JPH0469637B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is based on the following general formula () (In the formula, R ₁ represents the active hydrogen residue of glucose,
M represents H or a cation. [Prior Art] Conventionally, moisturizing agents have been added to shampoos, conditioners, cosmetics, etc. for the purpose of imparting a moist feel to the hair. Conventional moisturizers include propylene glycol, glycerin,
Urea, sorbitol, alkylene oxide adducts of alcohols, etc. are used. However, these were not satisfactory in terms of moisture retention, moisture absorption rate, etc. On the other hand, it is known that compounds having hydroxyl groups, polyether groups, etc. in their structures exhibit moisture retention and hygroscopicity. E-10 (Amacor)
etc. are provided. However, this also had low moisturizing properties under low humidity conditions, and was not satisfactory as a moisturizing agent due to its sticky feel. Under these circumstances, as a result of various studies, the present inventors have found that a compound represented by the formula ( ), 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 the formula (), a method of hydrolyzing Teichonic acid extracted from Gram-positive bacteria is known [Biochem.J.,
151 (1975)], and no chemical synthesis method was known. In addition, a method for chemically synthesizing the β form of the compound represented by formula () is known [Bioorg.
Khim., 3, 248, (1977)], but this method could not be said to be suitable as an industrial production method because it required complicated operations such as introduction and removal of protecting groups. [Problems to be Solved by the Invention] Therefore, it has been desired to develop a chemical synthesis method that allows industrial production of the compound represented by the formula (). [Means for Solving the 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. (In the formula, R ₁ and M have the same meanings as above.) That is, the present invention is a method for producing a sugar phosphate ester () by reacting a phosphoric acid monoester or a salt thereof () with glycidol (). be. The active hydrogen residue of glucose represented by R ₁ in the general formula () of the present invention is a glucose molecule with one hydrogen atom of the hydroxyl group removed, and is, for example, a phosphoric acid residue represented by the formula (). Glucose-1-phosphate, glucose-1 as monoester
Examples include 2-phosphoric acid, glucose-4-phosphoric acid, glucose-6-phosphoric acid or a salt thereof. Glucose may have other hydroxyl groups protected with protective groups. Examples of the protecting group include acetyl, benzyl, benzoyl, methylene acetal, isopropylidene acetal, and the like. Furthermore, M in the general formula () of the present invention refers to hydrogen or a cation such as an alkali metal, an alkanolamine, a basic amino acid, or ammonia. Examples of the alkali metal include sodium, potassium, etc.
As alkanolamines, 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. To carry out the present invention, 1 to 10 times the mole of glycidol represented by the formula (), preferably 1 to 5 times the mole, is reacted with the phosphoric acid monoester represented by the formula (). The reaction is carried out in the presence of an inert solvent at 30-150°C, preferably 40-90°C.
It is carried out at a temperature of °C. As the inert solvent, for example, polar solvents such as water, methanol, ethanol, and isopropanol are used, and among them, water is particularly preferred. In addition to the sugar phosphate ester represented by the general formula (), which is the object of the present invention, the reaction products include inorganic salts as by-products, unreacted phosphates, glycidol, or its epoxy ring-opened product. include. Furthermore, depending on the reaction conditions, a small amount of sugar phosphate represented by the general formula (), which is an isomer of the sugar phosphate represented by the general formula (), may be produced. (In the formula, R ₁ and M have the same meanings as above.) The proportion of each component in this reaction product depends on the type of phosphoric acid monoester or its salt used, the reaction between the phosphoric acid monoester or its salt and glycidol. molar ratio,
