JPS60163894A - 1-o-methyl-6-o-alkylgalactofuranoside and cosmetic containing same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is 8-24C aliphatic hydrocarbon group). EXAMPLE:1-O-Methyl-6-O-n-octylgalactofuranoside. USE:A cosmetic base. PREPARATION:1,2:3,4-Di-O-isopropylidene galactopyranose obtained by the reaction of galactose with acetone is made to react with the compound of formula RX (X is halogen) in an alkaline aqueous solution in the presence of a phase- transfer catalyst (e.g. quaternary onium salt) to effect the etherification of the 6-OH group. The resultant 6-O-alkyl-1,2:3,4-di-O-isopropylidene galactopyranose of formula II is subjected to the solvolysis in methonol in the presence of an acid catalyst such as a protonic acid to effect the removal of the protecting group and obtain the objective compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel monosaccharide derivatives, 1-0-methyl-6-
The present invention relates to 0-alkylgalactofuranoside and cosmetics containing the same.

In the oil and fat chemical industry, polyhydric alcohols such as glycerin, zoglycerin, sorbitol, mannitol, and sugars are widely used as one of the highly hydrophilic raw materials such as baking soda. In addition, these polyhydric alcohol esters and ethers are widely distributed in the natural world, and play an essential role in the life activities of living things, as well as in detergents, foods, industrial chemicals, and pharmaceuticals. As many industrial products, they also contribute greatly to human daily life.1 Traditionally, polyhydric alcohols have been subjected to esterification or etherification reactions (however, in this case, alkylene oxide type ether compounds are mostly used), etc. Attempts have been made in many fields to synthesize and apply nonionic surfactants.

Among these polyhydric alcohol derivatives, sorbitan fatty acid esters derived from turbyol, which is one of the sugar alcohols, and its ethylene oxide adducts are particularly popular in the industry due to their characteristic emulsifying properties and safety. It is used in a wide range of fields including pharmaceuticals, cosmetic bases, food additives, and pharmaceutical bases. In addition, sucrose fatty acid ester, which is one of the two types of sucrose, is also used due to its safety and good biodegradability.
It is applied in the fields of food, pharmaceuticals, cosmetics, detergents, etc. (for example, Oil Chemistry, Vol. 16, Vol. 3).
95-401 (1967)). On the other hand, sugar alcohols (e.g., maltitol), which are trisaccharides in which linear monosaccharides and monocyclic monosaccharides are ether-linked, are expected to be applied to cosmetic bases as moisturizing agents (e.g., , Hlegfunszoyanar (Bian 14), pp. 86-9
3 pages (1975)).

In addition, regarding octyl β-D-glycoside derived from D~glucose, which is one of the representative monosaccharides,
Since it is effective as a softening agent for phosphorous membranes, its application to pharmaceutical bases has been reported (for example, B
iOCbemittry, Vol. 20, p. 6776 (1981)). Similarly, it has been disclosed that a derivative obtained by alkylating the 3-position of the D-glucose skeleton is effective as an antitumor agent (% Kaisho). 56-103196, etc.).

Researchers have focused on the above-mentioned usefulness of polyhydric alcohols, especially saccharides, and have been studying the use of saccharides that are abundantly present in nature. As one of the achievements, we recently discovered mono- and sialkyl ethers of D-mannitol and proposed the use of these as cosmetics (Japanese Patent Application No. 138-227-1987).
).

The present inventors further conducted intensive research to chemically modify galactose, which is a monocyclic monosaccharide, to obtain a useful surfactant, and as a result, they made galactose act with chthon, After protecting the four hydroxyl groups, the free hydroxyl group at the 6-position is treated with an alkylating agent, and then the protecting group is removed with methanol A to obtain a galactoninoside with ether bonds at the 1- and 6-positions. The inventors have discovered that the compound is useful as a cosmetic base, and have completed the present invention.

That is, the present invention provides 1-0- expressed by the following formula (1) % formula % (wherein, Rid represents a saturated or unsaturated straight-chain or branched aliphatic hydrocarbon group having 8 to 24 carbon atoms) The present invention provides methyl-6-0-alkylgalactofuranoside and a cosmetic containing all of the same.

