JPH04503453A - How to prepare glycoside esters - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Method for preparing glycoside esters and Glycoside ester-containing composition field of invention The present invention includes a method for the enzyme-catalyzed preparation of methyl glycoside esters and cleaning compositions and personal care products.

Background of the invention Surfactants are used in a variety of applications, such as detergents for cleaning purposes, emulsifiers in food products, and and in various personal care products such as shampoos, soaps or creams. It is a very important industrial chemical with uses as an active ingredient in

At the molecular level, surfactants have hydrophobic and hydrophobic properties within each individual surfactant molecule. It is characterized by the presence of a hydrophilic range, which reduces the interfacial tension due to its specific structure. It is something that can be reduced. Set of hydrophobic and hydrophilic ranges within the same molecule Combinations can be obtained in a number of different ways, for example with sulfonic acid residues, quaternary amino acids, etc. A combination of an ammonium moiety or a glycerol moiety and an alkyl chain, such as of linear alkyl surfactants, quaternized alkyl amines or monoglycerides, respectively. This is the case. When designing surfactant molecules, the detailed molecular structure of the compound is the main focus. The correct balance between the hydrophobic and hydrophilic ranges of the surfactant molecule is a key issue. and the preferred spatial arrangement of these individual ranges of molecules. Attention is paid to Apart from this, high-yield methods and cheap and easily available The possibility of making surfactants based on available raw materials is always carefully considered. Ru. Environmental issues regarding the ultimate environmental burden of surfactants are the last major issue. Ru.

As a result of these considerations, surfactants based on sugars and fatty acids such as sugar Many researchers have shown considerable interest in the production of tel. substances like this is expected to exhibit a surfactant effect due to the hydrophilicity of the sugar moiety and the hydrophobicity of the fatty acid residue. Waited. The balance between hydrophobicity and hydrophilicity depends on the addition of a large number of substituents. It can be changed by denaturing sugars and/or fatty acids. A world like this Surfactants are prepared from very cheap starting materials and are made from naturally occurring ingredients; These do not constitute an environmental hazard.

One traditional method of preparing sugar esters, including glycoside esters, is transesterification. It is carried out by a conversion reaction. That is, in U.S. Patent No. 3,597,417, A two-step process in which lycosides are reacted with short-chain esters and then reacted with fatty acid esters. Preparing alkyl monoglycoside esters by transesterification in the method It is stated that. Another method is described in U.S. Patent No. 2.759.922. This involves the reaction of glycosides and fatty acids at temperatures of 160-300°C. A method for preparing esterified glycosides such as methyl glycosides by Ru.

Despite strong interest in preparing sugar esters of fatty acids, conventional synthetic It turned out that it is rather difficult to make surface-active sugar esters by a synthetic method. . Among other things, this is due to the presence of several chemically similar groups in sugar molecules; in many different positions and to different degrees when exposed to esterification reagents. This is because it is esterified. Sugar esters prepared by conventional chemical synthesis therefore, differ in the degree of esterification and the position of the acyl group in the sugar moiety. It is heterogeneous in that it consists of a mixture of different compounds. This is due to the surface active properties of the compound. cause gender differences. Furthermore, the preparation of sugar esters by conventional chemical synthesis is rather difficult. Recent inputs prepared by these methods have been found to It can be seen that the available sugar esters have only limited uses.

Difficulties encountered during chemical synthesis of sugar esters and surfactants In view of the attractiveness of these compounds as sugars, modified methods have been proposed for the preparation of esterified sugars. One interesting method is known to be highly range-selective and enantioselective. Therefore, for selective esterification of one or more hydroxy groups in sugar molecules, including the use of enzymes that can be used for

Such enzymatic methods can take advantage of inexpensive raw materials because the resulting sugar esters This means that it is inexpensive despite its high quality.

Efforts to develop an efficient enzymatic synthesis method for Tang esters have so far been particularly successful. I can't say that it is. Namely, Sweers (5weers) and Wong ( Wong) U, A+wer, Chem, Soc.