It depends on the type and amount of solvent used, reaction temperature, and other conditions. 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, Alternatively, a sugar phosphate ester () with a purity of 99% or more can be obtained by ultrafiltration or the like. For example, if a commercially available polysulfone-based ultrafiltration membrane is used to remove inorganic salts as by-products, unreacted phosphate monoester salts, glycidol or its epoxy ring-opened products, only sugar phosphate esters () are removed. remains, other impurities are removed, and water is distilled off from the residue to obtain a highly pure sugar phosphate ester. In addition, after passing the sugar phosphate ester obtained in this way through an ion exchange resin (Dowex50W-X8), an alkali metal,
Salt exchange can also be carried out by neutralizing with alkanolamines, basic amino acids, or ammonia. [Effects of the Invention] The method for producing sugar phosphate esters of the present invention as described above does not require an operation to introduce a protecting group for the sugar skeleton, and can produce sugar phosphate esters with excellent moisture retention properties through simple operations. It can be manufactured with industrial advantage. [Example] Next, the present invention will be described with reference to Examples and Test Examples. Example 1 α-D-glucopyranose, 1-(2,3-dihydroxypropyl hydrogen phosphate) sodium salt: 107 g (0.3 mol) of α-D-glucopyranose-1-phosphate disodium salt trihydrate was added to a reactor. ) in 80 g (0.3 mol) of 4N hydrochloric acid aqueous solution and 64 g of water, and the temperature was raised to 60°C. Next, while maintaining the reaction system at 60°C, 67 g (0.9 mol) of glycidol was gradually added dropwise, and the mixture was allowed to react at 60°C for 9 hours. After the reaction is complete, it is filtered to remove floating impurities. This solution is passed through an ultrafiltration device (polysulfone-based ultrafiltration membrane, NaCl rejection rate 45%) to remove impurities.
Further freeze-drying yields 40g of white powder compound.
(0.11 mol) was obtained. Reaction rate 100%, isolated yield 37% Elemental analysis value (weight %) (molecular formula C ₉ H ₁₈ O ₁₁ PNa) C H P Calculated value 30.3 5.1 8.7 Actual value 30.0 5.1 8.3 Proton NMR (ppm) Solvent; D ₂ O δ5.37~5.57 (q, 1H) 3.43~4.00 (m, 11H) Example 2 α-D-glucopyranose, 6-(2,3-dihydroxypropyl hydrogen phosphate) sodium salt: α- 107 g (0.3 mol) of D-glucose-6-phosphate disodium salt trihydrate was dissolved in 80 g (0.3 mol) of a 4N aqueous hydrochloric acid solution and 64 g of water, and the temperature was raised to 60°C. Next, while maintaining the reaction system at 60°C, 67 g (0.9 mol) of glycidol was gradually added dropwise, and the mixture was allowed to react at 60°C for 9 hours. After the reaction is complete,
In the same manner as in Example 1, 36 g (0.10 mol) of the target compound was obtained. Reaction rate 100%, isolated yield 33% Example 3 α-D-glucopyranose, 1-(2,3-dihydroxypropyl hydrogen phosphate) potassium salt: α-D-glucose-1-phosphate was added to the reactor. 89 g (0.3 mol) of monopotassium salt is dissolved in 64 g of water and the temperature is raised to 60°C. Next, while maintaining the reaction system at 60°C, 67 g (0.9 mol) of glycidol was gradually added dropwise, and the mixture was allowed to react at 60°C for 9 hours. After the reaction, 45 g (0.12 g) of the target compound was added in the same manner as in Example 1.
mole) was obtained. Reaction rate: 100%, isolated yield: 40% Test Example 1 The moisturizing properties of the compound of Example 1 and glycerin and glycum E-10, which are known as humectants, were compared. Method: Moisture retention test - Add 50 parts by weight of water to the sample, take 1 g of it in a glass container, and add 0% Rh
(silica gel), 20% Rh (CH ₃ COOK salt solution),
44% Rh (K ₂ CO ₃ 2H ₂ O salt solution), 65% Rh (Mg
( _CH3COO ) _2.4H2O salt solution), ₈₀ % Rh ( _NH4Cl
The samples were left for 3 days under various humidity conditions (salt solution) and evaluated based on the weight change. The results are shown in Table 1.

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

Claims (1)

[Claims] 1 General formula () (In the formula, R ₁ represents the active hydrogen residue of glucose,
General formula () characterized by reacting glycidol with a phosphoric acid monoester or its salt represented by (M represents H or a cation) (In the formula, R ₁ and M have the same meanings as above.) A method for producing a sugar phosphate ester represented by the following.