JPH01319432A - Production of 4,4'-dihydroxytetraphenylmethanes - Google Patents

Abstract

PURPOSE:To easily obtain the subject substance in high yield at a low cost by mixing and reacting phenols with a reaction mixture of benzenes and benzotrichlorides in the presence of a Lewis acid catalyst and contacting the reaction product with water and a halogen-containing compound. CONSTITUTION:Benzenes are made to react with benzotrichlorides in the presence of a Lewis catalyst (preferably AlCl3) at 0-40 deg.C to obtain diphenylchloromethanes as an intermediate, which is reacted with phenols at 80-180 deg.C without separating the product from the reaction system. The obtained reaction product is made to contact with water to deactivate the Lewis acid catalyst and then with a halogen-containing compound (e.g., halogen-containing acids, oxyhalides, phosphorous halides and metal halides) to obtain the subject substance. The substance is useful as a raw material for engineering resin and optical disk material, an intermediate for organic synthesis, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing 4,4'-dihydroxytetraphenylmethanes, and specifically relates to a method for producing 4,4'-dihydroxytetraphenylmethanes. From,
The present invention relates to a method for producing intermediate diphenyldichloromethane in a high yield through a simple process without separation and purification.

[Prior Art] 4.4'-Dihydroxytetraphenylmethanes are known to be useful compounds as raw materials for engineering resins, optical disk materials, etc., or as synthetic intermediates.

Conventionally, a method for producing diphenyldichloromethane by reacting benzene and benzotrichloride in the presence of aluminum chloride has been known (Chemical Abstracts Vol. 53, page 3140b).

Furthermore, a method for producing 4,4'-dihydroxytetraphenylmethanes by condensing diphenyldichloromethanes and phenol has been known.

Among these methods, to increase the yield of 4.4'-dihydroxytetraphenylmethanes, pure diphenyldichloromethane and phenol are mixed in a molar ratio of 1:2.
There is a method of reacting at a ratio of 1:2.4 to 1:2.4 and treating the product with alcohol (Japanese Patent Publication No. 11651/1983). However, this method requires pure 4,4'-diphenyldichloromethane as a raw material, so when producing 4.4'-'; phenyldichloromethane, 4,4'-diphenyldichloromethane is extracted from the product mixture. Separation and purification is required, which makes the operation complicated, and there is also the disadvantage that some diphenyldichloromethane is lost.

[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of the conventional method for producing 4,4'-dihydroxytetraphenylmethanes, and can produce intermediate diphenyldichloromethanes without separating and purifying them. The purpose of this invention is to provide a method for producing 4,4'-dihydroxytetraphenylmethanes in good yield through a simple process.

[Means for Solving the Problems] As a result of extensive research to achieve the above object, the present inventors have developed a method of producing a compound obtained by reacting benzenes and benzotrichlorides in the presence of a Lewis acid catalyst. They discovered that the objective could be achieved by mixing the reaction mixture with phenols and further treating the reaction product by bringing it into contact with water and a halide. Based on this, the present invention has been completed.

That is, the first invention of the present application is characterized in that the reaction mixture obtained by reacting benzenes and benzotrichlorides in the presence of a Lewis acid catalyst and phenols are mixed and reacted. - A method for producing dihydroxytetraphenylmethanes. In addition, the second invention of the present application is to mix and react a reaction mixture obtained by reacting benzenes and benzotrichlorides with 7 enols in the presence of a Lewis acid catalyst, and then convert the reaction product into This is a method for producing 4,4'-dihydroxytetraphenylmethanes, which comprises contacting with water and a halide-containing compound.

Since the main parts of the structure of the first invention of the present application and the second invention of the present application are common, the following description will focus on the first invention of the present application.

In the first invention of the present application, benzenes and benzotrichlorides are first reacted in the presence of a Lewis acid catalyst. The benzenes used here include, for example, the general formula (in the formula, R1 is a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, aralkyl group or other substituent that does not inhibit the reaction in the first invention of the present application, t is an integer of 1 to 6, preferably 1 to 3, and when a is 2 or more, R1 are different from each other; ) can be mentioned.

The alkyl group for R1 in the general formula (I) is a lower alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a 5eC-butyl group, t-butyl group,
Preferred examples include various amyl groups and various hexyl groups, among which methyl and ethyl groups are particularly preferred.

