JPH05277351A - Novel sugar amino acid compound, its production and surfactant composition containing the compound - Google Patents

Abstract

PURPOSE:To produce a novel sugar amino acid compd. of a specified structure acting mildly on the skin, especially on the eye mucosa, having excellent frothing power and detergency and useful as a surfactant to clean the hair, face and body. CONSTITUTION:This novel sugar amino acid compd. is shown by the formula. In the formula, R is straight-chain or branched-chain a 5-22C alkyl, alkenyl, hydroxyalkyl or an alklphenyl, R' is H or the residue formed by removing a glycoside group from sugar, (m+1) pieces of R's are the same or may be different from each other, (m) is 3 or 4, R'' is H or a 1-10C alkyl, (n) is 0 to 10, and X is H, an Alkali metal, alkaline-earth metal, ammonium, 2-4C mono, di or trialkanol ammonium or basic amino acid group. Consequently, a surfactant for cleaning the body having excellent frothing power and detergency is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a sugar amino acid compound useful as a novel surfactant and a method for producing the same. More specifically, a sugar amino acid compound useful as a surfactant for hair, face, and body cleansing, which has a mild action on the skin and especially the ocular mucosa, and has excellent foaming power and detergency, and its The present invention relates to a manufacturing method.

[0002]

2. Description of the Related Art In recent years,
Cleanliness, which is centered on young people, is rapidly spreading, and it is becoming a major social phenomenon. For example, hair washing habits have changed drastically over the last few years, and most people now wash their hair daily. On the other hand, this change in awareness of cleanliness
With respect to surfactants, not only detergency but also less irritation has been required. Also, the recent increasing awareness of the environment has encouraged the use of natural raw materials in surfactants. Considering these situations together, it is most desirable to effectively utilize reproducible natural raw materials to synthesize a surfactant that is mild to skin and ocular mucosa.

Alkyl glycosides have heretofore been widely used as surfactants using sugar as a raw material and are known to have low skin irritation. On the other hand, sugar amino acids obtained by reductive amination reaction of sugars and amino acids are known substances and reported as skin protectants for cosmetics, but there are no sugar amino acids having a surface-active function.
In addition, N-acylated amino acid is Schotten-
It is known as a mild surfactant that is easily synthesized by the Baumann reaction, but there has been no attempt to further reduce the irritation by introducing a polyhydroxyl group.

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors on a novel sugar amino acid derivative useful as a mild surfactant, an N-acylated derivative of a sugar amino acid was found to be applied to the skin and especially to the ocular mucosa. The inventors have found that they have extremely excellent properties as a surfactant, i.e., low irritation, good foaming power, biodegradability, and good solubility in water, and completed the present invention. That is, the present invention provides a novel sugar amino acid compound represented by the general formula (1), a method for producing the same, and a surfactant composition containing the same.

[0005]

[Chemical 4]

[In the formula, R represents a linear or branched alkyl group having 5 to 22 carbon atoms, an alkenyl group, a hydroxyalkyl group, or an alkylphenyl group. R'represents a residue remaining after removal of a glycosidic hydroxyl group from a hydrogen atom or sugar, and (m + 1) R's may be the same or different from each other. m: Indicates the number of 3 or 4. R ": represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. N: represents a number of 0 to 10. X: a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a monoalkyl group having 2 to 3 carbon atoms, A di- or trialkanol ammonium, an alkyl group-substituted ammonium having 1 to 5 carbon atoms, or a basic amino acid group is shown.] Hereinafter, the present invention will be described in detail.

