JPH0510352B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel monosaccharide derivative, 1-O-methyl-6-O-alkylgalactofuranoside. In the oleochemical industry, polyhydric alcohols represented by glycerin, diglycerin, sorbitol, mannitol, sugars, etc. are widely used as one of the important groups of highly hydrophilic raw materials.
In addition, these polyhydric alcohol esters and ethers are widely distributed in the natural world, and play an important role in the life activities of living things, as well as in many other applications such as detergents, foods, industrial chemicals, and pharmaceuticals. As an industrial product, it greatly contributes to human daily life. Conventionally, nonionic surfactants have been synthesized by subjecting polyhydric alcohols to esterification reactions or etherification reactions (however, in this case, alkylene oxide type ether compounds are mostly used).
Attempts to apply it have been made in many fields. Among these polyhydric alcohol derivatives, in particular, sorbitan fatty acid ester derived from sorbitol, a sugar alcohol, and its ethylene oxide adduct are used as industrial chemicals and cosmetics due to their characteristic emulsifying properties and safety. It is used in a wide range of fields such as bases, food additives, and pharmaceutical bases. In addition, sucrose fatty acid ester derived from sucrose, a disaccharide, is used in fields such as food, pharmaceuticals, cosmetics, and detergents due to its safety and good microbial degradability. For example, Oil Chemistry, Vol. 16, pp. 395-401 (1967)). On the other hand, sugar alcohols (e.g. maltitol), which are disaccharides in which linear monosaccharides and monocyclic monosaccharides are ether-linked, are expected to be applied to cosmetic bases as moisturizing agents (e.g. fragrances). Journal (No. 14) pp. 86-93 (1975
Year)). In addition, D-
Octyl β-D-glycoside derived from glucose is effective as a solubilizing agent for protein membranes, and its application to pharmaceutical bases has been reported (e.g., biochemistry,
Volume 20, page 6776 (1981)). Similarly, it has been disclosed that a series of derivatives obtained by alkylating the 3-position of the D-glucose skeleton using D-glucose as a raw material are effective as antitumor agents (Japanese Patent Application Laid-Open No. 56-103196). Such). The present inventors have focused on the above-mentioned usefulness exhibited by polyhydric alcohols, especially saccharides, and have been studying the use of saccharides that are abundantly present in nature. As one of the results, we recently discovered mono- and dialkyl ethers of D-mannitol and proposed the use of these as cosmetics (Japanese Patent Application No. 138,227/1986). The present inventors further chemically modified galactose, which is one of the monocyclic monosaccharides,
As a result of intensive research in order to obtain a useful surfactant, we made galactose act with a ketone to protect the four hydroxyl groups, then we made the free 6-position hydroxyl group act with an alkylating agent, and then protected it in methanol. The present invention was completed based on the discovery that a galactofuranoside having ether bonds at the 1 and 6 positions can be obtained by removing the group, and that this compound is useful as a cosmetic base. That is, the present invention provides the following formula () (wherein, R represents a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 8 to 24 carbon atoms) It is something to do. As an alkyl ether compound derived from galactose, 6-O-dodecylgalactose can be used as a general surfactant (Tenside Detergents, Vol. 15, No. 72).
