JPS61148138A - Production of dichlorocyclopropanecarboxylic acid - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as an intermediate of insecticide, economically on an industrial scale, in high yield, with >=2 steps, from an acetophenone compound and chloroform using an aqueous solution of a base and a phase-transfer catalyst and if necessary an alcohol. CONSTITUTION:The compound of formula I [X is H, lower alkyl, lower alkoxy, benzyloxy, halogen, or phenoxy which may have substituent group (lower alkyl, lower alkoxy or halogen)] is made to react with chloroform in the presence of an aqueous solution of a base and a phase-transfer catalyst to obtain a mixture of the compounds of formula II - formula IV. The objective compound of formula IV can be produced economically on an industrial scale, either by reacting the mixture with chloroform under the above condition or by reacting the mixture with chloroform in the presence of an alcohol under the above condition and hydrolyzing the mixture of the resultant compound of formula IV and the ester of the compound and the above alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel method for producing dichlorocyclopropanecarboxylic acids, which are compounds useful as intermediates for insecticides.

[Conventional technology]

A method for producing the dichlorocyclopropanecarboxylic acid derivative of formula [I] below is shown in Japanese Patent Publication No. 55-2101). That is, the method of Japanese Patent Publication No. 55-2101) is based on the formula [I
The 4-ethoxyphenylacetate of I] is condensed with diethyl acetate in the presence of a base catalyst to produce a compound of formula 1 below and 4-ethoxyphenyl oxaloacetate of formula 1 below. 2) is reacted with formaldehyde under alkaline conditions to form 4-ethoxyphenylhydroxymethyl acetate, and this compound is dehydrated to form a compound of formula [v] below. The compound of formula [I] is produced by reacting the compound of formula [V] with dichlorocarbene and then hydrolyzing it.

[■]

0OEt [V] [I] [Problems to be solved by the invention] Conventional methods for producing dichlorocyclopropanecarboxylic acids all skillfully combine well-known chemical reactions, but generally the process The procedure is long, the operation is complicated, and it is not necessarily industrially advantageous. Therefore, it is desired to develop an industrially advantageous and safe method. The present invention provides an industrially convenient method that does not have these drawbacks, that is, a method in which the reaction conditions are mild, the reaction and post-treatment are simple, and the number of reaction steps is small.

[Means for solving problems]

As a result of extensive research into an industrially advantageous production method for dichlorocyclopropanecarboxylic acids, the present inventors have determined that the formula (wherein, X is a hydrogen atom; a lower alkyl group; Lower alkoxy group: penzyloxy group;
halogen atom or lower alkyl group, lower alkoxy group,
or (indicating a phenoxy group optionally substituted with a halogen atom)) can be obtained in good yield.

(A): Formula (wherein, X represents a hydrogen atom; a lower alkyl group; a lower alkoxy group: a benzyloxy group; a halogen atom or a phenoxy group optionally substituted with a lower alkyl group, a lower alkoxy group, or a halogen atom) The compound represented by 9 and chloroform are reacted in the presence of an aqueous base solution and a phase transfer catalyst to obtain a mixture of compounds represented by the formula (wherein, X is the same as formula (1)) ■ A compound of formula (4) obtained by reacting with chloroform in the presence of an aqueous base solution and a phase transfer catalyst, or ■ A compound of formula (4) obtained by reacting with chloroform in the presence of an aqueous base solution, a phase transfer catalyst, and an alcohol; A method for producing dichlorocyclopropanecarboxylic acids represented by formula (4), which comprises hydrolyzing a mixture of a compound of formula (4) and an ester from an alcohol.

(Bl: Formula (wherein, X represents a hydrogen atom, a lower alkyl group; a lower alkoxy group; a benzidioxy group; a phenoxy group optionally substituted with a rogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom) ) and chloroform in the presence of an aqueous base solution and a phase transfer catalyst to obtain a mixture of compounds represented by the formula (wherein X is the same as formula (1)). A mixture of alkyl esters of formulas (21i31 and (4)) is obtained by reacting with an alkylating agent, and the ester mixture is reacted with chloroform in the presence of an aqueous base solution and a phase transfer catalyst or by dehydration. The ester of the compound of formula (3) is converted into the ester of the compound of formula (2) by carrying out the following steps, and then reacted with chloroform in the presence of an aqueous base solution and a phase transfer catalyst to obtain the formula ( 4) A method for producing dichlorocyclopropanecarboxylic acids represented by formula (4), which comprises hydrolyzing an ester of the compound.