There is no report on the sugar amino acid compound represented by the above general formula (1) in the conventional literatures, patents and the like, and the sugar amino acid compound of the present invention is a novel substance. The general formula
The sugar amino acid compound represented by (1) is represented by the general formula (2)

[0008]

[Chemical 5]

[In the formula, R represents the same meaning as described above, and Y represents a halogen atom. ] A fatty acid halide represented by,
General formula (3)

[0010]

[Chemical 6]

[0011] [wherein R ', m, R ", n and X have the same meanings as described above] and produced by reacting with a polyhydroxyamino acid in the presence of an alkaline substance. You can

The fatty acid halide represented by the general formula (2) used in the present invention is, for example, a single composition such as capric acid chloride, caproic acid chloride, lauric acid chloride, oleic acid chloride or isostearic acid chloride. Examples thereof include fatty acid chlorides having a mixed composition such as fatty acid chloride, coconut oil fatty acid chloride, and beef tallow fatty acid chloride.

The polyhydroxyamino acid represented by the general formula (3), which is the other raw material used in the present invention, is, for example, N- (1-deoxy-D-sorbitol-).
1-yl) aminoacetic acid, N- (1-deoxy-D-sorbitol-1-yl) -3-aminopropionic acid, N-
(1-deoxy-D-maltitol-1-yl) -2-
Aminopropionic acid, N- (1-deoxy-D-sorbitol-1-yl) -2-aminobutyric acid, N- (1-deoxy-D-sorbitol-1-yl) -3-aminobutyric acid, N- (1 -Deoxy-D-sorbitol-1-yl) -6-aminocaproic acid, N- (1-deoxy-D
-Sorbitol-1-yl) -8-aminocaprylic acid and the like. These Polyhydroxy Amino Acids (3)
Can be obtained, for example, by reductively aminating the corresponding monosaccharide, disaccharide or oligosaccharide with the corresponding amino acid using a known method (Japanese Patent Laid-Open No. 50952/1975).

In the reaction of the present invention, the fatty acid halide (2) is usually added to the polyhydroxyamino acid (3).
It is used in a molar amount of 0.9 to 3.0 times, preferably 1.0 to 1.2 times. When the amount of fatty acid halide is less than this range, a large amount of polyhydroxyamino acid (3) remains in the reaction product, and when it is more than this range, a large amount of fatty acid from unreacted fatty acid halide (2) is generated. Is a by-product.

In the reaction of the present invention, in order to secure the reactivity and allow the reaction to proceed to a certain level, an alkaline substance is added to the reaction system to bring the pH in the system to the alkaline side, preferably pH 9.0 to 9.0.
It is desirable to keep it in the range of 11.0. If the pH of the reaction system is lower than this range, hydrogen halide by-produced by the reaction progress and unreacted polyhydroxyamino acid (3) form a salt and the reaction does not proceed sufficiently. When is higher than this range, the decomposition of the raw material fatty acid halide (2) is promoted and a large amount of fatty acid is by-produced. Examples of the alkaline substance used include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and sodium carbonate, and organic bases such as triethylamine, pyridine and 4- (dimethylamino) pyridine. Especially, sodium hydroxide and potassium hydroxide are practical. The amount of these alkaline substances used is such that the reaction system is maintained at the above pH.

In the present invention, the reaction temperature is 3 to 50 ° C., especially
15-30 degreeC is preferable. When the temperature is lower than this range, the viscosity in the system increases and the stirring efficiency deteriorates, and when the temperature is higher than this range, the decomposition rate of the raw material fatty acid halide (2) increases remarkably. The fatty acid by-product increases.

The reaction solvent in the present invention is water, or water and ketones such as acetone and methyl ethyl ketone, lower alcohols such as methanol, ethanol and isopropanol, and diols such as 1,3-propanediol and propylene glycol. Any of the mixed solutions described above can be used.

The above general formula obtained by the method of the present invention
The novel sugar amino acid compound represented by (1) has excellent surface activity, and the surfactant composition containing such a sugar amino acid compound as a main component is excellent in foaming power and detergency, and has low irritation. In particular, since it is mild to the eye mucous membrane, it can be used not only as a hair washing base and a body washing base, but also as a face washing base. General formula relating to the present invention
When the sugar amino acid compound represented by (1) is used as a base of a surfactant composition, the amount used is usually 1 to 100% by weight.
(Equivalent ingredient conversion).

