JP2002128715A - Method for producing phytantriol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily and industrially advantageously producing a high-purity phytantriol. SOLUTION: This method for producing the phytantriol is characterized in that 1,2-epoxy-3,7,11,15-tetramethylhexadecan-3-ol is hydrolyzed in a mixed solvent of a tertiary alcohol and water in the presence of an acid at the temperature of <50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing phytantriol (3,7,11,15-tetramethyl-1,2,3-trihydroxyhexadecane). Phytantriol is used in cosmetics as a wetting agent and as a penetration enhancer for cosmetically active ingredients such as panthenol, vitamin A and vitamin E.

[0002]

BACKGROUND OF THE INVENTION Phytantriol is produced industrially by (1) reacting isophytol with an organic peroxide such as formic acid and then hydrolyzing the product with an alkali such as caustic potassium or caustic soda. (See German Patent 1,149,700), (2) isophytol is reacted with t-butyl hydroperoxide in the presence of a vanadium compound or a molybdenum compound, and the resulting epoxy compound is dissolved in a solvent such as isopropanol or tetrahydrofuran. A method of opening a ring using an acidic catalyst (see JP-A-61-236737) is known.

[0003]

In the methods (1) and (2), an expensive organic peroxide is used for epoxidation. Further, in the method (1), many compounds having a boiling point almost as high as phytantriol which are easily decomposed at a high temperature are produced as by-products. Therefore, under a high vacuum (about 10 ⁻⁾ such as short-path distillation or molecular distillation. ¹ to 10 ^-5 mbar)
Even if the fractionation method is adopted, phytantriol cannot be produced with the purity required for cosmetics use. In the method (2), the solvent used may be involved in the reaction depending on the hydrolysis reaction conditions. For example, when isopropanol is used, isopropyl ether is by-produced, and when tetrahydrofuran is used, The generated phytantriol has a tendency to gel, and in any case, suitable reaction conditions are very limited, and process control is difficult.

An object of the present invention, therefore, is to provide a method for industrially and advantageously producing high-purity phytantriol easily and with high yield.

[0005]

SUMMARY OF THE INVENTION According to the present invention, an object of the present invention is to provide 1,2-epoxy-3,7,11,15-tetramethylhexadecane-3-ol with a tertiary alcohol and water. This is achieved by providing a process for producing phytantriol, characterized in that it is hydrolyzed at a temperature of less than 50 ° C. in the presence of an acid in a mixed solvent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION 1,2-Epoxy-3,7,11,15-tetramethylhexadecane-3-ol used as a raw material in the present invention can be prepared, for example, by converting isophytol to ammonium tungstate, phosphoric acid and It can be easily produced by reacting with hydrogen peroxide in the presence of a quaternary ammonium.

[0007] The reaction of the present invention must be carried out in a mixed solvent of tertiary alcohol and water. In the present invention, when a primary alcohol or a secondary alcohol is used instead of the tertiary alcohol, there is a strong tendency that a solvolysis (alcohol addition) reaction occurs in addition to the hydrolysis reaction to produce an ether by-product. Therefore, its use should be avoided.

[0008] Tertiary alcohols include water and 1,2-
There is no particular limitation as long as it plays a role in mixing epoxy-3,7,11,15-tetramethylhexadecane-3-ol. Preferred tertiary alcohols include t-butyl alcohol, 1,1-dimethylpropanol, 1-ethyl-1-methylpropanol, 1,1-diethylpropanol, 1,1-dimethylbutanol, 1-ethyl-1-methyl Butanol, 1,
1-diethylbutanol, 1,1-dimethylpentanol, 1-ethyl-1-methylpentanol, 1,1-diethylpentanol, 1,1-dimethylbenzyl alcohol, 1-ethyl-1-methylbenzyl alcohol,
Examples thereof include 1,1-diethylbenzyl alcohol. In consideration of economy, hydrolysis efficiency, and the like, it is particularly preferable to use t-butyl alcohol.

The amount of water used is 1,2-epoxy-3,
It is sufficient that the amount is 1 equivalent or more with respect to 7,11,15-tetramethylhexadecane-3-ol, but the range of 1 to 100 equivalents is preferable in consideration of the reaction efficiency and selectivity, and from the viewpoint of the volumetric efficiency of the reaction. A range of 1 to 20 equivalents is more preferred. The mixing ratio of water with the tertiary alcohol is not particularly limited as long as it does not inhibit the progress of the reaction, but the amount of water is 0.01 to tertiary alcohol from the viewpoint of volumetric efficiency. The range is preferably 100 times by weight, more preferably 0.1 to 50 times by weight, particularly preferably 0.5 to 10 times by weight in consideration of reaction efficiency and selectivity.

As the acid, for example, sulfuric acid, hydrochloric acid, nitric acid,
Mineral acids such as phosphoric acid and perchloric acid; and organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid and trifluoromethanesulfonic acid are used. In consideration of the reaction efficiency and the influence of acid residues, mineral acids are preferred, and sulfuric acid and perchloric acid are particularly preferred. The amount of the acid to be used is not particularly limited as long as the amount is sufficient for the reaction to proceed, but 1,2-epoxy-3,7,1
The range is preferably from 0.01 to 100 mol%, more preferably from 0.01 to 10 mol%, in consideration of operability and safety, based on 1,15-tetramethylhexadecane-3-ol. A range of 0.1 to 5 mol% is particularly preferred.