By the way, galactose! As the alkyl ether compound to be introduced, 6-0-dodecylgalactose has conventionally been used as a general III active agent (Ten5ide Detergente).

Vol. 15, pp. 72-74 (1978) Synthesis and reactions of alkyl galactoside compounds having various chain lengths (Pharmaceutical Journal, Vol. 79, Vol. 8)
Pages 0 to 83 (1959), Oar baby4
r, Res, Vol. 25, pp. 59-65 (197
2 years) etc.) are known. However, the formula (1
); 7'(1-0-methyl-6-〇-alkylgalactofuranoside has not been described in any literature and is a new compound.

The 1-0-methyl-6-0-alkylgalactofuranoside (1) of the present invention is preferably produced by the reaction shown in the following formula.

t＞:t't-<'1 1.2:3.4-C〇-isoderopylidenegalactobinose ([1) 6-o-alkyl-1,2:3.4-C〇- Inzolobylidene galactopyranose (IV) (In the formula, R has the meaning described above and is a halogen atom, etc.) That is, first, galactose is exposed to acetone according to a known method, so that the four hydroxyl groups are retained. Captured 1 and 2:
3,4-C0-isopropylidene galactose (U)
Journal of An18rlCan Oh
θnoical 5ociθ℃y,.

Volume 76, pages 3188-3193 (1954)
). Next, the obtained galactose diacetonide (0) is fully exposed to an alkylating agent by a known method to etherify the free hydroxyl group at the 6-position. give M to implement this industrially
An advantageous method includes etherification with an alkaline earth metal using a phase transfer catalyst typified by a quaternary onium salt. According to this method, etherification proceeds under mild conditions, and the desired 6-0-alkyl lactopyranose diacetonide (IV) is obtained in a good yield. The obtained 6-0-alkylgalactobyranose diacetonide (IV) is solvolyzed in methanol in the presence of an acid catalyst such as a protic acid to completely remove the pus-retaining group, and the desired 1-0- Methyl-6-0-alkylgalactofuranoside (1) is obtained.

More detailed reaction conditions of the above reaction are as follows.

The etherification reaction of galactobyranose diacetonide (II) is preferably carried out in the presence of an alkaline substance. Examples of alkaline substances include alkali metal hydroxide, alkali metal carbonate, alkali metal phosphates, etc. Among these, alkali substances such as sodium hydroxide and potassium hydroxide Metal hydroxides are industrially preferred. The amount of alkaline substance used is galactobiranose diacetonide (II)
91 to 10 mol per 1 mol is suitable, and the alkaline substance has a content of 10 to 80%, more preferably 40 to 60%.
It is best to use it as a water bath solution. As the etherification agent, alkyl halides, alkyl sulfonic acid esters, and alkyl sulfate esters are used. Among these, preferred etherification agents include alkyl halides. Particularly preferred etherifying agents are alkyl bromides and alkyl iodo-12-dites. 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 octyl, dodecyl, decyl, and straight-chain aliphatic hydrocarbon groups.
Cetyl, stearyl, oleyl, etc. are excluded, and branched aliphatic hydrocarbon groups include 2-ethylhexyl, 2-ethylhexyl,
heditylundecyl, 5,717-”) methyl-2-(
1,3,3-trimethylbutyl)octyl and the following formula (where m is the total number of kidneys from 4 to 10, n is an integer from 5 to 11, rn-1-n is 11 to 17, And m=7
+n=8? A methyl-branched isostearyl group, etc., shown as 1'l (with 1'l at the apex), etc., is rubbed off. The amount of the etherification agent to be used is suitably 2 to 10 mol, preferably 2 to 4 mol, per 1 mol of galactobylanose diacetonide ([D).

The etherification reaction of galactopyranose diacetonide (I) is preferably carried out in the presence of a catalytic amount of the 41J1 onium salt. Ammonium salts are preferred for ease of use.Specific examples of quaternary ammonium salts include tetraalkylammonium salts (e.g., tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmenal ammonium chloride, lauryltrimethylammonium chloride). ,
stearyltrimethylammonium chloride, etc.):
A group of alkylammonium salts with i-broken oxyalkylene groups (e.g., tetraoxyethylenestearyldimethylammonium chloride, bistetraoxyethylenestearylmethylammonium chloride, etc.)
;Betaine compounds, crown ethers, amine oxide compounds, ion exchange resins, etc. are cooled. These quaternary onium compounds are 0.01 to 0.20 mol per 1 mol of galactobylanose diacetonide (II),
It is preferable to use 0.05 to 0.10 mol.

