide catalyst as a method for producing cyclopropanecarboxylic acid esters aimed at by the present invention. Also, many reports have been made on transition metal alkoxide catalysts such as Ti (British Patent No. 15582/76, German Patent No. 2822472,
UK Patent 2005005269). However, the method using these transesterification catalysts is not necessarily sufficient for an industrial production method because there are many by-products. Further, the sodium alkoxide catalyst has problems such as affecting the cis-trans ratio of the target product. In addition, as a method for producing a carboxylic acid ester by transesterification, see Japanese Patent Application Laid-Open No.
JP-A-239270 describes a method of reacting vinyl acetate or the like with octyl alcohol or the like in the presence of samarium (II) iodide, di (η ⁵ -pentamethylcyclopentadienyl) samarium or the like. There is no description regarding the production of carboxylic esters. Also,
JP-A-7-330671 discloses a method in which a transesterification reaction of a benzoate or the like is carried out in the presence of tri-t-butoxysilanetan or tri-t-butoxyyttrium, but cyclopropanecarboxylic esters are disclosed. There is no description regarding the production of.

[0003]

DISCLOSURE OF THE INVENTION The present invention is intended to easily produce a desired cyclopropanecarboxylic acid ester in an excellent yield by a transesterification reaction of the cyclopropanecarboxylic acid ester with a corresponding monohydroxy compound. The aim is to provide a production method which can be obtained.

[0004]

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 alkyl group which may have a substituent, A good alkenyl group, an optionally substituted aralkyl group or an optionally substituted aryl group is shown, and R ⁶ is an alkyl group or an optionally substituted phenyl group. ) And a general formula (2) R ⁷ OH (2) (where R ⁷ is an alkyl group which may have a substituent, A aralkyl group or an aryl group which may have a substituent.) A transesterification reaction of the monohydroxy compound represented by the general formula (3) in the presence of an alkoxide compound of a lanthanoid group metal. (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁷ have the same meanings as described above).

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The present invention provides a method for producing cyclopropanecarboxylic acid esters (3) by transesterification by reacting cyclopropanecarboxylic acid esters (1) with a monohydroxy compound (2) in the presence of a lanthanoid metal alkoxide. Features. In the present invention, La, Ce, Pr, Nd, Pm, S
m, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
At least one compound selected from the group consisting of b and Lu alkoxy compounds can be used. Preferably, La and Sm alkoxy compounds that are industrially easily available are used.

[0006] alkoxide compound of lanthanide metals, for example, the general formula ^{(4) Ln (OR 8)} (OR 9) (OR 10) (4) ( wherein, Ln represents a lanthanoid metal element, R ^8, R ⁹
And R ¹⁰ are the same or different and represent an alkyl group having 1 to 10 carbon atoms. )).
R ⁸ , R ⁹ and R ¹⁰ include an alkyl group having 1 to ¹⁰ carbon atoms, which may be linear, branched or cyclic, such as methyl, ethyl, n-propyl, i- Propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Further, they may combine with each other to form a divalent or trivalent alkoxide.

Further, depending on the kind of the metal or the kind of the aliphatic hydrocarbon group, a polymer may be formed in addition to the monomer represented by the general formula (4), and these may be used in the present invention. .

As the alkoxide, methoxide, ethoxide, n-propoxide, i-propoxide, butoxide and the like are preferably used because of ease of preparation. More preferably, because it is soluble in the solvent described below, n-propoxide, i-propoxide, butoxide, more preferably because the cost of catalyst preparation is inexpensive, because the production operation is advantageous, etc. -Propoxide.

These lanthanoid metal alkoxide catalysts can be prepared by a known method, and may be subjected to a reaction after isolation, or may be used as a solution after preparation. Further, the alkoxide of the lanthanoid metal once prepared may be reacted with the monohydroxy compound (2) as a reaction raw material, and used as an alkoxide catalyst containing the monohydroxy compound (2) as a reaction raw material.

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

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
Are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, Represents an aryl group which may have

The alkyl group of the alkyl group which may have a substituent is a straight-chain, branched-chain or cyclic C 1 -C 1 alkyl group.
Examples of the substituent include halogen, alkoxy, phenoxyimino, alkoxyimino, alkenyloxyimino, alkynyloxyimino, hydroxyimino, alkoxycarbonyl, and alkylsulfinyl, and have a substituent. Specific examples of the alkyl group which may be, for example, 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-dibromoethyl, 2,2,2-trichloroethyl, 2,2,2-tribromoethyl, methoxymethyl, 2-methoxyethyl, phenoxyiminomethyl, methoxyiminomethyl, Allyloxyiminomethyl, propargyloxyiminomethyl, hydroxyiminomethyl and the like can be mentioned.