The reaction temperature is set to 1,2-epoxy-3,7,11,15-tetramethylhexadecane-3 as a raw material.
Elimination of the tertiary alcohol moiety of the ol and the tertiary alcohol moiety of the product phytantriol, generation of an olefin by decomposition of the tertiary alcohol, conversion of ethers by addition of the generated olefin to phytantriol The reaction temperature needs to be adjusted to less than 50 ° C. in consideration of formation and the like. Further, in consideration of the formation of aldehydes and ketones which may hinder the purification, the temperature is preferably in the range of 15 ° C to 46 ° C. The reaction pressure is not particularly limited, but a pressure under atmospheric pressure is usually sufficient. Also,
The reaction of the present invention may be carried out in the atmosphere, but is preferably carried out under an inert gas such as nitrogen or argon for safety.

[0012]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples.

Reference Example 1 3 equipped with a mechanical stirrer, a reflux tube and a thermometer
In a L three-necked flask, 1036.8 g of isophytol
(3.5 mol) and 14.5 g of trioctylmethylammonium chloride were taken, and a catalyst solution obtained by dissolving 8.7 g of sodium tungstate dihydrate and 39 g of phosphoric acid in 200 g of water was added. This mixture is
℃, 30% hydrogen peroxide solution 430
g (3.85 mol) was added over 6 hours. 4 more
Stirring was continued for 60 hours at 60 ° C., and after cooling to room temperature, the mixture was allowed to stand still, the aqueous layer (lower layer) was separated, and water 400
g and washed with water, and this was repeated twice to obtain 1070.9 g of 1,2-epoxy-3,7,11,15-tetramethylhexadecane-3-ol. This product was analyzed by gas chromatography GC-14B (manufactured by Shimadzu Corporation, column: G-100, manufactured by The Chemicals Inspection Association, 30 m, constant at 210 ° C.), and the content of 1038.2 g (purity 96.9) was obtained.
%, 95% yield).

Example 1 The 1,2-epoxy-3,7,11,15-tetramethylhexadecane obtained in Reference Example 1 was placed in a 300 ml three-necked flask equipped with a mechanical stirrer, a reflux tube, a thermometer and a dropping funnel. 107 g of 3-ol (net: 10
3.8 g), 250 g of t-butanol and water 1
Then, 00 g was added and mixed, and the inside of the system was replaced with nitrogen. 2.1 g (15 mmol) of 70% perchloric acid was added thereto,
Warmed to 0 ° C. The mixture was stirred for 12 hours as it was, and the reaction was followed by gas chromatography (analytical conditions were the same as in Reference Example 1). Then cool to room temperature, 500m water
l and extracted twice with 250 g of hexane. After the obtained organic layer was back-extracted with 100 ml of water, hexane was distilled off under reduced pressure. The obtained reaction solution was subjected to molecular distillation under a reduced pressure of 1 Pascal at a bottom temperature of 200 ° C., and a purity of 98.3%
Of phytantriol (100 g, yield 90.3%).

Example 2 In Example 1, 100 g of t-butanol was used.
The reaction and separation operations were carried out in the same manner except that the reaction time was changed to 18 hours, to obtain 96.4 g (88% yield) of phytantriol having a purity of 99.1%.

Example 3 A reaction and separation operation were carried out in the same manner as in Example 1 except that 4.2 g of perchloric acid was used and the reaction time was 8.5 hours, and phytantriol having a purity of 98.7% was obtained. 98.
4 g (yield 90%) was obtained.

Example 4 The same procedure as in Example 1 was repeated except that 1.5 g (15 mmol) of sulfuric acid was used instead of 2.1 g of perchloric acid, and the reaction time was changed to 26 hours. 93.1 g of phytantriol having a purity of 99.1% (yield: 8
5.5%).

Comparative Example 1 The same reaction and separation procedure as in Example 1 was carried out except that the reaction temperature was 50 ° C. and the reaction time was 6 hours.
78.6 g (yield: 72.2%) of phytantriol having a purity of 92.3% was obtained. The dimer of phytantriol and the one in which the primary alcohol portion of phytantriol was t-butyl etherified were by-produced.

Comparative Example 2 The same procedure as in Example 1 was repeated except that 250 g of isopropyl alcohol was used instead of 250 g of t-butanol, and the reaction time was changed to 3.5 hours. 78.3g of phytantriol
(72.2% yield). The phytantriol in which the primary alcohol moiety was converted to isopropyl ether was by-produced.

[0020]

According to the present invention, high-purity phytantriol can be easily and industrially advantageously produced with high yield.

Claims (1)

[Claims] 1. A 1,2-epoxy-3,7,11,15
-A method for producing phytantriol, comprising hydrolyzing tetramethylhexadecane-3-ol in a mixed solvent of tertiary alcohol and water at a temperature of less than 50 ° C in the presence of an acid.