In addition, as the reaction solvent, any solvent that does not affect this reaction can be used, and among these, aliphatic hydrocarbons such as hexane, hezotane, and octane,
Alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, 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°C.
The temperature is ~60°C, and by vigorous stirring, etherification is completed in several hours to over ten hours. The reaction product is treated by a conventional method and then distilled under reduced pressure to obtain p, 6-o
-Alkylgalactopyranose diacetonide (■) can be obtained. By subjecting the crushed compound (IV) to solvolysis using norotonic acid as a catalyst, 1-0-methyl-6-0-alkylgalactofuranoside (1) is obtained. Solvolysis is preferably carried out by heating in methanol using a zolotonic acid catalyst such as sulfuric acid, saltwater, nitric acid, phosphoric acid, benzenesulfonic acid, or acetic acid. 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, 1-0-methyl-6-〇-alkyl galact 16 can be obtained in a higher yield than 6-0-alkylgalactobyranose diacetonide (IV). - Furanoside (1) is obtained.

The thus obtained 1-0-methyl-6-0-alkylgalactofuranoside (1) of the present invention has a lower melting point due to the effect of the O-methyl group at the 1-position, and becomes liquid even at room temperature. There are many things.

Next, the properties of a typical compound of the present invention compound (1) are as follows.

Table 1 Umbrella Performance of the product of the present invention 1-0-Methyl-6-0-alkylgalactofuranoside (1) exhibits relatively high hygroscopicity as t' has a small number of carbon atoms in R in formula (1). However, on the other hand, long alkyl groups′
ft, and as the number of carbon atoms in H increases, it becomes easier to form liquid crystals, which makes it difficult to release moisture once absorbed. In particular, those in formula (I) in which R has 8 to 18 carbon atoms are useful as moisturizing agents for cosmetics because they have a good balance between moisture absorption and moisture release resistance.

Furthermore, those having 14 or more carbon atoms in formula (1) have strong emulsifying power and are useful as emulsifiers for emulsified cosmetics.

The amount of these compounds incorporated into cosmetics may vary depending on the hardness of the product, but when used as a humectant, the amount is 5 to 50% by weight, and when used as an emulsifier, it is 0.2 to 15% by weight. is appropriate.

As mentioned above, the 1-0-methyl-6-〇-alkylgalactofuranoside of the present invention does not have bonds such as ester groups that are easily diluted, so it is chemically stable, and there is little irritation to the skin. Because of its active properties, it is useful as an emulsifier, self-emulsifying oil, wetting agent, and thickener, and has a wide range of applications 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-c〇-inzolobylidene galactopyranose
1! D-galactose 2007, acetone 2.5 in a four-necked reaction vessel! and while stirring vigorously, add 240 tons of anhydrous expanded zinc finely ground at room temperature and concentrated sulfuric acid B tne.
Add.

After continuing stirring at room temperature for an additional 4 to 5 hours, the mixture was neutralized with an aqueous solution containing 4009@ of sodium carbonate, and further 9 equivalents of sodium bicarbonate were added, and stirring was continued for a while. After neutralization, the reactor was kept overnight to allow all salts to precipitate out. The precipitated salts are removed by furnace, and the P solution is concentrated under reduced pressure to obtain a pale yellow viscous liquid. The resulting viscous liquid was mixed with chloroform (5
After dissolving in 00g), the solution is washed with 2001nl of water to completely remove inorganic salts. Then, chloroform was distilled off under reduced pressure, and the mixture was distilled under reduced pressure to obtain a viscous colorless and transparent liquid of 1.2:3.
．． 4-C0-inzolobylidene galactose 227g
The obtained fCo yield was 78%.

