JPH051083A - New phosphobetaine and its production - Google Patents

Abstract

PURPOSE:To obtain the subject inexpensive compound, excellent in humectant properties and useful as a blending ingredient for shampoos, rinses, etc., by reacting a phosphoric acid ester with an epoxy compound. CONSTITUTION:A compound (e.g. sorbitol phosphate) expressed by formula I [Z is sugar alcohol, tlycerol, etc.; M<1> and M<2> are H or cationic group; (m) is >=0; (n) is >=1, provided that (m+n) is a number without exceeding the number of OH groups in the sugar alcohol, glycerol, etc.] is made to react with a compound expressed by formula II (R<1> to R<3> are H, 1-4C alkyl, etc.; X is anionic group) in a molar amount of preferably 1-5 times based on the number (m+n) of phosphate groups in the compound expressed by formula I, preferably in a solvent such as water at preferably 40-90 deg.C to afford the objective compound expressed by formula III (groups expressed by formulas IV and V are groups capable of bonding to carbon atoms to which the removed OH groups of Z were bonded). The compound expressed by formula III is, e.g. 2,3,4,5,6- pentahydroxyhexyl-{(2-hydroxy-3-N,N,N-trimethylammonio)propyl}phosphate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphobetaine useful as a base for hair, skin cosmetics and the like, a moisturizing agent and the like and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
A moisturizing agent has been added to shampoos, rinses, cosmetics and the like for the purpose of imparting a moist feel to hair and skin. Moisturizers that have been practically used so far include propylene glycol, glycerin, urea, sorbitol, and alkylene oxide adducts of alcohols. However, these are not satisfactory in terms of moisture retention, hygroscopicity, hygroscopic rate, feel and the like. Also,
Although natural polysaccharide components such as hyaluronic acid are relatively excellent in moisturizing performance and feel, they are expensive, so that they have a drawback that their use range is limited to relatively expensive cosmetics.

That is, it has been desired to develop a compound which has excellent moisturizing properties and is inexpensive and which can be compounded and used in shampoos, rinses, cosmetics and the like.

[0004]

Under the circumstances, as a result of intensive studies by the present inventors, a new phospho, which has excellent moisturizing properties and is inexpensive, is useful as a base for moisturizing hair and skin cosmetics, a moisturizing agent, and the like. The present invention has been completed by finding betaine and a manufacturing method thereof. That is, the present invention provides a novel phosphobetaine represented by the general formula (1) and a method for producing the same.

[0005]

[Chemical 4]

Examples of the sugar alcohol which is the source of the residue Z in the above general formula (1) include, for example, sorbitol, mannitol, galactitol, xylitol, arabinitol, ribitol and oligosaccharides obtained by reducing a monosaccharide. Examples include maltitol and lactitol obtained by reducing the. Further, these sugar alcohols may be modified with an appropriate organic residue such as acylation, etherification, alkylene oxide addition, or acetalization, except for at least one hydroxyl group.

Examples of oligosaccharides are maltose, isomaltose, maltotriose, maltotetraose,
Malto-oligosaccharides such as maltoheptaose; cellooligosaccharides such as cyclodextrin and cellobiose; manno-oligosaccharides, fructooligosaccharides, sucrose, lactose and the like. The hydroxyl groups of these oligosaccharides may be modified with appropriate organic residues such as acylation, etherification, alkylene oxide addition, and acetalization, except for at least one hydroxyl group.

Examples of the alkyl group among R ¹ , R ² and R ³ in the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a sec-butyl group. However, examples of the alkenyl group include a propenyl group and a butenyl group.

Further, M ¹ and M ² in the general formula (1)
Examples of the cationic group include an alkali metal, an ammonium group, an alkylammonium group, an acidic amino acid group, a trialkanolamine cationic residue, and the like.

Among the phosphobetaines (1) of the present invention, those in which m is 0, particularly those in which m is 0 and Z is a residue remaining after removing n hydroxyl groups from sorbitol or maltitol. Is preferred.

The compound (1) of the present invention is produced, for example, according to the following reaction formula.