Examples of the substituent of the alkenyl group which may have a substituent include halogen, phenyl, haloalkyl, alkoxycarbonyl, alkylsulfonyl, alkylsulfonyloxy and hydroxyimino, wherein the hydrogen of hydroxy is phenyl, alkyl , Alkenyl or alkynyl. Specific examples of the alkenyl group include 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- Examples thereof include 2-tribromomethylvinyl and the like.

The aralkyl group which may have a substituent is phenylalkyl or naphthylalkyl, which may be substituted with alkyl, alkoxy or halogen. Specific examples of the aralkyl group include benzyl, diphenyl Methyl, phenylethyl, naphthylmethyl, naphthylethyl and the like can be mentioned.

The aryl group which may have a substituent is phenyl or naphthyl, which may be substituted with alkyl, alkoxy or halogen. Specific examples include phenyl, 1-naphthyl, 2 -Naphthyl and the like, and examples thereof include those in which these aromatic rings are substituted with an alkyl group, an alkoxyl group, a halogen atom or the like.

In the general formula (1), R ⁶ has 1 to 1 carbon atoms.
And 10 represents an alkyl group or a phenyl group which may have a substituent. 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 phenyl group which may have a substituent include an alkyl group, an alkoxyl group, and a halogen atom.

Specific examples of the cyclopropane carboxylate (1) as a raw material include, for example, methyl cyclopropane carboxylate, methyl 2-fluorocyclopropane carboxylate, methyl 2,2-dichlorocyclopropane carboxylate, Methyl 2,2,3,3-tetramethylcyclopropanecarboxylate, methyl 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate, 2,2-dimethyl-3- (2-methyl-1-propenyl) ) Methyl cyclopropanecarboxylate, methyl 2,2-dimethyl-3- (3-methyl-2-butenyl) cyclopropanecarboxylate, 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylic acid Methyl, 2,2-dimethyl-3- (2,2,2-
(Trichloroethyl) methyl cyclopropanecarboxylate,
Methyl 2,2-dimethyl-3- (2-chloro-2-fluorovinyl) cyclopropanecarboxylate, Methyl 2,2-dimethyl-3- (2-bromovinyl) cyclopropanecarboxylate, 2,2-dimethyl-
Methyl 3- (2,2-dibromovinyl) cyclopropanecarboxylate, Methyl 2,2-dimethyl-3- (1,2,2,2-tetrabromoethyl) cyclopropanecarboxylate, 2,2-dimethyl-3 -(1,2-
Methyl dibromo-2,2, -dichloroethyl) cyclopropanecarboxylate, methyl 2,2-dimethyl-3- (2-chloro-3,3,3-trifluoro-1-propenyl) cyclopropanecarboxylate, 2, Methyl 2-dimethyl-3- {3,3,3-trifluoro-2- (trifluoromethyl) -1-propenyl} cyclopropanecarboxylate, 2,2-dimethyl-3- (2-phenyl-1-propenyl) ) Methyl cyclopropanecarboxylate, methyl 2,2-dimethyl-3- (2-phenylvinyl) cyclopropanecarboxylate, 2,2-
Methyl dimethyl-3- (2-methyl-3-phenyl-2-butenyl) cyclopropanecarboxylate, methyl 2,2-dimethyl-3-{(2,2-difluorocyclopropylidene) methyl} cyclopropanecarboxylate, Methyl 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- (4-aza-4-methoxy-3-methylbuta-1,3-dienyl)
Methyl cyclopropanecarboxylate, 2,2-dimethyl-3- [2
-{(tert-Butyl) sulfonyl} -2- (tert-butoxycarbonyl) vinyl] cyclopropanecarboxylate, 2,2-
Dimethyl-3- {2,2-dibromo-2- (hydroxysulfinyl) -1- (methoxy) ethyl} cyclopropanecarboxylate, 2,2-dimethyl-3- (methylsulfonyl) -3- {2- ( tert
-Butylsulfonyl) -2- (tert-butoxycarbonyl) ethyl} methyl 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 Methyl -3- (2,2-dichlorovinyl) cyclopropanecarboxylate, methyl 2-methyl-2-phenyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate,
Methyl 2,2-dimethyl-3- (methoxyiminomethyl) cyclopropanecarboxylate, 2,2-dimethyl-3-
Methyl (phenoxyiminomethyl) cyclopropanecarboxylate, methyl 2,2-dimethyl-3- (allyloxyiminomethyl) cyclopropanecarboxylate, methyl 2,2-dimethyl-3- (propargyloxyiminomethyl) cyclopropanecarboxylate , 2,2-dimethyl-3-
Methyl (hydroxyiminomethyl) cyclopropanecarboxylate, and those in which the methyl group at the ester site in these cyclopropanecarboxylic acid esters is replaced with an ethyl group, a butyl group, a menthyl group, and the like. Preferably, 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylic acid ester,
Examples thereof include 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylic acid ester and 2,2-dimethyl-3- (methoxyiminomethyl) cyclopropanecarboxylic acid ester.