In the above, other components can be used in combination, and examples of such substances that can be used in combination include general anionic surfactants (alkyl sulfate ester salt, alkyl ether sulfate ester salt, α-olefin sulfonate salt). ,
Alkyl sulfonate, taurine-based surfactant, sarcosinate-based surfactant, isethionate-based surfactant,
N-acyl acidic amino acid surfactants, higher fatty acid salts, acylated polypeptides, etc.); amphoteric surfactants (alkyl betaine type surfactants, amidopropyl betaine type surfactants, imidazolinium betaine type surfactants, Sulfobetaine type surfactants, phosphobetaine type surfactants and amino acid type surfactants such as sodium laurylaminopropionate); Nonionic surfactants (coconut oil fatty acid diethanolamide, stearic acid monoglyceride, lauryl dimethylamine oxide, Polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, etc .; cationic surfactant (stearyl trimethyl ammonium chloride, distearyl dimethyl chloride) Moniumu and ethyl lanolin fatty acid aminopropyl ethyl dimethyl ammonium sulfate), known humectants, thickeners, polymeric compounds (carboxyethyl cellulose, hydroxyethyl cellulose, cationized cellulose), flavoring, preservatives, and the like.

[0020]

EXAMPLES Next, the present invention will be described in detail based on examples, but the scope of the present invention is not limited by these.

Example 1 a) Synthesis of sugar glycine 2160 g (12 mol) of glucose and 900 g (12 mol) of glycine
Mol) and 106 g of 5% Pd-carbon (50% water content) together with 10 kg of ion-exchanged water were sealed in a 20 liter autoclave and stirred. After heating to 80 ℃, hydrogen pressure 140kg /
The reaction was performed at cm ² for 12 hours. After cooling, the catalyst was filtered off, water was distilled off, methanol was added to crystallize, and N having the following structure was obtained.
-(1-Deoxy-D-sorbitol-1-yl) aminoacetic acid was obtained. Yield: 1775 g (yield 62%), light brown powder Acid value analysis value: Measured value 230.5 / theoretical value 234.8 Hydroxyl value analysis value: Measured value 1101 / theoretical value 1173.8

[0022]

[Chemical 7]

B) Acylation 239 g (1 mol) of N- (1-deoxy-D-sorbitol-1-yl) aminoacetic acid obtained in a) was added to 750 g of water.
The mixture was stirred at 30 ° C. in a mixed solvent of 150 g of acetone. 273 g (1.25 mol) of lauric acid chloride and 40% aqueous sodium hydroxide solution were separately added dropwise over 4 hours while keeping the pH in the system at 10. The time course of the reaction was followed by gas chromatography. After confirming the disappearance of the raw materials, 120 g of concentrated hydrochloric acid was added to maintain the system pH at 2, and the target acylated sugar amino acid was obtained as a precipitate. The precipitate was filtered off, washed with water, and further washed with ethyl acetate to remove by-produced lauric acid, and then dried under reduced pressure to obtain N- (1-deoxy-D-sorbitol-1-yl) -N having the following structure. -Lauroylaminoacetic acid was obtained.

Yield: 337 g (80%), colorless crystals Melting point: 108-110 ° C

[0025]

[Chemical 8]

¹ H-of the obtained N- (1-deoxy-D-sorbitol-1-yl) -N-lauroylaminoacetic acid
The measurement results of NMR, IR and MS are shown below. ¹ H-NMR (δ, ppm, heavy water, internal standard; Na 3- (trimethylsilyl) propanesulfonate): shown in FIG. 0.85 (3H, methyl group), 1.3 (16H, lauroyl group methylene), 1.6 (2H, lauroyl group methylene, amide β position),
2.25, 2.5 (1H each, methylene lauroyl group, amide α
Rank), 3-4 (8H, sorbitol hydrogen), 4.0, 4.25 (1 each)
H, glycine hydrogen) IR (cm ^-1 , KBr tablet); shown in Fig. 2. 3440 (OH), 2920, 2848, 1742, 1708 (COOH), 1584 (amide) MS (FAB ionization method, negative ion detection method) C ₂₀ H ₃₉ O ₈ N =
421: shown in FIG.