Pages to pages 74 (1978)), and the synthesis and reactions of alkyl galactoside compounds with various chain lengths (Pharmaceutical Journal, Vol. 79, pages 80 to
No. 83 (1959), Carbobydr.Res. Vol. 25, No. 59
Pages 65 to 65 (1972), etc.) are known. However, the 1-O-methyl-6-O-alkylgalactofuranoside represented by the formula () of the present invention has not been described in any literature and is a new compound. The 1-O-methyl-6-O-alkylgalactofuranoside () of the present invention is preferably produced by the reaction shown in the following formula. (In the formula, R has the above-mentioned meaning, and X is a halogen atom, etc.) That is, first, galactose is treated with acetone according to a known method, and four hydroxyl groups are protected, 1,2: Obtain 3,4-di-O-isopropylidene galactose () (hereinafter abbreviated as galactose diacetonide) (Journal of
American Chemical Society., Volume 76, No. 3188
Pages 3193 (1954)). Next, the obtained galactose diacetonide () is treated with an alkylating agent by a known method to etherify the free hydroxyl group at the 6-position. An advantageous method for carrying out this industrially is a method in which etherification is carried out in an alkaline aqueous solution using a phase transfer catalyst typified by a quaternary onium salt. According to this method, etherification proceeds under mild conditions and the desired 6-
O-alkylgalactopyranose diacetonide () is obtained in good yield. Obtained 6-O-alkylgalactopyranose diacetonide ()
is solvolyzed in methanol in the presence of an acid catalyst such as protonic acid to remove the protecting group to obtain the desired 1-O-methyl-6-O-alkylgalactofuranoside (). More detailed reaction conditions for the reaction are as follows. First, galactopyranose diacetonide ()
The etherification reaction is preferably carried out in the presence of an alkaline substance. Alkaline substances include alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates, etc. Among these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are particularly used industrially. suitable. The appropriate amount of the alkaline substance used is 1 to 10 mol per 1 mol of galactopyranose diacetonide (), and the alkaline substance accounts for 10 to 80%,
More preferably, it is a 40-60% aqueous solution. As the etherification agent, alkyl halide,
Alkyl sulfonic acid esters, alkyl sulfuric esters, etc. are used, and among these, a more suitable etherifying agent is an alkyl halide. Particularly preferred etherifying agents are alkyl bromides and alkyl iodides. Further, the alkyl group of these etherifying agents includes a saturated or unsaturated straight-chain or branched aliphatic hydrocarbon group having 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms. Specific examples of the alkyl group of the etherification agent include:
Straight-chain aliphatic hydrocarbon groups include octyl, dodecyl, decyl, cetyl, stearyl, oleyl, etc., and branched aliphatic hydrocarbon groups include 2-ethylhexyl, 2-heptylundecyl, 5,7, 7-trimethyl-2-(1,3,3
-trimethylbutyl)octyl and the formula (In the formula, m represents an integer of 4 to 10, n represents an integer of 5 to 11, m+n represents 11 to 17, and m=
7, having a distribution with n=8 at the peak). The amount of etherification agent used is 1 to 10 per mole of galactopyranose diacetonide ().
A mole is suitable, preferably 1.2. The etherification reaction of galactopyranose diacetonide () is preferably carried out in the presence of a catalytic amount of a quaternary onium salt. Ammonium salts are preferred because of their ease of use. Specific examples of quaternary ammonium salts include tetraalkylammonium salts (e.g., tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, etc.): polyoxyalkylene groups A group of alkyl ammonium salts having (for example, tetraoxyethylene stearyl dimethyl ammonium chloride, bistetraoxyethylene stearyl methyl ammonium chloride, etc.) include betaine compounds, crown ethers, amine oxide compounds, and ion exchange resins. These quaternary onium salts are 0.01 to 1 mole of galactopyranose diacetonide ().
It is good to use 0.20 mol, preferably 0.05 to 0.10 mol. In addition, as a reaction solvent, any solvent that does not affect this reaction can be used, and among these, aliphatic hydrocarbons such as hexane, heptane, and octane, and alicyclic hydrocarbons such as cyclopentane and cyclohexane are particularly suitable. Hydrocarbons, benzene,
Aromatic hydrocarbons such as toluene and xylene are preferred. Furthermore, ether compounds such as diethyl ether, THF, diglyme, and dioxane can also be used. The reaction temperature for etherification is 25 to 80°C, preferably 40 to 60°C, and by vigorous stirring, etherification is completed in several hours to more than ten hours.
The reaction product is treated in a conventional manner and then distilled under reduced pressure to obtain 6-O-alkylgalactopyranose diacetonide (). By subjecting the obtained compound () to solvolysis using protonic acid as a catalyst, 1-O-methyl-6-
O-alkylgalactofuranoside () is obtained. Solvolysis can be performed using sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid,
It is preferable to use a protonic acid catalyst such as benzenesulfonic acid or acetic acid and heat in methanol. The amount of the acid catalyst used is not particularly limited, but is suitably 1 to 10%, particularly preferably 1 to 5%. The reaction temperature is 40-70°C, preferably 45-50°C. If solvolysis is carried out under such conditions, the target product 1-O-methyl-6- can be obtained in high yield from 6-O-alkylgalactopyranose diacetonide
O-alkylgalactofuranoside () is obtained. The 1-O-methyl-6 of the present invention thus obtained
-O-alkylgalactofuranoside () is 1
Due to the effect of the O-methyl group in the position, the melting point is lowered, and many of them become liquid even at room temperature. Next, the properties of representative compounds of the present invention are as follows.

