JPH08188567A - Method for producing sugar ester of α-sulfo fatty acid - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] To provide a method for producing a sugar ester of an α-sulfonic acid fatty acid having an excellent color tone in a high yield. [Configuration] The following general formula (1) In the method for producing an α-sulfofatty acid derivative represented by the following general formula (2) And a sugar derivative represented by the following general formula (3) The method according to the above, which comprises reacting the α-sulfofatty acid ester represented by the following in the presence of an alkaline catalyst.
(In the above formula, Z- (OH) qw-1-s is the q in a sugar (Z- (OH) q) having q free hydroxyl groups in the molecule.
(W + 1 + s) of the free hydroxyl groups represent a sugar residue formed by participating in the reaction, R ¹ and R ⁴ are chain aliphatic groups, R ² is an aliphatic group, R ³ and R ⁵ represents an alkylene group, M represents a hydrogen atom or a salt-forming cation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a sugar ester of α-sulfofatty acid.

[0002]

Conventionally, it has been known that polyhydric alcohol esters of α-sulfofatty acids and salts thereof are useful surfactants. For example, these are known as fiber treating agents (Japanese Patent Application Laid-Open No. 4-153368). ), An emulsifier for petroleum resin emulsion (JP-A-4-156934), an activator for oil recovery (GB2143563), a detergent composition (JP-A-6-6).
No. 5,593, JP-A-6-172784) and the like have been attempted to be applied. On the other hand, as a method for producing an α-sulfofatty acid ester, a method in which an α-sulfofatty acid lower alkyl ester and a polyhydric alcohol are transesterified is known. In this transesterification reaction, the α-sulfofatty acid lower alkyl ester used as the reaction raw material acts as an acid catalyst, so that the reaction proceeds smoothly without using a special catalyst. Therefore, in the transesterification reaction, a reaction without a catalyst is general. By the way, when an α-sulfofatty lower alkyl ester is reacted with glucose as described above, the quality of glucose is altered during the reaction, resulting in coloration of the obtained product, and the yield of the target product is also low. Causes the problem.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a sugar ester of α-sulfonic acid fatty acid having an excellent color tone in a high yield.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, the following general formula (1)

Embedded image (In the above formula, Z- (OH) qw-1-s is the q in a sugar (Z- (OH) q) having q free hydroxyl groups in the molecule.
Of the free hydroxyl groups, (w + 1 + s) hydroxyl groups represent sugar residues formed by participating in the reaction, [(R ¹ O)-
(R ³ O) t] is bonded to the anomeric position of the sugar residue,
[(R ⁴ O)-(R ⁵ O) u] and [OCOCH (SO
₃ M) R ² ] s is bonded to a position other than the anomeric position of the sugar residue, R ¹ and R ⁴ are chain aliphatic groups having 1 to 30 carbon atoms, and R
² is an aliphatic group having 4 to 30 carbon atoms, R ³ and R ⁵ are 1 carbon atoms
~ 4 alkylene group, M each represents a hydrogen atom or a salt-forming cation, q is a number of 3 or more, w is a number of 0 or 1 or more,
s is a number of 1 or more, t and u are numbers of 0 to 20, respectively,
(W + 1 + s) is q or less) In the method for producing an α-sulfofatty acid derivative represented by the following general formula (2)

Embedded image (In the formula, Z- (OH) qw-1 is a sugar (Z- (OH) q) having q free hydroxyl groups in the molecule, and (w + 1) of the q free hydroxyl groups are involved in the reaction. And a sugar derivative represented by R ¹ , R ³ , R ⁴ , R ⁵ , q, t, u and w has the same meaning as described above, and a sugar chain represented by the following general formula (3 )

Embedded image Wherein R ⁶ represents a lower alkyl group and R ² and M have the same meanings as described above, and the reaction is carried out in the presence of an alkaline catalyst. Will be provided.

Examples of the salt-forming cation M include an alkali metal ion, an alkaline earth metal ion, and a substituted or unsubstituted ammonium ion. In the general formula (1), when w> 0, w and s
The ratio w / s is preferably 2/1 to 1/5, more preferably 1 to 0.5. If this ratio is too large, there is a problem such that the water solubility of the resulting α-sulfofatty acid sugar ester (hereinafter, also simply referred to as α-sulfofatty acid ester) is decreased, which is not preferable, while if it is too small,
The hydrophilicity is too high, which causes problems such as reduction in surface activity, which is not preferable.

The sugar derivative represented by the general formula (2) can be derived from the sugar represented by the following general formula (4).

[Chemical 4] In this formula, Z represents the sugar skeleton after removing the hydroxyl group from the sugar molecule. The sugars include monosaccharides, oligosaccharides and polysaccharides, and specific examples thereof are shown below. (1) Monosaccharides Monosaccharides include those represented by the following general formula (5).

Embedded image In the above formula, n represents a number of 5 or 6. Specific examples of such monosaccharides include arabinose, ribose, xylose, xylylose, ribulose, glucose, galactose, fructose, mannose, sorbose, talose, fucose, glucoheptose, sedoheptulose,
Examples thereof include mannoheptulose and glucoheptulose. (2) Oligosaccharides Examples of oligosaccharides include those represented by the following formula.

[Chemical 6] In the above formula, n represents a number of 5 or 6. P shows the number of 1-10. Such oligosaccharides include maltose, lactose, lactose, cellobiose, isomaltose, gentiobiose, laminaribiose, xylobiose, mannobiose, maltotriose, cellotriose, manninotriose, maltotetraose, and the like,
Examples thereof include those obtained by hydrolyzing polysaccharides (cellulose, hemicellulose, starch, inulin, dextrin, dextran, xylan, etc.) into low molecular weight compounds. (3) Polysaccharides Examples of polysaccharides include cellulose, hemicellulose,
Examples thereof include starch, inulin, dextrin, dextran, xylan and the like.

In the sugar derivative represented by the general formula (2), an aliphatic ether group (R ^{1 which} is bonded to the anomeric position (carbon atom to which the semiacetal-type hydroxyl group is bonded) is attached.
^{O) - (R 3 O)} t- the general formula with respect to sugar ^{(7) (R 1 O)} - (R 3 O) t-H (7) ( wherein, R ^1, R ³ and t are It can be introduced by reacting an aliphatic alcohol having the same meaning as above). The reaction in this case is a conventionally known method using an acid catalyst [Fischer method, BIO, etc.
INDUSTRY, 10 , 408 (1993)]. In the sugar derivative represented by the general formula (2), the ether group (R ⁴ O)-(R ⁵ O) u- bonded to the carbon other than the anomeric position is
Formula ^{(8) (R 4 O)} - (R 5 O) u- 1 -R 5 -Y (8) ( wherein, Y represents a hydrogen atom or a chlorine or a halogen atom such as bromine, R ^4, R ⁵ and u have the same meanings as described above) and can be introduced by reacting a halide or the like of an aliphatic oxy compound represented by the formula ( ⁵ ) with the hydroxyl group of the sugar in the presence of a basic catalyst. In this case, the reaction for introducing an aliphatic ether group is carried out by the conventionally known O-alkylation method by the Williamson method [Reference: J. Chem, Soc, 4 , 22
9 (1852)]. Further, it can be carried out by using an epoxy ring-opening reaction or the like using an acid or base catalyst.

In order to preferably produce the method of the present invention, first, a hemiacetal type aliphatic ether group is introduced at the anomeric position of sugar, and then an ether group is introduced at a position other than the anomeric position of sugar, if necessary. . Of course, it is also possible to introduce an aliphatic ether group at the anomeric position and at other positions at the same time.

In the aliphatic oxy compounds represented by the general formulas (7) and (8), the aliphatic groups R ¹ and R ⁴ are
The aliphatic groups R ¹ and R ⁴ , which may be the same or different, may be an alkyl group, an alkenyl group, a polyhydric alcohol residue or an alkylated polyhydric alcohol residue. Examples of the (alkyl) polyhydric alcohol residue include residues derived from alkylene glycols such as ethylene glycol, propylene glycol and butylene glycol; residues derived from polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycerin and poly In addition to residues derived from glycerin or alkyl (poly) glycerin, residues derived from various polyhydric alcohols such as trimethylolpropane, trimethylolpropane, erythritol, sorbitol and pentaerythritol can be mentioned. Although the carbon number of the aliphatic groups R ¹ and R ⁴ is not particularly limited, it is usually 1 to 30, preferably 6 to 22, and more preferably 8 to 18. The aliphatic groups R ¹ and R ⁴ may have an unsaturated bond. Examples of such aliphatic groups R ¹ and R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl,
Linear alkyl groups such as n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl ; 1-
Methyl-pentyl, 1-ethyl-butyl, 1-methyl-
Branched-chain alkyl groups such as hexyl, 1-methyl-heptyl, 1-butyl-hexyl; alkenyl groups such as 2-octenyl, 4-tetradecenyl, oleyl, etc., and various polyhydric alcohol residues described above. You can The lower alkylene groups R ³ and R ⁵ may be the same or different, and examples thereof include an ethylene group, a propylene group and a butylene group.

In the above general formulas (7) and (8), t and u are numbers of 0 to 20, preferably 1 to 15, and more preferably 1 to 10.