Regarding R1, examples of the aryl group include phenyl group, biphenyl group, or phenyl group substituted with a lower alkyl group such as methylphenyl group and ethylphenyl group, and examples of the aralkyl group include phenylmethyl group, phenylethyl group, etc. group, methylphenylethyl group, etc.

Furthermore, examples of the halogen atom for R1 include fluorine atom, chlorine atom, bromine atom and iodine, and among these, chlorine atom is particularly preferred.

As R1, various groups or atoms can be mentioned as described above, but groups that have little steric hindrance during the reaction, such as a hydrogen atom or a lower alkyl group, are preferable, and a hydrogen atom is particularly preferable.

In the first invention of the present application, specific examples of benzenes that can be suitably used include benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene, and chlorobenzene. Among them, benzene, toluene, ethylbenzene, and chlorobenzene are preferred, and benzene is particularly preferred. These benzenes may be used alone or in combination of two or more.

Furthermore, bensitrichlorides can be expressed by the general formula (wherein R2 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, or another substituent that does not inhibit the reaction of the present invention, and m is a 1 to 4 substituent. An integer, preferably 1 or 2, and when m is 2 or more, R2 may be different from each other).

The halogen atom, alkyl group, aryl group, and aralkyl group for R2 in the general formula (II) include:
The same compounds as those listed for R1 in the general formula (I) can be mentioned.

Preferred examples of R2 include a hydrogen atom, a chlorine atom,
Examples include those having little steric hindrance during the reaction, such as a fluorine atom or a lower alkyl group such as a methyl group or an ethyl group, but more preferred examples of R2 include a hydrogen atom and a lower alkyl group, particularly a hydrogen atom and a methyl group. I can do it.

In the first invention of the present application, specific examples of benzotrichlorides that can be suitably used include benzotrichloride,
Methyl bensi trichloride, dimethyl bensi trichloride, ethyl bensi trichloride, propyl bensi trichloride, butyl bensi trichloride, chlorobensi trichloride, among others, bensi trichloride, methyl benzo trichloride, 1 ethyl bensi trichloride, etc. trichloride, chlorobenzotri/)
a-ride is preferred, and benzotrichloride is particularly preferred. These benzotrichlorides may be used alone or in combination of two or more.

In addition, known Lewis acid catalysts are used, such as aluminum chloride, aluminum bromide, boron heptadide, boron chloride, ferric chloride, zinc chloride, titanium tetrachloride, zirconium tetrachloride, tin tetrachloride, and pentachloride. Among these, aluminum chloride is particularly preferred. One type of these Lewis acids may be used, or two or more types may be used in combination.

In the first invention of the present application, first, benzenes and benzotrichlorides are reacted in the presence of the Lewis acid catalyst to produce intermediate diphenylchloromethanes. At this time, the proportions of benzenes (A), Lewis acid catalyst (B) and benzotrichlorides (C) are as follows:
(A)/(B) molar ratio is usually 1/10 to 1000/1,
Preferably 115 to Zoo/1, more preferably 1/
(B)/(C) molar ratio is 10/1 to 1/1000. Preferably 5/1 to 1/1
00. It is particularly desirable to use the proportion in the range of 3/1 to 1/20. In addition, the reaction temperature is usually -
The temperature is selected from 5 to 80°C, preferably from 0 to 40°C. If the reaction temperature is lower than 15°C, the reaction rate will be too slow to be practical; Exceeding this is not preferable as it tends to cause many side reactions.

Since this reaction is an exothermic reaction, it is desirable to perform a heat removal operation, such as water cooling, as appropriate.
There is no particular restriction on the order in which the Lewis acid catalyst and benzotrichloride are added, but usually benzenes or a mixture of benzene and benzotrichloride are gradually added to the mixture of bensitrichloride and Lewis acid catalyst. A method of adding is used. According to such a method, the reaction temperature can be easily controlled, and the production of by-products such as triphenylchloromethanes can be suppressed, and the yield of diphenyldichloromethanes can be improved.

The reaction time depends on the type of benzene and Lewis acid catalyst used and the temperature, and cannot be determined generally, but for example, when the reaction is carried out in a batch or semi-batch manner, it is usually 30 minutes to 48 minutes. time, preferably 1 to 1
The reaction time is about 2 hours, and when the reaction is carried out continuously, the reaction may be carried out at a residence time corresponding to these hours.

In the method of the present invention, once a desired conversion rate is obtained in the reaction, the reaction mixture and phenols are mixed and reacted with diphenyldichloromethane produced in the reaction.

The phenols used here have the general formula (in the formula, R3 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, or another substituent that does not inhibit the reaction of the present invention, and n is 1 to 4 , preferably 1 or 2, and when n is 2 or more, R3 may be different from each other).

Examples of the halogen atom, alkyl group, aryl group, and aralkyl group for R3 in the general formula (III) include those listed for R1 in the general formula (I).

Preferred examples of R3 include a hydrogen atom, a chlorine atom,
Examples of R1 include those having little steric hindrance during the reaction, such as a fluorine atom or a lower alkyl group such as a methyl group or an ethyl group; more preferred examples of R1 include a hydrogen atom and a lower alkyl group, particularly a hydrogen atom and a methyl group. I can do it.

In the first invention of the present application, specific examples of phenols that can be suitably used include phenol, 0-cresol, 0-
Ethylphenol, 0-chlorophenol, 2,6-dichlorophenol, 2,6-dimethylphenol, 0-
Propylphenol, 0-fluorophenol, 2.6
-difluorophenol, 〇-phenylphenol, O
-benzenephenol, etc. Among these, phenol, 0-cresol, 0-ethylphenol, 0-chlorophenol, O-fluorophenol, 2,6-dimethylphenol, 2,6-dichlorophenol, 2,6-difluorophenol and the like are preferred, with phenol and 0-cresol being particularly preferred.

These phenols may be used alone or in combination of two or more.

In addition, in the first invention of the present application, these phenols may contain moisture to the extent that it does not interfere with the reaction, but
Its content is usually 20% by weight or less, preferably 5% by weight.
The following is desirable.

If the water content is too high, the amount of by-products of benzophenones and tobidroxyphenyldiphenylcarbinols due to hydrolysis of the produced diphenyldichloromethanes will increase, which is not preferable.

At this time, the molar ratio of Lewis acid/phenols is usually 1/1000 to 10/1.
1, preferably 1/Zoo to 5/1.

Further, the reaction temperature of this reaction is usually 0 to 250°C, preferably 30 to 200°C, and particularly preferably 80 to 180'C. If the reaction temperature is too low, the reaction rate will be slow, while if the reaction temperature is too high, side reactions will occur, which is not preferable.

The reaction time depends on the types of benzenes, Lewis acid catalysts and phenols used, and the temperature, and cannot be determined generally, but for example, when the reaction is carried out in a palindromic or semi-palindromic manner, The reaction time is usually 30 minutes to 48 hours, preferably about 2 to 20 hours, and when carried out continuously, the reaction may be carried out at a corresponding residence time.

The second invention of the present application is one in which a reaction product obtained by the same configuration as the first invention of the present application is brought into contact with water and a halide-containing substance.

Preferred examples of the halide used here include halogen-containing acids, oxyhalides, phosphorus halides, and metal halides. Examples of the halogen-containing acids include hydrogen halides such as hydrogen chloride, hydrogen fluoride, hydrogen bromide, and hydrogen iodide, and hypochlorous acid such as hypochlorous acid. Examples of oxyhalides include thionyl chloride, sulf.
Examples of phosphorus halides include lyl chloride, vanadium oxychloride, and phosphorus trichloride, phosphorus pentachloride,
Examples of metal halides include phosphorus tribromide and phosphorus pentabromide, and examples of the metal halides include boron trichloride, boron trifluoride, and Sarashiko powder. These halides may be used alone or in combination of two or more.

There is no particular restriction on the order of addition of water and the halide, which may be brought into contact at the same time or separately, but usually water is brought into contact first, the Lewis acid catalyst is deactivated, and then the Lewis acid catalyst is deactivated. , a method of contacting with a halide-containing substance is used. At this time, the water in contact may be pure water, acidic aqueous solutions containing hydrochloric acid, sulfuric acid, nitric acid, etc., neutral aqueous solutions containing sodium chloride, potassium chloride, etc., sodium hydroxide, potassium hydroxide, etc. or an aqueous solution containing water-soluble organic compounds such as alcohols and carboxylic acids.

