JPH0460455B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to 3,7,11,15-tetramethyl-1,
The present invention relates to a method for producing 2,3-trihydroxyhexadecane (hereinafter, this compound is referred to as phytantriol). The phytantriol produced by the method of the present invention has the effect of caring for the skin or hair, and is useful as a base component of cosmetics used for the purpose of protecting the skin or hair (Japanese Patent Publication No. 38-5050 (see official bulletin). [Prior Art] Conventionally, there is a known method for producing phytantriol by reacting isophytol with formic acid, then allowing hydrogen peroxide to act on the reaction mixture, and saponifying the resulting hydroxydiformate with concentrated ammonia. (Refer to Special Publication No. 38-13859). The reaction of this conventional method is as follows. [Problems to be Solved by the Invention] It has been reported that the crude phytantriol obtained by the above conventional method is colored pale yellow, and as shown in Comparative Example 1 below, the crude phytantriol is colored pale yellow. The purified product obtained by molecular distillation of tantriol is still pale yellow in color and has an unpleasant odor. Such colored and odorized phytantriol cannot be used as a base component of cosmetics, and requires more precise purification means for use as a base component of cosmetics. Therefore, one object of the present invention is to provide a method for producing phytantriol that is free from coloration and unpleasant odor. Another object of the present invention is to provide a method for producing crude phytantriol, which can be easily purified to phytantriol free from coloration and unpleasant odor by molecular distillation. [Means for solving the problem] According to the present invention, the above object is achieved by treating isophytol with tert-butyl hydroperoxide (hereinafter referred to as TBTP) in the presence of a metal catalyst consisting of a derivative of vanadium or molybdenum. )
The present invention is achieved by providing a method for producing phytantriol, which is characterized by obtaining an epoxy compound by reacting with a compound, and then ring-opening the epoxy compound in the presence of an acidic catalyst; This is achieved by providing a method for producing phytantriol, which is characterized by carrying out molecular distillation of phytantriol. The reaction formula of the method of the present invention is as follows. When carrying out the epoxidation reaction of isophytol according to the present invention, TBHP is added in an amount of about 0.5 to 5 mol, preferably 1.0 to 1.5 mol, per 1 mol of isophytol.
Use moles. TBHP is commercially available as a 70% aqueous solution, and it is convenient and safe to use it as is. The metal catalyst present in this reaction system consists of vanadium or molybdenum derivatives. These derivatives include halides, chalcogenides, chalcohalides, nitrosohalides and nitrosylhalides; mixed salts of vanadium or molybdenum with other metals; salts of aliphatic, cycloaliphatic or aromatic carboxylic acids or alcohols or phenols, e.g. Examples include acetate, propionate, stearate, benzoate, oxalate, succinate, sulfonate, tartrate, citrate, salicylate, naphthenate, lower alkoxide, and phenate. These salts can also contain oxygen-containing metal cations such as vanadyl and molybdenum. Other derivatives that may also be used include salts and esters of acids derived from one or more of these metals, such as vanadates, molybdates;
Ortho, meta, para, pyro, thio or halogeno congeners; tungstovanadate, phosphomolybdate, molybdocitrate, molybdoformate, molybdolactate, molybdomaleate, molybdomandelate , molybdomutate, molybdooxalate, molybdoquinate, molybdosaccharate, molybdotartrate, and molybdotungstate. Furthermore, acetylacetonate,
Chelates such as benzoylacetonate, glyoximate, quinolinate, salicylaldehydate, benzyl hydroxymate, ethylenediamine in which the ligand may be substituted with, for example, an aliphatic or alicyclic group or a halogen atom, 〓, 〓
- Complexes of diviridyl, o-nitrosophenol, -nitrosonaphthol, salicylaldimidine and porphyrin; and carbon monoxide, monoolefin, diolefin, acetylene compound,
