JPS5976037A - Preparation of benzoquinone compound - Google Patents

Abstract

PURPOSE:To prepare the titled compound useful as a preparation raw material of perfumes, pharmaceuticals, etc., safely, in high yield, without causing the problems of post-treatment, etc., by reacting a phenolic compound with hydrogen peroxide in the presence of a metallic catalyst. CONSTITUTION:The objective compound of formula II (R<1>, R<2>, R<3> and R<4> are H, alkyl or aryl) can be prepared by reacting the phenolic compound of formula I with hydrogen peroxide in the presence of a metallic catalyst in a solvent preferably acetic acid, etc. at 0-100 deg.C, preferably 20-60 deg.C. The metallic catalyst is preferably a compound of a VIII-group metal such as chloroplatinic acid, palladium chloride, rhodium chloride, osmium chloride, etc. It may be used as a homogeneous catalyst or a heterogeneous catalyst by supporting on an inert carrier such as silica gel. Only a catalytic amount of the catalyst is sufficient for the purpose.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing benzoquinones represented by the general formula (wherein 1, R2, R3, and R4 are hydrogen, an alkyl group, an alkenyl group, or an aryl group). It is. More specifically, the present invention provides the above-mentioned general formula by reacting a phenol represented by the general formula (wherein R1, R2, R3 and R4 are the same as above) with hydrogen peroxide in the presence of a metal catalyst. The present invention relates to a method for producing benzoquinones represented by formula CI).

The benzoquinones represented by the general formula (I) are fragrances,
It is widely used as a raw material for pharmaceutical products and their production.

Conventionally, in order to directly produce benzoquinones represented by the above general formula (I) from phenols represented by the general formula (a) Fremy salt (trosodisulfonate), New experimental chemistry course.

15, see Marutake (1976)], (b) Manganese dioxide R, Miche I, West German Published Patent No. 25023
No. 32 (1975) Seriho], e) Reagent oxidation method using thallium salts [New Experimental Chemistry Course, see Lb Marusaki (1976)], etc.) Oxygen oxidation method using cobalt tonnov base chloride [New Experimental Chemistry] Lecture &, 15. See Maruzen (1976)],
(e) Basic autowJ1112 conversion method [New Fuken Chemistry Course.

1, Marumarutake 1976)] are known.

However, the method of
m y ) It is difficult to adopt it industrially because there are problems with the stability of the salt and the preparation in large quantities. Methods (b) and (e) require the use of reagents in a stoichiometric manner, and there are problems with post-processing, so they are difficult to adopt industrially. Method (c) has a problem with the toxicity of thallium. ) has not been industrially adopted due to the cost of the rough base.

The present invention was developed as a result of studies to overcome the drawbacks of conventional methods.
The present inventors have discovered an industrial method for easily converting substituted phenols into the corresponding benzoquinones with high yields, and have completed the present invention.

Examples of the phenols represented by the general formula (Company), which are raw materials of the present invention, include cresol, xylenol, trimethylphenol, tetramethylphenol, phenylphenol, and allylphenol. On the other hand, hydrogen peroxide that is commercially available as a water bath solution is usually used, and 30% hydrogen peroxide is suitable for use.

The present invention is carried out in the presence of a Kanasu catalyst.

The Kinpo catalyst of the present invention includes iron chloride, ruthenium chloride,
Iron oxide, ruthenium bromide, μ3-oxotriruthenium complex, μ3-oxotrimetal complex such as μ3-oxotriiron complex, ruthenium phosphine complex such as triphenylphosphine ruthenium dichloride-triphenylphosphine hydridoruthenium, nickel chloride Group 8 metal catalysts such as palladium chloride, rhodium chloride, nickel chloride, cobalt chloride, ilinium chloride, osmium chloride, steel chloride, oxovanadium acetylacetonate, molybten oxo complex, etc. can be used, but the point where the activity is suitable is The use of Group 8 metal catalysts is preferred. When using the catalyst, it may be used as a homogeneous catalyst, or it may be used as a heterogeneous catalyst by being supported on a carrier that does not participate in the reaction, such as silica gel, alumina, or foil. Further, it is sufficient to use a so-called catalytic amount.