The monohydroxy compound represented by the general formula (2) used in the present invention includes an alkyl alcohol which may have a substituent, an aralkyl alcohol which may have a substituent, and a compound having a substituent. And the like. Examples of the substituent for the alkyl alcohol include halogen, alkenyl optionally substituted with halo, alkynyl, cycloalkyl, cycloalkenyl, furyl (optionally substituted with phenoxy, benzyl, difluoromethyl or propynyl),
Propynyl-substituted pyrrolyl (optionally substituted with halomethyl), thiazolyl (optionally substituted with halomethyl or halomethoxy), isoxazolyl optionally substituted with methyl, 4,5,6,7-tetrahydroisoindole- 1,3-dione-2-yl, 1-propynyl-imidazolidin-2,4-dione-3-yl, pyrazolyl (optionally substituted with propynyl or halomethyl),
Halopyridyl, thiazolin-2-one-5-yl (optionally substituted with methyl or propynyl), (methyl,
Propynyl or propenyl substituted) oxocycloalkenyl, indolyl (optionally substituted with alkyl, alkenyl, alkynyl, phenyl or thienyl), pyridyl (optionally substituted with halogen or alkyl) and the like. The aralkyl group of the aralkyl alcohol is phenylalkyl, naphthylalkyl or anthracenylalkyl, and examples thereof include aralkyl groups in which these aromatic rings may be substituted with the following groups. Alkyl group, halogen atom, haloalkyl group, cyanoalkyl group, cyano, nitro, alkoxyalkyl group, phenyl group (optionally substituted with halogen, amino or alkyl), (optionally substituted with halogen or alkyl) Phenoxy group. Aryl alcohols include a phenyl or naphthyl group in which the aryl group is optionally substituted by halogen, alkyl, alkoxy, formyl, alkenyl or alkynyl.

Specific examples of the alkyl alcohol which may have a substituent 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-propargylfurfuryl
Alcohol, (5-methylisoxazol-3-yl) methane-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-
All, 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-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
Alkyl alcohols such as -thiazolin-2-one, 4-methylhept-4-en-1-yn-3-ol, fluoromethyl alcohol, trifluoromethyl alcohol, 3,3-dibromo-2-propen-1-ol, Hexafluoroisopropyl alcohol, perfluorobutyl alcohol, perfluoropentyl alcohol, perfluorohexyl alcohol, perfluorooctyl alcohol, perfluorodecyl alcohol, {1- (2-propynyl) -5- (trifluoromethyl) -4-pyrazolyl } Halogenated alkyl alcohols such as methane-1-ol, 4-fluorohept-4-en-1-yn-3-ol, (1-prop-2-ynyl-2-methylindol-3-yl) methane- 1-ol, {1-prop-
2-ynyl-2- (trifluoromethyl) indole-3-
Yl} methane-1-ol, 4-prop-2-enylindane
-1-ol, 4-phenylindan-2-ol, 4- (2-thienyl) indan-2-ol, (2,3,6-trifluoro-4-pyridyl) methane-1-ol, and the like. .

The aralkyl alcohol which may have a substituent includes, for example, benzyl alcohol, 2-methyl
-3-phenylbenzyl alcohol, 2,3,5,6-tetrafluorobenzyl 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, 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) methane-1-ol, and these are fluorine, chlorine, bromine A haloaralkyl alcohol substituted with a halogen such as an atom, and a halogen atom in the haloaralkyl alcohol is methoxy,
Alkoxy aralkyl alcohol arbitrarily changed to ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, etc., and cyano aralkyl alcohol, nitroaralkyl alcohol, and the like.