108, 1986. p6421-6422) is Candida cylindracea ca. sugar using pentanoic acid in the presence of ndida cylindracea lipase For example, we briefly consider the range-selective esterification of methyl glycosides, and They report that the yield of the method is very low (2-3%). Similarly, U.S. Pat. No. 4,614.718 describes finely divided sugars or sugar alcohols in the presence of lipase. Reacting to equilibrium with higher fatty acids in dispersed or emulsified form The preparation of sugar or sugar alcohol esters is described. Large amounts of Water is used as a solvent so that the equilibrium of the reaction is not shifted and this reduces the yield. It means not the best. Furthermore, even if a large amount of enzyme is used, the reaction will be slow. It goes on for a long time.

One in which known enzymatic methods give low yields and/or require long reaction times. The reason for this is that the polarity between the sugar component and the fatty acid component is quite different, which causes both to dissolve. The problem is that it is difficult to find a solvent that does. U.S. Patent No. 4.614. When water is used as a solvent as shown in No. 7j8, fatty acids do not dissolve. This results in insufficient reaction and low utilization of fatty acid reagent. for both sugars and fatty acids A few solvents are available (e.g. dimethylformamide) for this Such solvents generally inactivate enzymes and are often toxic, resulting in environmental pollution. .

Japanese Patent Application Laid-open No. 62-195292 discloses that in the presence of lipase, In this method, sugar alcohol is reacted with fatty acids, the condensate is gradually removed, and incubation is carried out. A method is described for preparing sugar or sugar alcohol esters by following 9 Japanese Patent Application Publication No. 62-289190 describes sugars or sugar alcohols, fatty acids and sugar or by mixing lipase and adding only a small amount of water to the reaction mixture. A method for preparing sugar alcohol esters is described. Japanese Unexamined Publication No. 62-112 No. 993 discloses that acetylated sugars or sugar alcohols are prepared in an organic solvent in the presence of lipase. A method for preparing sugar or sugar alcohol esters by reaction with fatty acids is described. has been done.

The purpose of the present invention is to produce high yields from inexpensive materials using an enzyme-catalyzed method without using toxic solvents. The present invention provides a method for producing methyl glycoside esters at high yields.

Another object of the invention is to provide surfactants in cleaning compositions and personal care products. The present invention provides methyl glycoside esters that are particularly useful as sex agents.

Outline of the invention Therefore, the present invention provides general formula I (R-Coo), -χ-OCH! (wherein, R is a carbon group optionally substituted with a hydroxy group or a halogen atom) It is an alkyl group having 4 to 24 atoms, and X is a carbohydrate consisting of 1 to 3 monosaccharide units. and n is 1, 2 or 3), the method is a general formula■ R'-COOR' (wherein R is as defined above and R' is H or a lower alkyl group) The acid or ester represented by General formula ■X-0CR.

It consists of reacting with a glycoside represented by

In another aspect, the invention provides compounds of general formula I as defined above. Regarding personal care products, including:

In a further aspect, the present invention provides compounds of general formula I as defined above. The present invention relates to a cleaning composition comprising a nonionic surfactant containing a compound.

Detailed description of the invention In the general formula I, the preferred meaning of n is 1, and the following formula Hs (I’) Corresponds to a monoester represented by (wherein R and X are as defined above) do. The method of the present invention allows a methyl glycoside monoester represented by the formula It is believed that this is the only method that can be prepared with acceptable purity.

Japanese Patent Publication No. 62-1 for the enzymatic preparation of sugars or sugar alcohol esters Compared to the methods described in No. 95292 and No. 62-289190, this method Necessary for preparing methyl glucoside ester represented by formula ■ by the method of the invention reaction time is significantly shorter. The method of the invention thus represents significant economic advantages.

Furthermore, when this is used as a starting reactant, esters such as mono-, di-, tri-, etc. from the free sugars (or sugar alcohols) that would form a mixture of alcohols. Due to the use of white methyl glycosides, a range-specific esterification of formula I Monoesters (e.g. 6-0 monoester of methyl glucoside) are obtained in high yields. This results in Producing the monoester represented by formula ■ in high yield is As shown below (Example 8), these compounds have been shown to be particularly useful for arbor cleaning applications. It is preferable because it was found.

Each monosaccharide unit in carbohydrate X is preferably in the pentose or hexose form, especially in cyclic (furanose or pyranose) form. Glycoside moiety X 0CHs Carbohydrate X in is preferably a monosaccharide. