JPH0753431A - Production of glyceryl ether - Google Patents

Abstract

PURPOSE:To readily produce an alpha-monoalkyl glyceryl ether useful as an emulsifying agent, etc., in high yield and purity by carrying out the hydrolytic reaction of a glycidyl ether in the presence of a tertiary amine. CONSTITUTION:This method for producing a glyceryl ether expressed by formula II (R is a 1-32C saturated or unsaturated straight-chain or a branched chain alkyl) is to hydrolyze a glycidyl ether expressed by formula I in the presence of a tertiary amine. A compound expressed by formula III [R<1> to R<4> are 1-10C alkyls; (n) is 2-5; (m) is 0-3] (e.g. tetramethyl-1,3-diaminopropane) is especially cited as the tertiary amine. The compound expressed by formula II has excellent performances as a W/O type emulsifying agent and is capable of manifesting pharmacological actions such as hematopoietic promoting effects, antiinflammatory actions and antitumor activities and further utilizable as an antimicrobial and an antifungal agents, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing glyceryl ether, and more particularly to a method for easily producing glyceryl ether with high yield and high purity.

[0002]

2. Description of the Related Art As α-monoalkyl glyceryl ethers, palmitic glyceryl ether, stearyl glyceryl ether, oleyl glyceryl ether, etc., which are conventionally present in lipids of fish, are known, and these are emulsifiers, especially W / O. Having excellent performance as a mold emulsifier (JP-A-49-87612, 49-92239, 52
-12109), as well as pharmacological actions such as hematopoiesis-promoting effect in bone marrow, anti-inflammatory action and antitumor activity (Japanese Patent Publication Nos. 49-10724 and 52-18171).
issue). Furthermore, in recent years, it has been reported to be used as an antibacterial and antifungal agent (Japanese Patent Publication No. 54-2249). The following methods are conventionally known as methods for producing these α-monoalkyl glyceryl ethers from the corresponding alcohols.

[0003]

[Chemical 4]

(In the formula, R ⁵ is a hydrocarbon group, R ⁶ and R ⁷ are lower alkyl groups, X is a halogen atom, and M is an alkali metal.) That is, an alcohol is a halide. 4-Alkoxymethyl-1,3 by reacting with hydroxyl group-protected glycerol alkali metal alcoholate
A method of leading to dioxolane and then hydrolyzing this.

[0005]

[Chemical 5]

(In the formula, R ⁵ and X have the same meaning as described above.) That is, a method in which an alcohol and an epihalohydrin are reacted to obtain a glycidyl ether, which is hydrolyzed.

[0007]

[Chemical 6]

(In the formula, R ⁸ represents a hydrocarbon group and R ⁵ has the same meaning as described above.) That is, the above-mentioned known method (2)
In this method, the glycidyl ether obtained in step 1 is reacted with a carboxylic acid to obtain an α-glycerol monoester compound, which is then hydrolyzed.

[0009]

[Chemical 7]

(In the formula, R ⁹ and R ¹⁰ represent a hydrocarbon group, and R ⁵ has the same meaning as described above.) That is, a carbonyl compound is added to glycidyl ether to give 1,3-
This is a method in which a dioxolane compound is introduced and hydrolyzed (JP-A-56-133281).

[0011]

[Chemical 8]

(In the formula, R ¹¹ represents a hydrocarbon group and R ⁵ has the same meaning as described above.) That is, glycidyl ether is reacted with a carboxylic acid anhydride in the presence of a catalyst to give a diester compound, Is a method of hydrolyzing (JP-A-58-134049).

[0013]

[Chemical 9]

(In the formula, R ⁵ has the same meaning as described above.)
That is, it is a method in which benzyl alcohol is reacted with glycidyl ether in the presence of a base to obtain benzyl ether, which is hydrolyzed (JP-A-62-84036).

[0015]

[Chemical 10]

(In the formula, R ⁵ has the same meaning as described above.)
That is, it is a method of hydrolyzing glycidyl ether in a monoalkyl ether solvent of propylene glycol or dipropylene glycol in the presence of phosphoric acid or an activated clay catalyst (JP-A-5-43501).

