JP3218071B2 - Novel sugar amino acid compound, method for producing the same, and surfactant composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 having a mild action on the skin and especially the ocular mucous membrane, and also having excellent foaming power and detergency, useful as a surfactant for cleaning hair, face, and body, and the same. It relates to a manufacturing method.

[0002]

2. Description of the Related Art In recent years,
The desire for cleanliness, especially among young people, is rapidly spreading and has become a major social phenomenon. For example, hair washing habits have changed drastically in recent years, with most people washing their hair every day. On the other hand, this change in awareness of cleanliness
Surfactants have been required to have not only detergency but also low irritation. In addition, recent environmental awareness has prompted the use of natural materials in surfactants. In consideration of these circumstances, it is most desirable to synthesize a low-irritating surfactant for skin and ocular mucosa by effectively utilizing renewable natural materials.

[0003] Hitherto, alkyl glycosides have 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 between sugar and amino acids are known substances and there are examples reported as skin protective agents for cosmetics, but there is no sugar amino acid having a surfactant function.
In addition, N-acylated amino acids are more Schotten-amino acids than amino acids.
Although known as a low-irritant surfactant easily synthesized by the Baumann reaction, no attempt has been made to introduce a polyhydroxyl group to further reduce irritation.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on novel sugar amino acid derivatives useful as hypoallergenic surfactants. The present inventors have found that they have extremely excellent properties as a surfactant, that is, they have low irritation and good foaming power, biodegradability and solubility in water, and have 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]

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[Wherein, R represents a linear or branched alkyl, alkenyl, hydroxyalkyl or alkylphenyl group having 5 to 22 carbon atoms]. R ′: represents a hydrogen atom . m: 3 or 4 is indicated. R ": represents a hydrogen atom or an alkyl group having 1 to 10 carbons. N represents a number of 0 to 10. X: a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a monovalent having 2 to 3 carbons, A di- or trialkanol ammonium, an alkyl-substituted ammonium having 1 to 5 carbon atoms or a basic amino acid group.] The present invention will be described in detail below.

[0007] There are no reports on the sugar amino acid compound represented by the above general formula (1) in the conventional literature and patents, 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) has a general formula (2)

[0008]

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

[0010]

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Wherein R ′, m, R ″, n and X have the same meanings as described above, by reacting with a polyhydroxyamino acid in the presence of an alkaline substance. Can be.

The fatty acid halide represented by the above general formula (2) used in the present invention includes, for example, a single composition such as capric chloride, caproic chloride, lauric chloride, oleic chloride and isostearic chloride. Fatty acid chlorides having a mixed composition such as fatty acid chloride, coconut oil fatty acid chloride and tallow fatty acid chloride are exemplified.

The polyhydroxyamino acid represented by the general formula (3), which is another raw material used in the present invention, includes, 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; 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 (JP-A-50-95201).

In the reaction of the present invention, the above-mentioned fatty acid halide (2) usually reacts with the above-mentioned polyhydroxyamino acid (3).
It is used in a molar amount of 0.9 to 3.0 times, preferably 1.0 to 1.2 times. If the amount of the fatty acid halide is less than this range, a large amount of the polyhydroxyamino acid (3) remains in the reaction product.If the amount is larger than this range, the unreacted fatty acid halide (2) is converted into a large amount of the fatty acid. Is by-produced.

In the reaction of the present invention, in order to ensure reactivity and promote a certain reaction, an alkaline substance is added to the reaction system to adjust the pH in the system to the alkali side, preferably to a pH of 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 progress of the reaction and unreacted polyhydroxyamino acid (3) form a salt, and the reaction does not proceed sufficiently. Is higher than this range, the decomposition of the raw material fatty acid halide (2) is promoted, and a large amount of fatty acids 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. Particularly, sodium hydroxide and potassium hydroxide are practical. The amount of these alkaline substances used is such that the reaction system is maintained at the aforementioned pH.

