JPH0533217B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to a method for producing 3-cyano-3,5,5-trimethylcyclohexanone. Specifically, 3-cyano-3,5,
The present invention relates to a method for producing 5-trimethylcyclohexanone.

Prior art 3-cyano-3,5,5-trimethylcyclohexanone is converted into 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane through hydrogenation and amination, and used as a curing agent for epoxy resin. Furthermore, 3-isocyanate methyl-
3,5,5-trimethylcyclohexyl isocyanate is used as a quaternary elastomer, polyurethane paint, raw material for leather surface treatment, etc.

It has been known to produce 3-cyano-3,5,5-trimethylcyclohexanone using isophorone and hydrocyanic acid as raw materials. For example, WF
Whitmore and C.W. Roberts, JOC, 13 . 31
(1948), isophorone and sodium cyanide were mixed at room temperature in a mixed solvent of methanol, water, and acetic acid.
By reacting for weeks, 3-cyano-3,5,5-trimethylcyclohexanone was obtained with a yield of about 45%. However, it is clear that this method does not pose a problem as an industrial method because it provides a low yield and requires a long reaction time.

According to Japanese Patent Publication No. 40-7486, an isophorone-hydrocyanic acid mixture containing about 10% by weight or less of hydrocyanic acid relative to isophorone is supplied in a gaseous state onto an alkaline catalyst attached to a solid carrier. ,5,5
-Trimethylcyclohexanone is synthesized continuously. However, this method has problems as an industrial method because the catalyst is poisoned by the by-produced hydrocyanic acid polymer and has a short life, and it requires recovery of a large amount of isophorone.

Furthermore, according to West German Patent No. 1085871, 3-cyano-3,5,5-trimethylcyclohexanone is synthesized by reacting isophorone with hydrocyanic acid in a polar solvent such as dimethylacetamide using an alkali metal salt as a catalyst. . However, the yield of 3-cyano-3,5,5-trimethylcyclohexanone by this method is as low as about 70%, and in addition, a large amount of expense is required for recovering the solvent.

Furthermore, according to West German Patent No. 1240854, 3-cyano-3,5,5-trimethylcyclohexanone is synthesized by reacting isophorone and hydrocyanic acid in the presence of an alkali metal salt catalyst using methanol as a solvent. However, when this method was tested again, it was found that a large amount of hydrocyanic acid polymer was produced as a by-product, and the yield of 3-cyano-3,5,5-trimethylcyclohexanone was as low as about 80%.

Next, according to JP-A No. 57-116038, in order to avoid the by-product of polymerization of hydrocyanic acid in the presence of an inorganic basic catalyst and glycols, a large excess of isophorone is reacted with hydrocyanic acid to produce 3-cyano -3,5,5-trimethylcyclohexanone is synthesized. However, when this method was repeated, the yield of 3-cyano-3,5,5-trimethylcyclohexanone (based on hydrocyanic acid) was as low as about 80%, and it was necessary to recover a large amount of unreacted isophorone. There is a problem with that.

OBJECT OF THE INVENTION Therefore, an object of the present invention is to provide a novel method for producing 3-cyano-3,5,5-trimethylcyclohexanone. Another object of the present invention is that there is no need for a solvent to solubilize a basic compound, and there is no need to recover a large amount of unreacted isophorone by using excess isophorone in order to avoid the by-product of cyanide polymer. , 3-cyano- in high yield
An object of the present invention is to provide a method for producing 3,5,5-trimethylcyclohexanone.

These objects are achieved by reacting isophorone with hydrocyanic acid in the presence of quaternary ammonium hydroxide or quaternary phosphonium hydroxide.
- Achieved by a method for producing trimethylcyclohexanone.

Further, the present invention provides 3-cyano-3,5,
This is a method for producing 5-trimethylcyclohexanone.

Structure of the Invention As described above, the present invention provides 3-cyano-3,5,5-
-Trimethylcyclohexanone is produced, and examples of the quaternary ammonium hydroxide used in this method include compounds represented by the general formula or.

(However, in the formula, R ₁ and R ₂ have 1 carbon atom
~24, preferably 1 to 12 alkyl groups or optionally substituted benzyl groups, and
R ₃ and R ₄ each have 1 to 10 carbon atoms, preferably 1
~12 alkyl groups. ) (However, in the formula, R ₅ is an alkyl group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and R ₆ is a hydrogen atom or a methyl group.) Specific examples of quaternary ammonium hydroxide include Examples include the following compounds.