[0017]

However, these known methods have some drawbacks as follows. In the method of (1), (a) the raw material hydroxyl group-protected glycerol compound (4-hydroxymethyl-1,3-dioxolane) can be synthesized from glycerin and a carbonyl compound in the presence of an acid catalyst. Since the time is long and the dehydration reaction is required, a large amount of dehydrating agent is required. (B) In the condensation reaction of an alkyl halide with an alkali metal alcoholate of 4-hydroxymethyl-1,3-dioxolane, since a strong base exists in the reaction system, part of the alkyl halide is converted into a terminal olefin by dehydrohalogenation reaction. Generate,
The yield of the desired 4-alkoxymethyl-1,3-dioxolane is reduced.

In the method (2), since the reaction system is a heterogeneous system of water and oil, it becomes difficult to carry out a homogeneous reaction, and a large amount of a polymer in which glycidyl ethers are added in addition to the desired glyceryl ether is generated. . Therefore, the yield of glyceryl ether decreases and the quality becomes poor.
Therefore, an operation such as molecular distillation is required to obtain high-purity glyceryl ether, which is an obstacle to implementation on an industrial scale.

In the method (3), the α-alkylglycerol monoester compound produced by the addition of an acid to glycidyl ether has a free hydroxyl group having active hydrogen.
There is a drawback that more than a mole of glycidyl ether is added to form a high molecular weight compound as a by-product. Therefore, the glyceryl ether obtained by this method has extremely low purity.

In the method (4), the ketone or aldehyde produced by the hydrolysis of the 1,3-dioxolane compound is
The acid catalyst present in the reaction system causes aldol condensation, which causes coloration and odor.

In the method (5), since the diester is hydrolyzed under a strongly basic condition, a large amount of water is required for neutralization and washing in the post-treatment stage, so that when industrially used, There are still problems to solve.

The method (6) has a drawback that the yield of benzyl ether synthesis is low. In the method (7), the by-product of the acid catalyst causes coloration and odor.

As described above, none of the conventional methods is a sufficient production method for obtaining glyceryl ether in high purity, high yield and easily. Therefore, an object of the present invention is to provide a method for producing glyceryl ether having a high purity in a large amount in a high yield and at a low cost by an extremely simple method as compared with the conventional method.

[0024]

[Means for Solving the Problems] The inventors of the present invention have made intensive studies on a method for overcoming the various drawbacks of the conventional method and for easily producing an α-monoalkylglyceryl ether in a high yield and a high purity. The inventors have found that these problems can be solved by carrying out the hydrolysis reaction of glycidyl ether in the presence of a tertiary amine, and completed the present invention. That is, the present invention provides the compound of formula (I)

[0025]

[Chemical 11]

The glycidyl ether represented by the formula (wherein R represents a saturated or unsaturated, straight-chain or branched alkyl group having 1 to 32 carbon atoms) is hydrolyzed in the presence of a tertiary amine. Formula (II) characterized by

[0027]

[Chemical 12]

(In the formula, R has the same meaning as described above.)
The present invention provides a method for producing glyceryl ether represented by

The R group in the glycidyl ether represented by the formula (I) used in the present invention represents a saturated or unsaturated, linear or branched alkyl group having 1 to 32 carbon atoms, and specifically, Is methyl, ethyl, n-propyl, n-butyl, n
-Pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl , N-
Octadecyl, n-nonadecyl, n-eicosyl, n-
Hene eicosyl, n-docosyl, n-tricosyl, n-
Linear saturated primary alkyl groups such as tetracosyl, n-pentacosyl, n-hexacosyl; 2-ethylhexyl, 2
-Butyldecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-ethyltetradecyl, 2-hexyldecyl,
2-butyltetradecyl, 2-ethylhexadecyl, 2
-Hexyldecyl, 2-butylhexadecyl, 2-ethyloctadecyl, 2-hexyltetradecyl, 2-octyldodecyl, 2-butyloctadecyl, 2-ethyleicosyl, 2-hexylhexadecyl, 2-octyltetradecyl, 2 -Butyleicosyl, 2-ethyldocosyl, 2-hexyloctadecyl, 2-octylhexadecyl, 2-butyldocosyl, 2-ethyltetracosyl, 2-hexyleicosyl, 2-octyloctadecyl, 2-heptylundecyl, 2- (1,3,3-trimethylbutyl) octyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl,
5,7,7-Trimethyl-2- (1,3,3-trimethylbutyl)
Octyl and the following formula

[0030]

[Chemical 13]

(In the formula, p is an integer of 4 to 10, q is an integer of 5 to 11, p + q is 11 to 17, and p = 7 and q =
A branched primary saturated alkyl group such as methyl-branched isostearyl having a distribution having 8 as the apex; 2-propyl, sec-butyl, sec-pentyl, sec-hexyl, sec-heptyl, sec-octyl, sec-nonyl,
Secondary saturated alkyl groups such as sec-decyl, sec-undecyl, sec-dodecyl and the like can be mentioned, preferably 6 to 10 carbon atoms.
20 saturated or unsaturated, linear or branched alkyl groups,
A methyl-branched isostearyl group is particularly preferred.

The glycidyl ether represented by the formula (I) may be produced by any method, and can be obtained, for example, by reacting a corresponding alcohol with epihalohydrin.

The tertiary amine used in the present invention may be any one, for example, triethylamine, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,3-diaminopropane, tetramethyl-1, 6-diaminohexane, triethylenediamine, pyridine, dimethylaniline, quinoline, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, dimethylpiperazine, dimethylimidazole, dimethylaminoethanol, bis (2-dimethylaminoethyl) ether, triphenylamine, 2 , 6-lutidine, hexamethylenetetramine,
1,8-diazabicyclo [5.4.0] undec-7-ene,
Examples thereof include dimethyloctylamine and the like, preferably the formula (III)

[0034]

[Chemical 14]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and have 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and a straight chain or branched alkyl group. Group, n is 2-5
, And m is a number from 0 to 3. ) Is a compound represented by.

In the present invention, the tertiary amine may be used alone or in combination of two or more. The amount of the tertiary amine used is 0.1 with respect to the glycidyl ether represented by the formula (I).
It is preferably 100 to 100% by weight, more preferably 0.5 to 20% by weight. In the present invention, the amount of water used is 1 mol to 50 mol per 1 mol of the glycidyl ether represented by the formula (I).
The amount is preferably mol, and more preferably 2 to 10 mol.

In the present invention, the solvent may not be used, but it may be used depending on the case because the reaction proceeds rapidly. As the solvent used, those which are inactive and compatible with the glycidyl ether represented by the formula (I) are preferable, and dimethyl sulfoxide, xylene, toluene, benzene, hexane, tetrahydrofuran (THF), dioxane, ethylene. Glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butanol and the like can be mentioned. The amount of the solvent used is preferably 0.1 to 10 times, more preferably 1 to 3 times the weight of the glycidyl ether represented by the formula (I).

The reaction temperature in the present invention is preferably 40 to 200 ° C, more preferably 100 to 160 ° C. If the temperature is lower than 40 ° C, the reaction takes a long time, and if the temperature exceeds 200 ° C, a side reaction is promoted, resulting in deterioration of quality. Although the reaction time is largely influenced by the amount of catalyst, temperature and amount of solvent, it is generally 1 to 50 hours, and usually 5 to 30 hours.

After completion of the reaction, the tertiary amine is removed from the reaction solution by a method such as neutralization, filtration, distillation, extraction, etc., and distillation purification or crystallization is carried out to obtain a high yield and high purity of the above formula ( A glyceryl ether represented by II) can be obtained.

[0040]

EFFECTS OF THE INVENTION The present reaction is a multi-step reaction in which the conventional method synthesizes glyceryl ether from glycidyl ether via an intermediate, whereas it is possible to synthesize glyceryl ether from glycidyl ether in one step, and When a catalyst is used, a polymer of glycidyl ether is produced, but these are excellent in that they are hardly produced in this reaction, which is advantageous for industrial production. According to the present invention, a high yield of glyceryl ether represented by the formula (II),
It has become possible to easily manufacture with high purity.

[0041]

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

Example 1 Isostearyl glycidyl ether 32 in a 4-neck flask
6 g, diethylene glycol dimethyl ether (980 g), tetramethyl-1,3-diaminopropane (65 g) and water (73 g) were charged and the reaction was carried out at 130 ° C. for 43 hours. After the reaction, amine,
Water and solvent were collected by distillation under reduced pressure. The residue was extracted and washed with ethyl acetate and 1% sodium sulfate aqueous solution, and then ethyl acetate in the organic layer was distilled off. By distilling and purifying the residue, 285 g (yield 84%) of isostearyl glyceryl ether was obtained.

IR (liquid film, cm ^-1 ): 3400, 1100, 1040 ¹ H-NMR (CDCl ₃ solvent, TMS internal standard δ):

[0044]

[Chemical 15]

Acid value: 0.10 (calculated value 0) Saponification value: 0.52 (calculated value 0) Hydroxyl value: 316 (calculated value 328) Iodine value: 0.36 (calculated value 0) Example 2 4 mouths 326 g of stearyl glycidyl ether in a flask,
Dimethyl sulfoxide (1027 g), tetramethyl-1,3-diaminopropane (13 g), and water (40 g) were charged, and the mixture was stored at 130 ° C for 21
Reacted for hours. After completion of the reaction, the catalyst, water and solvent were recovered by distillation under reduced pressure. The residue was extracted and washed with ethyl acetate and 1% sodium sulfate aqueous solution, and then ethyl acetate in the organic layer was distilled off. Stearyl glyceryl ether by recrystallizing the residue
239 g (yield 69%) was obtained.

IR (liquid film, cm ^-1 ): 3400, 1100, 1040 ¹ H-NMR (CCl ₄ solvent, TMS internal standard, δ):

[0047]

[Chemical 16]

Acid value: 0.08 (calculated value 0) Saponification value: 0.36 (calculated value 0) Hydroxyl value: 314 (calculated value 328) Iodine value: 0.32 (calculated value 0) Example 3 4 mouths Isostearyl glycidyl ether 32 in a flask
6 g, 1001 g of dimethyl sulfoxide, 17 g of pentamethyldiethylenetriamine and 36 g of water were charged, and the reaction was carried out at 130 ° C for 8 hours. After completion of the reaction, the catalyst, water, and solvent were distilled off under reduced pressure. The residue was extracted and washed with ethyl acetate and water, and then ethyl acetate in the organic layer was distilled off. The residue was purified by distillation to obtain 216 g of isostearyl glyceryl ether (yield 64%).

IR (liquid film, cm ^-1 ): 3400, 1100, 1040 ¹ H-NMR (CDCl ₃ solvent, TMS internal standard δ):

[0050]

[Chemical 17]

Acid value: 0.08 (calculated value 0) Saponification value: 0.30 (calculated value 0) Hydroxyl value: 315 (calculated value 328) Iodine value: 0.30 (calculated value 0) Example 4 4 mouths Add 158 g of hexyl glycidyl ether to the flask, T
Charge 316 g of HF, 10 g of triethylamine and 36 g of water,
The reaction was carried out at 60 ° C for 20 hours. After completion of the reaction, neutralize with sulfuric acid,
The solvent and water were collected by distillation under reduced pressure. The residue was extracted and washed with ethyl acetate and water, and then ethyl acetate in the organic layer was distilled off. The residue was purified by distillation to obtain 123 g of hexyl glyceryl ether (yield 70%).

IR (liquid film, cm ^-1 ): 3400, 1100, 1040 ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, δ):

[0053]

[Chemical 18]

Acid value: 0.1 (calculated value 0) Saponification value: 0.3 (calculated value 0) Hydroxyl value: 628 (calculated value 638) Iodine value: 0.3 (calculated value 0)

Claims (2)

[Claims] 1. Formula (I): (In the formula, R represents a saturated or unsaturated, linear or branched alkyl group having 1 to 32 carbon atoms.) The glycidyl ether represented by the formula is hydrolyzed in the presence of a tertiary amine. Formula (II) (In the formula, R has the same meaning as described above.) A method for producing glyceryl ether. 2. A tertiary amine has the formula (III): (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same or different and are linear or branched alkyl groups having 1 to 10 carbon atoms, n is a number of 2 to 5 and m is 0 to 3 The method for producing glyceryl ether according to claim 1, which is a compound represented by the following formula.