JPS5862127A - Preparation of p-phenylphenol compound - Google Patents

Abstract

PURPOSE:To prepare the titled substance useful as a raw material for the preparation of a phenolic resin for particular use, by using a 1,1-bis(4-hydroxyphenyl)cyclohexane compound and a styrene compound as raw materials, and heating the materials at a specific temperature in a liquid phase in the presence of a catalyst. CONSTITUTION:The p-phenylphenol compound of formula II (R is H, OH or lower alkyl) is prepared by heating a 1,1-bis(4-hydroxyphenyl)cyclohexane compound of formulaIand a styrene compound (e.g. alpha-methylstyrene, p-diisopropenylbenzene, etc.) in a liquid phase in the presence of a hydrogenative reduction catalyst such as Raney nickel, Pd-carrier, etc. The reaction is carried out usually in a solvent, preferably benzene, toluene, cumene, etc. The weight ratio of the solvent to the starting compound of formulaIis usually 0.2-10.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing p-phenylphenols. More specifically, the present invention provides a method that can produce p-phenylphenols more selectively and in higher yields than conventionally known methods.

p-Phenylphenols are used as raw materials for the production of phenolic resins for special purposes such as festivals, adhesives, and coating treatment agents, as intermediates for the production of pharmaceuticals and agricultural chemicals, and as antifungal agents.

Conventionally, many methods have been proposed for producing p-phenylphenols.

For example, a method has been proposed for producing p-phenylphenol by sulfonating biphenyl to produce p-phenylbenzenesulfonic acid, melting and decomposing this in the presence of a base, and then precipitating it with acid. However, these methods have the disadvantage that, in addition to requiring large amounts of acids and bases, this melt decomposition must be carried out under harsh reaction conditions, usually at 320 to 400°C.

There is also a need for a method that does not have the drawbacks of the sulfonated melt method described above, and several methods have been proposed.

For example, one method is to
No. 75''C1 discloses that p-phenylphenol is produced by heating 1,1-bis(4-hydroxyphenylcyclohexane to a temperature of 200 to 350°C in the presence of a catalyst to cause a dehydrogenation reaction. However, as a result of repeating any of the examples in the publication, the selectivity to p-phenylphenol was 41 to 66 mol% due to the formation of many by-products, and the p-phenylphenol concentration relative to the raw material was 41 to 66 mol%. The yield of phenol is 41 to 6
It was found that it was extremely low at 6 mol%. In addition, as other methods, Japanese Patent Publication No. 44-3584, Japanese Patent Publication No. 45-7
047 and Japanese Patent Publication No. 45-7046, etc., 1,1-bis(4-hydroxyphenyl) obtained by a condensation reaction of 2 moles of phenol and cyclohexanone is disclosed.
A method has been proposed in which cyclohexane is decomposed to produce p-cyclohexenylphenol, and then p-phenylphenol is obtained by causing a dehydrogenation reaction. Among the above-mentioned known documents, Japanese Patent Publication No. 45-7047 describes p-cyclohexenylphenol obtained by the above-mentioned method in a gas phase at 300 to 450°C in the presence of a dehydrogenation catalyst and in the presence of hydrogen. A method has been proposed for producing p-phenylphenol by causing a dehydrogenation reaction by heating to a high temperature. Japanese Patent Publication No. 45/7046 was obtained using a similar method.

- Cyclohexenylphenol is treated in the liquid phase in the presence of a dehydrogenation catalyst and a hydrogen acceptor such as α-methylstyrene.
A method has been proposed for producing -phenylphenol by causing a dehydrogenation reaction by heating to a temperature of 00 to 200°C. However, in the former method, p
- The yield of p-phenylphenol is 79 to 95 mol%, and the disadvantage is that the activity of the catalyst is significantly reduced.
It has the disadvantage that it is extremely low, ranging from 80 to 80 mol%. Equity 6, Mug*gabeni, Yosame. A method has been proposed in which p-phenylphenol is produced by causing a dehydrogenation reaction using uclohexenylphenol as a hydrogen acceptor in the presence of sulfur, but the rate is 47 to 77.
It has the disadvantage that the mol% is extremely low.

