JPS61122243A - Production of cycloalkanecarboxylic acid salt compound - Google Patents

Abstract

PURPOSE:To obtain the titled substance economically in high yield, by using a mixture of an alcohol and other organic solvent as a reaction solvent, in contacting a 2-halogenocycloalkanone compound with an alkali metal hydroxide. CONSTITUTION:The titled compound can be produced by reacting a 2- halogenocycloalkanone compound (e.g. 2-chlorocyclohexane) with anhydrous alkali metal hydroxide in a mixture of an alcoholic solvent and other organic solvent (preferably a hydro-carbon such as benzene, xylene, hexane, etc.) at 10-150 deg.C, preferably 40-120 deg.C under atmospheric pressure. The amount of the alkali metal hydroxide is preferably 2-4 equivalent based on the above raw material. The amount of the mixed solventis usually 0.5-20pts.wt. per 1pt. of the raw materal, and the ratio of the alcohol to the other organic solvent is 50-97wt% to 3-50wt%.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a cycloalkane carboxylate compound, and more specifically, a method for producing a 7-chloroalkane carboxylate compound economically and in high yield. Regarding.

(Prior art) Conventionally, as a method for synthesizing 7-a-alkane carboxylic acids, 2-halogeno-7-chloroalkanone is reacted with an alkali metal hydroxide in an alcohol solvent (A, Fav
orsky st V, , 9 ojovaky, 13
ull+Soc, ahim, France, 18.
615 (1915)), or a method in which the carboxylic acid ester is synthesized as an intermediate by reacting it with sodium alcoholade in an alcoholic solvent and then hydrolyzed (
GOh...nana Vaughan, Org, 8y
ntheses, 39.57 (1959).

R-B, Lottfi-la, J, A-C, S.
, 73.4707 (1951)] is known.

This reaction is usually called the 7-Aborski single rearrangement reaction.

(Problems to be Solved by the Invention) However, method (2) has a complicated process because it involves a hydrolysis step of ester, and the utility costs such as electricity and steam are high. This method is advantageous in terms of cost, but it is difficult to remove heat because the reaction is in a suspended state, making it difficult to implement on an industrial scale. It is.

Therefore, the inventors of the present invention conducted intensive studies to improve these drawbacks, and found that using a mixed solvent of an alcohol solvent and another organic bath agent as the solvent was extremely efficient ().
(Means for solving the problem) O (According to the present invention, a 2-halogenocycloalkanone compound is converted into an alcohol A method for producing a single-membered cycloalkane carboxylate compound is provided, which comprises contacting the compound with anhydrous alkali metal hydroxide in the presence of a mixed solvent of a solvent and another organic solvent.

Specific examples of the 2-halogenocycloalkanone compounds used as raw materials in the present invention include 2-chlorocyclohexanone, 2-promucchlorhexanone, 2-chloro7clopentanone, and 2-chloro7clopentanone, and these methyl This also includes alkyl-substituted substances such as substituted substances, ethyl-substituted substances, and butyl-substituted substances.

Such 2-...rogeno-7-alkanone usually contains about 5 to 50% by weight of polyhalogeno-7-chloroalkanone as an impurity, which is a rounded and by-product synthesized by halogenation of cycloalkanone. In the invention, even such a crude 2-halogenocycloalkanone can be used in the same way as a highly purified 2-halogenocycloalkanone.

In the present invention, such raw materials are brought into contact with anhydrous alkali metal hydroxide in the presence of an alcohol solvent and another organic solvent to carry out a reaction. Specific examples of the alcohol that can be used include methanol, ethanol, butanol, hexanol, octatool, fuclopentanol, cyclohexanol, and the like. Specific examples of other organic solvents include benzene, toluene, xylene, hexane,
Examples thereof include hydrocarbons such as heptane and cyclohexane, ethers such as diethyl ether, diptyl ether, tetrahydro-7rane, and dioxane, and nitrites such as acetonitrile and benzonitrile. Among them, hydrocarbons are prized for their ease of handling and efficiency in extracting the produced cycloalkane carboxylate into water.

Specific examples of the alkali metal hydroxide used include lithium hydroxide, sodium hydroxide, potassium hydroxide, etc., which are used in anhydrous form. Here, anhydrous means substantially anhydrous, and may contain a small amount of water as long as it does not essentially impede the effects of the present invention.

However, when an ordinary aqueous alkali metal hydroxide solution is used, by-products are likely to be produced, and this tendency is particularly noticeable when a crude 2-halogenoalkanone containing a polyhalogenocycloalkanone is used as a raw material.

The amount of the solvent to be used can be selected as appropriate, but usually the amount of mixed solvent is (15 to 20 times by weight, preferably 0.6 to 15 times by weight) relative to the 2-halogenocycloalkanone and the dialcohol and other solvents. The ratio of use with the former is usually 50 to 97
t%, preferably 70 to 95% by weight and the latter 3 to 50% by weight, preferably 5 to 30% by weight.◇If the amount of other organic solvents used is small, it will be difficult to control the reaction and the yield will be low. If the amount is too high, by-products will increase and productivity will decrease.

The amount of alkali metal hydroxide used is usually 5 to 6 equivalents, preferably 2 to 4 equivalents, based on the 2-halogenocycloalkanone compound. If the amount used is too large, the stirring efficiency will decrease. It becomes extremely difficult to control your depression response.

The mixed organic solvent can be added by allowing it to exist with the alkali metal hydroxide in the reactor from the beginning, or by adding a part of it to the raw material 2-
It may be added at the same time as the halogeno heptachloroalkyl compound.

Although the reaction conditions employed in the present invention are not particularly limited, the reaction is usually carried out at a temperature of 10 to 150°C, preferably 40 to 120°C, under atmospheric pressure, and the 2-halogenocycloalkanone compound is 15 minutes to 15 hours, preferably 5
Added over a period of 0 minutes to 10 hours. If the temperature is too high, high-additional by-products are likely to be produced (◇) After the reaction is completed, the produced cycloalkane carboxylate compound is separated from the reaction system according to a conventional method.

For example, a method of extraction into an aqueous phase by adding water to the reaction system is used. Further, if desired, a cycloalkane carboxylic acid compound can be synthesized by hydrolyzing the cycloalkane carboxylate compound.

(Effects of the Invention) According to the present invention, a cycloalkane carboxylate compound can be produced economically and efficiently using an inexpensive alkali metal hydroxide.

The present invention will be explained in more detail with reference to Examples below. In addition, parts and parts in Examples and Comparative Examples are based on weight unless otherwise specified.

Example 1 Water dispersion in a stainless steel reactor equipped with a stirrer and a cooling jacket (content: gks oi)) IJumwo 3
．． 6 parts, 7.5 parts of ruhexanol,) 1 part of ruene
0 reaction in which 10 parts of crude M 2-chloro 7-chlorohexanone (containing about 2091+ polychloro-7-glohexanone such as dichlorocyclohexanone, trichlorocyclohexanone, etc.) with a purity of 80% was gradually added under atmospheric pressure with stirring. When the mixture was added to maintain the temperature at 80°C, it took 3 hours.

After the reaction was completed, 10 parts of water was added to bath-dissolve the precipitated salt to obtain 16H as a sodium cyclopentanecarboxylate water bath solution.

Next, 955% hydrochloric acid was added little by little to a portion of this aqueous solution until the pH reached 5, converting it to cyclobentanecarboxylic acid, which was extracted with toluene, and the toluene phase was quantitatively determined by gas chromatography (7 chromatography). The conversion of sodium pentanecarboxylate to 7-chlorobentanecarboxylic acid proceeded quantitatively.) As a result, the yield of 0 moles of sodium cyclopentanecarboxylate was 70%.

Example 2 Into the same reactor as in Example 1, 6 parts of sodium hydroxide was added.
Add 60 parts of lubutanol and 2.0 parts of xylene, and add the same crude product 2 as used in Example 1 under atmospheric pressure with stirring.
- 10 parts of chlorocyclohexanone were slowly added. The reaction temperature was 80°C, and the addition time required 5 hours.

The same treatment as in Example 1 was carried out, and the quantitative determination by gas chromatography was carried out, resulting in a molar yield of 695 mol.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that toluene was not added. The addition time required 6 hours to maintain the reaction temperature at 80°C. The reaction acid m was 65.5 mol), and stirring was difficult due to the high viscosity of the system.

Comparative Example 2 In the same reactor as in Example 1, 15 parts of rouhexanol and 4 parts
9.0 parts of 0% sodium hydroxide aqueous solution was added, and while stirring under atmospheric pressure, the same crude 2-
0 reaction source with addition of 10 parts of chlorocyclohexanone 8
When it was added while maintaining the temperature at 0°C, it took 2.0 hours. The molar yield was 40%.

Claims (1)

[Claims] A cycloalkane carbon having one member condensed therein, which is produced by contacting a 1,2-halogenocycloalkanone compound with anhydrous alkali metal hydroxide in the presence of a mixed solvent of an alcohol solvent and another organic solvent. Method for producing acid salt compounds.