Hereinafter, one aspect of the present invention will be explained in detail.

The prisoner's method is carried out as follows. First, the compound of formula (1) and chloroform, preferably 2 to 10 times the mole thereof, are mixed with a phase transfer catalyst, preferably 5 to 20 times the mole of the compound of formula (1), and 0.7 to 3 times the mole thereof. A mixture of the compounds of formulas (2), (3) and (4) can be produced in a yield of 90% or more by carrying out the reaction preferably at -10 to 50°C in the presence of a double molar aqueous base solution. After the above reaction, when the reaction solution is allowed to stand still, it separates into an organic layer, an aqueous layer, and an inorganic salt layer, but the mixture consists mostly of compounds of formulas (2), (3), and (4) and a phase transfer catalyst. Present in the organic phase in the form of salts.

This organic layer can then be separated from the aqueous layer and the inorganic salt layer or subjected to the next reaction without separation.

That is, in the separated organic layer or in the mixture of the organic layer, aqueous layer, and inorganic salt layer after the above reaction, chloroform is added in an amount of preferably 5 to 10 times the mole of the compound of formula (1), preferably 10 Formula 5 (4
) can be obtained in good yield.

The prisoner's method is carried out as follows. That is, in the mixture of the organic layer, aqueous layer, and inorganic salt layer obtained by the method (1), or in the separated organic layer, chloroform, preferably in an amount of 5 to 10 times the mole of the compound of formula (1), is added. Preferably 10
The compound of formula (4), the compound of formula (4), and the alcohol are reacted at -10 to 50°C in the presence of ~50 times the mole of an aqueous base solution, preferably 1.5 to 3 times the mole of alcohol. Obtain a mixture with ester from or hydrochloric acid,
By heating and hydrolyzing at room temperature to 100°C in the presence of an acid such as sulfuric acid and water and/or an alcohol such as methanol.

The compound of formula (4) can be obtained in good yield. The action of alcohol seems to help stabilize the product.

The organic layer is separated from the mixture with the formula (1).
The alkyl esters of the compounds of formulas (2), (3) and (41) are reacted in the presence of an alkylating agent in an amount of preferably 1 to 3 times the mole of the compound, preferably at 0 to 90°C. The mixture can be obtained quantitatively. Alternatively, the above organic layer is made acidic with hydrochloric acid, sulfuric acid, etc. and extracted with an organic solvent such as dichloromethane, chloroform, etc. to obtain the formula (
A mixture of 2), (3) and (4) is obtained and the mixture is esterified using an alkylating agent as described above to give formula (2)
, (3) and (4) can be obtained. Preferably chloroform in an amount of 2 to 10 times the mole of the mixture of alkyl esters of the compounds of formulas (2), (3) and (4), preferably 2 to 20 times the mole
The alkyl ester of Formula 1 (4) can be obtained by reacting in the presence of a double molar aqueous base solution and a catalytic amount mΦ of a phase transfer catalyst, preferably at 20 to 70°C. The alkyl ester is then treated by a known method 5, for example, in the presence of an alkali hydroxide such as sodium hydroxide or potassium hydroxide, or an acid such as hydrochloric acid or sulfuric acid, and water and/or an alcohol such as methanol from room temperature to 100 ml.
By heating and hydrolyzing at °C.

The compound of formula (4) can be obtained in good yield.

Method (B) (■) is implemented as follows. [F]) A mixture of the alkyl ester of the compound of formula (21i31 and (4)) obtained by the method (1) of (1) is preferably 0.05 to 0.5 times the mole of the compound of formula (1). aromatic or aliphatic sulfonic acid, preferably from 40 to 150°C.
By heating and dehydrating under reflux, a mixture of alkyl esters of formulas (2) and (4) can be obtained in good yield. The mixture of alkyl esters is heated preferably at 20 to 70°C in the presence of chloroform, preferably 2 to 20 times the molar amount of chloroform, preferably 2 to 20 times the molar amount of an aqueous base solution, and a catalytic amount of a phase transfer catalyst. By reacting with , the alkyl ester of formula (4) can be obtained. The alkyl ester is then prepared using known methods 1, such as alkali hydroxides such as sodium hydroxide, potassium hydroxide, or hydrochloric acid.