Boiling point 132-140℃ (Q, 8mmHg) Literature value 110-120℃ (0.1-0.2mmHg) Literature, rOurna'l of American Ch
Chemical Society, +Volume 76, No. 318
8 to 3193 (1954) Reference Example 2 Synthesis of methyl branched instearyl alcohol: In a 201 autoclave, isozolobyl isostearate [EMIJ-(Il:mθry) 2310
Isostearic acid inzolopyl ester, commercially available from Emery Co., USA] 4170 and a copper chromium catalyst (
Prepare 239 Pi (1 Vol.). Next, 97cm to 150
The reaction mixture was then heated to 275°C. 15 ol (9/cv?).
After hydrogenation at /275°C for about 7 hours, the reaction product was cooled and all the catalyst residue was removed by filtration to give a crude product of 350°C.
(1 was obtained. By distilling the crude product under reduced pressure, 80
Colorless and transparent isostearyl alcohol 33 as a fraction of ~b
I got 0Llfc. The resulting instearyl alcohol (
Monomethyl branched isostearyl alcohol) C, acid value 0
．． 05, saponification value of 5.5, and hydroxyl value of 181.4. 3340, 1055crn for engineering R (liquid film)
-', δ3.50 in NMR (00/4 bath medium)
(Broad triplet line, 23-10H2-OH) showed absorption. According to the gas chromatograph, the main components of this alcohol are those in which the total number of carbon atoms in the alkyl group is 18, accounting for approximately 75 units, and the remaining components are those in which the total number of carbon atoms is 14.16, and branched methyl groups. It was found that all of these are mixtures of molecules located near the center of the alkyl main chain.

Reference Example 3 Synthesis of methyl branched isostearyl bromide: 5! equipped with a thermometer, reflux condenser, and stirrer. On the kita ware of
Methyl branched isostearyl alcohol 8131 (3 mol) obtained in Reference Example 2, 147% aqueous solution of hydrogen bromide and hydrogen bromide 132 F (6.1 mol), and trimethylstearylammonium chloride 50.1f (0.15 mol) 100~ in a mantle heater while stirring.
Heat to 120°C. After stirring at this temperature for about 6 hours, gas chromatography of the reaction mixture shows that the peak of methyl branched isostearyl alcohol has disappeared. After the reaction product is completely cooled, the entire organic layer is collected by liquid separation. Add ether (1,5) to the lower layer (aqueous layer) and extract with ether. Diether layer by separation? Collect. The organic layers obtained earlier are combined and an aqueous sodium bicarbonate solution is added to neutralize the remaining acid content. Diether J- was collected by liquid separation, and after adding Glauber's salt to it and drying it,
The ether was distilled off under reduced pressure, and then distilled under reduced pressure.
Methyl branched isostearyl bromide 24-de 800f was obtained. Yield 80g6 Boiling point 145-169°C (0.3mmHg) IR (liquid film, cIn-'') 1200-1300.720.640.
56O NMR (0014, δ, TH8 internal standard) 3.30 (
Triple line, J = 7. OHz, -OH2Br) Elemental analysis 016 Hp Br (calculated value) C64
,7%<64.85chi):Hll,2%(11,1,
9%): Br24.4% (23,97%) average molecular weight (
vpo method/H (!01. ) 327 (calculated value 333)
Example 1 Synthesis of 1-〇-methyl-6-0-methyl branched isostearyl galactofuranoside: (1) Reflux condenser, thermometer, dropping funnel and stirring equipment.
96 t of 0% aqueous sodium hydroxide solution (48 f (1.2 mol) of sodium hydroxide), 1 obtained in Reference Example 1.

2: 3.4-cy0-isozolobylidene galactobylanose 52.1 r (0.2 mol), n-hexane 18
U++++/! , 13.6 t (0.02 mol) of 50% tetrabutylammonium hydrogen sulfate aqueous fa solution were added in this order, and the mixture was kept at 25°C in a water bath and stirred slowly. Isostearyl bromide 1 obtained in Reference Example 3
00t (0.3 mol) was added dropwise little by little. After about 1.5 hours in which all the methyl branched isostearyl bromide was added dropwise, the temperature of the reaction mixture was raised to 50-55 DEG C. and stirred at this temperature for 20 hours. After confirming that galac 1-% lanosezoacetonide had completely disappeared by gas chromatography of the reaction mixture, 40 Ovl of water was added and stirred, followed by complete irradiation. After collecting the organic layer, hexane is distilled off under reduced pressure. The residue was then subjected to vacuum distillation to obtain 87.8fk of 6-0-methyl branched isostearyl-1.2:3.4-cy-0-isozolobylidene galactobyranose as a colorless transparent liquid.

