JPH04103595A - New saccharide derivative - Google Patents

Abstract

NEW MATERIAL:Compound of formula G-(A)n [G is (substituted) 5-6C reducing sugar, condensate thereof or residue obtained when n X hydroxyl groups are removed from saccharide selected from (substituted) oligosaccharide constituting 5-6C reducing sugar; A is group to be bonded to C atom to which n X eliminated hydroxyl groups were bonded in G and represented by formulae I-IV (R is 5-23C branched chain alkyl or branched chain alkenyl); n is from/to the number of hydroxyl groups in saccharide.]. EXAMPLE:3-0-(2-Heptylundecanoyl)-1-0-glucosylglycerol. USE:A base material for hair care or skin care cosmetics, a humectant, a detergent, an emulsifier, etc. PREPARATION:A compound of formula G-(B)n [B is group to be bonded to C atom to which n X eliminated hydroxyl groups were bonded in G and represented by formulae VI-VIII (X is halogen), etc.] is allowed to react with a compound of formula RCOOM (M is H or cation).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to hair and skin cosmetic bases, moisturizing agents, cleaning agents,
This invention relates to novel sugar derivatives useful as emulsifiers, etc.

[Problems to be solved by conventional techniques and inventions] 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 denaturation ability and are irritating to the skin, so there has been a desire to develop surfactants that are less irritating. In addition to this, recently, as consumers have become increasingly aware of natural materials and the global environment, naturally derived surfactants, their derivatives, and their similar compounds, which are highly safe and biodegradable, are being used in hair, skin, and cosmetics. It is attracting attention as a surfactant and moisturizing agent. Among these, glyceroglycolipids are natural surfactants found in plants, etc., and are expected to be excellent in terms of safety and biodegradability. It is expected to be used as an agent, emulsifier, etc. However, conventionally known glyceroglycolipids have relatively high melting points and crystallinity, and are difficult to incorporate into products due to poor compatibility with various solvents. Glycolipids have a relatively low melting point, but they also have drawbacks such as deterioration in quality due to oxidation of the double bond in the acyl group, and low stability due to hydrolysis of the ester bond. However, the performance was not always satisfactory.

Therefore, it has been desired to develop a new glyceroglycolipid that has a low melting point and low crystallinity, can be easily incorporated into various products, and has excellent stability.

[Means to solve the problem]

Under these circumstances, the present inventors conducted intensive studies to solve the above problems, and as a result, a novel glycerosugar having a branched alkyl group or alkenyl group in the acyl group represented by the following general formula (I) was developed. The lipid has properties not seen in previously known glyceroglycolipids, namely,
It exhibits fluidity at room temperature, exhibits excellent compatibility with almost all solvents, and has characteristics such as being almost uniformly dispersed when mixed with water, and is also useful as a cosmetic base, emulsifier, and moisturizer. The present invention was completed based on the fact that it exhibits extremely excellent performance never seen before as an agent, lubricant, etc.

That is, the present invention relates to the following general formula (I) G-(A)n (I) [wherein G is a reducing sugar having 5 to 6 carbon atoms which may have a substituent, a condensate thereof, and a carbon Indicates a residue obtained by removing n hydroxyl groups from a saccharide (hereinafter referred to as saccharide) selected from oligosaccharides that may have substituents having a number of 5 to 6 reducing sugars as constituent units, and A represents a residue in G. A group that bonds to the carbon atom to which the removed n hydroxyl groups were bonded, and is the same or different as 0C82CHCH2DCOR, -0CH2CHCH
,011.

0ft DCOR CH20)1-[1CI(-0C)12cl(CLOC[lR or CH,0COR0COR CH2DCOR 0CH CH2DCOR (here, R represents a branched alkyl group or a branched alketriyl group having 5 to 23 carbon atoms) ), where n is a number from 1 to the number of hydroxyl groups of the sugar.

In the present invention, G in the present compound represented by the general formula (I) is a residue obtained by removing n hydroxyl groups from the saccharide, and specific examples of this saccharide include ribose, arabinose, xylose, lyxose, Pentoses such as ribulose; allose, aldrose, glucose, mannose, gulose, idose, galactose, gulose,
Monosaccharides such as hexoses such as fructose and their condensates, maltooligosaccharides such as maltose, isomaltose, isomaltotriose, cyclodextrin,
Cellooligosaccharides such as cellobiose; galactooligosaccharides,
Examples include oligosaccharides such as mannooligosaccharide, fructooligosaccharide, sucrose, and lactose. Furthermore, examples of groups that can be substituted for these monosaccharides or oligosaccharides include groups modified by acylation, etherification, alkylene oxide addition, acetalization, sulfation, phosphorylation, and the like.