The compound of formula (4) can be obtained in good yield by thermal decomposition at room temperature to 100° C. in the presence of an acid such as sulfuric acid and water and/or an alcohol such as methanol.

Next, examples of the aqueous base solution used in the present invention include aqueous solutions of sodium hydroxide, potassium hydroxide, and the like.

The phase transfer catalyst used in the present invention includes benzyltriethylammonium chloride, benzyltriethylammonium puromite, benzyltrimethylammonium chloride, benzyltrimethylammonium puromite, benzyltriethylammonium sulfate, tetrabutylammonium puromite, benzyltriethylammonium methylsulfate, Examples include trioctylmethylammonium chloride, benzyltributylammonium chloride, and tetramethylammonium chloride.

Examples of the alcohol used in the present invention include methanol, ethanol, flobyl alcohol, and methyl alcohol. Particularly preferred are methanol and ethanol.

Examples of the alkylating agent used in the present invention include benzyl chloride, dimethyl sulfate, diethyl sulfate, and the like.

Examples of the dehydrating agent used in the present invention include 4-toluenesulfonic acid, benzenesulfonic acid, and methanesulfonic acid. Particularly preferred is 4-toluenesulfonic acid.

In the present invention, "lower" means one having 1 to 6 carbon atoms, and halogen atom means chloro atom, bromine atom, fluorine atom or iodine atom.

Furthermore, formula (1) which is a raw material for the compound of formula (4) of the present invention
Examples of the compound include 4-ethoxyacetophenone, 4-methoxyacetophenone, 4-butoxyacetophenone, 3-phenoxyacetophenone, 3-(4'
-chlorophenoxy)acetophenone, 3-(4'-ethoxyphenoxy)acetophenone, 4-isopropylacetophenone, 4-chloroacetophenone, 4-imp tylacetophenone, 4-hexylacetophenone, 4-benzyloxyacetophenone, and the like.

〔Effect of the invention〕

By the method of the present invention, it is possible to produce dichlorocyclopropanecarboxylic acids useful as intermediates for insecticides at an industrially low cost and with a high yield.

[-Example of real power]

The present invention will be explained below with reference to practical examples.

The invention is not limited to this example.

Example 1゜Chloroform 318P, 4-ethoxyacetophenone 1
685', 100 g of water, and benzyltriethylammonium chloride 2501 were placed in a reactor and dissolved with stirring. While maintaining the internal temperature at 10°C to 15°C, an aqueous solution of 924 g of potassium hydroxide dissolved in 1,023 parts of water was prepared.
Drip over 0 hours.

After the dropwise addition, the mixture was allowed to react at the same temperature for 2 hours. Furthermore, 1,075 fi' of chloroform is added at the same temperature. An aqueous solution in which 2,013!7 of sodium hydroxide was dissolved in 2.01354 of water was added dropwise over 10 hours. After the dropwise addition, after reacting at the same temperature for 2 hours, dichloromethane 5ooP and water 1500
P is added and the organic layer is separated by standing. The separated organic layer is acidified with hydrochloric acid, washed with water, and concentrated under reduced pressure. The obtained solid substance is recrystallized from 70% methanol water 8 (1-). After that, it is washed with 50% methanol water 200 J and dried to obtain white crystals 132P. A part of this material is further recrystallized from toluene. The physical properties of the target compound are as follows: Molecular formula C1□HI203 Elemental analysis measurement value as C12 C52,37%) (4,1)% C
l25.48% elemental analysis theoretical value C52,38% H
4.40% Cl2 5.77% The above crystal 1321 was found to have a purity of 93.1% as a result of quantitative analysis.

Example 2 Chloroform 318. P, 4-ethoxyacetophenone 168P, water 100P, benzyl alcohol 1.51
Add 25 oz of benzyltriethylammonium chloride to a reactor and stir to dissolve.