In the present invention, the reaction temperature is 3 to 50 ° C., especially
15-30 ° C is preferred. When the temperature is lower than this range, the viscosity in the system increases and the stirring efficiency becomes poor, and when the temperature is higher than this range, the decomposition rate of the raw material fatty acid halide (2) increases remarkably, and in any case, Even fatty acid by-products increase.

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 of the above may 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 a surfactant composition containing such a sugar amino acid compound as a main component has excellent foaming power, detergency, and low irritation. Since it is mild to the eye mucosa, it can be used not only as a base for washing hair and a base for washing body, but also as a base for washing face. General formula according 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.
(Effective ingredient conversion).

In the above, other components can be used in combination. Examples of such usable materials include general anionic surfactants (alkyl sulfates, alkyl ether sulfates, α-olefin sulfonates). ,
Alkyl sulfonate, taurine-based surfactant, sarcosinate-based surfactant, isethionate-based surfactant,
N-acyl acidic amino acid surfactants, higher fatty acid salts, acylated polypeptides and the like); amphoteric surfactants (alkyl betaine surfactants, amidopropyl betaine surfactants, imidazolinium betaine surfactants); A sulfobetaine-type surfactant, a phosphobetaine-type surfactant and an amino acid-type surfactant such as sodium laurylaminopropionate); a nonionic surfactant (coconut fatty acid diethanolamide, monoglyceride stearate, lauryl dimethylamine oxide) Polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, etc.); cationic surfactants (stearyltrimethylammonium chloride, distearyldimethylamine 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]

Next, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited by these examples.

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% hydrate) were sealed in a 20 liter autoclave together with 10 kg of ion-exchanged water and stirred. After heating to 80 ° C, hydrogen pressure 140kg /
The reaction was performed in cm ² for 12 hours. After cooling, the catalyst was filtered off, water was distilled off, and methanol was added for crystallization to give N 2 having the following structure.
-(1-Deoxy-D-sorbitol-1-yl) aminoacetic acid was obtained. Yield: 1775 g (62% yield), pale brown powder Acid value analysis value: actual value 230.5 / theoretical value 234.8 Hydroxyl value analysis value: actual value 1101 / theoretical value 1173.8

[0022]

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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 chloride and a 40% aqueous sodium hydroxide solution were separately added dropwise over 4 hours while keeping the pH of the system at 10. The time course of the reaction was monitored by gas chromatography. After confirming the disappearance of the raw materials, 120 g of concentrated hydrochloric acid was added, and the pH in the system was maintained at 2, whereby the target acylated saccharide amino acid was obtained as a precipitate. The precipitate is separated by filtration, washed with water, and further washed with ethyl acetate to remove by-product 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]

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[0026] The resulting N-(1-deoxy -D- sorbitol-1-yl) -N- lauroyl amino acid ¹ H-
The measurement results of NMR, IR and MS are shown below. ¹ H-NMR (δ, ppm, heavy water, internal standard; 3- (trimethylsilyl) propanesulfonic acid Na): shown in FIG. 0.85 (3H, lauroyl group methylene), 1.6 (2H, lauroyl group methylene, amide β-position),
2.25, 2.5 (1H each, lauroyl group methylene, amide α
3-4 (8H, sorbitol hydrogen), 4.0, 4.25 (1 each)
H, glycine hydrogen) IR (cm ^-1 , KBr tablet); 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.

[0027] ^{420 (M-H) - 97} % Example 2 a) glucose in a synthetic 500 ml autoclave sugar β- alanine 54.14g (0.3mo
l), β-alanine 26.77 g (0.3 mol), 5% Pd-carbon (50%
(Hydrated) 3.43 g, and 180 ml of water as a solvent are charged at 80 ° C.
Until heated. After that, pressurize hydrogen and increase internal pressure to 140
The mixture was stirred for 6 hours while keeping it constant at kg / cm ² . The reaction-completed product is obtained as a colorless and transparent aqueous solution, and Pd-carbon is recovered by filtration, water is partially distilled off, methanol is added for crystallization to give N- (1-deoxy -D-sorbitol-1-yl) -3-aminopropionic acid was obtained. Yield: 34.97 g (46% purification yield), colorless needles

