JPH024232B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the production of glycerides from alcohols and poly- and/or monosaccharides and to their use in cosmetic, pharmaceutical and household products. Typical products of the above reactions are mixtures of substituted monosaccharides and substituted polys, primarily oligosaccharides, with surface activity and color properties such that they can be used in cosmetic, pharmaceutical and household products. The glycosides of the present invention are generally mixtures of various monomeric and oligomeric materials and are nonionic surfactants with high foaming capacity, emulsifying properties, and softening and cleaning properties. These products are easily biodegradable. As used herein, the prefix "oligo" is intended to include 11 repeating units. Alkyl saccharides are molecules that have been known for a long time, as already described by Fischier in 1909, but the manufacturing methods to obtain specific products are either too difficult or expensive. Therefore, industrialization is impossible. The method used is as follows: (1) acetic anhydride is reacted with glucose to form glucose pentacetate, and the product is then converted to bromo-tetracetate by the action of hydrobromic acid. Reacting this glucose bromotetracetate with a fatty alcohol in the presence of silver oxide gives the glycoside tetracetate, which can be simply hydrolyzed to give the glucoside; (2) or as described above. The obtained glucose pentacetate is reacted with fatty alcohol in the presence of zinc chloride to obtain glucoside tetracetate, which is further hydrolyzed. 1965, U.S. Patent No. 3170915 (Monsanto Company)
describes a method for producing ethers from glucose fatty alcohols. The method consists of reacting the sugar with sodium methylate in dimethyl sulfoxide and reacting the resulting sodium derivative with a halogenated paraffin. These methods are too expensive and yield limited products. U.S. Pat. No. 3,219,656 to Rohm and Haas, 1965, discloses a method for producing glucosides by transetherification between methylglucose and heavy alcohol. In fact, etherification of sugars with methyl alcohol is easily carried out by conventional ether methods to yield methylglucose, which is considerably more stable to heat and oligomerization than glucose. . The Rohm and Haas process consists of transetherifying this methylglucose with butyl alcohol to obtain butyl ether from glucose, wherein the glucose is itself transetherified by the action of a fatty alcohol. These two reactions are carried out in the presence of a cation exchange resin of the type disclosed in the company's US Pat. No. 3,037,052 as a catalyst. Although this method is cheaper, it requires the sequential removal of two light alcohols, and these two operations are expensive and solvent losses are inevitable. In 1974, Rohm and Haas, US Pat. No. 3,839,318, disclosed that fatty alcohols and The preparation of mixtures of mono-substituted mono- and oligosaccharides obtained by direct reaction of mono-saccharides is described. Since the reaction conditions are strictly limited, the basic monosaccharide is not excessively decomposed during the condensation process. The excess of fatty alcohol over mono-saccharide must be sufficient; the excess required increases as the molecular weight of the alcohol increases. In the drawing accompanying the specification of the above-mentioned US patent, a curve shows the minimum excess amount of fatty alcohol used as a function of the number of carbon atoms contained in the molecule. Although this method yields a mixture of glycosides with very useful surface activity and a high degree of stability towards salt and alkaline agents, the color of this mixture is too dark and strong oxidizing agents make it difficult to purify. Otherwise, it cannot be used in the cosmetic or pharmaceutical industry or in formulating household products without further bleaching. We have developed such fatty alcohol ethers that yield useful surface-active products and that do not require a subsequent bleaching step and that have a purity and color that allow them to be used as cosmetic or pharmaceutical products and as household products. We have now found a method by which mixtures of mono- and oligo-saccharides can be prepared. Since the decolorization process involves the formation of unstable oxidation products that later alter the color or pH value, the advantage of omitting the decolorization process is not only economical but also product quality. This point is also recognized. The present invention particularly relates to a compound having the structural formula: R-O[M] _o M' [wherein n is preferably 0 to 10, but may be larger, for example obtained by the reaction of hydrolyzed starch or cellulose] M and M' represent the same or different monoses or polyoses residues, which in the case of M may be a mixture, and R is (a) 8 to
having 18 carbon atoms (linear paraffin chain; (b)
a branched primary or secondary hydrocarbon chain (having from 8 to 18 carbon atoms); or of the _formula : R'[-O- ^CHR2 - ^CHR3 ]- 8 and R′ is a linear paraffinic chain; a branched hydrocarbon chain; or a monoalkyl or dialkylphenol; R ² and R ³ are both hydrogen or one hydrogen and the other methyl It relates to a glycoside represented by ]. The term "monose" above refers to mono-aldoses or mono-ketoses. According to the invention, surface-active glycosides are obtained by reacting alcohols with aldoses or ketoses in the presence of an acid catalyst composition comprising an acid catalyst and a reducing agent. Suitable catalysts are acid catalysts known to be useful in etherification reactions such as sulfur, hydrochloric acid, nitric acid, sulfonic acids and strong acid cation exchange resins. Suitable reducing agents include reducing agents such as phosphoric acid, hypophosphorous acid, sulfurous acid, hyposulfite, nitrous acid, and hyponitrous acid. These reducing agents are
As long as the composition of the catalyst and reducing agent is acidic as a whole, they can also be used in the form of their salts. The reaction time required for etherification depends on conventional factors such as the catalyst used, the amount of catalyst used and the temperature. The conditions described in U.S. Patent No. 3,839,318 are:
Most of them can also be used in the present invention. These conditions usually represent an optimal and acceptable balance between quality and price of the resulting product. The molar ratio of fatty alcohol to aldose or ketose ranges from 4:1 to 1.25:1. The reaction temperature is preferably in the range of 80-130°C. The total amount of catalyst and reducing agent is preferably equal to the weight of the aldose and/or ketose charged.
