JP2516233B2 - Process for producing bis (4-hydroxyphenyl) -cyclohexane - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing bis (4-hydroxyphenyl) -cyclohexane. More specifically, formula (I) (In the formula, two benzene rings (a) are bonded to the same cyclohexane ring carbon.) Tetrakis (4-hydroxyphenyl) -cyclohexane represented by the formula is characterized by being decomposed without using a hydrogen acceptor. Expression (II) And a method for producing bis (4-hydroxyphenyl) -cyclohexane represented by

Bis (4-hydroxyphenyl) -cyclohexane is a compound useful as a polymer raw material or a pharmaceutical intermediate.

[Conventional technology]

Phenol is reacted with 1,3-cyclohexadiene in the presence of a catalyst to give 1,4-bis (4-hydroxyphenyl)
-It is known to obtain cyclohexane (UK patent
1122372 ('68) etc.).

[Problems to be solved by the invention]

However, in the above conventional method, 1,3-
Cyclohexadiene is expensive and industrially difficult to obtain, so it cannot be said to be an advantageous method.

[Means for solving problems]

The present inventors have earnestly studied the method for producing bis (4-hydroxyphenyl) -cyclohexane using inexpensive industrially available raw materials, and arrived at the present invention.

That is, the present invention has the formula (I) (In the formula, two benzene rings (a) are bonded to the same cyclohexane ring carbon.) Tetrakis (4-hydroxyphenyl) -cyclohexane represented by the formula is characterized by being decomposed without using a hydrogen acceptor. Expression (II) Is a process for producing bis (4-hydroxyphenyl) -cyclohexane.

Tetrakis (4 used as a raw material in the present invention
-Hydroxyphenyl) -cyclohexane can be obtained, for example, by reacting cyclohexanedione with phenol as described in JP-A-56-55328 in the presence of a catalyst.

Further, cyclohexanedione can be obtained by reduction of the corresponding dihydroxybenzene, that is, catechol, resorcin, hydroquinone, or oxidation of cyclohexanediol.

In the present invention, the tetrakis (4-hydroxyphenyl) -cyclohexane of the formula (I) thus obtained is decomposed without using a hydrogen acceptor to give a bis (4-hydroxyphenyl) of the formula (II). ) -Cyclohexane, and the target product can be obtained more efficiently than dihydroxybenzene (catechol, resorcin, hydroquinone) and phenol, which are inexpensive and industrially easily available.

This decomposition reaction proceeds as follows. 1,1,4,4-Tetrakis (4-hydroxyphenyl) -cyclohexane (I ′) will be described below as an example.

That is, the compound of formula (I ') is decomposed into an intermediate represented by formula (A), and this compound (A) undergoes a disproportionation reaction to give the desired compound (II') at about 2: 1. It becomes a by-product (B). Since this disproportionation reaction is a hydrogen transfer reaction, it is preferable to proceed the reaction under mild conditions by using a hydrogen transfer catalyst.

In addition, the present inventors have separately proposed that by adding a hydrogen transfer catalyst and a hydrogen acceptor to the reaction system, only (4) 4,4 ″ -dihydroxyterphenyl can be efficiently produced. Does not use a hydrogen acceptor.Use of a hydrogen acceptor increases the reaction to (B) only, and the yield of the desired (II ') decreases.

A base or acid catalyst is used in the decomposition reaction. The base catalyst includes alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and barium hydroxide, carbonates, acetates and phenoxides. Includes salts of weak organic acids.

The catalysts also include acids such as p-toluenesulfonic acid, weakly acidic acid salts such as potassium bisulfite, aluminum chloride, stannous chloride and other acidic metal chlorides.

A particularly preferred catalyst is a strongly basic catalyst such as sodium hydroxide. The amount used is usually in the range of 0.1 to 40% by weight, preferably 1 to 20% by weight, based on the tetrakis (4-hydroxyphenyl) -cyclohexane of formula (I).

The method of the present invention can be carried out without a hydrogen transfer catalyst, but by coexisting with a hydrogen transfer catalyst, it can be carried out at a higher yield and under milder conditions.

The hydrogen transfer catalyst is not particularly limited as long as it is known,
For example, Raney nickel, reduced nickel, nickel-supported catalysts of nickel supported on various supports such as diatomaceous earth, alumina, pumice, silica gel, acid clay, Raney cobalt, reduced cobalt, cobalt catalysts such as cobalt-supported catalysts, Raney. Copper catalysts such as copper, reduced copper, copper-supported catalysts,
Palladium black, palladium oxide, colloidal palladium,
Palladium catalysts such as palladium-carbon, palladium-barium sulfate, palladium-magnesium oxide, palladium-calcium oxide and palladium-alumina, platinum-support catalysts such as platinum black, colloidal platinum, platinum oxide, platinum sulfide and platinum-carbon. Platinum catalyst, colloidal rhodium,
Rhodium-carbon, rhodium catalyst such as rhodium oxide, platinum group catalyst such as ruthenium catalyst, dirhenium heptoxide, rhenium catalyst such as rhenium-carbon, copper chromium oxide catalyst, molybdenum oxide catalyst, vanadium oxide catalyst, tungsten oxide catalyst, Examples thereof include silver catalysts.