[Table] * Concentration of the product of the present invention 1-O-Methyl-6-O-alkylgalactofuranoside () exhibits relatively high hygroscopicity as the number of carbon atoms in R in formula () decreases, but on the other hand, the longer the alkyl Because it has a group, it becomes easier to form liquid crystal as the number of carbon atoms in R increases, and therefore it has a property that it is difficult to release water once absorbed. In particular, those in formula () in which R has 8 to 18 carbon atoms have a good balance between ease of absorbing moisture and difficulty releasing moisture, and are useful as moisturizing agents for cosmetics. Furthermore, those in formula () in which R has 14 or more carbon atoms have strong emulsifying power and are useful as emulsifiers for emulsified cosmetics. The amount of these compounds incorporated into cosmetics may vary depending on various factors, but 5 to 50% by weight is appropriate when used as a moisturizer, and 0.2 to 15% by weight when used as an emulsifier. be. As mentioned above, the 1-O-methyl-6-O of the present invention
- Alkylgalactofuranosides () are chemically stable because they do not have easily decomposable bonds such as ester groups, and they are less irritating to the skin and have surfactant properties, so they can be used as emulsifiers, self-emulsifying oils, wetting agents, etc. It is useful as a thickener and has a wide range of applications, primarily as a component of cosmetics. The present invention will be explained in more detail below using reference examples and examples, but the present invention is not limited to these examples. Reference Example 1 Synthesis of 1,2:3,4-di-O-isopropylidene galactopyranose: D-galactose was placed in a 4-neck reaction vessel equipped with a thermometer, reflux condenser, dropping funnel, and stirrer.
Take 200g of acetone, 240g of anhydrous zinc chloride finely ground at room temperature while stirring vigorously,
Add 8 ml of concentrated sulfuric acid. After stirring for another 4-5 hours at room temperature, the mixture is neutralized with an aqueous solution containing 400 g of sodium carbonate, and a small amount of sodium bicarbonate is added and stirring is continued for a while. After neutralization, let stand overnight to precipitate salts. The precipitated salts are removed separately, and the liquid is concentrated under reduced pressure to obtain a pale yellow viscous liquid. The resulting viscous liquid is dissolved in chloroform (500 ml) and then washed with 200 ml of water to completely remove inorganic salts. Then, chloroform was distilled off under reduced pressure, and 227 g of viscous colorless and transparent liquid 1,2:3,4-di-O-isopropylidene galactose was obtained by distillation under reduced pressure. yield
78%. Boiling point 132-140℃ (0.8mmHg) Literature value 110-120℃ (0.1-0.2mmHg) Literature Journal of American Chemical
Society., vol. 76, pp. 3188-3193
(1954) Reference example 2 Synthesis of methyl branched isostearyl alcohol: 20 In an autoclave, 4770 g of isostearic acid isopropyl ester [Emery 2310 isostearic acid isopropyl ester, commercially available from Emery Company, USA] and a copper chromium catalyst ( Prepare 239g (manufactured by JGC). Next, 150Kg/
Fill with hydrogen gas at a pressure of cm ² and then heat the reaction mixture to 275°C. 150Kg/ ^cm2 /
After hydrogenation at 275°C for about 7 hours, the reaction product was cooled and the catalyst residue was removed by filtration to obtain the crude product.
Obtained 3500g. By distilling the crude product under reduced pressure, 3300 g of transparent and colorless isostearyl alcohol was obtained as a fraction of 80 to 167°C/0.6 mmHg. The obtained isostearyl alcohol (monomethyl branched isostearyl alcohol) had an acid value of 0.05, a saponification value of 5.5, and a hydroxyl value of 181.4. It showed absorption at 3340 and 1055 cm ^-1 in IR (liquid film) and at δ3.50 (broad triplet, -CH ₂ -OH) in NMR (CCl ₄ solvent), respectively. As for the main components of this alcohol, about 75% are those whose alkyl groups have a total number of carbon atoms of 18, and the remaining components are those whose total number of carbon atoms is 14 or 16, and the branched methyl groups are was also found to be a mixture of those located near the center of the alkyl main chain. Reference Example 3 Synthesis of methyl branched isostearyl bromide: 813 g (3 mol) of methyl branched isostearyl alcohol obtained in Reference Example 2 and 47% bromide were placed in a container No. 5 equipped with a thermometer, reflux condenser, and stirrer. Add 1032 g (6.1 mol) of hydrogen acid aqueous solution and 50.1 g (0.15 mol) of trimethylstearylammonium chloride, and heat in a mantle heater while stirring.