Compounds having the general formula include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-
Propylammonium hydroxide, tetra-n-butylammonium hydroxide, triethylpropylammonium hydroxide, octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octadecyltrimethylammonium hydroxide, tetracosyltrimethylammonium There are tetraalkyl quaternary ammonium hydroxides such as hydroxide, dioctadecyldimethylammonium hydroxide, and trioctylmethylammonium hydroxide.

In addition, as a compound having the general formula, benzyltrimethylammonium hydroxide,
Benzyltriethylammonium hydroxide, benzylpropylammonium hydroxide, benzylethyldipropylammonium hydroxide, dodecyldimethylbenzylammonium hydroxide, o-, m-
or p-methoxybenzyltriethylammonium hydroxide, o-, m- or p-
Benzyltrialkylammonium hydroxide and dibenzylalkylammonium hydroxide such as chlorobenzyltriethylammonium hydroxide, octylbenzyldimethylammonium hydroxide, diethylbenzylammonium hydroxide, N-methylpyridinium hydroxide, N-ethylpyridinium hydroxide, N - N-alkylpyridinium such as butylpyridinium hydroxide, N-dodecylpyridinium hydroxide, N-octadecylpyridium hydroxide, N-methylpicolinium hydroxide, N-butylpicolinium hydroxide, N-dodecylpicolinium hydroxide, etc. There are hydroxides and N-alkylpicolinium hydroxides.

Industrially, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, etc. are preferably used.

Examples of the quaternary phosphonium hydroxide used in the present invention include quaternary phosphonium hydroxides represented by the general formula.

(However, in the formula, R ₇ , R ₈ , R ₉ and R ₁₀ represent an alkyl group or a phenyl group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and R ₇ may be a benzyl group. ) Specific examples of quaternary phosphonium hydroxide include tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphonium hydroxide, octyltriethylphosphonium hydroxide, hexadecyltriethylphosphonium hydroxide, hexadecyltributylphosphonium hydroxide. oxide, tetraalkylphosphonium hydroxide such as dodecyltrimethylphosphonium hydroxide, trioctylethylphosphonium hydroxide, tetracosyltriethylphosphonium hydroxide, benzyltrialkylphosphonium hydroxide such as benzyltriethylphosphonium hydroxide, benzyltributylphosphonium hydroxide, Examples include alkyltriphenylphosphonium hydroxide such as methyltriphenylphosphonium hydroxide and ethyltriphenylphosphonium hydroxide, and tetraphenylphosphonium hydroxide.

Although the method of the present invention can be carried out without a solvent, a solvent may also be used. Preferred solvents include aliphatic and aromatic hydrocarbons and halogenated hydrocarbons.
Although the method of the present invention can be carried out in the absence of water, the presence of some amount of water is preferred. The preferred amount of water is 0.1 to 50% by weight, more preferably 1 to 10% by weight based on isophorone.

The method of the invention is carried out as follows.

Isophorone and quaternary ammonium hydroxide or quaternary phosphonium hydroxide are mixed, and hydrocyanic acid is supplied in liquid or gaseous form to react. The ratio of quaternary ammonium hydroxide or quaternary phosphonium hydroxide used in the reaction is 0.001 to 0.5 mol per mol of isophorone;
Preferably it is 0.01 to 0.1 mol. The proportion of hydrocyanic acid used in the reaction is 0.5 to 1.5 times by mole, preferably 0.8 to 1.2 times by mole relative to isophorone. The reaction temperature ranges from 50 to 200°C, preferably from 80 to 150°C. In addition, the reaction time is 1 to 30 hours, preferably 1 to 30 hours.
~10 hours. After the reaction is completed, the target compound can be obtained by separation by a conventional method. The quaternary ammonium hydroxide or quaternary phosphonium hydroxide used in the reaction can be recovered by extraction with water and recycled for the next reaction.

The following examples illustrate the invention but are not limited thereto.