The amount of water in contact with the Lewis acid catalyst is usually selected in the range of equimolar or more, preferably equimolar to 100 times the mole, and the treatment temperature is usually -10 to 200°C, preferably 0 to 50°C. Selected in the range of °C.

The Lewis acid catalyst deactivated in this treatment step is washed with water and then
The water may be removed from the system, or the water within the system may be distilled off by heating or reduced pressure treatment.

Next, the reaction product treated in this manner is brought into contact with the halide-containing compound to be treated.

At this time, the amount of the halide to be used is usually such that the molar ratio of Lewis acid catalyst/halide is from 0.01 to 1000, preferably from 0.1 to 100, more preferably from 0.5 to 10.
is selected to be within the range of

In addition, the treatment temperature is usually 0 to 250'C, preferably 3
The temperature is selected within the range of 0 to 150°C, more preferably 80 to 150°C. Furthermore, the processing time is usually 30 minutes to 4 minutes.
8 hours, preferably 1 to 20 hours. This process is
This may be done after adding the halide-containing compound at once, or
It may be added or introduced continuously.

There is no particular restriction on the pressure of the reaction system in each of the above steps, and the reaction can be carried out under reduced pressure, normal pressure, the own pressure of the reaction system, or under pressure using an inert gas. Since hydrochloric acid gas is generated in the reaction with benzotrichlorides, it is preferable to adopt a method in which the reaction is carried out while removing this gas from the reaction system.

Further, each of the above steps is usually carried out without a solvent, but can also be carried out using an inert solvent if desired. In the reaction between benzenes and benzotrichlorides, an aprotic solvent such as an aliphatic saturated hydrocarbon such as pentane or hexane can be used as the solvent. In addition, for the reaction between the intermediate diphenyldichloromethane and phenol, an aprotic solvent such as an aliphatic saturated hydrocarbon such as pentane or hexane, an aromatic hydrocarbon such as benzene or toluene, or ether is used as a solvent. be able to.

Furthermore, in the first invention of the present application and the second invention of the present application, after reacting benzenes and benzotrichlorides,
Before adding phenols, if desired, excess benzotrichlorides and unreacted benzenes are distilled off,
The yield of the target 4,4'-dihydroxytetraphenylmethane can be further improved.

In the method of the second invention of the present application, by adding a halide-containing compound, crude 4.4''-dihydroxytetraphenylmethane is usually precipitated as crystals, so it is separated and recovered by means such as filtration.

The crude 4,4'-dihydroxytetraphenylmethanes obtained by the method of the first invention and the method of the second invention of the present application can be processed, if desired, by a known method, for example, using a solvent such as ethanol, tetrahydrofuran, or hexane. It can be recrystallized to produce high purity products.

[Examples] Next, the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples in any way.

Example 1 Into 21 four-hour flasks equipped with a Stark, separatory funnel, reflux condenser, and thermometer, 67% of aluminum chloride was charged.
5g (0.5ml), benzene 3909 (5.0ml)
) was added and the flask was cooled in a water bath. Next, add benzotrichloride 1959 (1,01111
), and benzotrichloride was gradually dropped into the flask. The dropping was carried out so that the internal temperature was maintained at 5 to 10°C. After the addition, stirring was continued for 12 hours, the separatory funnel and reflux condenser were removed from the flask, the flask was sealed tightly, and the pressure was reduced using an aspirator to distill off unreacted benzene from the reaction mixture. The residue was then treated with phenol 2829 at room temperature.
(3.0ml) was added and stirred at room temperature for 1 hour, then the temperature was raised to 150'O without continuing stirring, and after reacting at that temperature for 5 hours, the temperature was lowered to room temperature and distilled water was gradually added to the reaction product. In addition, aluminum chloride was deactivated. After removing deactivated aluminum chloride by washing with water, hydrogen chloride gas was added at 40cc/mi.
When the reaction was carried out at 120° C. for 13 hours at a flow rate of n, crystals were precipitated. This was recrystallized with tetrahydro 7 runs and purified 4
．． 4'-dihydroxytetraphenylmethane 253.4
9 (yield 72% based on benzotrichloride) was obtained.

Example 2 In Example 1, aluminum chloride was added to 67.59 (0
The reaction was carried out in exactly the same manner as in Example 1 except that 27 g (0.2 m11) was added instead of 4,4'-dihydroxytetraphenylmethane 24
0.39 (yield 68% based on benzotrichloride) was obtained.

Example 3 In Example 1, phenol was added and stirred at room temperature for 1 hour, and then reacted at 150°C for 5 hours, but at 120°C
The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out for 3 hours, and 228.89 liters of 4,4'-dihydroxytetraphenylmethane (yield based on benzotrichloride: 65%) was obtained. child .

Example 4 The reaction was carried out in exactly the same manner as in Example 1 except that thionyl chloride 509 was added instead of adding hydrogen chloride gas at 40 cc/min in Example 1, and 4,4'-dihydroxytetraphenylmethane 246 .49 (benzotrichloride standard yield 7%) was obtained Example 5 The procedure was exactly the same as in Example 1 except that 324 g (3.0 mA) of orthocresol was used instead of 282 g of phenol in Example 1. When the reaction occurred, the mouth hissed (4-
Hydroxy-3-methylphenyl)diphenylmethane 2
24.2 g (yield 59% based on benzotrichloride) was obtained.

Example 6 In Example 1, hydrogen chloride gas was supplied at a flow rate of 40 cc/mi.
When the reaction was carried out in the same manner as in Example 1 except that n was not added at all, 1,4'-dihydroxytetraphenylmethane 211.29 (yield 6% based on benzotrichloride) was obtained. Ta.

Comparative Example 1 67.5 ml of aluminum chloride was added to 21 4-tubular flasks equipped with a stirrer, a separatory funnel, a reflux condenser, and a thermometer.
g (0.5 mA) and Benzea 3909 (5.0 ml) were added, and the flask was cooled in a water bath. Then, benzotrichloride 1959 (1, O ml) was placed in a separating funnel and slowly dropped into the flask. Drop at internal temperature 5~
The temperature was maintained at 10'O. After dropping, stir at room temperature for 12 minutes.
After continuing for a period of time, the aluminum chloride is deactivated by placing it in 500 cc of ice water. Take the oil layer and add calcium chloride 2
After adding 0 g of water and dehydrating it, distillation was performed under reduced pressure.

The fractions at 134-135°C under 1 mmHy were collected to give 163.59 of dichlorodiphenylmethane.

This was 69% based on benzotrichloride.

Next, the benzotrichloride obtained here was transferred to a 21 4-volume flask equipped with a stirrer, a reflux condenser, and a thermometer, and the 7 enol 1499 (1,58
1 l) was added. The temperature of the reactant was maintained at 30°C, stirred for 2 hours, and then reacted on an oil bath at 15.0°C for 30 minutes, crystals precipitated.

This was recrystallized with tetrahydrofuran and purified 4,4
'-Dihydroxytetraphenylmethane 193.6g (
A yield of 55% based on benzotrichloride was obtained.

[Effects of the Invention] According to the method of the present invention, from benzenes, hydrogen tetrachloride, and phenols, which are inexpensive and easily available industrially, 4.
．． 4'-dihydroxytetraphenylmethanes can be produced with good yield through a simple process.

The 4,4'-dihydroxytetraphenylmethanes obtained by the method of the present invention are useful as raw materials for engineering resins, optical disk materials, etc., or as intermediates for organic synthesis.

Claims (1)

[Claims] 1. 4,4' characterized in that a reaction mixture obtained by reacting benzenes and benzotrichlorides in the presence of a Lewis acid catalyst and phenols are mixed and reacted.
- A method for producing dihydroxytetraphenylmethanes. 2. Mixing and reacting the reaction mixture obtained by reacting benzenes and benzotrichlorides with phenols in the presence of a Lewis acid catalyst, and then contacting the reaction product with water and a halide-containing compound. 4,4' characterized by
- A method for producing dihydroxytetraphenylmethanes. 3. The manufacturing method according to claim 2, wherein the reaction product is brought into contact with water and then brought into contact with a halide-containing compound. 4. The manufacturing method according to claim 2, wherein the halide is a halogen-containing acid, an oxyhalide, a phosphorus halide, or a metal halide.