It is also possible to use complexes of coordinating agents such as cyclopentadiene, ammonia, cyanide, tertiary nitrogenous bases, phosphine, arsine, stibine and nitriles with metals, metal salts or metal alkyls of vanadium or molybdenum. Among these metal catalysts, catalysts containing chains represented by the following formula are preferred. -M=O -O-M=O -M←O= -O-M←O= where M can be further bonded to other atoms by one or more ionic or covalent bonds. Represents vanadium or molybdenum that can be produced. Catalysts of this type include metal oxides, salts and esters of oxyacids derived from metals, salts of oxygen-containing metal ions, and chelates derived from -diketones. In particular, pentavalent vanadium compounds such as vanadium pentoxide, ammonium metavanadate, tertiary butyl orthovanadate, neopentyl orthovanadate, cyclohexyl orthovanadate, vanadyl acetylacetonate; and molybdenum trioxide, hexacarbonylmolybdenum,
Hexavalent molybdenum compounds such as tricarbonyltriacetonitrile budene are preferably used. The catalyst may be soluble or insoluble in the reaction medium. The amount of metal catalyst used is approximately
0.001-10% by weight, preferably about 0.01-1.0% by weight
It is. The epoxidation reaction is carried out in the presence or absence of a solvent inert to the reaction. Aromatic hydrocarbons such as benzene, toluene, and xylene as solvents;
Halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane; aliphatic hydrocarbons such as hexane and heptane are used. The reaction temperature is not particularly limited, but is usually in the range of about 50 to 150°C, preferably 80 to 110°C. After the reaction is complete,
It is preferable to wash the reaction mixture with an aqueous sodium sulfite solution so that no unreacted TBHP or by-product peroxide remains. Phitanetriol can be produced by ring-opening the epoxy compound thus obtained in the presence of an acidic catalyst. As the acidic catalyst, sulfuric acid, hydrochloric acid, phosphoric acid, perchloric acid, etc. are used. The amount of acidic catalyst used is about 1 to 100% by weight, preferably 5 to 20% by weight, based on the epoxy compound. This reaction is suitably carried out at around room temperature, and preferably in the presence of a solvent. As the solvent, for example, a water-soluble and inert solvent such as tetrahydrofuran or isopropyl alcohol is used. The reaction ends when the epoxy compound disappears. This confirmation is conveniently performed by GLC analysis. After the reaction is complete, the reaction mixture is treated with sodium hydroxide,
After neutralization with an aqueous alkali solution such as potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, diethyl ether,
Ethers such as diisopropyl ether; aliphatic hydrocarbons such as pentane, hexane, heptane;
Extract with a solvent such as an aliphatic carboxylic acid ester such as ethyl acetate or isobutyl acetate, and wash the extract with water until it becomes neutral. By distilling off the solvent from the extract thus obtained, a viscous liquid of phytantriol is obtained. By molecularly distilling this crude phytantriol, colorless, transparent and odorless phytantriol can be obtained. [Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 463.6 g (1.57 mole) of isophytol was added to a 2 L three-necked flask equipped with a stirrer, condenser, and thermometer.
% (weight) TBHP aqueous solution (221.8 g (1.72 mole)) and 710 mg of vanadium pentoxide were charged and reacted at 90° C. for 6 hours. After the reaction is complete, add 14% to the reaction mixture.
(Weight) Add 350.4g of sodium sulfite aqueous solution,
After stirring and mixing at room temperature for 30 minutes, the mixture was transferred to a separatory funnel and separated. Add the upper layer solution to an equal volume of 1N
- After stirring and mixing with an aqueous sodium hydroxide solution at room temperature, the mixture was extracted with n-hexane. The extract was washed three times with equal volumes of water. Then, by distilling off n-hexane from the extract, 1,2-epoxy-
3,7,11,15-tetramethylhexadecane-3
-518.6g of oar was obtained. Next, a 3l tank with a stirrer, cooler and thermometer.