[0012]

[Chemical 5]

[In the formula, Z, R ¹ , R ² , R ³ , M ¹ and M
² , m and n have the same meanings as described above, and X ⁻ represents an anion. ]

That is, the compound (1) of the present invention is synthesized by reacting the phosphoric acid ester (2) with the epoxy compound (3).

Specific examples of the phosphoric acid ester (2) include:
Sorbitol phosphate, mannitol phosphate, galactitol phosphate, xylitol phosphate, arabinitol phosphate, ribitol phosphate, maltitol phosphate, glycerophosphate, maltose phosphate, maltotriose phosphate,
Maltotetraose phosphate, maltoheptaose phosphate, cyclodextrin phosphate, cellobiose phosphate,
Examples thereof include lactose phosphate, sucrose phosphate and the like, which are mono or di salts of M ¹ and M ² .

X ⁻ in the general formula (3) is not particularly limited, but examples thereof include a halogen ion and an alkylsulfate anion group.

The epoxy compound (3) can be easily produced, for example, according to a known method by reacting a corresponding trialkylamine or trialkenylamine with epihalohydrin.

To carry out the production method of the present invention, the number of phosphoric acid groups (m + n) of phosphoric acid monoester (2) is
The epoxy compound (3) is reacted in an amount of 0.1 to 10 times mol, preferably 1 to 5 times mol. Reaction in an inert solvent 3
It is carried out at a temperature of 0 to 120 ° C, preferably 40 to 90 ° C.

As the inert solvent, for example, polar solvents such as water, methanol, ethanol, 2-propanol, dimethylformamide, dimethylsulfoxide and the like, or a mixed solvent of two or more selected from these are used. Water or a mixed solvent of water and a lower alcohol is particularly preferable.

In addition to phosphobetaine (1) which is the object of the present invention, the reaction products include inorganic salts as by-products, unreacted phosphoric acid ester (2), epoxy compound (3) or epoxy ring-opening thereof. Things are included. The proportion of each component in this reaction product depends on the conditions such as the type of raw materials used, the reaction ratio thereof, the type and amount of the solvent used, and the reaction temperature. Therefore, although the reaction product can be used as it is depending on the purpose of use, when a higher purity product is required, for example, known methods such as a solvent fractionation method, an ion exchange chromatography method, and an electrodialysis method are known. It can be purified by the purification method of.

A specific example of the method for producing the phosphobetaine (1) of the present invention is as follows.

[0022]

[Chemical 6]

[In the formula, R ¹ , R ² and R ³ have the same meanings as described above. ]

[0024]

INDUSTRIAL APPLICABILITY The novel phosphobetaine (1) of the present invention has excellent moisturizing properties and is inexpensive, and can be suitably used as a blending component for shampoos, rinses, cosmetics and the like.

[0025]

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

Synthesis Example 1 Synthesis of sorbitol phosphate sodium salt: publicly known method (Japanese Patent Publication No. 50-8052)
Sorbitol phosphate sodium salt was synthesized on the basis of the above-mentioned publication). 45.5 g of sorbitol was dissolved in 125 ml of water, to which 38.4 g of phosphorus oxychloride was added dropwise at 0 to 5 ° C with stirring for about 2 hours. At this time, a 10N caustic soda aqueous solution was added to maintain the pH of the reaction solution at 13.5 at all times, and alkali was added dropwise until no change in pH was observed even after the addition of phosphorus oxychloride. The reaction mixture was neutralized with a cation exchange resin (Dowex 50X4H ⁺ type), concentrated under reduced pressure, and a caustic soda aqueous solution was added to adjust the pH to 1
Adjusted to 0. Next, 120 ml of ethanol was added and cooled, the precipitated inorganic salt was filtered off, and the lower layer of the filtrate separated into two layers was separated. Add water to make it 250 ml,
Further, 1 l of methanol was added, and the precipitated sodium salt of sorbitol phosphate ester was separated by filtration and dried. The crude product was dissolved again in 100 ml of water, and ethanol was added thereto to cause reprecipitation, whereby 45 g of purified sorbitol phosphate sodium salt was obtained.

Synthesis Example 2 Synthesis of maltose phosphate sodium salt: Maltose phosphate sodium salt was synthesized according to a known method (Japanese Patent Publication No. 50-8052). The reaction and purification were carried out in the same manner as in Synthesis Example 1 except that 85.4 g of maltose was dissolved in 250 ml of water to obtain 60 g of purified maltose phosphate sodium salt.