The aryl alcohol which may have a substituent includes, for example, phenol, 1-naphthol,
-Naphthol, 4-prop-2-ynylphenol, 3
-Prop-2-ynylphenol, 4-hydroxyacetophenone, 4-hydroxybenzaldehyde, and those in which the aromatic ring is substituted with an alkyl group, an alkoxyl group, a halogen atom, or the like.

Preferred examples of the monohydroxy compound (2) include primary alcohols and benzyl alcohols, and more preferred are 3-phenoxybenzyl alcohol, 2,3,5,6-tetrafluorobenzyl alcohol, 3,5,6-tetrafluoro-4-methylbenzyl alcohol and 2,3,5,6-tetrafluoro-4-methoxybenzyl alcohol.

The amount of the monohydroxy compound (2) to be used is usually 1 equivalent or more based on the cyclopropanecarboxylic 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 monohydroxy compound (2) in the presence of a lanthanoid metal alkoxide compound 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 biased toward the raw material, alcohols derived from cyclopropanecarboxylic acid ester (1), which is generally a raw material having a low boiling point, are reacted with the reaction system. It is preferable to carry out the reaction while removing continuously by a method such as distillation.

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. Also, by adding a solvent that causes azeotropic distillation with the alcohol derived from the cyclopropanecarboxylic acid ester (1) as the 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 catalyst can be removed from the cyclopropane carboxylate (3) produced by the above reaction by washing or the like with water or acidic water, and by performing an operation such as distillation if necessary. It can be easily separated from the reaction mixture.

[0028]

According to the present invention, cyclopropanecarboxylic acid esters (3) can be easily obtained in excellent yield, which is advantageous as an industrial production method.

[0029]

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 0.13 g (0.4 mmol) of triisopropoxysamarium (III) and methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanoate were placed in a Schlenk tube purged with nitrogen. After adding 78 g (8 mmol) and 3.39 g (16 mmol) of 3-phenoxybenzyl alcohol, the mixture was stirred at 90 ° C for 1.5 hours. The reaction mixture was analyzed by gas chromatography to find that (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2-
The yield of (dichlorovinyl) cyclopropanecarboxylate was 99%.

Example 2 0.13 g (0.4 mmol) of triisopropoxysilanetan (III) and methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanoate were placed in a Schlenk tube purged with nitrogen. After adding 75 g (8 mmol) and 3.27 g (16 mmol) of 3-phenoxybenzyl alcohol, the mixture was stirred at 90 ° C for 1.5 hours. The reaction mixture was analyzed by gas chromatography to find that (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2-
The yield of (dichlorovinyl) cyclopropanecarboxylate was 94%.

Example 3 0.19 g (0.6 mmol) of triisopropoxysamarium (III) and methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanoate were placed in a Schlenk tube purged with nitrogen. After adding 87 g (12.8 mmol) and 2.56 g (12.8 mmol) of 3-phenoxybenzyl alcohol, the mixture was stirred at 90 ° C. for 6 hours. The reaction mixture was analyzed by gas chromatography and found to be (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2
The yield of-(dichlorovinyl) cyclopropanecarboxylate was 93%.

Example 4 0.16 g (0.5 mmol) of triisopropoxysamarium (III) and ethyl 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanoate were placed in a Schlenk tube purged with nitrogen. .96 g (10.0 mmol), 3-phenoxybenzyl alcohol 4.00 g (20.0 mm
ol) and stirred at 130 ° C. for 12 hours. When the reaction mixture was analyzed by gas chromatography,
The yield of (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2-dimethylvinyl) cyclopropanecarboxylate was 92%.

Example 5 0.16 g (0.5 mmol) of triisopropoxysilanetan (III) and ethyl 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanoate were placed in a Schlenk tube purged with nitrogen. .96 g (10.0 mmol), 3-phenoxybenzyl alcohol 4.00 g (20.0 mmol)
After l) was added, the mixture was stirred at 130 ° C for 12 hours. When the reaction mixture was analyzed by gas chromatography, (3
-Phenoxyphenyl) methyl 2,2-dimethyl-3
The yield of-(2,2-dimethylvinyl) cyclopropanecarboxylate was 90%.