It ranges from 0.03 to 10%. Under these conditions, it is possible to obtain less colored condensation products using the present invention than in the absence of a reducing agent as in the prior art, without significantly changing the reaction rate. be. Furthermore, it has been found that by adding a reducing acid to a conventional etherification catalyst, the amount of catalyst used can be reduced without changing the reaction rate. The reaction rate obtained by using 0.014 mol of sulfuric acid per mol of glucose can be maintained by halving the amount of sulfuric acid used, for example, by adding hypophosphorous acid (0.007 mol). Furthermore, it is clear that whatever catalyst is used it is desirable to remove excess alcohol as quickly as possible in order to minimize the time required to heat the reaction product to the desired temperature. It is preferable to carry out this alcohol removal in the presence of a reducing agent to minimize further coloring and deterioration. Removal of excess alcohol can be carried out by any of the known methods such as vacuum distillation, molecular distillation and thin film evaporation. Suitable alcohols include fatty alcohols of 10 or more carbon atoms and may be linear or branched, primary or secondary. These alcohols may contain phenyl, alkylphenyl or alkoxy groups in their molecules. The ketoses and aldoses used in the method of the invention may be monoses or polyoses,
Examples of suitable monoses include arabinose, galactose, glucose, mannose, ribose and xylose; examples of suitable polyoses include sutucarose, maltose, lactose, raffinose, as well as higher polysaccharides such as starch and cellulose. Examples include saccharides obtained by hydrolysis. The glycosides obtained by the method of the invention are usually transparent, glassy solids with a sticky surface. Glycosides can be diluted with water and commercially available as aqueous solutions. The following examples illustrating embodiments of the invention are merely illustrative. Example 1 n-octanol and n-decanol in 45/
732.5 g (5 moles) of a mixture containing 55%, 360 g (2 moles) of glucose, 1.4 g (0.014 moles) of 98% sulfuric acid, and 1.85 g (0.014 moles) of 50% hypophosphorous acid.
The mixture containing was treated under a 40 mm mercury vacuum at 95° C. for 6 hours. After removing approximately 0.5% of unreacted glucose by centrifugation (under alcohol excess)
The resulting solution contains 19% monoalkyl glucosides and has a VCS value of 3. Neutralize this mixture with caustic soda to bring the pH value to 4~
6 and remove excess fatty alcohol by vacuum stripping. The product obtained as a 70% solution in water is
The color has a VCS value of 6 and the pH of its 5% aqueous solution
The value was 5. Comparative Test A The same amounts of n-octanol, n-decanol, and glucose as in Example 1 were used, except that 0.02 mol of sulfuric acid was used and no hypophosphorous acid was used, and the same amounts of n-octanol, n-decanol, and glucose were used as in Example 1.
The product prepared by the method described in No. 3,839,318 and having a composition similar to that of Example 1 was a glucoside having a color with a VCS value of 17-18, separated in a manner similar to that of Example 1. Although nearly twice as much sulfuric acid was used in this example, the monoglucoside content and reaction rate were the same for this example and Example 1. Example 2 45 pairs of n-octanol and n-decanol
55 mixture 732.5g (5 moles), glucose 360g
(2 moles), 1.4 g (0.014 moles) of 98% sulfuric acid and 50
A mixture containing 3.44 g (0.026 mol) of % hypophosphorous acid was treated under the same conditions. The product obtained has a color of VCS value 6 in 70% aqueous solution,
The pH value of the 5% aqueous solution was 3.3. Example 3 45 pairs of n-octanol and n-decanol
55 mixture 732.5g (5 moles), glucose 360g
(2 moles), 1.4 g (0.014 moles) of 98% sulfuric acid, and
A mixture containing 6.88 g (0.052 mol) of 50% hypophosphorous acid was treated under conditions similar to Example 1. The resulting 70% aqueous solution has a color with a VCS value of 5;
The pH value of the 5% aqueous solution was 2.9. Example 4 510 g (5 moles) of n-hexanol, glucose
360g (2 mol), 98% sulfuric acid 1.4g (0.014 mol),
and 1.85 g (0.014 mol) of 50% hypophosphorous acid was treated according to the method of Example 1.