Yield 87.4%.

Point 205-240℃ (0.3mmHg) Elemental analysis 03o"5aOi (calculated value) 0: 70.5%
(70,26%), H: 11.3% (11 swords 1%) ■R
(Liquid film, country-') 1380,1255,1215゜1170.1110,1070.1000IH-'NM
R (CDCl2. TMS internal pressure, δ) 5.50 (2
m-line, I H# 0+-H)2 l-3,35~4.70 (multiple i# f3H,0,-H
~06-HC"-0-OH2-) 1.25, 1.29, 1.33, 1.43 (4 -N
line, 12H, two ingropylidene groups) (11) 1j equipped with a reflux condenser, thermometer, and stirring device
57 t (0,111
-t-, A, ), methanol 20Of, and while stirring in the water bath, concentrated sulfuric acid 91 (methanol 91
Add the solution of 1F) little by little. After the dropwise addition was completed, the temperature of the reaction mixture was gradually raised and stirred at 40 to 45°C for about 1 hour. The reaction mixture turned into a homogeneous solution. After further stirring at the same temperature for 5 to 6 hours, the reaction mixture was cooled, and the acid content was completely neutralized with bicarbonate. After removing the formed precipitate separately, methanol is completely distilled off under reduced pressure. Furthermore, drying was performed at 50 to 60° C. for about 3 hours under reduced pressure (5 mmHg). 48 t of 1-0-methyl-6-0-methyl branched instearyl galactofuranoside was obtained as a colorless transparent liquid. Yield 97.2%.

Elemental analysis CM Hllill o, as (calculated value) 0
: 66.4% (67.2%), H: 11.3 whispers (11
, 3 whispers) Hydroxyl value 370.3 (376,9) IR (liquid film, α-ri 3660-3000, 1460).

1375, 1195.1210.1020-1100.
870 IH-NMR (CD0I3.TMB internal standard, δ)3
．． 2 to 4.3 (multiple, llH, o, -H~0, -H+
3 OH 〇, -0-OH,-)4.7~4.95
(Multiple line, IH, (31-H) 3.37 (- double line, 3
H* Oc1! J) Example 2 Synthesis of 1-〇-methyl-5-0-n-octergalactof 2-noside: (1) In (1) of Example 1, octyl bromide (0
, 3 mol)'t- was used, but the etherification was carried out under the same reaction conditions. A colorless and transparent liquid was obtained by total vacuum distillation. 6-0-n-octyl-1,2:3.4-celow isozolobylidene galactobyranose 61.8f was obtained.

Yield 83%.

Boiling point 150-170℃10.4mmHgElemental analysis
0. oH380, (calculated value) 0: 64.6% (
64.5%), H: 9.7% (9.7%) engineering R (liquid film μm 1380, 1255.121U.

1110.1070.1065, 101000IH-B
I(01)C1s, TME internal standard, δ)5.
50 (double line, tu+at-H) 3.35-4.70
(Multiple lines, 8H, 0, -H to 39-06-HC, -0-%-) 1.24, 1.30, 1.34, 1.44 (4 singlets, 12H, 2 lines) isozolopylidene group) (II
) In (11) of Example 1, in place of 6-0-methyl branched isostearyl-1,2: 3,4-cy〇-inzolobylidene galactopyranose, (1
) obtained 7'c6-0-octyl-1,2:3,4-celowisozolobylidenegalactobyranose? r0.11
All solvolysis was carried out under the same reaction conditions except that 1 mol was used. 1-0-Methyl-6- as a colorless liquid.

-n-octylgalactofuranoside 32.2f was obtained.

Yield 85%.

