JPH0579053B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel method for producing polyhydroxybenzophenones. More specifically, the present invention relates to a method for producing polyhydroxybenzophenones useful as intermediates for, for example, ultraviolet absorbers, agricultural chemicals, pharmaceuticals, photosensitizers for photoresists, etc., in a high yield and with industrial advantage. It is. PRIOR ART Polyhydroxybenzophenones are extremely important compounds, for example, as ultraviolet absorbers, or as intermediates for agricultural chemicals, pharmaceuticals, photosensitizers for photoresists, etc., and various methods have been known to date to produce them. It is being For example, a method of condensing benzoic acids and phenols in the presence of a catalyst such as zinc chloride, polyphosphoric acid, or boron trifluoride [J.Pharm.Soc.Jpn. ” Volume 95, No.
Pages 378-381 (1955), Journal of
Organ Chemistry (J.Org.Chem.)
Volume 19, pages 1243-1251 (1954), Tokukai Sho
61-97240, etc.], or a method of condensing benzoic acids and phenols in the presence of a hydrogen fluoride catalyst [Journal of Organics, etc.].
Chemistry (J.Org.Chem)” Volume 19, No. 1243~
1251 (1954)] are known. However, in the former method, since a catalyst is used in an amount equal to or more than the same mole relative to the phenols, a large amount of waste liquid is inevitably produced, and its treatment is difficult. The latter method, which uses hydrogen fluoride, has many disadvantages in industrial implementation, such as environmental pollution due to the toxicity of the hydrogen fluoride and equipment costs due to the need to use a pressurized vessel for the reaction. . Furthermore, a method is known in which benzoic acids are converted into acid chlorides and condensed with phenols in the presence of an aluminum chloride catalyst [J.Org.
Chem.) Volume 19, pages 1243-1251 (1954
], this method requires one additional step to convert benzoic acids into acid chloride, the acid chloride is unstable and has storage problems, and moreover, more than the same mole of aluminum chloride must be used. First, the problem of waste liquid treatment associated with this must be solved. Furthermore, as an improvement on the method using acid chloride, a method has been proposed in which acid chloride and phenols are condensed in the presence of an acidic ion exchange resin (Japanese Patent Application Laid-Open No. 185743/1983).
However, this method also does not solve the problem of using acid chloride, which is chemically unstable and has storage problems. Problems to be Solved by the Invention The present invention overcomes the drawbacks of the conventional production method, and produces polyhydroxybenzolyl benzene of good quality, which is easy to operate, free from problems such as environmental pollution and waste liquid treatment, etc. The purpose of this invention is to provide a new method for producing phenones, particularly polyhydroxybenzophenones having a hydroxyl group at the 2-position, in high yield. Means for Solving the Problems As a result of extensive research to achieve the above object, the present inventors have discovered that benzoic acids and phenols can be combined in the presence of a specific catalyst and under specific reaction conditions. The inventors have discovered that the objective can be achieved by dehydrating and condensing , and have completed the present invention based on this knowledge. That is, the present invention provides the general formula

[Formula] (In the formula, X is a halogen atom, a hydroxyl group, an alkyl group, or an alkoxy group, m is 0 or 1
-5, and when m is 2 or more, each X may be the same or different);

[Formula] (In the formula, Y is a halogen atom, hydroxyl group, alkyl group, or alkoxy group, n is 0 or 1
an integer of ~4, and when n is 2 or more, each Y may be the same or different) and approximately equimolar amounts of phenols represented by
0.01 per mole of benzoic acids or phenols
A general formula characterized in that the reaction is carried out in the presence of ~0.5 mol of an organic sulfonic acid catalyst and while continuously removing water produced by the reaction.