The present inventors have investigated methods for selectively producing p-phenylphenols at high yields by improving the above-mentioned drawbacks in the production of p-phenylphenols using conventional methods. .1-bis(4-hydroxyphenyl)zshi♀
The inventors have discovered that the above object can be achieved by heating Σ-s and styrenes in a liquid phase in the presence of a hydrogenation reduction catalyst to a specific temperature, and have thus arrived at the present invention.

That is, the present invention provides 1,1-bis(4-hydroxyphenyl)cyclohexanes and tostyrenes represented by the general formula (1) (wherein R represents a hydrogen atom, a hydroxyl group, or a lower alkyl group), General formula (1) (wherein R represents the same group as above), which is heated to a temperature in the range of 210 to 290 ° C. in the presence of a hydrogenation reduction catalyst in a liquid phase. p expressed
-Al in the production process of phenylphenols.

The 1,1-bis(4-hydroxyphenyl)cyclohexane used in the method of the present invention is a compound represented by the general formula (1) (wherein R represents a hydrogen atom, a hydroxyl group, or a lower alkyl group). It is. Here, the lower alkyl group for R is usually an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and specifically, a methyl group, an ethyl group, an n- Examples include propyl group, isopropyl group, n-butyl group, BθC-butyl group, tert-butyl group, and isobutyl group. 1,1- represented by the general formula (1) above
Bis(4-hydroxyphenyl)cyclohexane, specifically, 1,1-bis(4-hydroxyphenylcocyclohexane, 1,1-bis(4-hydroxy-2
-methylphenyl)cyclohexane, 1.1-1:'s(4-hydroxy-6-methylphenyl)cyclohexane, 1,1-bis(2,4-dihydroxyphenylcyclohexane), etc. 1
, 1-bis(4-hydroxyphenyl)cyclohexanes, compounds in which R in the general formula (1) is a hydrogen atom or a methyl group are preferred, particularly 1.1
Nibis(4-hydroxyphenyl)cyclohexane is preferred. These raw materials, 1,1-bis(4-hydroxyphenyl)cyclohexanes, can also be used in the form of adducts of these and phenols.

The 1,1-bis(4-hydroxyphenyl)cyclohexanes represented by the general formula (1) used in the method of the present invention can be produced by conventionally known methods. For example, it can be produced by a method of condensing phenols and cyclohexanones in the presence of an acidic catalyst, as represented by the following formula (1).

(1) The styrene used in the method of the present invention is styrene, its nuclear substituted product, or its side chain substituted product. Specifically, the styrenes include styrene, α-methylstyrene, α-ethylstyrene, β-methylstyrene, and β-methylstyrene.
Ethylstyrene, 〇-vinyltoluene, m-vinyltoluene, p-vinyltoluene, O-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 0-isopropenylcumene, m-isopropenylcumene, p- Impropenylcumene, O-diisopropenylbenzene, m-diisopropenylbenzene, p
-Diisopropenylbenzene and the like can be exemplified. Among these styrenes, it is preferable to use styrene substituted at the α-position or its nuclear substituted product because p-phenylphenols can be obtained selectively and in high yield, and in particular, isopropenylbenzene or its The proportion of the styrenes in which nuclear substituted products are preferably used is usually 1 to 10 styrenes per mole of the 1,1-bis(4-hydroxyphenyl)cyclohexane.
mol, preferably in the range of 1.5 to mol.

Examples of the catalyst used in the method of the present invention include hydrogenation-reduction catalysts used in ordinary catalytic hydrogenation-reduction reactions. Specifically, Raney nickel, reduced nickel, nickel supported catalysts in which nickel is supported on various supports such as diatomaceous earth, alumina, pumice, silica gel, and acid clay; cobalt catalysts such as Raney cobalt, reduced cobalt, and cobalt/supported catalysts; ; Copper catalysts such as Raney copper, reduced copper, copper/carrier catalysts; Palladium black 1. Palladium #, colloidal palladium, palladium/carbon, palladium/barium sulfate, palladium/barium carbonate, palladium/magnesium oxide, palladium/calcium oxide,
Padded catalysts such as palladium and alumina; platinum black,
Platinum catalysts such as colloidal platinum, platinum/sponge, platinum oxide, platinum sulfide, platinum/carrier catalysts such as platinum/carbon; rhodium catalysts such as colloidal rhodium, rhodium/carbon, rhodium oxide; platinum group catalysts such as ruthenium catalysts; Rhenium catalysts such as nyrhenium and cylinium/carbon; copper chromic acid.

