JPS61140595A - Production of sugar phosphate - Google Patents

Abstract

PURPOSE:To produce the titled compound having excellent heat-insulation, with simple procedure, economically on an industrial scale, without necessitating the introduction of a protective group to the sugar skeleton, by reacting a specific phosphoric acid monoester with glycidol. CONSTITUTION:The objective compound of formula I can be produced by reacting 1mol of a phosphoric acid monoester (salt) of formula II (R1 is active hydrogen residue of glucose; M is H or cation) (e.g. glucose-1-phosphate) with preferably 1-5mol of glycidol of formula III in the presence of an inert solvent (preferably water) at 40-90 deg.C.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to the following general formula (1) (wherein R1 represents an active hydrogen residue of glucose, and Mi
jH represents a cation) The present invention relates to a method for producing a sugar phosphate ester represented by:

[Conventional technology]

BACKGROUND ART Conventionally, humectants have been added to shampoos, conditioners, cosmetics, etc. for the purpose of imparting a moist feel to the hair. Conventional humectants used include propylene glycol, glycerin, urea, sorbitol, alkylene oxide adducts of alcohol, and the like. However, these were not satisfactory in terms of moisture retention, moisture absorption rate, etc.

On the other hand, hydroxyl group in the structure? It is known that compounds with riether groups exhibit moisturizing and hygroscopic properties9.
From this point of view, glucam E-
1O (Amarsha), etc. are available. However, this also had low moisturizing properties under low humidity conditions, and was not satisfactory as a moisturizing agent in terms of feeling such as stickiness.

Under such circumstances, as a result of various studies, the present inventors have
It has been found that a compound represented by formula (1), in which glycerin having a hydroxyl group is introduced into a sugar phosphate ester, has excellent moisturizing properties.

However, as a method for producing the sugar phosphate ester represented by formula (I), a method of hydrolyzing tichonic acid (Telchonic acid) extracted from Durham-positive bacteria is known (Bloeh@m, J., 15
1 (1975)), and no chemical synthesis method was known. A method for chemically synthesizing the β form of the compound represented by formula (1) is known (Bioorg, Khim
, 3-248, (1977)), but this method also required complicated operations such as introduction and removal of a protecting group, and therefore could not be said to be suitable as an industrial production method.

[Problem that the invention seeks to solve]

Therefore, it has been desired to develop a chemical synthesis method that allows industrial production of the compound represented by formula (1).

[Means for solving problems]

Under such circumstances, the present inventors completed the present invention as a result of intensive research.

The method of the present invention is shown by the following reaction formula.

0M 0 0M QHO1'1 (Summer) (In the formula, R1 and M have the same meanings as above) That is, in the present invention, the phosphoric acid monoester is its salt (1)K
Sugar phosphate ester (1
).

The active hydrogen residue of glucose represented by R1 in the general formula (1) of the present invention is a glucose molecule obtained by removing one hydrogen atom of the hydroxyl group, and for example, the active hydrogen residue of glucose represented by the formula (1). Acid%/, Zsteel glucose-1-
IJ phosphate, glucose-2-phosphate, glucose-4-
Examples of phosphoric acid and glucose-6-phosphate include salts thereof. Glucose may have other hydroxyl groups protected with a protecting group. Examples of protecting groups include acetyl,
Examples include benzyl, pensoyl, methylene acetal, inzolobylidene acetal, and the like. Further, M in the general formula (1) of the present invention refers to a cation such as an alkali metal, an alkanolamine, a basic amino acid, or ammonia. For example, the alkali metal is sodium, potassium, etc., and the alkanolamine is ethanolamine. ,
Examples of the basic amino acid include triethanolamine and the like, and examples of the basic amino acid include arginine and lysine, and sodium and potassium monosalts are preferably used.

K used in the present invention is reacted with glycidol represented by the formula (formula) in an amount of 1 to 10 times the mole, preferably 1 to 5 times the mole, with respect to the phosphoric acid monoester represented by the formula (character). The reaction is carried out in the presence of an inert solvent for 30 to
It is carried out at a temperature of 150°C, preferably 40-90°C.

As the inert solvent, for example, polar solvents such as water, methanol, ethanol, and isoglono-9ol are used, and among them, water is particularly preferred.

In addition to the sugar phosphate ester represented by the general formula (ri), which is the object of the present invention, the reaction product includes an inorganic salt as a by-product,
Unreacted phosphate or glycidol or its derivatives? Contains xy ring-opened product. The ratio of each component in this reaction product is determined by conditions such as the type of salt of the phosphoric acid monoester used, the reaction molar ratio of the salt of the phosphoric acid monoester used and glycidol, the type and amount of the solvent used, and the reaction temperature. Depends on.

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, a method of precipitating the reaction product with a solvent such as acetone or ethanol, or a method of precipitating the reaction product with a solvent such as acetone or ethanol, or 99% due to filtration etc.
The above-mentioned highly purified sugar phosphate ester (1) can be obtained.