In addition, A of the compound (I) of the present invention is n removed in G.
is a group that bonds to the carbon atom to which the hydroxyl group was bonded, and R is a branched alkyl group or branched alkenyl group having 5 to 23 carbon atoms, such as methylbutyl,
Methylpentyl, ethylbutyl, methylhexyl, ethylpentyl, methylhebutyl, ethylhexyl, propylpentyl, methyloctyl, dimethylheptyl, methylnonyl, methyldecyl, butylheptyl, methylundecyl, methyldodecyl, pentyloctyl, methyltridecyl, trimethylundecyl , methyltetradecyl, ethyltridecyl, propyldodecyl, butylundecyl, pentyldecyl, hexylnonyl, heptyloctyl, methylpentadecyl, methylhexadecyl, ethylpentadecyl, propyltetradecyl, butyltridecyl, tetradodecyl, hexaun Decyl, heptyldecyl, octylnonyl, methylheptadecyl, methyloctadecyl, tetramethylpentadecyl, ethylheptadecyl, octylundecyl, methylnonadecyl,
Methyl eicosyl, nonyldodecyl, methylheneicosyl, methyltocosyl, decyltridecyl, methyltetradecenyl, methylhexadecenyl, dimethylhebutenyl, dimethylhebutagenyl, trimethylundecatrienyl, tetramethylpentadecatetraenyl groups, etc. . Among them, -CH-R' (where R' and R2 are the same or different, straight or branched chain having 2 to 2 carbon atoms)
11 alkyl group) or each 0
is an integer of ˜20, and the sum of l and m is 6 to 20) is preferable.

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

G-(B)l, + RCOO-→G(A),,+
MX(I[) (III) (I)
[In the formula, G, R and n have the same meanings as above, and B is G
is a group that bonds to the carbon atom to which the n hydroxyl groups removed in step 2 were bonded, and is the same or different H H2X or -0-CH CH,X (where X represents a halogen atom), M represents a hydrogen atom or a cationic group] That is, the sugar derivative (I) of the present invention is produced by reacting the compound (n) and the compound (III).

Compound (I[) used in this method can be easily produced by a known method, such as reaction of a monosaccharide or oligosaccharide with glycerol monohalohydrin, glycerol dihalohydrin, or shrimp halohydrin.

Compound (III) can be produced, for example, by reacting a fatty acid with an alkali metal hydroxide such as sodium hydroxide, an amine, or the like in the presence of an appropriate solvent. In addition, examples of the cationic group represented by M in compound (III) include alkali metals, ammonium groups, alkylammonium groups, and trialkanolamines.

To carry out this method, for example, the above compound (II) and compound (III) are heated at 30-150°C, preferably at 70-150°C.
The reaction may be carried out at a temperature of 20°C. The amount of compound (III) used here is usually 0.3 to 3.0 times mole, particularly preferably 1.0 to 2.0 times mole, relative to compound (II).
It is 0 times the mole. Furthermore, when M in 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 alkoxides, and alkylamine hydroxides.

Further, in carrying out this reaction, a polar solvent can be used for the purpose of promoting mixing of compound (n) and compound (III) and making the reaction proceed smoothly. The polar solvent used here is at least one selected from dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, pyridine, water, and the like. Further, the amount of the polar solvent to be used may be selected as appropriate. Further, in carrying out this reaction, a phase transfer catalyst may be used if necessary for the purpose of promoting this reaction. The amount of the phase transfer catalyst used here may be selected appropriately, but it is usually 0.1 to 10% relative to the compound (I[[)
It is mole%. Further, as the phase transfer catalyst used here, for example, tetraethylammonium furomite, tetrapropylammonium bromide, tetrabutylammonium bromide, tetraheptylammonium bromide, tetrahexylammonium bromide, N
,N.

N-)rifthyl-N-octylammonium chloride, N,N,N-)rifthyl-N-decylammonium chloride, N,N,N-)limethyl-N-dedocylammonium chloride, N,N.

N-) IJ Methyl-N-hexadecyl ammonium chloride, N,N,N-trimethyl-N-octadedylammonium chloride, N,N-dimethyl-N,N-
Tetraalkylammonium chlorides such as dioctadecylammonium chloride, N,N-dimethyl-N,N-dioctadecylammonium chloride can be mentioned.

The reaction product of the above reaction usually contains, in addition to the target glyceroglycolipid (I), an inorganic salt as a by-product, unreacted compound (I[) or (III), etc.].

Therefore, depending on the purpose of use, it is possible to use the reaction product as it is, but if a higher purity product is required, methods such as partition chromatography, adsorption chromatography, solvent fractionation, recrystallization, etc. can be used. It may be used after being appropriately purified by a known method.

〔Effect of the invention〕

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

〔Example〕

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

Synthesis Example 1 (Synthesis of 3-chloro-2-hydroxy-1-0-curcosylpropane) 160 g (0.88 mol) of glucose and 956 g (8.8 mol) of 3-chloro-1,2-propanediol were placed in a reactor. ) and DOWEX 50WX8 (H type,
50~1007'-i x) 40g,
The temperature was raised to 60° C. while stirring, and the reaction was allowed to proceed for 16 hours. After the reaction was completed, unreacted 3-chloro-1°2-propanediol was distilled off under reduced pressure by filtration through a glass filter. The resulting residue was washed three times with 500 g of acetone and then dried under reduced pressure to obtain 79 g of 3-chloro-2-hydroxy-1-0-glucosylpropane (yield: 33
%).