Preferred specific examples of sugar derivatives include, for example, methyl glucoside, ethyl glucoside, propyl glucoside, butyl glucoside, amyl glucoside, 6-
Hexyloxy-methyl glucoside, 6-octyloxy-methyl glucoside, 6-dodecyloxypolyoxyethylene-methyl glucoside, 6-octadecyloxy-methyl glucoside, 2,6-dihexyloxy-methyl glucoside, 3,6-dioctyloxy- Methyl glucoside, 3,6-didodecyloxy-methyl glucoside, 4,6-dioctadecyloxypolyoxyisopropylene-methyl glucoside, 2,3,6-trihexyloxy-methyl glucoside, 2,4,6-tridodecyl Oxy-methyl glucoside, 6-hexyloxy-ethyl glucoside, 6-octyloxy-ethyl glucoside, 6-dodecyloxy-ethyl glucoside, 6-octadecyloxy-methyl glucoside, 2,6-dihexyloxy polyoxye Ren - ethyl glucoside, 3,
6-dioctyloxy-ethyl glucoside, 4,6-didodecyloxy-ethyl glucoside, 2,6-dioctadecyloxy-ethyl glucoside, 2,3,6-trihexyloxy-ethyl glucoside, 3,4,6-tri Dodecyloxy-ethyl glucoside, 6-hexyloxy-octyl glucoside, 6-octyloxy-octyl glucoside, 6-dodecyloxy polyoxyethylene-
Octylglucoside, 6-octadecyloxy-octylglucoside, 2,6-dihexyloxy-octylglucoside, 3,6-dioctyloxy-octylglucoside, 4,6-didodecyloxy-octylglucoside, 2,6-dioctadecyloxy- Octyl glucoside, 2,4,6-trihexyloxy-octyl glucoside, 3,4,6-tridodecyloxy-octyl glucoside, 6-octyloxy-oleyl glucoside, 6
-Octyloxy-dodecylmaltoside, 6-octyloxy-hexadecylmaltotrioside, 6-hexyloxy- (3,4-dioxaheptyl) dodecylglucoside, 6-dodecyloxy- (3,4-dioxaheptyl) Ethyl glucoside, 6-dodecyloxy- (3-oxatridecyl) propyl glucoside, 6-octadecyloxy- (3,4-dioxaheptyl) methyl glucoside, 6-hexyloxy- (3,4-dioxaheptyl) butyl Glucoside, 6-dodecyloxy- (3-oxadodecyl) methyl glucoside, octyl glyceryl glucoside, decyl glyceryl glucoside, dodecyl triglyceryl glucoside, oleyl triglyceryl glucoside, stearyl polyglyceryl glucoside, ethyl polyoxyethylene Glucoside, ethyl dioxyethylene glucoside, methyl polyoxyethylene glucoside.

In the α-sulfofatty acid ester represented by the general formula (3), the aliphatic group R ² has 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 6 to 1 carbon atoms.
6. The aliphatic radical R ² can be saturated or unsaturated and can be straight-chain or branched. Specific examples of R ² include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-
Octyl, n-nonyl, n-decyl, n-undecyl,
n-dodecyl, n-tridecyl, n-tetradecyl, n
-Linear alkyl groups such as heptadecyl, n-hexadecyl, n-pentadecyl, n-octadecyl, n-nonadecyl; 1-methyl-pentyl, 1-ethyl-butyl,
Examples thereof include branched-chain alkyl groups such as 1-methyl-hexyl, 1-methyl-heptyl and 1-butyl-hexyl; alkenyl groups such as 2-octenyl, 4-tetradecenyl and cis-7-hexadecyl. Further, R ⁶ may be an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl and the like.

The reaction between the sugar derivative represented by the general formula (2) and the α-sulfofatty acid ester represented by the general formula (3) is represented by the following formula.

[Chemical 9]

Next, the transesterification reaction of the reaction formula (9) will be described in detail. In the present invention, an alkaline catalyst is used as the catalyst for carrying out the ester exchange reaction. As examples of the alkaline catalyst, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium methylate, sodium ethylate, sodium hydride, basic ion exchange resin and the like can be used. The amount of the alkaline catalyst used is not particularly limited, but sugar derivative 1
It is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 00 parts by weight.

To carry out the transesterification reaction, the sugar derivative and α-sulfofatty acid alkyl ester or a salt thereof are preliminarily heated at a temperature of 30 to 80 ° C., preferably 40 to 60.
Mix and dissolve at ℃. In this case, if necessary, the boiling point is 20
Organic solvents below 0 ° C, such as methanol and ethanol,
A lower alcohol such as propanol can be used as a dissolution aid. Note that this mixing and dissolving step can be omitted. Next, this mixed solution is used as it is or by adding a high-boiling point organic solvent thereto, and the temperature is 80 ° C to 150 ° C, preferably 85 ° C to 115 ° C, more preferably 95 ° C to 110 ° C.
Then, the ester exchange reaction is carried out in the presence of an alkaline catalyst. At this time, when the sulfonate is used as the raw material, the amount of the alkaline catalyst may be the amount shown above, but when the free sulfonate is used as the raw material, the sulfonate is used in the same amount as the alkali catalyst. It is necessary to use a further excess of alkaline catalyst after the formation of. In this case, if the reaction temperature is lower than 80 ° C., the viscosity of the reaction solution becomes high and the reaction does not proceed promptly. Also, if the temperature exceeds 150 ° C., the color of the reaction solution becomes severe.
During the reaction, it is desirable to carry out under reduced pressure (preferably 200 torr or less) in order to quickly distill the by-produced lower alcohol out of the reaction system, but normal pressure is also acceptable.
In the case of normal pressure, an inert gas is circulated in the reaction system to discharge the lower alcohol produced as a by-product to the outside of the system, or molecular sieves or the like adsorb and remove the by-produced alcohol. Examples of the high boiling point organic solvent include those having a boiling point of 80 ° C. or higher, such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, β-picoline, pyridine, acetonitrile, dioxane, toluene, xylene. The amount of the high boiling point organic solvent used is the total amount of the sugar derivative and the α-sulfofatty acid alkyl ester 1
The amount is 10 to 2000 parts by weight, preferably 50 to 1000 parts by weight, based on 00 parts by weight.

Α-used in the above transesterification reaction
The amount of the sulfo fatty acid ester or its salt used is appropriately selected according to the desired sugar ester of α-sulfo fatty acid.
For example, when it is desired to obtain a product containing as a main component a product in which s mol of α-sulfofatty acid groups are bonded, s to 1.3 s mol, preferably 1.1 s, per mol of the sugar derivative.
~ 1.2 smol of α-sulfofatty acid ester is used.
In addition, free hydroxyl groups (qw-
When trying to obtain a product containing as a main component a product in which α-sulfofatty acid groups are bound to all of 1), (qw
-1) to 1.3 (q-w-1) mol, preferably 1.1 (q
-W-1) to 1.2 (q-w-1) mol of α-sulfofatty acid ester or salt thereof is used.