Heat to 100-120℃. After stirring at this temperature for about 6 hours, it was observed in the gas chromatograph of the reaction mixture that the peak of methyl branched isostearyl alcohol had disappeared. After cooling the reaction product, the organic layer is collected by liquid separation. Add ether (1.5) to the lower layer (aqueous layer) and extract with ether. Collect the ether layer by liquid separation. The organic layers obtained earlier are combined and an aqueous sodium bicarbonate solution is added to neutralize the remaining acid content. The ether layer was collected by separation, and after drying by adding Glauber's salt to it, the ether was distilled off under reduced pressure, and then the ether layer was distilled under reduced pressure to obtain methyl branched isostearyl bromide.
Obtained 800g. Yield 80% Boiling point 145-169℃ (0.3mmHg) IR (Liquid film, cm ^-1 ) 1200-1300, 720, 640,
560 NMR (CCl ₄ , δ, THS internal standard) 3.30 (Triple line, J = 7.0 Hz, -CH ₂ Br) Elemental analysis As C ₁₈ H ₃₇ Br (calculated value) C64.7% (64.85%); H11 .2% (11.19%);
Br24.4% (23.97%) Average molecular weight (VPO method/ _HCCl3 ) 327 (calculated value
333) Example 1 Synthesis of 1-O-methyl-6-O-methyl branched isostearyl galactofuranoside: (i) 50% in one reaction vessel equipped with a reflux condenser, thermometer, addition funnel and stirring device. 96g of sodium hydroxide aqueous solution (48g of sodium hydroxide (1.2
mol)), 1,2:3,4-di- obtained in Reference Example 1
O-isopropylidene galactopyranose 52.1
g (0.2 mol), n-hexane 180 ml, 50% hydrogen sulfate tetrabutylammonium aqueous solution 13.6 g
Add (0.02 mol) in this order, keep at 25℃ in a water bath, and stir gently. 100g of isostearyl bromide obtained in Reference Example 3 from a dropping funnel
(0.3 mol) was added dropwise little by little. After adding the methyl branched isostearyl bromide dropwise over a period of about 1.5 hours, the temperature of the reaction mixture is raised to 50-55°C and stirred at this temperature for 20 hours. After confirming that galactopyranose diacetonide had completely disappeared from the reaction mixture by gas chromatography, 400 ml of water was added and stirred, followed by static separation. After collecting the organic layer, hexane is distilled off under reduced pressure. The residue was then subjected to vacuum distillation to obtain 87.8 g of 6-O-methyl branched isostearyl-1,2:3,4-di-O-isopropyldengalactopyranose as a colorless transparent liquid. Yield 87.4%. Boiling point 205-240℃ (0.3mmHg) Elemental analysis C ₃₀ H ₅₆ O ₆ (calculated value) C: 70.5% (70.26%), H: 11.3% (11.01
%) IR (liquid film, cm ^-1 ) 1380, 1255, 1215, 1170,
1110, 1070, 1000 1H-NMR (CDCl ₃ , TMS internal standard, δ) 5.50 (doublet, 1H, C ₁ -H) 3.35-4.70 (multiplet, 8H, C ₂ -H to _{C 6} -
HC ⁶ −O−CH ₂ −) 1.25, 1.29, 1.33.1.43 (4 singlets,
12H, 2 isopropylidene groups) (ii) 1 equipped with a reflux condenser, thermometer and stirring device;
6-O- obtained in Example 1 () in a reaction vessel of
Methyl branched isostearyl-1,2;3,4-
Di-O-isopropylidene galactopyranose
Add 57g (0.111 mol) and 200g of methanol,
Next, while stirring in a water bath, add 9 g of concentrated sulfuric acid.
(91 g of methanol) was added dropwise little by little.
After completing the dropwise addition, gradually raise the temperature of the reaction mixture.
Stir at 40-45℃ for about 1 hour. The reaction mixture turned into a homogeneous solution. After further stirring at the same temperature for 5-6 hours, the reaction mixture was cooled and the acid content was then neutralized with sodium bicarbonate. After separately removing the generated precipitate,
Methanol is distilled off under reduced pressure. Furthermore, drying was performed at 50 to 60° C. for about 3 hours under reduced pressure (5 mmHg). Colorless transparent liquid 1-O-methyl-6-O-
Methyl branched isostearyl galactofuranoside
Obtained 48g. Yield 97.2%. Elemental analysis C ₂₅ H ₅₆ O ₆ (calculated value) C: 66.4% (67.2%), H: 11.3% (11.3
%) Hydroxyl value 370.3 (376.9) IR (liquid film, cm ^-1 ) 3660-3000, 1460, 1375,
1195, 1210, 1020~1100, 870 1H-NMR ( _CDCl3 , TMS internal standard, δ) 3.2~4.3 (multiplet, 11H, C2 _- H~ _C6 -H
+3 OH+ _C6 -O- _CH2- ) 4.7~4.95 (multiplet, 1H, C1 _- H) 3.37 (singlet, 3H, OCH~ ₃ ) Example 2 Synthesis of 1-O-methyl-6-O-n-octylgalactofuranoside: (i) In (i) of Example 1, octyl bromide (0.3 mol) was used instead of methyl branched isostearyl bromide. The etherification was carried out under the same reaction conditions except for the following. A colorless and transparent liquid was obtained by vacuum distillation. 6-O-n-octyl-
61.8 g of 1,2:3,4-di-O-isopropylidene galactopyranose was obtained. Yield 83%. Boiling point 150-170℃/0.4mmHg Elemental analysis C ₂₀ H ₃₆ O ₆ (calculated value) C: 64.6% (64.5%), H: 9.7% (9.7%) IR (liquid film, cm ^-1 ) 1380, 1255 ,1210,1110,
1070, 1065, 1000 1H-NMR (CDCl ₃ , TMS internal standard, δ) 5.50 (doublet, 1H, C ₁ -H) 3.35-4.70 (multiplet, 8H, C ₂ -H to _{C 6} -H
_C6 -O-CH _~2- ) 1.24, 1.30, 1.34.1.44 (four single lines,
12H, 2 isopropylidene groups) (ii) In (ii) of Example 1, instead of 6-O-methyl branched isostearyl-1,2:3,4-di-O-isopropylidene galactopyranose,
6-O-octyl- obtained in Example 2 ()
Except that 0.111 mol of 1,2:3,4-di-O-isopropylidene galactopyranose was used.
All solvolysis was carried out under the same reaction conditions. 32.2 g of 1-O-methyl-6-O-n-octylgalactofuranoside was obtained as a colorless liquid. Yield 85
%. Elemental analysis C ₁₅ H ₂₉ O ₆ (calculated value) C: 58.5% (59.0%) H: 9.6% (9.57%) Hydroxyl value 550 (551) IR (liquid film, cm ^-1 ) 3660-3000, 1455, 1370,
1210, 1045~1110, 8601H ^- NMR ( _CDCl3 , TMS internal standard, δ) 3.35~4.3 (multiplet, 11H, C2 _- H~ _C6 -H
+3 OH~+C ₆ -O-CH~ ₂ -) 4.75~5.0 (multiplet, 1H, C ₁ -H) 3.38 (singlet, 3H, O-CH ₃ ) Example 3 Synthesis of 1-O-methyl-6-O-n-dodecylgalactofuranoside: (i) In (i) of Example 1, n-dodecyl bromide (0.3 mol) was used instead of methyl branched isostearyl bromide. ) was used, but the etherification was carried out under the same reaction conditions. Colorless and transparent viscous liquid 6-O-n-dodecyl-1,2:
68.6 g of 3,4-di-O-isopropylidene galactopyranose was obtained by vacuum distillation. Yield 80%. Boiling point: 185-190℃/0.4mmHg Elemental analysis: As C ₂₄ H ₄₄ O ₆ (calculated value) C: 67.4% (67.3%), H: 10.6% (10.6
%) IR (liquid film, cm ^-1 ): 2990, 2930, 2860,
1380, 1255, 1210, 1110, 1070, 1065,
1000 ¹ H-NMR (CDCl ₃ , TMS internal standard, δ) 5.50 (doublet, 1H, C ₁ -H) 3.4 to 3.7 (multiplet, 8H, C ₂ -H to _{C 6} -H,