Synthesis Example 3 Synthesis of maltitol phosphate sodium salt: publicly known method (Japanese Patent Publication No. 50-8052)
Japanese Patent Laid-Open Publication No. 2003-242242), maltitol phosphate sodium salt was synthesized. Reaction and purification were carried out in the same manner as in Synthesis Example 1 except that 50 g of maltitol was dissolved in 200 ml of water to obtain 45 g of purified sodium salt of maltitol phosphate.

Example 1 Synthesis of 2,3,4,5,6-pentahydroxyhexyl- (N, N, N-trimethylammoniopropyl) phosphate: Sorbitol phosphate sodium salt synthesized in a reactor according to Synthesis Example 1 89 g (0.32 mol) of salt and 500 g of water were added, and the mixture was heated to 60 ° C. Next, while maintaining the reaction system at 60 ° C., a solution prepared by dissolving 150 g (0.99 mol) of glycidyltrimethylammonium chloride in 500 g of ion-exchanged water was added dropwise over 3 hours. Then, the reaction was carried out for 15 hours at 60 ° C. After completion of the reaction, the solvent was distilled off under reduced pressure to remove the residue by 10
It was washed with a double amount of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product. The resulting crude product was purified by ion exchange chromatography (ion exchange resin; BIO-RAD AG501X8) to obtain 2,3,4,5,6-pentahydroxyhexyl- (N, N, N-trimethylammonium). Opropyl)
71.2 g of phosphate was obtained (isolation yield 59%). ¹ H-NMR (D ₂ O); (Fig. 1) δ (ppm) 3.12 (s, 9H, a ), 3.28-4.05 (m, 12H, b ), 4.33 (b
road, 1H, c )

[0030]

[Chemical 7]

Mass spectrometry (FAB ionization method); M / Z 378 (M + H) ⁺ (M = C ₁₂ H ₂₈ O ₁₀ NP)

Example 2 Synthesis of 2,3-dihydroxypropyl- (N, N, N-trimethylammoniopropyl) phosphate: 50 g (0.23 mol) of disodium α-glycerophosphate, 500 g of water and 23% of 1N hydrochloric acid were added to a reactor.
0 g was added and the mixture was heated to 60 ° C. Next, while maintaining the reaction system at 60 ° C., a solution prepared by dissolving 106 g (0.70 mol) of glycidyltrimethylammonium chloride in 500 g of ion-exchanged water was added dropwise over 5 hours. Then, the reaction was carried out for 15 hours at 60 ° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product. The resulting crude product is subjected to ion exchange chromatography (ion exchange resin; BIO-RA
It was purified by AG501X8 manufactured by D company to obtain 31 g of 2,3-dihydroxypropyl- (N, N, N-trimethylammoniopropyl) phosphate (isolation yield 38%). ¹ H-NMR (D ₂ O); δ (ppm) 3.18 (s, 9H, a ), 3.29-3.94 (m, 9H, b ), 4.33 (br
oad, 1H, c )

[0033]

[Chemical 8]

Mass spectrometry (FAB ionization method); M / Z 360 (M + H) ⁺ (M = C ₁₅ H ₂₂ O ₇ NP)

Example 3 Synthesis of maltose- (N, N, N-trimethylammoniopropyl) phosphate: 93 g (0.2 mol) of maltose phosphate disodium salt synthesized according to Synthesis Example 2 in a reactor, 500 g of ion-exchanged water and 200 g of 1N hydrochloric acid was added, and the mixture was heated to 60 ° C. While maintaining the reaction system at 60 ° C., a solution prepared by dissolving 106 g (0.70 mol) of glycidyltrimethylammonium chloride in 500 g of ion-exchanged water was added dropwise over 5 hours. After that, the temperature was kept at 60 ° C. and the reaction was performed for 15 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product. The resulting crude product was purified by ion exchange chromatography (ion exchange resin; AG501X8 manufactured by BIO-RAD) to obtain 55 g of maltose- (N, N, N-trimethylammoniopropyl) phosphate (isolated yield). 51%).