compound catalyst; molybdenum oxide catalyst; vanadium oxide catalyst;
Examples include tungsten oxide catalysts. Among these hydrogenation reduction catalysts, it is preferable to use a palladium catalyst, and it is particularly preferable to use a palladium-supported catalyst, and in particular, a palladium-carrier catalyst,
Preferably, palladium alumina is used. In some cases, the hydrogenation reduction catalyst may be subjected to a conventional treatment with hydrogen or an alcohol such as methanol or ethanol before being used in the reaction. The ratio of these hydrogenation-reduction catalysts used is usually 0.001 to 0.2 gram atom, preferably 0.001 to 0.2 gram atom of the metal atom of the hydrogenation-reduction catalyst per mole of the 1,1-bis(4-hydroxyphenyl)cyclohexane. It is in the range of 0.004 to 0.1 gram atom.

In the method of the present invention, the reaction between the 1,1-bis(4-hydroxyphenyl)cyclohexane represented by the general formula (1) and the styrene must be carried out in a liquid phase. For this purpose, a liquid mixture consisting only of the 1.1-bis(4-hydroxyphenyl)cyclohexane and the styrene can be reacted in the presence of the hydrogenation reduction catalyst, or (4-
A liquid mixture consisting of hydroxyphenyl)cyclohexanes, the styrenes, and a solvent can also be reacted in the presence of the hydrogenation reduction catalyst. Further, the temperature during the reaction needs to be in the range of 210 to 290°C, preferably in the range of 220 to 270°C. If the reaction temperature is lower than 210'C, the reaction rate will be low, which is industrially disadvantageous;
When the temperature is higher, the reaction rate is high, but undesirable side reactions occur, resulting in a decrease in the selective yield to p-phenylphenols, as well as a significant decrease in the activity of the catalyst. In addition, the pressure during the reaction is sufficient as long as the mixture in the reaction system maintains a liquid phase state, and is usually in the range of 5 to 60 kg/1all・G1, preferably 10 to 40 kg/3・G. be. In the method of the present invention, the reaction between the 1,1-bis(4-hydroxyphenyl)cyclohexanes and the styrenes is usually carried out in the presence of an inert gas such as nitrogen, helium, or argon.

In the method of the present invention, the reaction is usually carried out in the presence of a solvent. Specifically, the reaction solvent includes ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimyl oligolether,
Ethers such as diethylene glycol monomethyl ether, tetrahydrofuran, dioxane, dipropyl ether, diphenyl ether, ^tanol, inpropatol, ethylene glycol, diethylene glycol,
Examples include alcohols such as triethylene glycol and propylene glycol, nitriles such as acetonitrile, propionitrile, and benzonitrile, and aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethylbenzene, cumene, and cymene. Among these solvents, it is preferable to use aromatic hydrocarbons, and it is particularly preferable to use benzene, toluene, and cumene. The usage ratio of these solvents is as described above.
The weight ratio to 1.1-bis(4-hydroxyphenyl)cyclohexane is usually in the range of 0.2 to 10.

In the method of the present invention, a mixture consisting of the 1,1-bis(4-hydroxyphenyl)cyclohexane, the styrene, the hydrogenation reduction catalyst, and optionally a solvent is heated with stirring to produce the desired product. p-phenylphenols represented by the above general formula [broad] are produced. The p-phenylphenols can be isolated by treating the mixture after the completion of the reaction according to conventional methods such as distillation, crystallization, and extraction.

Next, the method of the present invention will be specifically explained using examples.