Potassium hydroxide 924 while keeping the same temperature at -5℃~5℃
P is dissolved in 1023P of water, and the aqueous solution is added dropwise over 10 hours. After the dropwise addition, the mixture was allowed to react at the same temperature for 2 hours. At this point, the stirring is no longer smooth, so 300P of dichloromethane is added and the mixture is allowed to stand still for dispersion, and the organic layer is collected. Chloroform 645 in the separated organic layer? Add 57.6ψ of methyl alcohol and maintain the internal temperature at -5°C to 5°C while adding 813% of sodium hydroxide to the mixture. An aqueous solution of 8131 in water was added dropwise over 10 hours. After the dropwise addition, the mixture was allowed to react at the same temperature for 2 hours, and then water 4001 was added thereto, and the mixture was allowed to stand still for liquid separation to collect the organic layer. The organic layer was washed with 200 P of 25% hydrochloric acid to remove the triethylammonium chloride. Add 5°C of methyl alcohol to the organic layer. Gradually add an aqueous solution of 77P of sodium hydroxide dissolved in 170P of water6.
React at 0°C to 70°C for 2 hours. After cooling, acidify with hydrochloric acid water and extract with toluene. The organic layer was washed with water and concentrated under reduced pressure, and the resulting solid was dissolved in 70% methanol water (90%).
? recrystallize from Then 50% methanol water 150ψ
After washing and drying, 1651 white crystals of the same target compound as in Example 1 are obtained. A part of this product was further recrystallized from toluene and the physical properties were the same as in Example 1. Quantitative analysis of 165g of crystals revealed a purity of 96.
It was 5%.

Example 3゜Chloroform 310g - 14-ethoxyacetophenone 1645', water 100P, benzyl alcohol 1.51
250 g of benzyltriethylammonium chloride was placed in a reactor and stirred to dissolve.

48% potassium hydroxide aqueous solution 1637 while keeping the internal temperature between 0 and 5℃! i' dropwise over 8 hours. After the dropwise addition, the reaction is continued at the same temperature for 2 hours. The generated potassium chloride is separated, the filtrate is allowed to stand, and the organic layer is separated. Chloroform 6457 and methanol 57.6 in the separated organic layer? was added, and 1500 ψ of a 48% aqueous sodium hydroxide solution was added dropwise over 10 hours while maintaining the internal temperature at 0 to 5°C. After the reaction was continued for another 2 hours at the same temperature after the dropwise addition, 400 g of water was added and left to stand, and the organic layer was separated. 20% of the separated organic layer
Wash with hydrochloric acid water 4001 to remove benzyltriethylammonium chloride. In the organic layer, 20% sodium hydroxide aqueous solution 450P, tetrabutylammonium bromide 10? and react at 70 to 80°C for 2 hours. After cooling, acidify with hydrochloric acid water and extract with toluene. After washing the organic layer with water, the solid matter obtained by concentrating under reduced pressure was reduced to 70%.
Recrystallize from methanol water. 175 white crystals of the same target compound as in Example 1 were obtained, and quantitative analysis showed that the purity was 97.8%.

Example 4 334 g of benzyltrimethylammonium chloride
1 water 84ψ, benzyl alcohol 1.5! Put i' into a reactor and stir to dissolve. While maintaining the internal temperature at -5 to 0°C, 57% potassium hydroxide aqueous solution 837F and 4-ethoxyacetophenone 164 Sl chloroform 275
The solution dissolved in 1 was added dropwise at the same time over a period of 5 hours. After the dropwise addition, the mixture was allowed to react at the same temperature for 2 hours. The generated potassium chloride 1 is distributed from door to door, the filtrate is allowed to stand, the liquid is separated, and the organic layer is separated. Potassium chloride is washed with dichloromethane 3001, and the washing liquid is combined with the previous organic layer. The combined organic layer was washed with 400 g of 25% hydrochloric acid to remove benzyltrimethylammonium chloride. Transfer the separated organic layer to a reactor, add tetrabutylammonium bromide 6P and dimethyl sulfate 1901, and adjust the internal temperature to 35-40.
48% sodium hydroxide aqueous solution 133 while keeping at ℃
Add 7 dropwise over 1 hour. After dropping, the mixture is allowed to react at the same temperature for 2 hours. Add 300 P of water to the reaction solution and separate the organic layer. Further, the organic layer is washed with dilute hydrochloric acid and water. Transfer the organic layer to a reactor and add benzyltriethylammonium chloride 91. Add 320P of chloroform and lower the internal temperature to 40~
48% sodium hydroxide 480P while keeping at 45℃
drip over 2 hours. After the dropwise addition, the mixture was allowed to react at the same temperature for 2 hours.

Add 300 g of water to the reaction solution, leave it to stand, and separate the organic layer. The organic layer was washed with dilute hydrochloric acid and water to drive off the organic solvent, and then distilled under reduced pressure to obtain 213 g of the desired methyl ester of the compound of Example 1. This methyl ester was hydrolyzed in the same manner as in Example 3, acidified with hydrochloric acid,
After filtration, washing with water, and drying, white crystals 202P of the same compound as in Example 1 were obtained. As a result of quantitative analysis, the purity was 98.
It was 4%.