[0036]

[Chemical 9]

Mass spectrometry (FAB ionization method); M / Z 538 (M + H) ⁺ (M = C ₁₈ H ₃₆ O ₁₅ NP)

Example 4 Synthesis of maltitol (N, N, N-trimethylammoniopropyl) phosphate: Maltitol phosphate sodium salt 47 synthesized according to Synthesis Example 3 in a reactor.
g (0.11 mol) and 300 g of water were added, and the mixture was heated to 60 ° C. Next, while maintaining the reaction system at 60 ° C., 2 g of 61 g (0.16 mol) of glycidyl trimethyl ammonium chloride was added.
A solution dissolved in 00 g of ion-exchanged water was added dropwise over 3 hours. Then, the reaction was carried out for 15 hours at 60 ° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 6 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product.
The resulting crude product was purified by ion exchange chromatography (ion exchange resin: BIO RAD AG501X8),
19.6 g of maltitol (N, N, N-trimethylammoniopropyl) phosphate was obtained (isolation yield 33%).

[0039]

[Chemical 10]

Mass spectrometry (FAB ionization method); M / Z 540 (M + H) ⁺ (M = C ₁₈ H ₃₈ O ₁₅ NP)

[Brief description of drawings]

1 is a ¹ H-NMR spectrum diagram of 2,3,4,5,6-pentahydroxyhexyl- (N, N, N-trimethylammoniopropyl) phosphate obtained in Example 1. FIG.

[Procedure amendment]

[Submission date] July 2, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

In the present invention, oligosaccharides have a degree of polymerization of 10 or less.
The full ones are mentioned, and examples thereof include maltooligosaccharides such as maltose, isomaltose, maltotriose, maltotetraose and maltoheptaose; cellooligosaccharides such as cyclodextrin and cellobiose; mannooligosaccharides, fructooligosaccharides, sucrose, Lactose etc. are mentioned. The hydroxyl groups of these oligosaccharides may be modified with appropriate organic residues such as acylation, etherification, alkylene oxide addition, and acetalization, except for at least one hydroxyl group.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

Among the phosphobetaines (1) of the present invention, those in which m is 0, particularly m is 0 and Z is n in number from sorbitol , maltitol, maltooligosaccharide, sucrose or lactose . Those which are residues remaining after the removal of the hydroxyl groups of are preferred.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

To carry out the production method of the present invention, phosphoric acid is used.
0.1 to 0.1 with respect to the number of phosphoric acid groups (m + n) of the ester (2)
A 10-fold molar amount of the epoxy compound (3), preferably a 1- to 5-fold molar amount, is reacted. The reaction is 30 to 1 in an inert solvent.
It is carried out at a temperature of 20 ° C, preferably 40-90 ° C. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 5, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

Example 1 2,3,4,5,6-pentahydroxyhexyl- {(2-hydroxy-3-N, N,
Synthesis of N-trimethylammonio) propyl} phosphate: 89 g (0.32 mol) of sorbitol phosphate sodium salt synthesized according to Synthesis Example 1 and 5 parts of water in a reactor.
00g was put and it heated at 60 degreeC. Next, the reaction system is set to 60
While maintaining the temperature at ℃, a solution prepared by dissolving 150 g (0.99 mol) of glycidyltrimethylammonium chloride in 500 g of ion-exchanged water was added dropwise over 3 hours. Then 60
The reaction was carried out for 15 hours while maintaining the temperature. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product. The obtained crude product was subjected to ion exchange chromatography (ion exchange resin; BI
Purified by O-RAD AG501X8), 2, 3, 4, 5,
6-Pentahydroxyhexyl- {(2-hydroxy-
71.2 g of 3-N, N, N-trimethylammonio) propyl} phosphate was obtained (isolated yield 59%). ¹ H-NMR (D ₂ O); (Fig. 1) δ (ppm) 3.12 (s, 9H, a ), 3.28-4.05 (m, 12H, b ), 4.33 (b
road, 1H, c )