Examples 1-2 In a stainless steel autoclave with an internal volume of 50 J, 1.
1-bis(4-hydroxyphenyl)cyclohexane 0
．． After charging 67 g (2.5 mmol), 0.59 g (5 mmol) of isopropenylbenzene, 2 ml of toluene, and the Pd catalyst (0,025 mg atom) listed in Table 1, and purging the inside of the autoclave with nitrogen,
Pressurize 201Q10112・G with nitrogen and shake for 2 hours.
The reaction was carried out at 50°C for 1 hour. After cooling to room temperature, the catalyst was separated and removed from the reaction mixture by filtration, and unreacted raw materials and products were quantified by graphography. The results are shown in Table 1.

Table 1 (Fist: 0.5 mg of KOH was added) Comparative Example 1 In wa example i, the reaction was carried out under the same conditions as in Example 1 except that isopropenylbenzene was not added. Results of the treatment and analysis 11. The reaction rate of 1-bis(4-hydroxyphenyl)cyclohexane was 100 mol%. At this time, p-phenylphenol, P-cyclohexylphenol, and diphenyl-cyclohexylbenzene were produced, and their yields were 41 mol%, 25 mol%, 13 mol%, and 4 mol%, respectively.

Examples 3-4, Comparative Examples 2-3 In Example 1, the reaction was carried out under the same conditions as in Example 1, except that the reaction was carried out at the reaction temperature listed in Table 2. Processed and analyzed. The results are shown in Table 2 (However, in Comparative Example 3, nitrogen was used at 35 kti/a.
Pressure was applied to x2·G. ) Example 5 In Example 1, 1,1-his(4-
Hydroxy-3-methylphenyl)cyclohexane 0.
Reaction, post-treatment and analysis were carried out under the same conditions as in Example 1, except that 74 g (2.5 mmol) was charged. As a result, the reaction rate of 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane was 100 mol%, and the yield of 6-methyl-4-phenylphenol and 3-methyl-4-cyclohexylphenol was 100% by mole. The ratios were 97 mol % and 2 mol A/%, respectively.

Example 6 In Example 1, 0.97 g of p-methylisopropenylbenzene (7,5
The reaction, post-treatment and analysis were carried out under the same conditions as in Example 1, except that 1 mmol) was used. As a result, 1.1-
The reaction rate of bis(4-hydroxyphenyl)cyclohexane was 100 mol%, and the yields of p-phenylphenol and p-cyclohexylphenol were 95 mol% and 3 mol%, respectively.

Example 7 The reaction, post-treatment and analysis were carried out under the same conditions as in Example 1 except that the amount of isopropenylbenzene used was 0.71 g (7 mmol). As a result, 1
．． The reaction rate of 1-bis(4-hydroxyphenyl)cyclohexane was 100 mol%. At this time, the yield of p-phenylphenol was 499 mol%.

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi

Claims (1)

[Scope of Claims] 1,1-bis(4-hydroxyphenyl)cyclohexanes represented by the formula (wherein R represents a hydrogen atom, a hydroxyl group, or a lower alkyl group) and styrenes are prepared in a liquid phase. General formula (1) characterized by heating to a temperature in the range of 210 to 290°C in the presence of a hydrogenation reduction catalyst (
In the formula, R represents the same group as above. ) expressed as p-
Process for producing phenylphenols. (2) The method according to item (1), wherein the 1.4-bis(4-hydroxyphenyl)cyclohexane is 1.4-bis(4-hydroxyphenyl)cyclohexane. (3) The method according to claim (1), wherein the hydrogenation reduction catalyst is a palladium catalyst. (4) The method according to claim (1), wherein the hydrogenation reduction catalyst is a palladium carrier. (5) The method according to claim (1), wherein the reaction is carried out in the presence of an aromatic hydrocarbon solvent. (6) The method according to claim (1), wherein the reaction is carried out at a temperature of 220 to 270°C. (7) The method according to claim (1), wherein the styrene is styrene substituted at the α-position or a nuclear substituted product thereof. (8) The method according to claim (1), wherein the styrene is isopropenylbenzene or a nuclear substituted product thereof.