Among these catalysts, a platinum group catalyst such as a palladium catalyst is preferable. The proportion of these hydrogen transfer catalysts used is usually 0.001 to 0.2 gram atom, preferably 0.002, as metal atom of the catalyst based on 1 mol of tetrakis (4-hydroxyphenyl) -cyclohexane represented by the general formula (I).
~ 0.01 gram atom range.

The reaction temperature is 100 to 400 ° C, preferably 150 to 300 ° C. When the reaction temperature is low, the reaction rate is low, and when it is high, side reactions tend to occur.

Although the method of the present invention can be carried out in the gas phase, since the melting point of the raw materials and products is high, a high temperature of 300 ° C. or higher is required in the case of the gas phase reaction, and in terms of yield, operability, energy, etc. It is preferably carried out in the liquid phase. At that time, it is better to carry out in the presence of a solvent, specifically, other than water, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, tetrahydrofuran, dioxane, dipropyl ether, ethers such as diphenyl ether, ethanol,
Examples include alcohols such as isopropanol, ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, nitriles such as acetonitrile, propionitrile and benzonitrile, and aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethylbenzene and cumene. .

In addition, styrenes, phenols, nitrobenzene,
The use of a hydrogen-accepting solvent such as acetone is a by-product of 4,4 "
-The amount of dihydroxyterphenyls produced is increased, and the yield of bis (4-hydroxyphenyl) -cyclohexane is reduced accordingly, which is not preferable.

The bis (4-hydroxyphenyl) -cyclohexane thus produced can be taken out by a method such as acid precipitation or recrystallization after separating the hydrogen transfer catalyst from the mixture after the reaction.

In the method of the present invention, the by-product 4,4 ″ -dihydroxyterphenyls are different from bis (4-hydroxyphenyl) -cyclohexane of the formula (II) in acidity, solubility, etc. Of bis (4-hydroxyphenyl)-of high purity can be separated by adjusting the acid precipitation and by performing extraction and recrystallization.
Cyclohexane can be obtained.

 Hereinafter, the present invention will be specifically described with reference to examples.

[Example-1] 1,4-Cyclohexanedione was reacted with phenol under an acid catalyst to obtain 1,1,4,4-tetrakis (4-hydroxyphenyl) -cyclohexane.

The thus obtained 1,1,4,4-tetrakis (4-
Hydroxyphenyl) -cyclohexane 45.3 g (0.10 mol), caustic soda 2.3 g, 5% palladium carbon 2.3 g, water 10
0 ml was charged into a 300 ml autoclave made of stainless steel, the inside was replaced with nitrogen gas, and the mixture was reacted at 190 ° C. for 6 hours.
After the reaction was completed, the pH was adjusted to 4 with hydrochloric acid water, and crystals were separated. Then, the crystals were dissolved in methanol by heating to separate and collect insoluble palladium carbon. Methanol was distilled off to obtain 20.4 g of white crystals. The purity of 1,4-bis (4-hydroxyphenyl) -cyclohexane by HPLC was 65.1%, and most of the impurities were 4,4 ″ -dihydroxy-p-terphenyl. The yield in terms of purity was 49.5%.

Example-2 From 1,3-cyclohexanedione and phenol 1,1,3,3
-Tetrakis (4-hydroxyphenyl) -cyclohexane was similarly synthesized. Next, change to 1, 1, 4, 4 bodies, and this 1,
Using 1,3,3 bodies, the reaction and treatment were carried out in the same manner as in Example-1,
-Bis (4-hydroxyphenyl) -cyclohexane 1
9.9 g was obtained. Purity was 63.9% by HPLC, and most of impurities were 4,4 ″ -dihydroxy-m-terphenyl.

 The yield in terms of purity was 47.4%.

Claims (1)

(57) [Claims] 1. A formula (I) (In the formula, two benzene rings (a) are bonded to the same cyclohexane ring carbon.) Tetrakis (4-hydroxyphenyl) -cyclohexane represented by the formula is decomposed without using a hydrogen acceptor. Expression (II) A method for producing bis (4-hydroxyphenyl) -cyclohexane represented by: