JP2939649B2 - Method for producing glyceroglycolipid - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an industrially advantageous method for producing glyceroglycolipid useful as a base for hair, skin cosmetics, a detergent, an emulsifier, a humectant, and the like.

[Problems to be solved by conventional technology and invention]

Conventionally, anionic surfactants have been widely used as detergents and emulsifiers for hair and skin cosmetics. However, many anionic surfactants have relatively high protein-modifying ability,
Since there is irritation to the skin, development of a surfactant having a lower irritation has been desired. In addition, in recent years, with the increase in consumers' awareness of natural materials and the global environment, surfactants and derivatives derived from natural sources with excellent safety and biodegradability, as well as similar compounds, have been developed for hair,
It has attracted attention as a surfactant and humectant for skin cosmetics. Among these, glyceroglycolipid is a natural surfactant contained in plants and the like, and is expected to be excellent in terms of safety and biodegradability. Therefore, use as a detergent or emulsifier for hair and skin cosmetics Is expected.

Various methods have been proposed so far for producing glyceroglycolipids, but none of these methods is industrially satisfactory. For example, a method for extracting and isolating glyceroglycolipid from a plant is not satisfactory as an industrial production method because glyceroglycolipid is usually contained only in a trace amount in a plant. In addition, most of the known methods for producing glyceroglycolipids by chemical synthesis are multi-step synthesis and require many protecting groups (for example, R. Gigg, Chem. Phy
s.Lipids, vol26,287 (1980) and AIBashkatova et al. Zhur.o
rg.Khim, vol9, 1393 (1973)] It is difficult to implement industrially. Further, a method of reacting a fatty acid with a compound having an epoxy group introduced into a sugar (CMLok et al., Chem. Phys. Lipids, vol16,
115 (1976)] is that the sugar epoxy compound used as a raw material is relatively unstable, and in terms of production of the sugar epoxy compound, for example, a synthesis method by an enzymatic reaction (European Patent No. 268461) has recently been used. Despite the proposal, there are problems such as insufficient yield and productivity, and the synthesis of glyceroglycolipids by these methods has not been industrially satisfactory.

Therefore, an industrial production method of glyceroglycolipid which is inexpensive and excellent in productivity has been desired.

[Means for solving the problem]

Under such circumstances, the present inventors have intensively studied to improve these disadvantages of the conventionally known methods for producing glyceroglycolipids and to provide an industrially advantageous method for producing glyceroglycolipids. The inventors have found that a glyceroglycolipid can be industrially advantageously produced by reacting a compound represented by the formula (I) with a compound represented by the following general formula (II), and completed the present invention.

 The present invention is illustrated by the following reaction scheme.

(Wherein, G represents a glucosyl group which may have a substituent, R represents a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, and M represents a cation). Is a process for producing a glyceroglycolipid represented by the general formula (III), which comprises reacting a compound represented by the general formula (I) with a compound represented by the general formula (II).

In the method of the present invention, the group that can be substituted for the glucosyl group of the compound represented by the general formula (I) (hereinafter, referred to as “compound (I)”) includes acylation, etherification, alkylene oxide addition, acetalization, and sulfation. And a group modified by phosphorylation, etc. Examples of the halogen atom for X include fluorine, chlorine, bromine and iodine.

In the method of the present invention, R of the compound represented by the general formula (II) (hereinafter referred to as “compound (II)”) is a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, such as methyl, Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, ethenyl, propenyl, butenyl, pentenyl, hecequinyl, heptenyl,
Octenyl, nonenyl, decenyl, dodecenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,
Pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, docosenyl, tricosenyl, tetracosenyl, octadienyl,
Nonadienyl, decadienyl, dodecadienyl, undecadienyl, dodecadienyl, tridecadienyl, tetradecadienyl, pentadecadienyl, hexadecadienyl, heptadecadienyl, octadecadienyl, nonadecadienyl, eicosadienyl, hexadecatrienyl, hexadecatrienyl, hexadecatrienyl , Eicosatrienyl, methylethyl, methylpropyl, methylbutyl, methylpentyl, methylhexyl, methylheptyl, ethylhexyl, methyloctyl, ethylheptyl, methylnonyl,
Methylundecenyl, methylpentadecyl, methylhexadecyl, methylheptadecyl, methyloctadecyl,
Hexyldecyl, heptyldecyl, octylnonyl and the like can be mentioned. Examples of the cation group represented by M include an alkali metal, an ammonium group, an alkylammonium group, and a trialkanolamine.

Compound (I) used in the method of the present invention can be easily produced by a known method, for example, a reaction between glucose and glycerol monohalohydrin or epihalohydrin.

Compound (II) can be produced, for example, by reacting a fatty acid with an alkali metal hydroxide such as sodium hydroxide in the presence of a suitable solvent.

In order to carry out the method of the present invention, for example, the compound (I) and the compound (II) are mixed at 30 to 150 ° C, preferably 70 to 120 ° C.
The reaction may be performed at a temperature of ° C. The amount of compound (II) used here is usually 0.3 to 3.0 with respect to compound (I).
The molar amount is twice as much, particularly preferably 1.0 to 2.0 times. Also,
When M of compound (II) is a hydrogen atom, the reaction is performed in the presence of an alkaline substance. Examples of the alkaline substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alcoholates, and alkylamine hydroxides.

In carrying out the present reaction, a polar solvent can be used for the purpose of promoting the mixing of the compound (I) and the compound (II) and allowing the reaction to proceed smoothly. The polar solvent used here is at least one or more selected from dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, pyridine, water and the like. The amount of the polar solvent used may be appropriately selected. In carrying out this reaction, a phase-transfer catalyst can be used for the purpose of accelerating the reaction, if necessary. The amount of the phase transfer catalyst used here may be appropriately selected, but is usually 0.1 to 10 mol% based on the compound (II). Examples of the phase transfer catalyst used herein include, for example, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetraheptylammonium bromide, tetrahexylammonium bromide, N, N, N-
Trimethyl-N-octylammonium chloride, N,
N, N-trimethyl-N-decylammonium chloride, N, N, N-trimethyl-N-dodecylammonium chloride, N, N, N-trimethyl-N-hexadecylammonium chloride, N, N, N-trimethyl-N -Octadecyl ammonium chloride, N, N-dimethyl-N, N-
Examples thereof include tetraalkylammonium halides such as dihexadecyl ammonium chloride and N, N-dimethyl-N, N-dioctadecyl ammonium chloride.

The reaction product of the reaction of the present invention contains, in addition to the target glyceroglycolipid (III), usually an inorganic salt as a by-product, unreacted compound (I) or (II), and the like. Therefore, depending on the purpose of use, the reaction product can be used as it is, but when a higher purity product is required, for example, partition chromatography, adsorption chromatography, a solvent separation method, a recrystallization method, or the like. May be appropriately purified and used according to the known method described above.

〔The invention's effect〕

Since the production method of the present invention is simple, inexpensive, and excellent in productivity, it is extremely useful as an industrial production method of glyceroglycolipids useful as toiletries and cosmetics detergents, emulsifiers, humectants, and the like.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 Synthesis of 3-chloro-2-hydroxy-1-O-glucosylpropane: 160 g (0.88 mol) of glucose and 3-chloro-
956 g (8.8 mol) of 1,2-propanediol and 40 g of Dowex 50WX8 (H type, 50 to 100 mesh) as an acid catalyst were added, the temperature was raised to 60 ° C. with stirring, and the reaction was carried out for 16 hours. After the reaction, dowex by filtration with a glass filter
Except for 50WX8 (H type, 50-100 mesh), unreacted 3-chloro-1,2-propanediol was distilled off from the obtained filtrate under reduced pressure. The obtained residue was treated with 500 g of acetone for a total of 3
After washing twice, it was dried under reduced pressure to obtain 79 g of 3-chloro-2-hydroxy-1-O-glucosylpropane (yield 3).
3%).

Example 1 Production of 3-O-lauroyl-1-O-glucosylglycerol: In a reactor were placed 20 g (0.073 mol) of 3-chloro-2-hydroxy-1-O-glucosylpropane obtained in Synthesis Example 1, 14 g (0.063 mol) of sodium laurate, 0.5 g of tetrabutylammonium bromide and 600 g of dimethylformamide. The temperature was raised to 100 ° C. with stirring, and the reaction was carried out for 15 hours. After completion of the reaction, dimethylformamide was distilled off under reduced pressure. 200 g of water and 400 g of ethyl acetate were added to the obtained residue,
After shaking vigorously, leave still to collect the ethyl acetate layer,
Ethyl acetate was distilled off under reduced pressure to obtain a crude product. Further, the crude product was purified by silica gel column chromatography to obtain 6.2 g of 3-O-lauroyl-1-O-glucosylglycerol (yield: 22%). ¹ H-NMR (methanol-d ₄ ) δ (ppm): 0.91 (t, 3H), 1.
33 (broad s, 16H), 1.65 (m, 2H), 2.40 (m, 2H), 3.21-
4.35 (m, 11H), IR (liquid film) (cm ^-1 ); 3400, 2950, 2880, 1660, 1480 to 140,
Example 2 Preparation of 3-O-palmitoyl-1-O-glucosylglycerol In a reactor, 25 g (0.091 mol) of 3-chloro-2-hydroxy-1-O-glucosylpropane obtained in Synthesis Example 1, 20 g (0.073 mol) of sodium palmitate, 0.7 g of tetrabutylammonium bromide and 80 g of dimethylformamide 80
After adding 0 g, the temperature was raised to 100 ° C. with stirring, and the reaction was carried out for 18 hours. After completion of the reaction, dimethylformamide was distilled off under reduced pressure. 200 g of water and 400 g of ethyl acetate were added to the obtained residue, and the mixture was vigorously shaken. Then, the ethyl acetate layer was collected, and ethyl acetate was distilled off under reduced pressure to obtain a crude product. Further, the crude product was purified by silica gel column chromatography to obtain 10 g of 3-O-palmitoyl-1-O-glucosylglycerol.

(28% isolated yield). ¹ H-NMR (methanol-d ₄ ) δ (ppm): 0.90 (t, 3H), 1.
34 (broad, 24H), 1.65 (m, 2H), 2.39 (m, 2H), 3.19-4.
36 (m, 11H), 4.91 (broad, 1H) IR (liquid film) (cm ^-1 ); 3400, 2940, 2870, 1750, 1650, 1480-
1040,920

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-64-67237 (JP, A) JP-A-55-62046 (JP, A) JP-A-62-30739 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) C07H 15/06 A61K 7/00-7/50 CAplus (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. The following general formula (I) (Wherein G represents a glucosyl group which may have a substituent, and X represents a halogen atom) and a compound represented by the general formula (II) RCOOM (II) A compound represented by the formula (III): wherein a compound represented by the formula (III) is an alkyl or alkenyl group having 1 to 24 carbon atoms in the chain, and M represents a cation. (Wherein, G and R represent the same as described above).