The product obtained was a mixture of hexylglucose and hexyl oligoglucoside and had a color with a VCS value of 5-6. Example 5 45 pairs of n-octanol and n-decanol
55 mixture 732.5g (5 moles), fructose 360g
(2 mol), 98% sulfuric acid 1.4 g (0.014 mol) and 50
A mixture containing 1.85 g (0.014 mol) of % hypophosphorous acid was treated by the method described in Example 1 to obtain a 70%
A colored fructoside with a VCS value of 6 was obtained in aqueous solution. This product exhibited surface activity similar to glucose derivatives. Example 6 n-decanol 790g (5 mol), glucose
A mixture containing 360 g (2 moles), 4 g (0.04 moles) of 98% sulfuric acid, and 1.3 g (0.014 moles) of sodium hypophosphite was treated by the method described in Example 1 to obtain a VCS value in a 70% aqueous solution. A glucoside with a color of 6 was obtained. Example 7 45 pairs of n-octanol and n-decanol
55 mixture 732.5g (5 moles), glucose 360g
(2 moles), 1.4 g (0.014 moles) of 98% sulfuric acid, and 1.328 g (0.007 moles) of sodium meta-bisulfite were heated under vacuum at 40 mm of mercury at 95%
Treated at ℃ for an hour. After neutralization to a pH value of 4-6, the reaction product was treated under vacuum to remove excess alcohol. The obtained glucoside exhibited a color with a VCS value of 6 in a 70% aqueous solution. Example 8 45 pairs of n-octanol and n-decanol
55 mixture 732.5g (5 moles), glucose 360g
(2 mol), 98% sulfuric acid 0.7 g (0.007 mol) and 50
A mixture containing 0.925 g (0.007 mol) of % hypophosphorous acid was treated according to the method described in Example 1.
percent solids in the reaction mixture
solids) (volume/capacity) was measured every hour,
A drop in this percentage value indicates that the reaction is nearing completion. These measurement results can be used to calculate
Table 1 shows the VCS color in 70% solution. Comparative Examples B and C Example 8 was repeated except that instead of the sulfuric acid and hypophosphorous acid in Example 8, only sulfuric acid was used in the amount shown in Table-1. From Table 1, it can be seen that although the reaction rate according to the present invention was not significantly lower than that of the best of the comparative examples, the color was significantly improved. 【table】

Claims (1)

[Scope of Claims] 1. A method for producing a surface-active glycoside, which comprises reacting an alcohol with an aldose or ketose in the presence of an acid catalyst composition comprising an acid catalyst and a reducing agent. 2 The glycoside has the structural formula: R-O[M] _o M' [where n is 0 or an integer, M and M' represent the same or different monoses or polyoses, and the residue is M , and R may be (a) a linear paraffinic chain having 8 to 18 carbon atoms; (b) a branched primary or secondary carbonized chain having 8 to 18 carbon atoms; hydrogen chain; or (c) a group of the following formula: _R ' [-O-CHR ² -CHR ³ ]- a hydrocarbon chain; or a monoalkyl or dialkylphenol; R ² and R ³ are both hydrogen or one hydrogen and the other methyl). A method according to claim 1, characterized in: 3. The method according to claim 2, wherein n is 0 to 10 or a number obtained from the reaction of hydrolyzed starch or cellulose. 4. The method according to claim 2, wherein the molar ratio of alcohol to aldose and/or ketose is from 4:1 to 1.25:1. 5. The method of claim 2, wherein the method is carried out at a temperature of 80 to 130°C. 6. The method according to claim 2, wherein the total amount of catalyst and reducing agent is 0.03 to 10% by weight based on the weight of aldose and/or ketose. 7 The reducing agent is phosphorous acid, hypophosphorous acid, sulfite,
The method according to claim 2, which comprises hyposulfite, nitrous acid and/or hyponitrous acid, and/or salts thereof. 8. The method of claim 2, wherein excess alcohol is removed from the reaction product in the presence of a reducing agent.