Elemental analysis As 016H2906 (calculated value) 0: 5
8.5% (59.0%) H: 9.5% (9.57%) Hydroxyl value 550 (551) IR (Liquid film 1 country - 1) 3660-3000° 1455.
1370,1210.1045-1110.860 IH-NMR (ODOlg, TMB inner #Muku L δ) 3
．． 35 to 4.3 (multiple line 111H, C, -H to C6-H
+3 ke C H+O, -0-CH,-) 4.75~5.0
(multiple thoughts, IHIO, -H) 3.38 (-4 is a line, 3H
,0-OR,), -1, blank Example 3 Synthesis of 1-〇-methyl-5-0-n-dodecylgalactofuranoside: Mark In (1) of Example 1, instead of methyl branched isostearyl bromide and n-dodecyl bromide (0
The chemical reaction was carried out under the same reaction conditions, except that 3 mol of ether was used. Colorless and transparent viscous liquid 5-Q-
n-dodecyl-1,2:3,4-cy-0-isozolobylidene galactobyranose 68.6f lost in vacuum distillation.

Yield 80%.

-q Chi - Boiling point: 185~b Elemental analysis: O+4H4<O@ (calculated value) 0:6
7.4% (67.3%), H: 10.6% (10.6%
) IR (liquid film, cln-'): 2990, 293
0, 2860°1380.1255,1210,11
10゜1070.1065.1UOO' H-NMR (00013, T M 8 internal standard, δ
) 5.50 (21 line + I H+ O+ -H) 3.4
~3.7 (multiplet +8H+O!-HNO3-11°Oa
-00H! -) (11) In (11) of Example 1, 6-0-methyl branched instearyl-1,2: 3 #4-C〇-
6-on-dodecyl-1,2:3+ obtained in Example 3 (1) in place of inzolobylidene galactopyranose
4-C〇-Isozolobylidene galactobilanose'i
All solvolysis was carried out under the same reaction conditions except that 0.111 mol was used. A colorless liquid 1-〇-methyl-6-〇-n-dodecylgalactof 2-noside 22,92 was obtained.

Yield 57%.

Elemental analysis: As On Has Os (calculated value) C:
62.7% (63,0%), H: 10.5% (10,6
%) Hydroxyl value 453 (calculated value 464) Engineering R (y film, cm −' ): 30511-370
0 t2925.2855,1450.1370°11
85.1160-970,940,870'H-NMR
(OL) C13, TMS Naiyuki Jun, δ) o, 87 (-N
line, 3H1 commander 3) 1.1~17 (-double line, 2t)H, -0 ground-) 33~4
．． 3.
Multi-lane + I Hr Ct -H) Example 4 l-o-methyl-6-o-stearylgalactofuranoside 0 synthesis: (1) In (1) of Example 1, instead of methyl branched isostearyl bromide, Etherification was carried out under the same reaction conditions except that n-stearyl bromide (0,3)'r was used. Colorless transparent viscous liquid 6-0-n-
53.3 r of stearyl-1°2:3.4-isozolobylidenegalactobinose was obtained by vacuum distillation.

Yield 75.4%.

Boiling point 220-225℃/Q, 4mmHg elemental analysis
C3oH5aOa - ((ti calculation m) 0: 7112
% (70,26%), El: 11.2% (11,
01%) Engineering R (liquid film, m-') 13B0, 125
5 p1215.1170,1110.1070゜0
00'H-NMR (C!DO13, TM8 internal standard, δ)5
．． 5o (2i line r I Hr 01-H) 3.38~4
．． 70 (Multiple line, 5H, 02-H to 06-H) 3.48 (Triple line, 2n, a6-o-0H2R
') 1.23.1.3U, 1.32, 1.44 (4 singlets, 12H, 2 isozolopylidene groups) j, :J
l'-margin-q 〇-OH.

(11) In Example 1 (I), 6-O-methyl branched isostearyl-1,2:3,4-cy 0-isozolobylidene galactopyranose was replaced with (1) in Example 4.
) 6-o-n-steary, A-1+2:314
-C〇-Inzolobylidenegalactopyranose'i0
．． All solvolysis was carried out under the same conditions except that 111mo)b was used. White crystalline 1-0-methyl-6-〇-
n-stearyl gasictofuranoside 28t'? I got it.

Yield 54.2%.

Melting point 67-71℃ Elemental analysis 025H5oOs (calculated value) 0: 6
6.8% (67.2%) H: 11.3chi (11.3%)
Hydroxyl value 367 (376,9) IR (KBr, cIn-') 3600-3000°14
60.1370.1190,121tl.