Example 5 Pencil triethylammonium chlorite 2507,
Add 100 ml of water to the reactor and stir to dissolve. 55% potassium hydroxide aqueous solution 1 while keeping the internal temperature at 5-10℃
020! i' and 4-ethoxyacetophenone 164
! Pwo chloroform 358? The solution dissolved in the above was added dropwise at the same time over a period of 6 hours. After the dropwise addition, the mixture was allowed to react at the same temperature for 2 hours. The generated potassium chloride is taken from house to house, the filtrate is allowed to stand still and dispersed, and the organic layer is separated. Potassium chloride in chloroform 300? and combine the washings with the organic layer.

The organic layer with the combined washing liquid was transferred to a reactor and potassium carbonate 209
- was added, and dimethyl sulfate 177y- was added dropwise over 1 hour while maintaining the internal temperature at 30 to 35°C. After reacting for 1 hour at the same temperature after dropping, the mixture was washed with water 5001 and the organic layer was separated. Furthermore, the organic layer is washed with 25% hydrochloric acid water 4001, and the organic layer is separated. The separated organic layer was transferred to a reactor and 4-toluenesulfonic acid 16? was added and dehydrated under reflux for 30 minutes. After the reaction is completed, 300 ψ of water is added and left to stand, and the organic layer is separated. The separated organic layer was transferred to a reactor, and tetrabutylammonium proma()'' 15P and chloroform 3601 were added, and while maintaining the same temperature at 40 to 45°C,
480 g of a 48% aqueous sodium hydroxide solution is added dropwise over 2 hours. After dropping, the mixture is allowed to react at the same temperature for 2 hours. Add 300 ψ of water to the reaction solution, let stand for 1 minute, and separate the organic layer. The organic layer was washed with dilute hydrochloric acid and water, the organic solvent was expelled, and then distilled under reduced pressure to obtain the desired methyl ester 224 of the same compound as in Example 1. This methyl ester was hydrolyzed in the same manner as in Example 3, acidified with aqueous hydrochloric acid, filtered, washed with water, and dried to obtain 213 g of the desired white crystals of the same compound as in Example 1. As a result of quantitative analysis, the purity was 97.8%.

Example 6゜The potassium hydroxide 9241 used in Example 2 was replaced with 593 g of sodium hydroxide, and this was dissolved in water 6551 and reacted in the same manner.The white crystals were 1) 8P.
can get. Quantitative analysis of this product revealed that it contained 94.6% of the same target compound as in Example 2.

Example 7 The initial reaction temperature of Example 2 was changed from -5 to 5°C to 15 to 20°C, and the same reaction and treatment were performed to obtain white crystals 137f of the same compound as in Example 2.

As a result of quantitative analysis, the purity was 95.1%.

Example 8: In place of benzyltrimethylammonium chloride 3341 used in Example 4, benzyltrimethylammonium chloride 2791 and benzyltrimethylammonium chloride 231 were used and reacted in the same manner as Example 4 of 197P. White crystals of the same compound were obtained. The result of purity analysis was 98.5%.

Example 9゜Water used in Example 5 100? Instead, when 80 ψ of dichloromethane and 105 P of water were used to react in the same manner, white crystals of the same compound as in 21)1 Example 5 were obtained. The purity analysis result was 98.0%.

Example 10゜In place of the benzyltriethylammonium seventium chloride 250P used in Example 5, benzyltriethylammonium monomethyl sulfate 3341 was used and treated in the same manner at °C. 194g - white crystals of the same compound as in Example 5 were obtained. I got it. The result of purity analysis was 97.4%.

Example 1) 177 g of benzyl chloride used in Example 5 was replaced with 177 g of benzyl chloride, and the reaction was carried out at 65 to 70°C. The reaction was then carried out in the same manner as in Example 5 to drive out the organic solvent. A crude benzyl ester of the same compound as in Example 5 was obtained. This crude benzyl ester was hydrolyzed in the same manner as in Example 3 and recrystallized from 70% methanol water to obtain the desired white crystal 2061 of the same compound as in Example 5. The result of purity analysis was 98.9%.

In addition, the compounds shown in Table 1 below were synthesized under the conditions of Examples 1-1).