Example 1 3-chloro-2-hydroxy obtained in Synthesis Example 1 was placed in a reactor.
1-0-glucosylpropane 55g (0.2 mol) and 2
- Add 31 g (0.1 mol) of sodium heptyl undecanoate, 1.0 g of tetrabutylammonium bromide and 100 g of dimethylformamide, and add 1.0 g of sodium heptyl undecanoate while stirring.
The temperature was raised to 00°C and the reaction was carried out for 12 hours. After the reaction was completed, dimethylformamide was distilled off under reduced pressure. 300 g of water and 600 g of ethyl acetate were added to the resulting residue, and after shaking vigorously, the mixture was allowed to stand to collect the ethyl acetate layer, and the 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 1 g of 3-O-(2-heptylundecanoyl)-1-0-glucosylglycerol (jllllll ratio 21%). ).

'H-NMR (CDCj!,) δ (ppm, 7MS
Standard) (Figure 1); 0.89 or less margin C) 1,0D IR (liquid film) (Cm-') (Figure 2');
3400.2943.2860゜1?40.1650
．． 1460.1420-960 mass spectrometry (FAB ionization method) m/z: 521 (M+H)"Example 2 3-chloro-2-hydroxy- obtained in Synthesis Example 1 was placed in the reactor.
83 g (0.3 mol) of 1-0-glucosylpropane and 47 g (0.15 mol) of sodium isostearate
, 1.0 g of tetrabutylammonium bromide and 200 rnl of dimethylformamide were added, and the temperature was raised to 100° C. while stirring, and the reaction was allowed to proceed for 8 hours. After the reaction was completed, dimethylform-ramide was distilled off under reduced pressure. 300 g of water and 600 g of ethyl acetate were added to the resulting residue, and after shaking vigorously, the mixture was allowed to stand to collect the ethyl acetate layer, and the 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 3-0-isostearoyl-1-0-glucosylglycerol (isolated yield 26%).

'H-NMR (CDC1s) δ (ppm, 7MS standard); 0.79-1.03 (t, 6H), 1.
11~1.45 (broad, 25t(), 1.5
6 (broad, 2H), 2.33 (broad,
2H), 3.2:33-4J9(.

11H), 4.88 (broad, IH)IR
C liquid (cm-'); 3400.2950~2
860.1?40°1650, 1470.1390~9
50 mass spectrometry (FAB ionization method) m/z: 521 (M+H)” Synthesis Example 2 (Synthesis of 3-0-valmitoyl-1-〇-glucosylglycerol) 3-chloro-2 obtained in Synthesis Example 1 was placed in a reactor. -Hydroxy-
1-0-, 20 g (0,073 mol) glucosylpropane and 23 g (0,073 mol) sodium stearate.
mole), tetrabutylammonium bromide 0.7g
and dimethylformamide 4-800- were added, and the temperature was raised to 100° C. while stirring, and the reaction was allowed to proceed for 18 hours. After the reaction was completed, dimethylformamide was distilled off under reduced pressure. 200 g of water and 400 g of ethyl acetate were added to the resulting residue, and after shaking vigorously, the mixture was allowed to stand to collect the ethyl acetate layer, and the 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 = IQ: 1) to obtain 15 g of 3-0-valmitoyl-1-〇-glucosylglycerol (isolated yield 28%). ).

Test Example The properties of the compounds obtained in Examples 1 and 2 and conventionally known glyceroglycolipids at room temperature and their compatibility with water were investigated.

The results are shown in Table 1.

Table 1

[Brief explanation of the drawing]

Figures 1 and 2 show the N of the compound obtained in Example 1, respectively.
It is a drawing showing an MR spectrum and an IR spectrum.

Claims (1)

[Claims] 1. The following general formula (I) G-(A)_n(I) [In the formula, G is a reducing sugar having 5 to 6 carbon atoms which may have a substituent, or a condensation thereof Represents a residue obtained by removing n hydroxyl groups from a saccharide (hereinafter referred to as saccharide) selected from oligosaccharides that may have a substituent having a reducing sugar having 5 to 6 carbon atoms as a constituent unit, and A is a group that bonds to the carbon atom to which the n hydroxyl groups removed in G were bonded, and is the same or different ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. A sugar derivative represented by [indicates the number up to the number of hydroxyl groups]. 2. The sugar derivative according to claim 1, wherein G in the general formula (I) is a residue remaining after removing a glycosidic hydroxyl group from the sugar. 3. The sugar derivative according to claim 1, wherein G in the general formula (I) is a residue remaining after removing a glycosidic hydroxyl group from glucose or a condensate thereof. 4. In the general formula (I), R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R^1 and R^2 are the same or different, and are straight-chain or branched alkyl having 2 to 11 carbon atoms. The sugar derivative according to claim 1, 2 or 3, which is a group represented by the following formula. 5. In the general formula (I), R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, l and m each represent an integer from 0 to 20,
The sugar derivative according to claim 1, 2 or 3, wherein the sum of l and m is 6 to 20.