1020-1110.865' T(-NMR(CD013, T M 8 internal extension, δ) 33-4.3 (multiplet, 11H,O!-H~c
6-H+3 OH+06-0-OH,R') 4.7~
4.95 (Multiple line, IH, O, -H) 3.37 (-Hikikai 3H, 0OH3) Yoshi 1・Riki 2- 40 Example 5 l-o-methyl-6-〇-oleylgalactofuranoside Synthesis: (1) In (1) of Example 1, oleyl bromide (0
, 3 mol) was used all around, but the etherification was carried out under the same reaction conditions. Colorless and transparent viscous liquid 6-0-oleyl 1,2:3.4-cy0-isozolobylidene galactopyranose 80.89 k was obtained by vacuum distillation. Yield 79%.

Boiling point: 215-b Elemental analysis: As 40g of CsoHs (calculated value) 0:
70.5% (70,6%) H: 10.6 attack (10,7
%) Engineering R (liquid film, cll-'): 2990.293t1
．． 28601380.1255,1210,1110°1070,1065 . 1010 00IH-14 (CDCl2. TMS internal standard,
δ) 5.50 (doublet, IH, 0l-H) 5.2~5.5 (multiplet, 2H, olefin) 3.4~
3.7 (multi-N line + 8 EI + Cz -H~O, -
H.

0, -00H2-) (i) In (11) of Example 1, in place of 6-0-methyl branched instearyl-1,2:3.4-cy0-isozolobylidene galactopyranose, Example 5 of (1
) 6-0-oleyl-1,2:3.4-C〇-
All solvolysis was carried out under the same reaction conditions except that 0.111 mol of isozolopylidene galactopyranose i was used. Colorless liquid 1-0-methyl-6-〇-43-oleylgalactofuranoside 36. I got Of.

Yield 73%.

Elemental analysis: 025 as H41106 (calculated value) 0
: 67.0% (67.5chi), H: 10.7% (10,
9%) Hydroxyl value 369 (calculated value 379) Engineering R (liquid film pcPR-') 3050-3650°29
30.2855.1450,1370°1190.11
60-970' H-NMR (cl) Q13, T M 8l part standard, δ) 0.87 (- heavy line, 3 H* -OH3-
) 1.1 to 1.7 (-m line *24a, -aH, -) 1.
7-2,3 (multi-N line, 4 El, -0H20H=
cncaz-) 3.3-4.4 (multiplet, 3H,O,-?-06-
H.

c6-OcI(z -) 3.38 (- double line, 3H, -00Hs) 4.88 (polyN
line, l H, C1-H) 52-5.5 (three l line, 2H
, olefin zolotone) Next, the 130-NMR data of the compounds of the present invention of Examples 1 to 5 are shown in the second column.

Margins below 44--46- Example 6 All tests on hygroscopicity and moisturizing properties (Note 1) of i-o-methyl-6-〇-alkylgalacto-7lanoside were conducted to compare its performance as a humectant. The results are shown in the table below.

Table 3 (Note 1) Hygroscopicity: 2. Ot: m x 2. Ot:
Place 1.0Of of the pre-dried test compound in a cylindrical glass container of Rg, let it stand at constant temperature and humidity of 25°C and 93% humidity, measure the change in weight, and calculate the hygroscopicity using the following formula. I met.

Moisture retention: 1.00r of test compound containing water 'klU% in a cylindrical glass container of 52r2.0cIRX2.0cIn
t, humidity 20%, constant temperature and humidity of 25℃,
All changes in the amount of N were measured, and the moisture retention property was calculated from the following formula.

×100 From the results of this test, does 1-o-methyA--6-0-alkylgalactofuranoside have appropriate hygroscopicity and moisturizing properties? ＋ [and was suitable as a moisturizing agent for cosmetics.

Example 7 An emulsification test (Note 2) was conducted on 1-0-methyl-6-o-alkylgalactofuranoside to compare its performance as an emulsifier. The results are shown in the table below.

Table 4 (Note 2) Emulsification test: Flow) Mix 2 parts of the test compound with 28 parts of Q rough-in and heat to 75°C.