Claims (4)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A compound represented by (representing a phenoxy group that may be present) is reacted with chloroform in the presence of an aqueous base solution and a phase transfer catalyst to form the formula ▲Mathematical formula, chemical formula, table, etc.▼(2) ▲Mathematical formula, chemical formula, table, etc. etc.▼(3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(4) (In the formula, 1] A compound of formula (4) obtained by reacting with chloroform in the presence of an aqueous base solution and a phase transfer catalyst, or [2] a compound of formula (4) obtained by reacting with chloroform in the presence of an aqueous base solution, a phase transfer catalyst, and an alcohol; A method for producing dichlorocyclopropanecarboxylic acids represented by formula (4), which comprises hydrolyzing a mixture of the compound of (4) and an ester from an alcohol. (2) 5 to 20 times the molar amount of base relative to the compound of formula (1);
In the presence of a phase transfer catalyst of 0.7 to 3 times the mole, 2 to 10 times the mole of chloroform to the compound of formula (1) and -10 to
A mixture of the compounds represented by formulas (2), (3) and (4) is obtained by reacting at 50°C, and then the mixture is mixed with [1] a base in an amount of 10 to 50 times the mole of the compound of formula (1). [2] The compound of formula (1) is reacted with 5 to 10 times the mole of chloroform at -10 to 50°C in the presence of a phase transfer catalyst of 0.7 to 3 times the mole; In the presence of a base of 10 to 50 times the mole of the compound, a phase transfer catalyst of 0.7 to 3 times the mole and an alcohol of 1.5 to 3 times the mole of the compound, 5 to 10 times the mole of the compound of formula (1) Claims characterized in that a compound of formula (4) obtained by reacting with chloroform at -10 to 50°C and a mixture of an ester from the compound of formula (4) and an alcohol are hydrolyzed. The method for producing dichlorocyclocarboxylic acids according to item (1). (3) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is a hydrogen atom, a lower alkyl group; a lower alkoxy group; a benzyloxy group; substituted with a halogen atom or a lower alkyl group, a lower alkoxy group, or a halogen atom) A compound represented by (indicates a phenoxy group that may be present) is reacted with chloroform in the presence of an aqueous base solution and a phase transfer catalyst to form the formula ▲Mathematical formula, chemical formula, table, etc.▼(2) ▲Mathematical formula, chemical formula, table, etc. etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) (In the formula, X is the same as in formula (1)) Obtain a mixture of compounds represented by, and then alkylate the mixture A mixture of alkyl esters of formulas (2), (3) and (4) is obtained by reacting with a mixture of alkyl esters of formulas (2), (3) and (4), and the ester mixture is reacted with [1] chloroform in the presence of an aqueous base solution and a phase transfer catalyst. or [2] converting the ester of the compound of formula (3) into the ester of the compound of formula (2) by carrying out a dehydration reaction, and then reacting it with chloroform in the presence of an aqueous base solution and a phase transfer catalyst. A method for producing dichlorocyclopropanecarboxylic acids represented by formula (4), which comprises hydrolyzing the ester of the compound represented by formula (4) obtained by formula (4). (4) 5 to 20 times the mole base of the compound of formula (1),
In the presence of a phase transfer catalyst of 0.7 to 3 times the mole, 2 to 10 times the mole of chloroform to the compound of formula (1) and -10 to
A mixture of compounds of formulas (2), (3), and (4) is obtained by reacting at 50°C, and then the mixture is reacted with an alkylating agent to obtain compounds of formulas (2), (3), and (4). ) is obtained, and then the mixture of alkyl esters is treated with [1] an aqueous solution of a base in an amount of 2 to 20 times the mole of the compound of formula (1), and in the presence of a catalytic amount of a phase transfer catalyst. , the ester of the compound of formula (3) was converted to the ester of the compound of formula (2) by reacting with 2 to 10 times the mole of chloroform at 20 to 70°C or by performing a [2] dehydration reaction. Thereafter, in the presence of an aqueous solution of a base in an amount of 2 to 20 times the mole of the compound of formula (1) and a catalytic amount of a phase transfer catalyst, 2 to 1 mole of base was added to the compound of formula (1).
The dichlorocyclocarboxylic acid according to claim (3), characterized in that the ester of the compound of formula (4) obtained by reacting with 0 times the mole of chloroform at 20 to 70°C is hydrolyzed. manufacturing method.