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

Example 2 2,3-dihydroxypropyl- {(2-hydroxy-3-N, N, N-trimethylacrole
Synthesis of (mmonio) propyl} phosphate: α in the reactor
50 g (0.23 mol) of disodium glycerophosphate, 500 g of water and 230 g of 1N hydrochloric acid were added and heated to 60 ° C. Next, while maintaining the reaction system at 60 ° C., a solution prepared by dissolving 106 g (0.70 mol) of glycidyltrimethylammonium chloride in 500 g of ion-exchanged water was added dropwise over 5 hours. Then, the reaction was carried out for 15 hours at 60 ° C.
After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product. The obtained crude product was purified by ion exchange chromatography (ion exchange resin; AG501X8 manufactured by BIO-RAD), and 2,3-dihydroxypropyl- {(2 -hydroxyl
Ci-3-N, N, N-trimethylammonio) propy
31 g of ru} phosphate was obtained (isolation yield 38%). ¹ H-NMR (D ₂ O); δ (ppm) 3.18 (s, 9H, a ), 3.29-3.94 (m, 9H, b ), 4.33 (br
oad, 1H, c )

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

Example 3 Maltose- {(2-hydroxy
Ci-3-N, N, N-trimethylammonio) propy
Synthesis of ru} phosphate: 93 g (0.2 mol) of maltose phosphate disodium salt synthesized according to Synthesis Example 2, 500 g of ion-exchanged water and 200 g of 1N hydrochloric acid were placed in a reactor and heated to 60 ° C. While maintaining the reaction system at 60 ℃,
Glycidyl trimethyl ammonium chloride 106g
A solution prepared by dissolving (0.70 mol) in 500 g of ion-exchanged water was added dropwise over 5 hours. After that, the temperature was kept at 60 ° C. and the reaction was performed for 15 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 10 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product. The resulting crude product was subjected to ion exchange chromatography (ion exchange resin; BIO-RAD AG50).
1X8) and maltose- {(2-hydroxy
-3-N, N, N-trimethylammonio) propyl}
55 g of phosphate was obtained (isolation yield 51%).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

Example 4 Maltitol -{(2-hydroxy-3-N, N, N-
Synthesis of trimethylammonio) propyl} phosphate: 47 g (0.11 mol) of sodium salt of maltitol phosphate ester synthesized according to Synthesis Example 3 in a reactor and 30 parts of water.
0 g was added and the mixture was heated to 60 ° C. Next, while maintaining the reaction system at 60 ° C., a solution prepared by dissolving 61 g (0.16 mol) of glycidyltrimethylammonium chloride in 200 g of ion-exchanged water was added dropwise over 3 hours. Then, the reaction was carried out for 15 hours at 60 ° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was washed with 6 volumes of ethanol to remove unreacted glycidyl trimethyl ammonium chloride and its epoxy ring-opened product. The resulting crude product was purified by ion exchange chromatography (ion exchange resin: BIO RAD AG501X8), and maltitol -{(2-hi
Droxy-3-N, N, N-trimethylammonio) pu
19.6 g of ropyl } phosphate was obtained (isolation yield 33
%).

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] Figure 1

[Correction method] Change

[Correction content]

FIG. 1 shows 2,3,4,5,6-pentahydroxyhexyl- {(2-hydroxy-3-N, obtained in Example 1.
FIG. 2 is a ¹ H-NMR spectrum diagram of N, N-trimethylammonio) propyl} phosphate.

Claims (5)

[Claims] 1. Phosphobetaine represented by the following general formula (1): [Chemical 1] 2. The phosphobetaine according to claim 1, wherein m is 0 in the general formula (1). 3. In the general formula (1), m is 0,
The phosphobetaine according to claim 1, wherein Z is a residue remaining after removing n hydroxyl groups from sorbitol or maltitol. 4. In the general formula (1), m is 0,
The phosphobetaine according to claim 1, wherein Z is a residue remaining after removing n hydroxyl groups from maltooligosaccharide, sucrose or lactose having a condensation degree of less than 10. 5. The following general formula (2): [In the formula, Z, M ¹ , M ² , m and n have the same meanings as in formula (1). ] To the phosphoric acid ester represented by the following general formula (3) [In formula, R < ¹ >, R < ² > and R < ³ > shows the same meaning as General formula (1), and X < ^- > shows an anion group. ] The epoxy compound represented by these is made to react, The manufacturing method of the phosphobetaine of Claim 1 characterized by the above-mentioned.