Separately, 70 parts of ion-exchanged water was heated to 75° C., and added to the liquid Q rough-in and test compound while stirring, and emulsified. Thereafter, the mixture is cooled to room temperature while stirring at 49°C. Immediately after observing the emulsified state, the mixture was left to stand for 1 k at 25°C, and the separation rate was calculated using the following formula.

×100 From the results of this test, l-〇-methyl-6-〇-alkylgalactofuranosides with H in the formula having 12 or more carbon atoms have emulsifying power, those with 12 to 18 carbon atoms, IIO/W emulsions, It has become clear that a W10 emulsion can be obtained with a methyl branched isostearyl group.

Example 8 Lotion: A mixture having the following composition was prepared using 1-0-methyl-6-0-n-octylgactofuranoside.

〔composition〕

■1-0-methyl-5-0-n-octylgalacto7lanoside xoiJ (ml garden) ■Glycine 1.0 ■Sodium pyrrolidone carmenate 2.0 ■Ethanol 12.0 ■? Lioxyethylene lauryl ether 3 1.5 ■Fragrance 0.1 ■Purified water Remaining amount [Production method] ■~ were mixed to make it homogeneous. The resulting aqueous solution was suitable for use as a makeup lotion and had a smooth feeling on use of 50%.

Example 9 Emulsion: ■ An emulsion having the following composition was prepared using -0-methyl-6-0-n-dodecylgalactofuranoside.

〔composition〕

■Squalane 8.0 (□%) ■Vaseline 2.0 ■1-o-methyx-6-0-n-dodecylgalactofuranondo 4.0 ■Ethano-A-5,0 ■Glycerin 4.0 0 cal l Kisibini A-7 Lima 1% aqueous solution 20.0 ■Potassium hydroxide 0.1 ■Purified water Remaining amount [Production method] ■, ■, ■, ■All mixed together and heated to 70C.

This is mixed and heated in advance, and then gradually added to (1) to (2) while stirring to emulsify. After adding and mixing uniformly, the mixture was uniformly emulsified using a homomixer and cooled to room temperature. When the emulsion thus obtained was applied to the skin, it had a strong sticky feeling after use and had excellent properties as a cosmetic emulsion.

Example 10 Lip balm: An emulsion having the following composition -ζ q - was prepared using 1-o-methyx-6-0-methyl branched isostearyl galacto 7lanoside.

〔composition〕

■Carnauba wax 80 ■Microcrystan wax 12.0 ■Hohono 2 oil 8.0 ■Vaseli 7 10. U Ol-0-methyl-6-〇-methyl branched isostearyl galactofuranoside 5.0 Zoropylene glycol 5.0 ■Remaining water [Production method] Heat ■～■ to 85℃ and mix uniformly. And this ■,■
Complete heating, add the mixture, stir thoroughly to emulsify, and then immediately pour into a molding machine and cool.

The obtained emulsion was a slightly soft solid W10 emulsion with a milky white luster, and had properties suitable for use as a lip balm when molded into a rod shape.

Applicant: Kao Soap Co., Ltd. 1"-1)] Nobuo Ben 9, 1", ゛i, -, j 34- Procedural amendment (spontaneous) 1. Indication of the case 1980 Patent Application No. 17992 -32 Title of the invention 1-o-Methyl-6-〇-alkylgalactofuranoside and cosmetics containing the same 3. Relationship to the amended case Applicant address 1-14 Kayabacho, Nihonbashi, Chuo-ku, Tokyo No. 10 Name (091) Kao Soap Co., Ltd., ・;”1゛:.

1 6. Column 7 of "Detailed Description of the Invention" of the specification to be amended, contents of the amendment (1) In the specification, page 14, line 7 [2 to 10 mol is appropriate, preferably 2 ” should be corrected to read “1 to 10 moles are appropriate, preferably 1.2”.

(2) Same, page 29, line 6

Claims (1)

[Claims] 1. Represented by formula (1), ROOH,oH (wherein R is a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 8 to 24 carbon atoms) 1-0-Methyl-6-o-alkylgalactofuranoside. 2, 1-0-methyl-6- represented by ROOH,OH (wherein R is a saturated or unsaturated straight-chain or branched aliphatic hydrocarbon group having 8 to 24 carbon atoms) A cosmetic containing 〇-alkylgalactofuranoside.