In the present invention, the production of the α-sulfofatty acid derivative in which s = 1 in the general formula (1), that is, one having one sulfone residue in the molecule is particularly preferable. Such an α-sulfofatty acid derivative is particularly excellent in mildness to skin and hair, and is also excellent in water solubility and performance as a surfactant. In the general formula (1), when s = 1, w is 0, 1 or 2, preferably 0 or 1, and R ¹ has 6 to 6 carbon atoms.
22, preferably 8 to 18, and the carbon number of R ⁴ is 6 to
22, preferably 8 to 18, and the carbon number of R ² is 4 to
20, preferably 6 to 16. Furthermore, the number of t and u is 1 to 7, preferably zero.

In the transesterification reaction according to the present invention, an alkaline catalyst is used as a catalyst, the reaction is carried out under alkaline conditions, and a sugar derivative having a substituent at the anomeric hydroxyl group is used as a sugar and is unlikely to undergo alteration during the reaction. Therefore, various sugar esters of α-sulfofatty acid having a good color tone with less by-products can be obtained in good yield. In particular, when a hydrogen peroxide-bleached α-sulfofatty acid ester is used as a raw material, the reaction product is less colored and a reaction product having a very good color tone can be obtained.

The α-sulfofatty acid salt obtained by the transesterification reaction may be reacted with an acid, if necessary, to contain a free sulfonic acid group (—SO ₃ H).
Further, it is possible to carry out post-treatment (pH adjustment, bleaching, etc.) depending on the application.

Next, the sugar residue [Z- (OH) qw-1-
[s] will be described more specifically. The (poly) sugar residue is
More specifically, it is represented by the following general formula (10) [mA- (OH) qw-1-s] (10) In this formula, mA is a monosaccharide (CnH ₂ nOn) condensed by m units. (Poly) sugar [m (CnHn + ₁ O)-(OH)] [q =
m (n-1) -2 (m-1)] is a (poly) sugar skeleton in which all hydroxyl groups contained therein are removed, and q (OH) qw-1-
s indicates that (w + 1 + s) hydroxyl groups are involved in the reaction among the total number q of hydroxyl groups bonded to the (poly) sugar skeleton mA. If monosaccharide (CnH ₂ nOn) residues of the pentose (C ₅ H ₁₀ O ₅₎ residues, the number q of all hydroxyl groups are n-1
Pieces, that is, four, one of those hydroxyl groups (hemiacetals type hydroxyl group) is a chain aliphatic hemiacetal form ether groups - substituted with ^{[(R 1 O) (R 3} O) t- ] , At least w of the other hydroxyl groups are substituted with a chain aliphatic ether group [(R ⁴ O)-(R ⁵ O) u-], and s of the other hydroxyl groups, preferably 1 It is substituted with an α-sulfofatty acid-containing group represented by the following formula (11). That is, the sugar residue in this case has the formula [Z- (OH) qw-1-
s] (however, q = 4, w = 0 to 2, s = 1 to 2, w + 1 +
s ≦ 4) or [(C ₅ H ₆ O)-(OH) qw-1-s] (however, q = 4, w = 0 to 2, s = 1 to 2, w + 1 + s ≦
4).

Monosaccharide (CnH ₂ nOn) residues are hexose (C
_{In the case of 6} H ₁₂ O ₆ ) residues, the number q of all hydroxyl groups is n−1, that is, 5 and one of these hydroxyl groups (semi-acetal type hydroxyl group) is a chain aliphatic hemiacetal type. It is substituted with an ether group [(R ¹ O)-(R ³ O) t-], and w of other hydroxyl groups are chain aliphatic ether groups [(R ⁴ O)-
(R ⁵ O) u-] is substituted with s of other hydroxyl groups,
Preferably, one is substituted with the α-sulfofatty acid-containing group represented by the above formula (11). That is, the sugar residue in this case has the formula [Z- (OH) qw-1-s] (where q = 5, w
= 0 to 3, s = 1 to 3, w + 1 + s ≦ 5) or [(C ₆ H
₇ O)-(OH) qw-1-s] (however, q = 5, w = 0 to
3, s = 1 to 3, w + 1 + s ≦ 5). On the other hand, in the case of a skeleton mA (m ≧ 2) of a monosaccharide polymer having a structure in which the monosaccharide A (CnH ₂ nOn) is polyetherified, the number q of all hydroxyl groups is m (n-1) -2 (m -1) and one of these hydroxyl groups (semi-acetal type hydroxyl group) is a chain aliphatic hemiacetal type ether [(R ¹ O)-
Substituted with (R ³ O) t], w pieces are chain aliphatic ether group of the other hydroxyl groups ^{[(R 4 O) - (R} 5 O) u- ] is substituted with, among other hydroxyl Of s, preferably one of which is substituted with an α-sulfofatty acid-containing group represented by the above formula (11). The sugar residue in this case has the formula [Z- (OH)
qw-1-s] (however, q = m (n-1) -2 (m-1),
w = 0 to 3, s = 1 to 3] is preferable.

The α-sulfofatty acid ester or salt thereof obtained by the present invention is used as a surfactant. This α-sulfo fatty acid ester or its salt can be used as a surfactant component of a detergent composition. In such a detergent composition, the concentration of the α-sulfo fatty acid ester or its salt in the detergent composition may be any concentration as long as a detergent effect can be obtained, but it is preferably 0. 1 to 50% by weight, more preferably 0.5 to
It is 40% by weight. In addition, other suitable compounds may be used in combination with the detergent composition. For example, zeolite, sodium carbonate (potassium), sodium silicate, sodium citrate, polyacrylic acid and other builders; (poly) glycerin, sorbitol and other humectants; methyl cellulose, (poly) ethylene glycol, (poly) propylene glycol, Polyoxyethylene glycol distearate, viscosity modifiers such as ethanol, preservatives such as methylparaben and butylparaben, anti-inflammatory agents such as potassium glycyrrhizinate and tocopherol acetate, other bactericides, pearlizing agents, antioxidants, and fragrances. , Dyes, enzymes, ultraviolet absorbers and the like can be added as necessary. Furthermore, it is also possible to use other surfactants in combination with the detergent composition. Examples of such a surfactant include alkylbenzene sulfonate, α-olefin sulfonate, α-sulfo fatty acid alkyl ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate salt, sulfosuccinic acid mono (di) salt. Alkyl (alkenyl) ester-based surfactant, alkyl phosphate ester-based surfactant, amino acid-based surfactant,
Anionic surfactants such as taurate-based surfactants and higher fatty acid salts, nonionic surfactants such as alkyl saccharide-based surfactants and polyoxyethylene alkyl ether-based surfactants are preferably used.

[0024]

According to the method of the present invention, various sugar esters of α-sulfofatty acids or salts thereof, which are excellent in coloring, can be obtained in good yield. Α-obtained by the present invention
The sulfo fatty acid ester salt has extremely low skin irritation, and in particular, it is used in a mode in which it contacts at least a part of the human body, that is, for hard surface, wood surface, leather surface, skin and It is preferably applied as a cleaning composition component for hair. In this case, the hard surface includes metal surfaces such as tableware and automobile bodies, plastic surfaces, and ceramic surfaces. Furniture and pillar surfaces are examples of wood surfaces. As the leather surface, there are surfaces such as handbags and boots. The above-mentioned skin and hair cleaner compositions include liquid cleaners for skin and hair such as soap, body shampoo and shampoo, oral products such as toothpaste and mouthwash. Furthermore, the detergent composition containing the α-sulfofatty acid ester or salt thereof according to the present invention has excellent hard water resistance and dispersibility, and exhibits a high anti-soil redeposition effect during washing.

[0025]

Next, the present invention will be described in more detail with reference to examples. The percentages and parts shown below are based on weight.

Example 1 41.0 g of methyl Na salt of α-sulfopalmitate (0.
11 mol) and 19.1 g of methyl-α-D-glucoside.
(0.10 mol) was added to 100 ml of dimethylformamide, 1.0 g of sodium methylate (28% methanol solution) was added, and the temperature was 100 ° C. and the pressure was 33 mmH.
The reaction was carried out under stirring under the condition of g for 7 hours. After dimethylformamide contained in the obtained reaction product was distilled off under reduced pressure, 100 ml of water was added, and then an acidic granular ion exchange resin (Dowex 50W-X4, H type) was obtained as an aqueous solution showing neutrality. Was added and stirred to convert Na ions in the basic catalyst into hydrogen ions. The ion exchange resin was filtered off from the mixture thus obtained, and the filtrate was freeze-dried to give a white solid [α-methylglucoside (α-sulfopalmitic acid) ester Na salt] with almost no coloration.
3.4 g was obtained. When the white solid [A] thus obtained is analyzed by high performance liquid chromatography (HPLC), α-methylglucoside (α-sulfopalmitic acid) is obtained.
It was confirmed that the monoester Na salt and the diester Na were obtained at the reaction rates of 95% and 2%, respectively. It was confirmed that the α-sulfopalmitic acid methyl Na salt used as the reaction raw material was not dissolved in water unless heated, whereas the white solid (Na salt) was easily dissolved in cold water.
In addition, proton NMR of the white solid (Na salt) [A]
According to the above, δ = 4.8 ppm (proton of α-methine proton of fatty acid) and 3.4 ppm (α-O-methyl proton of anomeric position of glucoside) were respectively observed.

Example 2 34.8 g (0.1% methyl α-sulfolauric acid Na salt)
1 mol) and alkyl polyglucoside A (mixture of octyl polyglucoside and decyl polyglucoside) 30.
6 g (0.1 mol) was dissolved in 100 ml toluene. The alkyl polyglucoside A is a mixture of octyl polyglucoside and decyl polyglucoside 7
It was obtained by freeze-drying a 0% aqueous solution (trade name “Glucopon 225CSUP”, manufactured by Henkel). Next, the sodium methylate (28
% Aqueous methanol solution), and the mixture was heated under reflux for 8 hours with stirring at 112 ° C. to carry out a transesterification reaction. In this reaction, the condensed reaction solvent (toluene) was passed through a column packed with 50 g of molecular sieves 4A to remove by-product methanol contained in the solvent and then returned to the reaction system again. After completion of the reaction, toluene was distilled off from the reaction product, and the resulting residue was mixed with water 10
It was dissolved in 0 ml to give an aqueous solution. Example 1 in this aqueous solution
After converting the sodium ion in the basic catalyst into hydrogen ion by adding the acidic ion exchange resin shown in, the resin was filtered off and the filtrate was lyophilized to give a white solid with almost no coloration [alkyl polyglucoside (α -Sulfolauric acid) ester Na salt] was obtained. When the white solid [B] thus obtained is analyzed by HPLC, alkyl polyglycoside (α-sulfolauric acid) monoester Na salt and diester Na salt are obtained at a reaction rate of 93% and 2%, respectively. It was confirmed. Further, when the white solid [B] is analyzed by proton NMR, δ = 4.9 pp
m (alpha methine proton of fatty acid) 4.2 and 4.8
ppm (proton in anomeric position) was observed. It was confirmed that the white solid [B] had good water solubility.