The present invention is preferably carried out in a solvent, and for example, a mixture of a carboxylic acid such as acetic acid or formic acid, or a saturated alcohol such as methanol or ethanol, and a mineral acid such as hydrochloric acid can be used. Further, although the reaction proceeds in the range of 0 to 100C, the range of 20 to 60tZ' is preferable in order to obtain the target product in good yield.

Hereinafter, the present invention will be explained in more detail with reference to Examples. 1 g of the solution was poured down at very high temperature and stirred for 5 hours. [Although dimer may form as a precipitate in the reaction solution, it can be easily removed by F separation (0-10%)]. After adding a small amount of sodium thiosulfate solution to the reaction mixture, it was extracted with ether, the ether layer was dried over magnesium chain acid, and the ether was distilled off under reduced pressure. 2,3,61-limethylbenzoquinone was obtained (496 ml (90%)). The physical properties of trimethylbenzoquinone are based on literature values [New Experimental Chemistry Course, L
Σ, Marutake (1976):] and -maki. 1 Example 2 The reaction was carried out in the same manner as in Example 1 except that triphenylphosphine ruthenium hydride acetate 10 to 10 was used in place of ruthenium chloride 9, and post-treatment was performed. Unreacted raw material 200
~ and 200 mg (61 arrows) of trimethylbenzoquinone were obtained.

Example 3 5% ruthenium-carbon 30 in place of ruthenium chloride
The reaction and treatment were carried out in the same manner as in Example 1, except that ~ was used, and 435~ (79%) of trimethylbenzoquinone was obtained.

Example 4 The reaction and treatment were carried out in the same manner as in Example 1, except that iron chloride was used in place of ruthenium chloride, and 395 μm (73%) of trimethylbenzoquinone was obtained.

Example 5 2.3.5-) When 500 mg of trimethylphenol and 10 μm of ruthenium chloride were reacted in the same manner as in Example 1 in acetic acid 5a and treated, 100~ of unreacted raw materials and 23M (51%) of trimethylbenzoquinone were obtained. I got it.

Example 6 500 μl of 2,3.5.6-titramethylphenol and 109 μl of ruthenium chloride were reacted in 5 Inl of acetic acid and treated in the same manner as in Example 1. Tetramethylbenzoquinone 2
88~ (53%) and a mixture of three unidentified substances 228~
I got it. Tetramethylbenzoquinone was obtained as yellow needle crystals with a melting point of 114-115°C by 8 crystals from hexane.

Mass spectrometry spectrum m/e 164 (M+, 94
).

136 (65), 121 (100)・Infrared absorption spectrum νC:. 1634(?F71”-Procedure
Amendment (spontaneous) August 19, 1958 Commissioner of the Japan Patent Office Kazuinu Wakasugi 1゜Display of the case 1982 Patent Application No. 184684 2゜Name of the inventionProduction method of benzoquinones 3゜Amendment case Relationship with Patent Applicant 4, [Claims JSS Uni (5 Detailed Description) of the specification to be stopped]
Column 5, Contents of amendment (1) The section ``Claims'' from line 105 to page 2, line 3 of this E6 Specification A is corrected as follows.

"(1) A method for producing benzoquinones represented by the general formula, characterized by reacting a phenol represented by the general formula with hydrogen peroxide in the presence of a metal catalyst [wherein l't, 1, where RlR and R are hydrogen, an alkyl group, or an aryl group.

(2) The method according to claim (1), wherein the metal catalyst is a Group 8 metal catalyst. ” (2) Page 2, line 8, “
, alkenyl group," is deleted.

(3) Delete [, alliltunor] on page 4, line 16.

that's all

Claims (2)

[Claims] (1) Presence of a metal catalyst 1. A method for producing benzoquinones represented by the general formula, which is characterized by reacting phenols represented by the general formula with hydrogen peroxide.
L2, kL3 and 几4 are hydrogen, an alkyl group, an alkenyl group or an aryl group. ]. (2) The method according to claim 1, wherein the metal catalyst is a Group 8 metal catalyst.