Example 1 138.2 parts by weight of isophorone and tetra-n-butylammonium hydroxide were placed in a reactor equipped with a stirrer, a thermometer, and a dropping funnel with a cooling tube.
Add 6.9 parts by weight and 6.9 parts by weight of water, and stir.
At a temperature of 110°C, 27.0 parts by weight of hydrocyanic acid was added dropwise over 3 hours to cause a reaction. After completion of the dropwise addition, the solution was aged at 110°C for 1 hour, then cooled to 90°C, and the reaction solution was analyzed using gas chromatography. No unreacted hydrocyanic acid was detected, and 6.9 parts by weight of unreacted isophorone and 156.8 parts by weight of 3-cyano-3,5,
Production of 5-trimethylcyclohexanone was confirmed. Therefore, the production rate of 3-cyano-3,5,5-trimethylcyclohexanone based on hydrocyanic acid is
It was 94.9%. The reaction solution was washed with water and then distilled.
153.7 parts by weight of 3-cyano-3,5,5-trimethylcyclohexanone was obtained. Yield for hydrocyanic acid 93.0
%.

Example 2 In a device similar to Example 1, the water washing solution obtained in Example 1 was concentrated to 13.8 parts by weight and isophorone was added.
138.2 parts by weight were charged, and 27.0 parts by weight of hydrocyanic acid was added dropwise at a temperature of 110° C. over 3 hours with stirring to cause a reaction. After completion of the dropwise addition, the solution was aged at 110°C for 1 hour, then cooled to 90°C, and the reaction solution was analyzed by gas chromatography. No unreacted hydrocyanic acid was detected, and 6.0 parts by weight of unreacted isophorone and 6.0 parts by weight of unreacted isophorone were detected. 158.0
Production of 3-cyano-3,5,5-trimethylcyclohexanone in parts by weight was confirmed. Therefore 3
The production rate of -cyano-3,5,5-trimethylcyclohexanone based on hydrocyanic acid was 95.6%. The reaction solution was washed with water and then distilled to obtain 154.2 parts by weight of 3-cyano-3,5,5-trimethylcyclohexanone. Yield of cyanide: 93.3%.

Example 3 Into the same apparatus as in Example 1, 138.2 parts by weight of isophorone, 6.9 parts by weight of tetra-n-butylphosphonium hydroxide and 6.9 parts by weight of water were charged,
While stirring, 27.0 parts by weight of hydrocyanic acid was added dropwise at a temperature of 110° C. over 3 hours to cause a reaction. 110 after completion of dripping
After aging at ℃ for 1 hour, the reaction solution was cooled to 90℃ and analyzed by gas chromatography. No unreacted hydrocyanic acid was detected, and 7.6 parts by weight of unreacted isophorone and 154.8 parts by weight were detected. The production of 3-cyano-3,5,5-trimethylcyclohexanone was confirmed. Therefore, 3-cyano-3,
The production rate of 5,5-trimethylcyclohexanone based on hydrocyanic acid was 93.7%. The reaction solution was washed with water and then distilled to obtain 151.5 parts by weight of 3-cyano-3,5,5-
Trimethylcyclohexanone was obtained. Yield of hydrocyanic acid
91.7%.

Example 4 138.2 parts by weight of isophorone, 6.9 parts by weight of benzyltrimethylammonium hydroxide and 6.9 parts by weight of water were charged into the same apparatus as in Example 1.
While stirring, 27.0 parts by weight of hydrocyanic acid was added dropwise at a temperature of 110° C. over 3 hours to cause a reaction. 110 after completion of dripping
After aging at ℃ for 1 hour, the reaction solution was cooled to 90℃ and analyzed by gas chromatography. No unreacted hydrocyanic acid was detected, and 6.5 parts by weight of unreacted isophorone and 156.5 parts by weight were detected. The production of 3-cyano-3,5,5-trimethylcyclohexanone was confirmed. Therefore, 3-cyano-3,
The production rate of 5,5-trimethylcyclohexanone based on hydrocyanic acid was 94.7%. The reaction solution was washed with water and then distilled to obtain 153.5 parts by weight of 3-cyano-3,5,5-
Trimethylcyclohexanone was obtained. Yield of hydrocyanic acid
92.9%.

Claims (1)

[Scope of Claims] 1. 3-Cyano-3,3,5-trimethylcyclohexanone, characterized in that isophorone and hydrocyanic acid are reacted in the presence of quaternary ammonium hydroxide or quaternary phosphonium hydroxide. manufacturing method. 2. The 3-cyano-3,5 according to claim 1, wherein the quaternary ammonium hydroxide or quaternary phosphonium hydroxide used in the reaction is recovered and recycled for use in the next reaction. , 5-trimethylcyclohexanone manufacturing method.