Example 3 Methyl α-sulfostearate Na salt 44.1 g (0.
11 mol) and 19.1 g of methyl-α-D-glucoside.
(0.10 mol) was dissolved in 100 ml of acetonitrile. To this solution, potassium t-butoxide (1.0) was added, and the mixture was heated under reflux at 82 ° C. for 7 hours with stirring to carry out the transesterification reaction. After the completion of the reaction, acetonitrile was distilled off from the reaction product, the obtained residue was treated with an acidic ion exchange resin in the same manner as in Example 1, and the obtained furnace liquid was freeze-dried to give a colored product. 56.5 g of almost white solid [α-methylglucoside (α-sulfostearic acid) ester Na salt] was obtained. When the white solid [C] thus obtained was analyzed by HPLC, it was confirmed that α-methylglucoside (α-sulfostearic acid) monoester Na salt 94% and diester N were obtained.
It was confirmed to contain 3% of salt a. Further, in the proton NMR analysis of the white solid [C], δ = 4.8 ppm
(Α-methine proton of fatty acid), 3.4 ppm (α-O-methyl proton of anomeric position) was observed.
The white solid [C] showed good water solubility.

Example 4 44.1 g (0.1% methyl α-sulfostearate Na salt)
11 mol) and 67.2 g (0.10) of lauryloxypolyoxyethylene glucoside represented by the following structural formula.
Mol) was dissolved in 200 ml of dimethylformamide.

[Chemical 12] (P represents the average number of moles added, p = 7) To the above solution was added 1.0 g of sodium methylate (28% methanol solution), and the mixture was depressurized at 100 ° C. (37 mmH).
The mixture was heated under reflux for 8 hours with stirring under g) to carry out the esterification reaction. After completion of the reaction, dimethylformamide was distilled off from the reaction product, the obtained residue was treated with an acidic ion exchange resin in the same manner as in Example 1, and the obtained filtrate was freeze-dried to give almost no coloring. There was obtained 104.7 g of a white solid [lauryloxypolyoxyethylene glucoside (α-sulfostearic acid) ester Na salt]. When the white solid [D] thus obtained is analyzed by HPLC,
This is a lauryloxypolyoxyethylene glucoside (α-sulfostearic acid) monoester Na salt 9
It was confirmed to contain 2% and diester Na salt 2%.
Further, in the proton NMR analysis of the white solid [D],
δ = 4.9 ppm (α-methine proton of fatty acid),
4.2 and 4.8 ppm (proton at anomeric position)
Was observed. The white solid [D] showed good water solubility.

Example 5 Methyl α-sulfolaurate Na salt 34.8 g (0.1
1 mol) and 36.3 g (0.10 mol) of 6-dodecyloxy-methylglucoside represented by the following structural formula were dissolved in 200 ml of dimethylformamide.

[Chemical 13] Sodium methylate (28% methanol solution) (1.0 g) was added to the above solution, and the mixture was vacuumed at 100 ° C. (37 mmH
The mixture was heated under reflux for 8 hours with stirring under g) to carry out the transesterification reaction. After completion of the reaction, dimethylformamide was distilled off from the reaction product, the obtained residue was treated with an acidic ion exchange resin in the same manner as in Example 1, and the obtained filtrate was freeze-dried to give almost no coloring. 64.9 g of a white solid [6-dodecyloxy-methylglucoside (α-sulfolauric acid) ester Na salt] was obtained. When the white solid [E] thus obtained is analyzed by HPLC, it contains 91% of 6-dodecyloxy-methylglucoside (α-sulfolauric acid) monoester Na salt and 1% of diester Na salt. Was confirmed. Further, in the proton NMR analysis of the white solid [E], δ = 4.8 pp
m (α-methine proton of fatty acid), 3.4 ppm (α-O-methyl proton of anomeric position) was observed. The white solid [E] showed good water solubility.

Example 6 44.1 g (0.
11 mol) and 6-lauryloxypolyoxyethylene-methylglucoside 68.7 represented by the following structural formula.
g (0.10 mol) to 200 ml of dimethylformamide
Dissolved in.