Comparative Example 1 0.13 g (0.4 mmol) of tetraisopropoxytitanium (IV) and methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanoate were placed in a Schlenk tube purged with nitrogen. After adding 75 g (8 mmol) and 3.27 g (16 mmol) of 3-phenoxybenzyl alcohol,
Stirred at 90 ° C. for 3 hours. When the reaction mixture was analyzed by gas chromatography, the yield of (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate was 31.
%Met.

Comparative Example 2 Anhydrous samarium (III) chloride was placed in a Schlenk tube purged with nitrogen.
0.11 g (0.4 mmol), 2,2-dimethyl-3-
After adding 1.86 g (8.3 mmol) of methyl (2,2-dichlorovinyl) cyclopropanoate and 3.45 g (17.2 mmol) of 3-phenoxybenzyl alcohol,
Stirred at 90 ° C. for 5 hours. When the reaction mixture was analyzed by gas chromatography, the yield of (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate was 5%.
Met.

Example 6 0.16 g (0.5 mmol) of triisopropoxysilanetan (III) and ethyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanoate were placed in a Schlenk tube purged with nitrogen. 23 g (10.0 mmol), 2.40 g (12.0 mmol) of 3-phenoxybenzyl alcohol
l), 5.5 g of heptane was added, and the mixture was stirred at heptane reflux temperature for 12 hours. When the reaction mixture was analyzed by gas chromatography, the yield of (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate was 96%.

Example 7 0.16 g (0.5 mmol) of triisopropoxysilanetan (III) and ethyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanoate were placed in a Schlenk tube purged with nitrogen. 23 g (10.0 mmol), 2.00 g of 3-phenoxybenzyl alcohol (10.0 mmol)
l), 5.5 g of heptane was added, and the mixture was stirred at a heptane reflux temperature for 18 hours. When the reaction mixture was analyzed by gas chromatography, the yield of (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate was 92%.

Example 8 0.16 g (0.5 mmol) of triisopropoxysilanetan (III) and 2.20 g (11.0 mmol) of 3-phenoxybenzyl alcohol were added to a Schlenk tube purged with nitrogen, and then added at 60 ° C. and 50 Torr. (Equivalent to 66.6 hPa) for 2 hours. Then, 2,2-dimethyl-3
After 2.23 g (10.0 mmol) of ethyl-(2,2-dichlorovinyl) cyclopropanoate and 5.5 g of heptane were added, the mixture was stirred at a heptane reflux temperature for 15 hours. When the reaction mixture was analyzed by gas chromatography,
The yield of (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate was 99%.

Example 9 0.08 g (0.25 mmol) of triisopropoxysilanetan (III) and vinyl 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanoate were placed in a Schlenk tube purged with nitrogen. 0.000 g (5.0 mmol), 3-phenoxybenzyl alcohol 1.20 g (6.0 mmol)
After adding l), the mixture was stirred at 80 ° C for 12 hours. When the reaction mixture was analyzed by gas chromatography, (3-
Phenoxyphenyl) methyl 2,2-dimethyl-3-
The yield of (2,2-dimethylvinyl) cyclopropanecarboxylate was 97%.

Example 10 29 mg (0.09 mmol) of triisopropoxysamarium (III) was placed in a 10 ml eggplant-shaped flask purged with nitrogen.
Methyl 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate 300 mg (1.78 mmol)
l), 714 mg of 3-phenoxybenzyl alcohol
(3.56 mmol) and then stirred at 110 ° C. for 8 hours. When the reaction mixture was analyzed by gas chromatography, (3-phenoxyphenyl) methyl 2,
The yield of 2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate was 64%.

Example 11 35.4 mg (0.11 mmol) of triisopropoxysamarium (III) was placed in a 10 ml eggplant-shaped flask purged with nitrogen.
l), methyl 2,2-dimethyl-3- (methoxyiminomethyl) cyclopropanecarboxylate 200 mg (1.
08 mmol), 3-phenoxybenzyl alcohol 4
After charging 32 mg (2.16 mmol), 110 ° C.
For 8 hours. When the reaction mixture was analyzed by gas chromatography, it was found that (3-phenoxyphenyl) methyl 2,2-dimethyl-3- (methoxyiminomethyl)
The yield of cyclopropane carboxylate was 83%.

