JPS5822451B2 - Method for producing 3,3',5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to the production of 3,3',5,5-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane in high yield by condensation of 2,4,6-dolyhydroxymethylphenol. Regarding how to.

3,3',5,5'-tetrahydroxymethyl-4,4
'-Dihydroxydiphenylmethane is a compound used as a polymerization raw material for phenol resins, epoxy resins, polyester resins, and the like.

Conventionally, 3, 3', 5 from phenol and formaldehyde
・Many methods for synthesizing 5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane have been reported in the literature.

However, in both of these methods, phenol and formaldehyde are reacted in the presence of a basic compound containing an alkali metal or alkaline earth metal, but since many high-boiling compounds are produced as by-products, The yield of 5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane is low (and cannot be satisfactorily adopted as an industrial production method).

The present inventors have found that when a condensation reaction of 2,4,6-dolyhydroxymethylphenol is carried out in the coexistence of a basic compound containing an alkali metal or an alkaline earth metal and an alkali metal salt or an alkaline earth metal salt, 3・3′・5・5
It has been found that '-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane can be obtained at a still high yield, and the present invention has been completed.

That is, the present invention provides at least one basic compound (a) selected from the group consisting of basic compounds containing alkali metals or alkaline earth metals, and at least one basic compound (a) selected from the group consisting of alkali metal salts and alkaline earth metal salts. 2, 4, 6 in the coexistence of a selected small amount (both one kind of metal salt (b))
-trihydroxymethylphenol); 3,3',5,5'-tetrahydrogysimethyl-4,4'-dihydroxydiphenylmethane.

The raw material used in the method of the invention is 2,4,6-dolyhydroxymethylphenol.

The basic compound used in the method of the present invention is a basic compound containing an alkali metal or an alkaline earth metal.

More specifically, lithium hydroxide, thorium hydroxide, potassium hydroxide, lithium oxide, thorium oxide, potassium oxide, lithium butoxide, lithium butoxide, lithium butoxide, lithium butoxide, sodium methoxide, sodium ethoxide, sodium Basic compounds containing alkali metals such as ethoxide, sodium butoxide, potassium ethoxide, potassium ethoxide, potassium butoxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium oxide, oxidized Examples include basic compounds containing alkaline earth metals such as calcium, strontium oxide, barium oxide, magnesium methoxide, calcium methoxide, strontium methoxide, and barium methoxide.

At least one kind of these basic compounds is used, and a mixture of two or more kinds can also be used.

Among these basic compounds, it is preferable to use a basic compound containing an alkali metal, and it is more preferable to use a basic compound containing sodium.

the. Among them, it is particularly preferable to use thorium hydroxide in the method of the present invention.

In the method of the present invention, the 2,4,6-dolyhydroxymethylphenol is reacted in the presence of the basic compound containing the alkali metal or alkaline earth metal.

and 2,4,6-doryhydroxymethylphenol changes into an alkali metal salt or an alkaline earth metal salt, so the above 2,4,6-1-! J Hydroxymethylphenol and 2.4 instead of the above basic compound
・Alkali metal salts or alkaline earth metal salts of 6-dolyhydroxymethylphenol can also be used,
This naturally also falls within the scope of the present invention.

The metal salt used in the method of the present invention is at least one metal salt selected from the group consisting of alkali metal salts and alkaline earth metal salts.

For example, specifically, halogen compounds such as fluorides, chlorides, bromides, and iodides of alkali metals such as lithium, sodium, and potassium, and inorganic acid salts such as nitrates, sulfates, perchlorates, and phosphates. , organic M salts such as formate, acetate, propionic acid salt, oxalate + magnesium,
Fluorides, chlorides, smelly substances, iodides, etc. of alkaline earth metals such as calcium, strontium, and barium.
Examples include inorganic acid salts such as nitrates, nitrates, sulfates, perchlorates, and phosphates, and organic acid ends such as formates, acetates, propionates, and oxalates.

Among these metal salts, it is preferable to use alkali metal halogen compounds or alkaline earth metal halogen compounds, and in particular, alkali metal chlorides or alkaline earth metal chlorides are used in the method of the present invention. It is preferable.

Furthermore, as mentioned above, it is preferable to use a basic compound containing an alkali metal as the basic compound, but in this case, it is preferable to carry out the reaction in the coexistence of an alkali metal salt. When a basic compound is used, it is preferable to react with 1ζ in the presence of a thorium salt as the metal salt.

Among these, it is particularly preferable to carry out the reaction in the coexistence of sodium hydroxide and sodium chloride.

The amount of the basic compound used is usually in the range of 0.5 to 1.5, preferably 0.7 to 1.2 in molar ratio to 2,4,6-dolyhydroxymethylphenol.

The amount of the metal salt to be used is 0.0% in concentration in the solution in the reaction system.
The solubility can be selected within a wide range from 2 mol/l to saturated solubility, but from an economical point of view (15 mol/.e to 2.0 mol/l).
It is preferably in the range of 0 mol/l.

The reaction of the present invention is usually carried out in an aqueous solution, but if necessary, other water-soluble organic solvents such as alcohols, ketones, or A mixture of nitriles can also be used.

Additionally, dimethyl sulfoxide, dimethylformamide, dimethylaceI amide, N-methylbiL1ridone, -'\, which can dissolve basic compounds and metal salts.
It can also be carried out in a solvent such as xamethylphosphortri]'amide.

In the process of the invention, the reaction is usually carried out at a temperature of 20 to 100°C, preferably 40 to 90°C.

24.6-) when carrying out the method of the present invention! J
The reaction proceeds simply by maintaining the mixture of hydroxymethylphenol, the basic compound, the metal salt and, if necessary, the solvent at the above-mentioned temperature.

After completion of the reaction, 33',5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane is a basic compound that usually precipitates as its alkali metal salt or alkaline earth metal salt in the reaction mixture. The amount used is 2.4.6-1-! When the amount is less than J hydroxymethylphenol, it may exist as 3,3',5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane.

After the reaction is completed, the mixture is isolated by filtering, concentrating, or otherwise treated in accordance with a conventional method, and then precipitated with acid to obtain the desired product 3, 3', 5, 5.
'-Tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane is obtained.

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

Example 1 Internal volume with condenser and stirrer1. After replacing the inside of the Ql separable flask with N2 gas,
Thorium hydroxide 407 (1 mol), water 80 y and sodium chloride 30 P (0.5 mol) were placed inside a flask, and while stirring while maintaining the temperature at 30°C, 2,4,6-drichtokoma xymethylphenol 92 y ( 0.5 mol) was added.

After the preparation was completed, the temperature was raised to 60°C and stirred for 8 hours.

After the completion of the reaction, a certain amount of the reaction mixture is taken and acetic acid is added to it to precipitate the product.
3,3',5,5'-TeI,Lahydroxymethyl-4,
The amount of 4'-dihydroxydiphenylmethane was determined.

As a result, 3.3',5 was generated by the reaction. 5
The total amount of '-detrahydroxymethyl-4,4'-dihydroxydiphenylmethane was 112.1''E, and the yield was 70 mol% based on the charged 2,4,6-dolihydroxynotylnoenol. .

In addition, after cooling the reaction mixture after the completion of the reaction, it was filtered with F1, dried, and
A monothorium base of dihydroxydiphenylmethane was obtained.

By acidifying this with dilute hydrochloric acid, 3, 3', 5, 5
67.29 of '-tetrahydroxymethyl-11.4-dihydroxydinoenylmethane was isolated.

3,3',5,5'-tetrahydroxymethyl-4,4
The yield of '-dihydroxydiphenylmethane is 2
・4 for 4,6-dolihydrogysimethylphenol
．． It was 2 mol%.

Comparative Example 1 The same procedure as in Example 1 was carried out except that thorium chloride was not used.

As a result, 3.
3', 5, 5-tetrahydroxymethyl-4, 4'-
The amount of dihydroxydiphenylmethane produced was 88 (55
(mol%), and the amount of isolated 3,3',5,5'-tetrahydroxymethyl-4,4-dihydroxydiphenylmethane is 38.4? (24 mol%).

Examples 2 to 6, Comparative Examples 2 to 5 Same as Example 1 except that the same reaction apparatus as Example 1 was used, and the composition of the mixture charged in the flask and the reaction conditions were changed as shown in Table 1. method was used to react.

After the reaction was completed, the mixture was post-treated in the same manner as in Example 1.

Claims (1)

[Scope of Claims] 1. At least one basic compound (a) selected from the group consisting of basic compounds containing alkali metals or alkaline earth metals, and the group consisting of alkali metal salts and alkaline earth metal salts. 3.3, characterized in that 2,4,6-dolyhydroxymethylphenol is condensed in the co-presence of at least one metal salt (b) selected from 3.3.
A method for producing ',5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane. 2. The method according to claim 1, wherein an alkali metal halogen compound or an alkaline earth metal halogen compound is used as the metal salt (b). 3 The molar ratio of basic compound (a) to 2,4,6-dolyhydroxymethylphenol is 0.7 to 1.
．． 2. The method according to claim 1, wherein the metal salt (b) is used in a concentration range of 0.5 to 2 mol/l in the solution in the reaction system. 4. The method according to claim 1, wherein the reaction is carried out in an aqueous solvent. 5. The method according to claim 1, wherein the reaction is carried out at a temperature of 40 to 90°C.