420 (M−H) ⁻ 97% Example 2 a) Synthesis of sugar β-alanine 54.14 g (0.3 mol) glucose in a 500 ml autoclave.
l), β-alanine 26.77 g (0.3 mol), 5% Pd-carbon (50%
(Hydrous substance) 3.43 g and water 180 ml as a solvent are charged at 80 ° C.
Heated up. Then, pressurize with hydrogen to increase the internal pressure to 140
The mixture was stirred for 6 hours while keeping it constant at kg / cm ² . The reaction-terminated product is obtained as a colorless and transparent aqueous solution, and Pd-carbon is recovered by filtering this, and water is partially distilled off and methanol is added for crystallization to obtain N- (1-deoxy) having the following structure. -D-sorbitol-1-yl) -3-aminopropionic acid was obtained. Yield: 34.97 g (purification yield 46%), colorless needle crystals

[0028]

[Chemical 9]

B) Acylation N- (1-deoxy-D-sorbitol-1-yl) -3-aminopropionic acid 8.93 g (0.035mo) obtained in a)
l) was dissolved in 20 ml of water / 9 ml of acetone and ice-cooled, and 15.4 g (0.070 mol) of lauric chloride and 40% aqueous sodium hydroxide solution were simultaneously added dropwise while keeping the system pH at 9.5 to 10.5. After 30 minutes, the dropping was completed, and after aging for 30 minutes, the temperature in the system was raised to room temperature, and the pH was adjusted to 2.0 with concentrated hydrochloric acid to complete the reaction. Lauric acid was removed by filtering off the target product and lauric acid that fell as a precipitate, and washing with water, and further with ethyl acetate to remove N- (1-deoxy-D-sorbitol-1-yl)-having the following structure. N-lauroyl-3-aminopropionic acid was obtained. Yield: 13.09 g (purification yield 85%), colorless crystals Melting point: 119.5-123.5 ° C

[0030]

[Chemical 10]

The measurement results of ¹ H-NMR, IR and MS of the obtained N- (1-deoxy-D-sorbitol-1-yl) -N-lauroyl-3-aminopropionic acid are shown below. ^{1 H-NMR (δ, ppm} , heavy water, internal standard; 3- (trimethylsilyl) propionic-2,2,3,3-d ₄ acid Na): 4 (measured at Na salt). 0.87 (3H, methyl group), 1.28 (16H, lauroyl group methylene), 1.56 (2H, carbonyl group β-lauroyl group methylene), 2.4 (4H, carbonyl group α-lauroyl group methylene, carboxyl group α-methylene ), 3.3 to 3.9 (10H,
Methylene at the β-position of the carboxyl group, sorbitol hydrogen) IR (cm ^-1 , KBr tablet);

3406 (OH), 2926, 2854, 1719 (COOH), 1608
(Amide), 1182, 1101, 1068 MS (FAB ionization method, negative ion detection method) C ₂₁ H ₄₁ NO ₈ ＝
435 435 (M−H) ⁻ 97% Test Example N- (1-deoxy-D-sorbitol-1-yl) -N-lauroylaminoacetic acid obtained in Example 1 and N-obtained in Example 2 With respect to (1-deoxy-D-sorbitol-1-yl) -N-lauroyl-3-aminopropionic acid, an irritation test and a foaming power test were conducted by the following methods. Further, as control compounds, sulphosuccinate (control compound 1), lauryl glucoside (control compound 2) and N-lauroyl-N-methyltaurine, which are conventionally known to be extremely mild to skin, are selected. Similarly, the irritation test and the foaming power test were performed. The results are shown in Table 1.