1,2-epoxy-3,7, in a three-necked flask
11,15-tetramethylhexadecane-3-ol
518.6g and 1l of isopropanol, 800ml of water and 70%
(Weight) 70 ml of perchloric acid was charged and reacted at room temperature for 9 hours. 1,2-epoxy-3,7,11,15-
After confirming the disappearance of tetramethylhexadecane-3-ol by GLC analysis (OV-12%, column length 1m, inlet temperature 230℃, column 200℃, detector FID), 1N water was added to the reaction mixture. Aqueous sodium oxide solution 1 was added and stirred at room temperature for 30 minutes. The resulting mixture was extracted with n-hexane.
After washing the extract three times with an equal volume of water, n-hexane was distilled off from the extract to obtain 514.5 g of crude phythanetriol. By molecularly distilling this crude phytantriol, a colorless, transparent, odorless, viscous liquid is produced as a distillate at 170°C/0.02 Torr.
Obtained 457.7g. As a result of GLC analysis (under the same analytical conditions as above), this fraction was found to be phytantriol with a purity of 99.0%. Example 2 236.2 g (0.8 mole) of isophytol was placed in a 1-volume three-necked flask equipped with a stirrer, a condenser, and a thermometer.
70% (weight) TBHP aqueous solution 113.5g (0.88mole)
and 236 mg of vanadyl acetylacetonate were charged and reacted at 96°C for 7 hours. After the reaction is complete, add 10% (by weight) sodium sulfite aqueous solution to the reaction mixture.
250g of 1,2-epoxy-3,7,11,
15-tetramethylhexadecane-3-ol
Obtained 277.4g. Then, a stirrer, a cooler and a thermometer were attached.
1,2-epoxy-3,7, in a three-necked flask
11,15-tetramethylhexadecane-3-ol
277.4 g, 500 ml of isopropanol, and 250 ml of 10% (by weight) sulfuric acid aqueous solution were charged, and reacted at room temperature for 3 hours. 1,2-epoxy-3,7,11,15-
After confirming the disappearance of tetramethylhexadecane-3-ol in the same manner as in Example 1, the reaction mixture was neutralized with IN-sodium hydroxide aqueous solution 1 and then extracted with n-hexane. After washing the extract three times with an equal volume of water, n-hexane was distilled off from the extract to obtain 220.3 g of crude phythanetriol. By molecularly distilling this crude phytantriol, 198.3 g of a fraction at 170° C./0.02 Torr was obtained. This product was a colorless, transparent, odorless, viscous liquid, and was phytantriol with a purity of 99.3%. Examples 3 to 8 1,2-epoxy-3,7,11, and 1,2-epoxy-3,7,11, and 15-tetramethylhexidosadecan-3-ol was obtained. The yields are shown in Table 1. Then, the obtained 1,
277.4 g of 2-epoxy-3,7,11,15-tetramethylhexadecane-3-ol were reacted and treated under the same conditions as in Example 2 to obtain crude phythanetriol, and these were similarly treated. A colorless, transparent, and odorless viscous liquid was obtained by molecular distillation of each. These results are shown in Table 1.

〔Effect of the invention〕

According to the method of the present invention, as is clear from the above examples, crude phytantriol, which is easily purified to colorless, transparent and odorless phytantriol by molecular distillation, can be easily produced in high yield. can. Furthermore, according to the method of the present invention, colorless, transparent, and odorless phytantriol can be easily produced, as is clear from the above examples.

Claims (1)

[Claims] 1. An epoxy compound is obtained by reacting isophytol with tert-butyl hydroperoxide in the presence of a metal catalyst consisting of a derivative of vanadium or molybdenum, and then the epoxy compound is opened in the presence of an acidic catalyst. 3,7,11,15-tetramethyl-1,2,3, characterized by being ringed
- A method for producing trihydroxyhexadecane. 2 An epoxy compound is obtained by reacting isophytol with tert-butyl hydroperoxide in the presence of a metal catalyst consisting of a derivative of vanadium or molybdenum, and then the epoxy compound is ring-opened in the presence of an acidic catalyst to produce 3 ，
3,7,11,15-tetramethyl-1,2, characterized by molecular distillation of 7,11,15-tetramethyl-1,2,3-trihydroxyhexadecane.
A method for producing 3-trihydroxyhexadecane.