For example, Ichihara's? Inorganic salts as by-products, unreacted phosphoric acid monoester salts, glycidol or its processing using a risulfon-based ultrafiltration membrane? When the xy ring-opened product is removed, only the sugar phosphate ester (1) remains, other impurities are removed, and when water is distilled off from the residue, a highly pure sugar phosphate ester is obtained. In addition, the nine-saccharide phosphate ester obtained in this way was treated with an ion exchange resin (Dovw+
After passing through K, it is also possible to perform salt exchange by neutralizing with an alkali metal, alkanolamine, basic amino acid, or ammonia.

〔Effect of the invention〕

The method for producing sugar sulfate esters of the present invention as described above does not require an operation to introduce a protecting group for the sugar skeleton, and it is possible to industrially advantageously produce sugar phosphate esters with excellent moisturizing properties through simple operations. can do.

〔Example〕

Next, the present invention will be explained with reference to Examples and Test Examples.

Example 1 α-D-glucobylanose, l-(2-3-dihydroxy f-tetrabiruhydrodanphosphate) sodium salt: α-D-glucose-1-phosphate zonatrichum salt trihydrate 1071 in a reactor (0.3 mol) was dissolved in 4N hydrochloric acid aqueous solution 80F (0.3 mol) and water 649.
Raise the temperature to 0°C. Next, while maintaining the reaction system at 60°C, glycidol 67f (0.9 mol) was gradually added dropwise.
React at 60°C for 9 hours. After the reaction is complete, it is filtered to remove floating impurities.

This solution was passed through an ultrafiltration device (Risulfone-based ultrafiltration membrane, NaCt rejection rate 45%) to remove impurities.
Further freeze-drying was performed to obtain a white powdery compound 40f (
0.1 mol) 1 was obtained.

Reaction rate 100%, isolated yield 3.7% Elemental analysis value (wt%) (molecular formula CJ 110BPNa
) Cg P Calculated value 30.3 5.1 8.7 Actual value 30.0 5.1 8.3 Proton NMR (ppm) Solvent; D, 0δ5.37
~5.57 (q, III) 3.43~4. OO
(m, 11H) Example 2 α-D-glucobylanose, 6-(2,3-dihydroxyzologylnoid tetraglynophosphate) sodium salt: α-D-glu;-su 1-phos 7ate in a reactor Add 107 t (0.3 mol) of zosodium salt trihydrate and dissolve in 80 f (0.3 mol) of 4N hydrochloric acid aqueous solution and 64 fK of water.
Raise the temperature to 0°C. Next, while maintaining the reaction system at 60°C, glycidol 67f (0.9 mol) was gradually added dropwise.
After the reaction was completed at 0° C. for 9 hours, the desired compound 36f (0.10 mol) was obtained in the same manner as in Example 1. Reaction rate: 100%, isolated yield: 433% Example 3 α-D-glucobylanose, 1-(2,3-zohydroxyzolobyl hydrogne phosphate) potassium salt: α-D-glucobylanose in the reactor - Dissolve 89 g (0.3 mok) of phosphate monopotassium salt in 64 f of water.
Raise the temperature to 0°C. Next, reaction system f: After gradually adding glycidol 67F (0.9 mol) dropwise while maintaining the temperature at 60°C,
React at 60°C for 9 hours. After the reaction was completed, the same procedure as in Example 1 was carried out to obtain the target compound 45f (0.12 mol). Reaction rate: 100%, isolation yield: 40% Test Example 1 The moisturizing properties of the compound of Example 1 and glycerin and glucam E-10, which are known as humectants, were compared.

Method: Moisture retention test - Add 50 parts by weight of water to the sample, take it in a glass container, and add 0% Rh (silica gel), 20% Rh (CH, C00K salt solution), 44
%Rh (K, Co, 2H10 salt solution), 65%Rh
(Mf(CH,Coo)!・4HIO salt solution), 80
%Rh (NH4Ct salt solution) for 3 days and evaluated based on the weight change.

The results are shown in Table 1.

Table 1 Moisturizing Test From the results shown in Table 1, it can be concluded that this compound has good moisturizing properties under low humidity conditions.

Above 1-i-,j Procedural amendment (voluntary) April 10, 1985 2. Name of the invention: Process for producing sugar phosphate ester 3. Relationship with the person making the amendment: Applicant address: Chuo-ku, Tokyo 1-14-10 Kayabacho, Nihonbashi Name (091) Kao Soap Co., Ltd. Representative Yoshibe Maruta 4, Agent Address Same as above - 1.D 6, "Detailed Description of the Invention" of the specification subject to amendment Column 7, Contents of amendment (1) In the specification, page 12, lines 12 to 13 “-
m-glucose-1-phosphate)-1-J is corrected to [-m-glucose-6-phosphate)---J.

Procedural amendment (voluntary) August 5, 1985

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents the active hydrogen residue of glucose, and M
General formula (I) characterized by reacting glycidol with a phosphoric acid monoester or its salt represented by H or a cation (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and M has the same meaning as above).