[0028]

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B) Acylation 8.93 g (0.035mo) of N- (1-deoxy-D-sorbitol-1-yl) -3-aminopropionic acid obtained in a)
l) was dissolved in 20 ml of water / 9 ml of acetone, cooled on ice, and 15.4 g (0.070 mol) of lauric chloride and a 40% aqueous sodium hydroxide solution were simultaneously added dropwise while maintaining the pH in the system at 9.5 to 10.5. After 30 minutes, the dropwise addition 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. The target substance falling as a precipitate and lauric acid are separated by filtration, washed with water, and further washed with ethyl acetate to remove lauric acid, and N- (1-deoxy-D-sorbitol-1-yl)-having the following structure is obtained. N-Lauroyl-3-aminopropionic acid was obtained. Yield: 13.09 g (purification yield: 85%), colorless crystals Melting point: 119.5-123.5 ° C

[0030]

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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-position lauroyl group methylene), 2.4 (4H, carbonyl group α-position lauroyl group methylene, carboxyl group α-position methylene ), 3.3 to 3.9 (10H,
Carboxyl group β-position methylene, 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-lauroylaminoacetic acid obtained in Example 2 (1-Deoxy-D-sorbitol-1-yl) -N-lauroyl-3-aminopropionic acid was subjected to an irritation test and a foaming test by the following methods. As control compounds, sulfosuccinate (control compound 1), lauryl glucoside (control compound 2) and N-lauroyl-N-methyltaurine, which are conventionally known to be very mild to the skin, were selected. Similarly, an irritation test and a foaming test were conducted. Table 1 shows the results.

<Test Method for Irritation> As a test method for irritation, a cytotoxicity test correlated with irritation of the ocular mucosa was performed. That is, SIRC (rabbit cornea-derived cells) was incubated at 37 ° C and 50% C
A surfactant was added to those pre-cultured for 2 days under O ₂ wet gas phase conditions, and further cultured under the same conditions for 2 days. Thereafter, methanol was added dropwise to fix the cells, the cells were stained with Giemsa, and the absorbance was measured to determine the IC ₅₀ value (the concentration at which cells survived 50%). As a guide for evaluation of measured values, less than 30 ppm is severe irritation, 30 ppm or more and less than 300 ppm is moderate irritation, and 300 ppm or more is low irritation.

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

[0035]

[Table 1]

[Brief description of the drawings]

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

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

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI A61K 7/50 A61K 7/50 (56) References European Patent Application Publication 282816 (EP, A2) (58) Fields investigated (Int. .Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A novel sugar amino acid compound represented by the general formula (1). Embedded image [In the formula, R represents a straight-chain or branched-chain alkyl group having 5 to 22 carbon atoms, an alkenyl group, a hydroxyalkyl group, or an alkylphenyl group. R ′: represents a hydrogen atom . m: 3 or 4 is indicated. R ": represents a hydrogen atom or an alkyl group having 1 to 10 carbons. N represents a number of 0 to 10. X: a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a monovalent having 2 to 3 carbons, It represents a di- or trialkanol ammonium, an alkyl-substituted ammonium having 1 to 5 carbon atoms or a basic amino acid group.] 2. A compound of the general formula (2) [In the formula, R represents a straight-chain or branched-chain alkyl group having 5 to 22 carbon atoms, an alkenyl group, a hydroxyalkyl group, or an alkylphenyl group. Y: represents a halogen atom. And a fatty acid halide represented by the general formula (3): [Wherein, R ′ represents a hydrogen atom . m: 3 or 4 is indicated. R ": represents a hydrogen atom or an alkyl group having 1 to 10 carbons. N represents a number of 0 to 10. X: a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, a monovalent having 2 to 3 carbons, A di- or trialkanol ammonium, an alkyl group-substituted ammonium having 1 to 5 carbon atoms or a basic amino acid group.] In the presence of an alkaline substance. 2. 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.