Embedded image (P represents the average number of moles added, p = 7) To the above solution was added 1.0 g of sodium methylate (28% methanol solution), and the mixture was depressurized at 100 ° C. (37 mmH).
The mixture was heated under reflux for 9 hours with stirring under g) to carry out the esterification reaction. After completion of the reaction, dimethylformamide was distilled off from the reaction product, the obtained residue was treated with an acidic ion exchange resin in the same manner as in Example 1, and the obtained filtrate was freeze-dried to give almost no coloring. White solid [6-lauryloxypolyoxyethyleneoxy-methylglucoside (α-sulfostearic acid) ester Na salt] 97.3
g was obtained. The white solid [F] obtained in this way is treated with HPL
When analyzed by C, it was confirmed to contain 93% of 6-lauryloxypolyoxyethyleneoxy-methylglucoside (α-sulfostearic acid) monoester Na salt and 2% of diester Na salt. Further, in the proton NMR analysis of the white solid [F], δ = 4.8 ppm
(Α-methine proton of fatty acid), 3.4 ppm (α-O-methyl proton of anomeric position) was observed.
The white solid [F] showed good water solubility.

Example 7 1.8 g (0.01 mol) of D-glucose and 21 g of 1-O-n-dodecyltriglycerin represented by the following formula (15):
(0.05 mol) and Nafion NR50 (acid type)
[Aldrich] 0.7 g was added to a 100 ml three-necked flask, and the pressure was reduced to 15 mmHg at 130 ° C. for 6 hours.
Heat and stir for an hour. After completion of the reaction, the reaction mixture was cooled to room temperature, the ion exchange resin was filtered off, and the filtrate was purified by silica gel column chromatography to give 1-O
5.2 g of -n-dodecyl triglyceryl glucoside was obtained as a white solid. (Yield 81%) At this time, almost no by-products were observed except that an excessive amount of 1-O-n-dodecyltriglyceryl ether and a small amount of unreacted glucose were recovered. HO- [C ₃ H ₅ (OH) O] ₃ -C ₁₂ H ₂₅ (15)

Next, in Example 1, methyl-α-D
The experiment was conducted in the same manner except that 0.10 mol of 1-O-n-dodecyltriglyceryl glucoside obtained above was used instead of glucoside. In this way, almost no white solid [G] [dodecyltriglyceryl glucoside (α-sulfopalmitic acid) ester Na] 9 was obtained.
1.3 g was obtained. This product had a yield of monoester Na of 82%.

Example 8 1.8 g (0.01 mol) of D-glucose and 1-O-oleyltriglycerin 2 represented by the following formula (16):
9.4 g (0.06 mol) and activated montmorillonite KSF (Siid-Chemie) 1.2 g N-
30 ml of methylpyrrolidone is added to a 100 ml three-necked flask, and heated and stirred at 120 ° C. for 6 hours under a reduced pressure of 15 mmHg. After completion of the reaction, the reaction mixture was cooled to room temperature, the ion exchange resin was filtered off, the solvent was distilled off from the filtrate, and the residue was purified by silica gel column chromatography to give 1-O-oleyltriglyceryl glucoside 5.8.
g was obtained as a white solid. (Yield 89%) At this time, almost no by-products were observed except that an excessive amount of 1-O-oleyl triglyceride and a small amount of unreacted glucose were recovered. HO- [C ₃ H ₅ (OH) O] ₃ -C ₁₈ H ₃₅ (16)

Next, in Example 1, methyl-α-D
The experiment was conducted in the same manner except that 0.10 mol of 1-O-oleyltriglyceryl glucoside obtained above was used instead of glucoside. In this way, a white solid [H] [oleyl triglyceryl glucoside (α-sulfopalmitic acid) ester Na] 99.4 with almost no coloring is obtained.
g was obtained. The yield of monoester Na was 83%.

Example 9 1.8 g (0.01 mol) of D-glucose and stearyl polyglycerin of the following formula (17) (average degree of polymerization m =
6) 29.3 g (0.04 mol) and Dowex 50
WX8 (acid type) [manufactured by Daw Chemical Co.] 0.
9 g and 30 ml of dimethylformamide were added to a 100 ml three-necked flask, and the pressure was reduced to 130 mm under reduced pressure of 15 mmHg.
The mixture is heated and stirred at ℃ for 6 hours. After completion of the reaction, Example 8
Post-treatment and purification were carried out in the same manner as in 1. to obtain 7.8 g (87% yield) of stearyl polyglyceryl glucoside. HO- [C ₃ H ₅ (OH) O] ₆ -C ₁₈ H ₃₇ (17)

Next, in Example 1, methyl-α-D
-The experiment was conducted in the same manner except that 0.10 mol of stearyl polyglyceryl glucoside obtained above was used instead of glucoside. In this way, a white solid [I] [stearyl triglyceryl glucoside (α-sulfopalmitic acid) ester Na] 123.7 with almost no color is obtained.
g was obtained. The yield of monoester Na was 82%.

Comparative Example 1 In Example 1, glucose was used instead of methyl-α-D-glucoside, and methyl α-sulfopalmitate N was used.
An experiment was conducted in the same manner except that methyl α-sulfopalmitate was used instead of a and sodium methylate was not used. The solid obtained in this case had a remarkable dark brown coloration, and the yield was 12%, which was low.

Comparative Example 2 Glucose 30 g (0.167 mol) and 50 g α-sulfopalmitic acid methyl ester Na salt (0.134 mol) were dried at 100 ° C. and 0.1 mmHg for 2 hours, and then dried.
Dissolve in 0 ml dimethylformamide. After adding 0.5 g of sodium methoxide, the mixture was heated at 100 ° C. for 5
Stir for a period of time under reduced pressure (40 mmHg) while distilling off methanol. After the reaction was completed, dimethylformamide was distilled off (0.1 mmHg), anhydrous ethanol was added to the residue,
After heating and stirring, unreacted glucose, glucose polymer and α-sulfopalmitic acid diNa are filtered off, and the filtrate is crystallized to give glucose (α-sulfopalmitic acid).
A monoester Na salt was obtained, which was markedly dark brown in color and had a low yield of 55%.