Claims (13)

[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 alkyl group which may have a substituent, A good alkenyl group, an optionally substituted aralkyl group or an optionally substituted aryl group is shown, and R ⁶ is an alkyl group or an optionally substituted phenyl group. ) And a general formula (2) R ⁷ OH (2) (where R ⁷ is an alkyl group which may have a substituent, A aralkyl group or an aryl group which may have a substituent.) A transesterification reaction of the monohydroxy compound represented by the general formula (3) in the presence of an alkoxide compound of a lanthanoid group metal. (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁷ have the same meanings as described above). 2. In the general formula (1), R ¹ , R ² , R ³ ,
The substituent of the alkyl group of R ⁴ and R ⁵ is halogen, alkoxy, alkoxycarbonyl, alkylsulfonyl or hydroxyimino, wherein the hydrogen of hydroxy is
A phenyl, alkyl, alkenyl, or alkynyl group;
Phenyl, haloalkyl, alkoxycarbonyl, alkylsulfonyl, alkylsulfonyloxy or hydroxyimino, wherein the hydrogen of hydroxy may be substituted by phenyl, alkyl, alkenyl or alkynyl; the aralkyl group is phenylalkyl or naphthylalkyl May be substituted with alkyl, alkoxy or halogen; the aryl group is phenyl or naphthyl, which may be substituted with alkyl, alkoxy or halogen; the phenyl group of R ⁶ is The method according to claim 1, wherein the compound may be substituted with alkoxy or halogen. 3. The alkyl group represented by R ^{7 in} the general formula (2) is substituted by halogen, alkenyl, alkynyl, cycloalkyl, cycloalkenyl which may be substituted with halo, (phenoxy, benzyl, difluoromethyl or propynyl). Furyl, propynyl-substituted pyrrolyl (optionally substituted with halomethyl), thiazolyl (optionally substituted with halomethyl or halomethoxy), isoxazolyl optionally substituted with methyl, 4,5,6, 7-tetrahydroisoindole-1,3-dione-2-yl, 1-propynyl-imidazolidin-2,4-dione-3-yl, pyrazolyl (optionally substituted with propynyl or halomethyl), halopyridyl, ( Thiazolin-2-one-5-yl, which may be substituted by methyl or propynyl, (methyl, Lopinyl or propenyl substituted) oxocycloalkenyl, indolyl (optionally substituted with alkyl, alkenyl, alkynyl, phenyl or thienyl), pyridyl (optionally substituted with halogen or alkyl) 3. The production method according to claim 1, wherein the production method is an alkyl group. 4. The aralkyl group of R ^{7 in} the general formula (2) is phenylalkyl, naphthylalkyl or anthracenylalkyl, and these aromatic rings are aralkyl groups which may be substituted with the following groups. Claim 1
Or the production method according to 2. Alkyl group, halogen atom,
Haloalkyl group, cyanoalkyl group, cyano, nitro,
An alkoxyalkyl group, a phenyl group (optionally substituted with halogen, amino or alkyl), and a phenoxy group (optionally substituted with halogen or alkyl). 5. The method according to claim 1, wherein the aryl group of R ^{7 in} the general formula (2) is a phenyl group (optionally substituted with halogen, alkyl, alkoxy, formyl, alkenyl or alkynyl) or a naphthyl group. The manufacturing method as described. 6. The method according to claim 1, wherein the lanthanoid metal is La or Sm. 7. The alkoxide compound of a lanthanoid metal is
The method according to claim 1, wherein the method is La (OiPr) ₃ or Sm (OiPr) ₃ . 8. The process according to claim 1, wherein R ^{6 of the} cyclopropanecarboxylic acid ester represented by the general formula (1) is methyl or ethyl. 9. 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- (methoxyiminomethyl) cyclopropanecarboxylic acid Ester or 2,2-dimethyl-3- (1
The method according to any one of claims 1 to 8, which is -propenyl) cyclopropanecarboxylic acid ester. 10. The method according to claim 1, wherein the monohydroxy compound represented by the general formula (2) is a primary alcohol. 11. The method according to claim 1, wherein the monohydroxy compound represented by the formula (2) is a phenylalkyl alcohol which may be substituted with phenoxy, nitro, cyano, halogen or alkoxy. Production method. 12. The method according to claim 1, wherein the monohydroxy compound represented by the general formula (2) is benzyl alcohol which may be substituted with a phenoxy group, a nitro group, a cyano group, a halogen atom or an alkoxy group. The production method described in 1. 13. The method according to claim 1, wherein the monohydroxy compound represented by the general formula (2) is 3-phenoxybenzyl alcohol.