<Test Method for Irritation> As a test method for irritation, a cytotoxicity test correlated with ocular mucosal irritation was carried out. That is, SIRC (rabbit cornea-derived cells) was incubated at 37 ° C, 50% C
A surfactant was added to the pre-cultured product under O ₂ humid gas phase condition for 2 days, and the mixture was further cultured for 2 days under the same condition. After that, methanol was added dropwise to fix it, Giemsa staining was performed, and the absorbance was measured to determine an IC ₅₀ value (concentration at which 50% of cells were engrafted). As a guideline for evaluation of measured values, less than 30 ppm is strong irritation, more than 30 ppm and less than 300 ppm is moderate irritation, and more than 300 ppm is less irritation.

<Testing Method for Foaming Power> The surfactant was diluted to 40% by diluting it with 4 ° DH hard water so that the weight concentration was 1.0%. The measurement was carried out by the inversion stirring method, and the amount of foaming (ml) was measured after stirring for 30 seconds and standing for 10 seconds.

[0035]

[Table 1]

[Brief description of drawings]

FIG. 1 shows N- (1-deoxy-D-obtained in Example 1).
1 is a ¹ H-NMR spectrum of sorbitol-1-yl) -N-lauroylaminoacetic acid.

FIG. 2 shows N- (1-deoxy-D-obtained in Example 1).
1 is an IR spectrum of sorbitol-1-yl) -N-lauroylaminoacetic acid.

FIG. 3 shows N- (1-deoxy-D-obtained in Example 1).
1 is an MS spectrum of sorbitol-1-yl) -N-lauroylaminoacetic acid.

FIG. 4 shows the N- (1-deoxy-D-obtained in Example 2).
1 is a ¹ H-NMR spectrum of sorbitol-1-yl) -N-lauroyl-3-aminopropionic acid.

FIG. 5 shows N- (1-deoxy-D-obtained in Example 2).
1 is an IR spectrum of sorbitol-1-yl) -N-lauroyl-3-aminopropionic acid.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C07C 235/12 7106-4H 235/26 7106-4H 235/32 7106-4H C07H 15/04 E C11D 1/52 // A61K 7/075 8615-4C 7/50 9051-4C

Claims (3)

[Claims] 1. A novel sugar amino acid compound represented by the general formula (1). [Chemical 1] [In the formula, R represents a linear or branched alkyl group having 5 to 22 carbon atoms, an alkenyl group, a hydroxyalkyl group, or an alkylphenyl group. R'represents a residue remaining after removal of a glycosidic hydroxyl group from a hydrogen atom or sugar, and (m + 1) R's may be the same or different from each other. m: Indicates the number of 3 or 4. R ": represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. N: represents a number of 0 to 10. X: a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a monoalkyl group having 2 to 3 carbon atoms, A di- or trialkanol ammonium, an alkyl group-substituted ammonium having 1 to 5 carbon atoms, or a basic amino acid group is shown.] 2. A general formula (2): [In the formula, R represents a linear or branched alkyl group having 5 to 22 carbon atoms, an alkenyl group, a hydroxyalkyl group, or an alkylphenyl group. Y: Indicates a halogen atom. ] And a fatty acid halide represented by the general formula (3): [In the formula, R'is a residue remaining after removing the glycosidic hydroxyl group from a hydrogen atom or sugar, and (m + 1) R's may be the same or different from each other. m: Indicates the number of 3 or 4. R ": represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. N: represents a number of 0 to 10. X: a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a monoalkyl group having 2 to 3 carbon atoms, A di- or trialkanol ammonium, an alkyl group-substituted ammonium having 1 to 5 carbon atoms, or a basic amino acid group.] Is reacted with the polyhydroxy amino acid in the presence of an alkaline substance. 1. The method for producing the sugar amino acid compound according to 1. 3. A surfactant composition comprising the sugar amino acid compound according to claim 1.