Example 10 The performances of the surfactants shown in Table 1 below were evaluated as follows. The results are shown in Table 2. (Skin irritation) A closed-batch test on the upper arm was performed on 20 samples for 5 days using a 5% by weight aqueous surfactant solution as a test solution. The evaluation method is as follows. <Evaluation method> ○: Cases of redness, rash, etc. = 0: △: Cases = 1 ×: Cases = 2 or more (protein denaturation) 100 ppm bovine serum albumin under phosphate buffer (pH 7.0) 1000 ppm Circular dichroism (220 nm value) was measured after leaving it in the aqueous surfactant solution at room temperature for 24 hours, and the reduction amount (%) from the value when the same was allowed to stand in water containing no surfactant was calculated. I asked. <Evaluation method> ○: Reduction amount = 0 to 4 Δ: 〃 = 5 to 10 ×: 〃 = 11 or more (foaming property) 10 ml of 0.5 wt% aqueous surfactant solution was put in a graduated test tube, and 25 After keeping the temperature constant at ℃, shake 20 times / 10 seconds, and measure the foam volume after 30 seconds. <Evaluation method> ○: Bubble volume = 80 ml or more △: 〃 = 55 to 79 ml ×: 〃 = 54 ml or less

(Emulsifying property) After putting 10 ml of a 0.5% aqueous solution of a surfactant in a 30 ml test tube with a stopper, 10 ml of salad oil was added to this test tube. Next, the bottle was capped, shaken vigorously 30 times, allowed to stand at 30 ° C. for 30 minutes, and then the volume (ml) of water separated in a test tube was measured. <Evaluation method> ○: Separated water content = 0 to 3 ml △: 〃 = 4 to 6 ml ×: 〃 = 7 to 10 ml (dispersibility) 0.01% by weight of carbon black and 0.1
50 ml of a sample aqueous solution containing a surfactant by weight was prepared and carried in a constant temperature bath at 25 ° C. for 5 hours. Then 24
After allowing to stand for a time, the dispersion state was evaluated according to the following method. <Evaluation method> ◯: Carbon black is uniformly dispersed. X: There is a separation layer. (Hard water resistance) 40 ml of 0.5 wt% aqueous surfactant solution
Was placed in a 100 ml beaker, 8.5 ml of a 1 wt% calcium acetate aqueous solution was added dropwise, and the hard water resistance was evaluated according to the following method. <Evaluation method> ○: The type letters pasted on the bottom of the beaker are visible. X: The type letters pasted on the bottom of the beaker cannot be seen. (Hydrolysis resistance) 1% by weight of surfactant at pH 9, 8
The ratio of the surfactant remaining after being treated at 0 ° C. for 60 minutes without being decomposed by heat was determined by liquid chromatography. <Evaluation Method> ○: Surfactant residual rate = 90% or more △: 〃 = 80 to 89% ×: 〃 = 79% or less (fragrance retention) Citrus (lemon) type fragrance 0.5%, surfactant 5 % Aqueous solution containing 0.5% was applied to the forearm, and the strength of odor after 2 hours was compared. <Evaluation method> O: Strong odor. △: 〃 is quite strong. X: The 〃 is weak or hardly felt.

[0043]

[Table 1] * Show a comparative example

[0044]

[Table 2] * Show a comparative example

Claims (1)

[Claims] 1. The following general formula (1): (In the above formula, Z- (OH) qw-1-s is the q in a sugar (Z- (OH) q) having q free hydroxyl groups in the molecule.
Of the free hydroxyl groups, (w + 1 + s) hydroxyl groups represent sugar residues formed by participating in the reaction, [(R ¹ O)-
(R ³ O) t] is bonded to the anomeric position of the sugar residue,
[(R ⁴ O)-(R ⁵ O) u] and [OCOCH (SO
₃ M) R ² ] s is bonded to a position other than the anomeric position of the sugar residue, R ¹ and R ⁴ are chain aliphatic groups having 1 to 30 carbon atoms, and R
² is an aliphatic group having 4 to 30 carbon atoms, R ³ and R ⁵ are 1 carbon atoms
~ 4 alkylene group, M each represents a hydrogen atom or a salt-forming cation, q is a number of 3 or more, w is a number of 0 or 1 or more,
s is a number of 1 or more, t and u are numbers of 0 to 20, respectively,
In the method for producing an α-sulfofatty acid derivative represented by (w + 1 + s) is q or less, the following general formula (2): (In the formula, Z- (OH) qw-1 is a sugar (Z- (OH) q) having q free hydroxyl groups in the molecule, and (w + 1) of the q free hydroxyl groups are involved in the reaction. And a sugar derivative represented by R ¹ , R ³ , R ⁴ , R ⁵ , q, t, u and w has the same meaning as described above, and a sugar chain represented by the following general formula (3 ) [Chemical 3] Wherein R ⁶ represents a lower alkyl group and R ² and M have the same meanings as described above, and the reaction is carried out in the presence of an alkaline catalyst. .