The present invention provides a method for producing polyhydroxybenzophenones represented by the following formula: (X, Y, m, and n have the same meanings as above). The present invention will be explained in detail below. As the benzoic acids which are one of the starting materials in the method of the present invention, a compound represented by the above general formula () is used. Such compounds include:
Examples include benzoic acid, methylbenzoic acid, chlorobenzoic acid, methoxybenzoic acid, hydroxybenzoic acid, dihydroxybenzoic acid, and gallic acid. As the other starting material, phenols, compounds represented by the general formula (), such as catechol, resorcinol, hydroquinone, orcinol, 3-methoxycatechol, and pyrogallol, are used. These compounds represented by the general formula () and the compound represented by the general formula () are used in approximately equimolar amounts. In the method of the present invention, organic sulfonic acids are used as catalysts. Examples of the organic sulfonic acid include alkylsulfonic acids such as methanesulfonic acid and ethanesulfonic acid, arylsulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, and naphthalenesulfonic acid, styrenesulfonic acid resin, fluorinated sulfonic acid resin, etc. Examples include strongly acidic ion exchange resins. Each of these organic sulfonic acids may be used alone or in combination of two or more, and the amount used is one of benzoic acid or phenols.
It is necessary to select it within the range of 0.01 to 0.5 mole. If the amount is less than this, the reaction will not proceed sufficiently, and if the amount is more than this, a large amount of by-products will be produced. In the method of the present invention, the reaction can be carried out in the absence of a solvent, but since the reaction proceeds by distilling the water produced by condensation out of the reaction system, the solvent that forms an azeotrope with water can be removed. It is advantageous to use Examples of such solvents include chlorinated hydrocarbons such as 1,2-dichloroethane, tetrachloroethylene, and trichloroethane;
Aromatic hydrocarbons such as benzene, toluene, and xylene are used. In order to suitably carry out the method of the present invention, for example, a benzoic acid represented by the general formula (), a phenol represented by the general formula (), and an organic sulfonic acid are dissolved or suspended in the solvent, and then this is heated to reflux, and the water produced by the reaction is distilled off from the reaction system as an azeotrope. At this time, the reaction temperature is usually selected in the range of 50 to 200°C, and
Regarding the reaction pressure, the reaction may be carried out at normal pressure, or if necessary, the reaction may be carried out under reduced pressure. Furthermore, the reaction time depends on the raw materials used, the type of organic sulfonic acid, the reaction temperature, the state of distillation of the reaction product water out of the system, etc.
It is about 100 hours. After the reaction is completed in this way, the reaction mixture is concentrated as necessary, cooled to precipitate crystals, separated by means such as filtration, and further recrystallized as desired. A polyhydroxybenzophenone represented by the formula () is obtained. In addition, when a strongly acidic ion exchange resin is used as a catalyst, the above operation may be performed after separating the ion exchange resin, or the resin and crystals may be filtered out at the same time and then filtered using a conventional method. It may be separated. The filtrate containing the catalyst after crystal filtration can be reused as is, or if a strongly acidic ion exchange resin is used as the catalyst, the ion exchange resin can be recovered and reused. . In this way, by reusing the filtrate and catalyst, there is no need to discharge waste liquid to the outside, and unreacted materials can be used repeatedly, so the method of the present invention is advantageous for industrial implementation. be. Effects of the Invention According to the present invention, high-purity polyhydroxybenzophenones, especially polyhydroxybenzophenones having a hydroxyl group at the 2-position, can be selectively produced in high yield by combining benzoic acids and phenols in one step. can be manufactured. Furthermore, it is an industrially valuable process that does not use harmful catalysts or produce waste liquid after the reaction. Since the reaction of the present invention does not use metal compounds such as zinc chloride or aluminum chloride as a catalyst, the polyhydroxybenzophenones obtained by the present invention can be used for applications where metal impurities are avoided, such as as raw materials for photoresists for the electronic industry. suitable. Photosensitive agents for positive photoresists currently used in the electronics industry include 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2', An ester of a polyhydroxybenzophenone having a hydroxyl group at the 2-position, such as 4,4'-toterahydroxybenzophenone, and naphthoquinodiazide sulfonic acid is used. Polyhydroxybenzophenones used as raw materials for such applications are required to have a metal content of several ppm or less. For this reason, purification is usually very complicated, but the polyhydroxybenzophenone of the present invention has a high metal content even without special purification.
Less than ppm can be obtained. Furthermore, the present invention has made it possible to produce benzophenones from hydroxybenzoic acid, which is difficult to do with conventional reactions involving acid chlorides. Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 Pyrogallol 20.2 g (0.16 mol), p-hydroxybenzoic acid 22.1 g (0.16 mol), Amberlyst 15 ("Anberlyst 15" polystyrene sulfonic acid resin manufactured by Rohm and Haas) 12.7 g (0.056 as sulfonic acid) A mixture of 300 ml of toluene and 300 ml of toluene was heated under reflux for 21 hours with azeotropic dehydration. After cooling, the precipitated mixture of crystals and resin was collected by filtration. Add 20% ethanol aqueous solution to the resulting cake
The resin was removed by adding 400 g, heating and filtering. The filtrate was cooled, and the precipitated crystals were filtered and dried to obtain 33.6 g (yield: 86%) of 2,3,4,4'-tetrahydroxybenzophenone. Example 2 Pyrogallol was added to the reaction filtrate obtained in Example 1.
20.2g (0.16mol), p-hydroxybenzoic acid 22.1
g (0.16 mol) and recovered in Example 1
Amberlyst 15 was added and the reaction was carried out in the same manner as in Example 1 to obtain 36.3 g (yield 93%) of 2,3,4,4'-tetrahydroxybenzophenone. Examples 3 to 5 Amberlyst 15 of Example 1
The reaction was carried out in the same manner as in Example 1, except that various organic sulfonic acids were used instead of. The results are shown in Table 1.

[Table] Resin Examples 6 to 9 Various benzoic acids were used in place of p-hydroxybenzoic acid in Example 1, and Amberlyst15
The reaction was carried out in the same manner as in Example 1, except that 8.5 g was used. The results are shown in Table 2.

【table】

[Table] Examples 10 and 11 The reaction was carried out in the same manner as in Example 1, using various polyhydric phenols instead of pyrogal in Example 1. The results are shown in Table 3.

[Table] Example 12 Pyrogallol 20.2g (0.16mol), benzoic acid 20
g (0.16 mol), Amberlyst15 8.5 g and xylene
280 ml of the mixture was heated to reflux for 22 hours with azeotropic dehydration. After cooling, it was treated in the same manner as in Example 1 to give 2,3,4-trihydroxybenzophenone 19.0
g (yield 52%) was obtained. Example 13 20.2 g (0.16 mol) of pyrogal and 22.1 g (0.16 mol) of p-hydroxybenzoic acid were added to the reaction filtrate containing the catalyst obtained in Example 4, and the reaction was carried out in the same manner as in Example 4. 2,3,4,4'-tetrahydroxybenzophenone 34.6g (yield 88%)
was gotten.

Claims (1)

[Claims] 1 General formula [Formula] (In the formula, X is a halogen atom, a hydroxyl group, an alkyl group, or an alkoxy group, m is 0 or 1
benzoic acids represented by the general formula [formula] (where m is an integer of 2 or more, each X may be the same or different) , halogen atom, hydroxyl group, alkyl group or alkoxy group, n is 0 or 1
an integer of ~4, and when n is 2 or more, each Y may be the same or different) and approximately equimolar amounts of phenols represented by
0.01 per mole of benzoic acids or phenols
The reaction is carried out in the presence of ~0.5 mol of an organic sulfonic acid catalyst while continuously removing water produced by the reaction. has the same meaning as above) A method for producing polyhydroxybenzophenones represented by: