JP2939650B2 - New sugar derivatives - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel sugar derivative useful as a base for hair and skin cosmetics, a humectant, a detergent, an emulsifier, 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 a relatively high protein-degrading ability and are irritating to the skin. Therefore, it has been desired to develop a surfactant having a lower irritation. In addition, in recent years, with the increase in consumers' awareness of the use of natural materials and the global environment, surfactants and derivatives derived from natural sources with excellent safety and biodegradability, and similar compounds have been used for hair and skin cosmetics. Has attracted attention as a surfactant and humectant. Among them, glyceroglycolipid is a natural surfactant contained in plants and the like, and is expected to be excellent in terms of safety and biodegradability, so that it is a base for hair and skin cosmetics, a humectant, and a washing agent. The use as an emulsifier, an emulsifier, etc. is expected. However, conventionally known glyceroglycolipids have a relatively high melting point and crystallinity, and have poor compatibility with various solvents, so that it is difficult to incorporate them into products, and glyceroglycols having an acyl group derived from an unsaturated fatty acid. Glycolipids have a relatively low melting point, but have problems such as deterioration of quality due to oxidation of the double bond of the acyl group, and low stability due to hydrolysis of the ester bond. However, the performance was not always satisfactory.

Therefore, development of a novel glyceroglycolipid which has a low melting point and low crystallinity, can be easily incorporated into various products, and has excellent stability has been desired.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted intensive studies in order to solve the above problems, and as a result, a novel glyceroglycolipid having a branched alkyl group in an acyl group represented by the following general formula (I): Glyceroglycolipids which have not been seen so far are performances that have not been seen, that is, they show fluidity at room temperature, show excellent compatibility with almost all solvents, and are almost uniform when mixed with water. Having properties such as dispersing, and further, cosmetic base, emulsifier, humectant,
The present inventors have found that they show extremely excellent performance as never before, and completed the present invention.

That is, the present invention provides the following general formula (I) [Wherein, G represents a glucosyl group, and R is (Where R ¹ and R ² are the same or different and represent a linear or branched alkyl group having 2 to 11 carbon atoms) or (Wherein l and m each represent an integer of 0 to 20, and the sum of l and m is 6 to 20).

In the present invention, in the general formula (I), examples of the branched alkyl group represented by R include ethylbutyl, ethylpentyl, ethylhexyl, propylpentyl, methyloctyl, methylnonyl, methyldecyl, butylheptyl, methylundecyl, methyldodecyl, Pentyl octyl, methyl tridecyl, methyl tetradecyl, propyl dodecyl, butyl undecyl, pentyl decyl, hexyl nonyl, heptyl octyl, methyl pentadecyl,
Methylhexadecyl, heptyldecyl, octylnonyl, methylheptadecyl, methyloctadecyl, octylundecyl, methylnonadecyl, methyleicosyl,
Nonyl dodecyl, methylhen eicosyl, methyl docosyl and the like can be mentioned.

The sugar derivative (I) of the present invention can be produced, for example, according to the following reaction formula.

(Wherein, X represents a halogen atom, and G and R have the same meanings as described above). That is, the sugar derivative (I) of the present invention is produced by reacting the compound (II) with the compound (III). Is done.

The compound (II) used in the present method can be easily produced by a known method, for example, a reaction between glucose and glycerol monohalohydrin or epihalohydrin.

The compound (III) can be produced, for example, by reacting a fatty acid with an alkali metal hydroxide such as sodium hydroxide or an amine in the presence of a suitable solvent. Examples of the cation group represented by M in the compound (III) include an alkali metal, an ammonium group, an alkylammonium group, and a trialkanolamine.

In order to carry out this method, for example, the compound (II) and the compound (III) may be reacted at a temperature of 30 to 150 ° C, preferably 70 to 120 ° C. Compound (III) used here
Is usually 0.3 to 3.0 moles, particularly preferably 1.0 to 2.0 moles, per mole of Compound (II). When M of compound (III) is a hydrogen atom, the reaction is carried out 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 (II) and the compound (III) 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 (III). 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-decylammonium 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 chlorides such as dihexadecyl ammonium chloride and N, N-dimethyl-N, N-dioctadecyl ammonium chloride.

The reaction products of the above reaction include, in addition to the target glyceroglycolipid (I), usually an inorganic salt as a by-product, unreacted compound (II) or (III), 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〕

The compound of the present invention exhibits fluidity at room temperature, and has very excellent lubricity, exhibits excellent compatibility with most solvents, and has properties such as being almost uniformly dispersed when mixed with water, It is extremely useful as a base, emulsifier, lubricant, and humectant for hair and skin cosmetics.

〔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, and the temperature was raised to 60 ° C. with stirring, followed by a reaction for 16 hours.
After completion of the reaction, unreacted 3-chloro-1,2-propanediol was distilled off under reduced pressure by filtration through a glass filter. The obtained residue was washed with 500 g of acetone a total of three times, and then dried under reduced pressure to give 3-chloro-2-hydroxy-1.
79 g of -O-glucosylpropane was obtained (33% yield).

Example 1 In a reactor, 55 g (0.2 mol) of 3-chloro-2-hydroxy-1-O-glucosylpropane obtained in Synthesis Example 1, 31 g (0.1 mol) of sodium 2-heptylundecanoate, and 1.0 g of tetrabutylammonium bromide And 100 ml of dimethylformamide, and the mixture was heated to 100 ° C. with stirring and reacted for 12 hours. After completion of the reaction, dimethylformamide was distilled off under reduced pressure. 300 g of water and 60 ethyl acetate were added to the obtained residue.
After adding 0 g, the mixture was vigorously shaken and allowed to stand to collect an ethyl acetate layer, and ethyl acetate was distilled off under reduced pressure to obtain a crude product. The crude product was further purified by silica gel chromatography (chloroform / methanol = 10: 1),
11 g of O- (2-heptylundecanoyl) -1-O-glucosylglycerol was obtained (21% isolated yield). ¹ H-NMR (CDCl ₃ ) δ (ppm, based on TMS) (FIG. 1); 0.89 (t,
6H, a ), 1.35 (broad, 24H, b ), 1.45 (broad, 2H, c ), 1.56
(Broad, 2H, d ), 2.37 (broad, 1H, e ), 3.23 ~ 4.39 (m, 11
H, f ), 4.89 (broad, 1H, g ) IR (liquid film) (cm ^-1 ) (Fig. 2); 3400,2943,2860,1740,165
0,1460, 1420-960 Mass spectrometry (FAB ionization method) m / z: 521 (M + H) ⁺ Example 2 83 g of 3-chloro-2-hydroxy-1-O-glucosylpropane obtained in Synthesis Example 1 in a reactor. (0.3 mol), 47 g (0.15 mol) of sodium isostearate, 1.0 g of tetrabutylammonium bromide and dimethylformamide
200 ml was added, the temperature was raised to 100 ° C. with stirring, and the reaction was carried out for 8 hours. After completion of the reaction, dimethylformamide was distilled off under reduced pressure. 300 g of water and 600 g of ethyl acetate were added to the obtained residue, and the mixture was vigorously shaken and allowed to stand to collect an ethyl acetate layer. Ethyl acetate was distilled off under reduced pressure to obtain a crude product. The crude product was further purified by silica gel chromatography (chloroform / methanol = 10: 1) to obtain 14 g of 3-O-isostearoyl-1-O-glucosylglycerol (isolation yield: 26%).

¹ H-NMR (CDCl ₃ ) δ (ppm, based on TMS); 0.79 to 1.03 (t, 6
H), 1.11 ~ 1.45 (broad, 25H), 1.56 (broad, 2H), 2.33
(Broad, 2H), 3.23 ~ 4.39 (m, 11H), 4.88 (broad, 1H) IR (liquid film) (cm ^-1 ); 3400,2950 ~ 2860,1740,1650,1470,
1390-950 Mass spectrometry (FAB ionization method) m / z: 521 (M + H) ⁺ Synthesis Example 2 (Synthesis of 3-O-palmitoyl-1-O-glucosylglycerol) 3-Chloro obtained in Synthesis Example 1 in a reactor 20 g (0.073 mol) of 2-hydroxy-1-O-glucosylpropane, 23 g (0.073 mol) of sodium stearate, 0.7 g of tetrabutylammonium bromide and 80 g of dimethylformamide
0 ml was added, the temperature was raised to 100 ° C. while 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 and allowed to stand to collect an 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 chromatography (chloroform / methanol = 10: 1) to obtain 15 g of 3-O-palmitoyl-1-O-glucosylglycerol (28% isolated yield).

Test Example The properties of the compound obtained in Examples 1 and 2 and a conventionally known glyceroglycolipid at room temperature and compatibility with water were examined.

 The results are shown in Table 1.

[Brief description of the drawings]

1 and 2 show the NM of the compound obtained in Example 1, respectively.
3 is a drawing showing an R spectrum and an IR spectrum.

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (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, and R is (Where R ¹ and R ² are the same or different and represent a linear or branched alkyl group having 2 to 11 carbon atoms) or (Wherein l and m each represent an integer of 0 to 20, and the sum of l and m is 6 to 20).