C ₆ -O-CH _{~ 2} -) (ii) In place of 6-O-methyl branched isostearyl-1,2:3,4-di-O-isopropylidene galactopyranose in (ii) of Example 1, 6-O-n-dodecyl- obtained in Example 3 ()
The solvolysis was carried out under the same reaction conditions except that 0.111 mol of 1,2:3,4-di-O-isopropylidene galactopyranose was used. 22.9 g of 1-O-methyl-6-O-n-dodecylgalactofuranoside was obtained as a colorless liquid. Yield 57
%. Elemental analysis: as C ₁₉ H ₃₃ O ₆ (calculated value) C: 62.7% (63.0%), H: 10.5% (10.6
%) Hydroxyl value 453 (calculated value 464) IR (liquid film, cm ^-1 ): 3050-3700, 2925,
2855, 1450, 1370, 1185, 1160~970,
940, 870 ¹ H-NMR (CDCl ₃ , TMS internal standard, δ) 0.87 (singlet, 3H, -CH~ ₃ ) 1.1~1.17 (singlet, 20H, -CH ₂ -) 3.3~4.3 (multiplet, 8H, _C2 -H~ _C6 -H,
C ₆ -OCH~ ₂ ) 3.39 (singlet, 3H, -OCH~ ₃ ) 4.85 (multiplet, 1H, C ₁ -H) Example 4 Synthesis of 1-O-methyl-6-O-stearylgalactofuranoside (i) Etherification was carried out under the same reaction conditions as in (i) of Example 1 except that n-stearyl bromide (0.3 mol) was used in place of methyl branched isostearyl bromide. Colorless transparent viscous liquid 6-O-n-stearyl-1,2:3,
53.3 g of 4-di-O-isopropylidene galactopyranose was obtained by vacuum distillation. Yield 75.4%. Boiling point: 220-225℃/0.4mmHg Elemental analysis As C ₃₀ H ₅₆ O ₆ (calculated value) C: 70.2% (70.26%), H: 11.2% (11.01
%) IR (liquid film, cm ^-1 ): 1380, 1255, 1215,
1170, 1110, 1070, 1000 ¹ H-NMR (CDCl ₃ , TMS internal standard, δ) 5.50 (doublet, 1H, C ₁ -H) 3.38-4.70 (multiplet, 6H, C ₂ -H to _{C 6} −
H) 3.48 (triple line, 2H, C ⁶ -O-CH ₂ R') 1.23, 1.30, 1.32, 1.44 (four singlet lines,
12H, 2 isopropylidene groups) (ii) In (ii) of Example 1, instead of 6-O-methyl branched isostearyl-1,2:3,4-di-O-isopropylidene galactopyranose,
Solvolysis was carried out under the same conditions except that 0.111 mol of 6-O-n-stearyl-1,2:3,4-di-O-isopropylidene galactopyranose obtained in () of Example 4 was used. Ivy. 28 g of 1-O-methyl-6-O-n-stearylgalactofuranoside as white crystals was obtained. yield
54.2%. Melting point 67-71℃ Elemental analysis C ₂₅ H ₅₆ O ₆ (calculated value) C: 66.8% (67.2%) H: 11.3% (11.3%) Hydroxyl value 367 (376.9) IR (KBr, cm ^-1 ) 3600 ~ 3000, 1460, 1370,
1190, 1210, 1020~1110, 865 1H-NMR ( _CDCl3 , TMS internal standard, δ) 3.3~4.3 (multiplet, 11H, C2 _- H~ _C6 -H
+3 OH+C ₆ −O−CH ₂ R′) 4.7 to 4.95 (multiplet, 1H, C ₁ −H) 3.37 (singlet, 3H, OCH ₃ ) Example 5 Synthesis of 1-O-methyl-6-O-oleylgalactofuranoside: (i) In (i) of Example 1, oleyl bromide (0.3 mol) was used in place of methyl branched isostearyl bromide. Etherification was otherwise carried out under the same reaction conditions. Colorless and transparent viscous liquid 6-O-oleyl-1,2:3,4-
Di-O-isopropylidene galactopyranose
80.8g was obtained by vacuum distillation. Yield 79%. Boiling point: 215-220℃/0.3mmHg Elemental analysis: as C ₃₀ H ₅₄ O ₆ (calculated value) C: 70.5% (70.6%) H: 10.6% (10.7%) IR (liquid film, cm ^-1 ): 2990 ,2930,2860,
1380, 1255, 1210, 1110, 1070, 1065,
1000 1H-NMR (CDCl ₃ , TMS internal standard, δ) 5.50 (doublet, 1H, C ₁ -H) 5.2~5.5 (multiplet, 2H, olefin) 3.4~3.7 (multiplet, 8H, C ₂ - H~ _C6 -H,
C ₆ -OCH ₂ -) (ii) In place of 6-O-methyl branched isostearyl-1,2:3,4-di-O-isopropylidene galactopyranose in (ii) of Example 1, Example 5 6-O-oleyl-1 obtained in () of
Solvolysis was carried out under the same reaction conditions except that 0.111 mol of 2:3,4-di-O-isopropylidene galactopyranose was used. 36.0 g of colorless liquid 1-O-methyl-6-O-oleylgalactofuranoside was obtained. Yield 73%. Elemental analysis: as C ₂₅ H ₄₈ O ₆ (calculated value) C: 67.0% (67.5%), H: 10.7% (10.9
%) Hydroxyl value 369 (calculated value 379) IR (liquid film, cm ^-1 ): 3050-3650, 2930,
2855, 1450, 1370, 1190, 1160~970 1H-NMR (CDCl ₃ , TMS internal standard, δ) 0.87 (singlet, 3H, CH ₃ -) 1.1 ~ 1.7 (singlet, 24H, -CH ₂ -) 1.7 ~2.3 (multiplet, 4H, −CH ₂ CH=CHCH ₂
−) 3.3 to 4.4 (multiplet, 8H, C ₂ −H to _{C 6} −H,
C ₆ −OCH ₂ −) 3.38 (singlet, 3H, −OCH ₃ ) 4.88 (multiplet, 1H, C ₁ −H) 5.2 to 5.5 (triplet, 2H, olefin proton) Next, Examples 1 to 5 ^13C- of the compound of the present invention
NMR data is shown in Table 2.

[Table] Test Example 1 The hygroscopicity and moisturizing properties (Note 1) of 1-O-methyl-6-O-alkylgalactofuranoside were tested to compare their performance as humectants. The results are shown in the table below.

[Table] Test Example 2 An emulsification test (Note 2) of 1-O-methyl-6-O-alkylgalactofuranoside was conducted to compare the performance as an emulsifier. The results are shown in the table below.

[Manufacturing method]

~ was mixed to make it homogeneous. The resulting aqueous solution blended well into the skin and had a moist feeling when used, making it suitable as a cosmetic lotion. Application Example 2 Emulsion: An emulsion having the following composition was prepared using 1-O-methyl-6-O-n-dodecylgalactofuranoside. [Composition] Squalane 8.0 (wt%) Vaseline 2.0 1-O-methyl-6-O-n-dodecylgalactofuranoside 4.0 Ethanol 5.0 Glycerin 4.0 1% aqueous solution of carboxyvinyl polymer 20.0 Potassium hydroxide 0.1 Purified water Remaining amount [Production method] , , , are mixed and heated to 70℃. This was gradually added to and emulsified while stirring into ~, which had been mixed and heated in advance. After the mixture was added and mixed uniformly, it was uniformly emulsified using a homomixer and cooled to room temperature. The emulsion thus obtained had excellent properties as a cosmetic emulsion, with a strong moisturizing feeling when applied to the skin after use. Application Example 3 Lip Cream: An emulsion having the following composition was prepared using 1-O-methyl-6-O-methyl branched isostearylgalactofuranoside. [Composition] Liquid paraffin 32.0 (wt%) Carnauba wax 8.0 Microcrystalline wax 12.0 Jojoba oil 8.0 Vaseline 10.0 1-O-methyl-6-O-methyl branched isostearyl galactofuranoside 5.0 Propylene glycol 5.0 Purified water Remaining amount [ Manufacturing method] Heat the . . The obtained emulsion was a slightly soft solid W/O emulsion with a milky white luster, and when molded into a rod shape, it had properties suitable as a lip cream.

Claims (1)

[Claims] 1 Formula (), 1-O-methyl-6-O-alkylgalactofuranoside represented by the formula (wherein R is a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 8 to 24 carbon atoms).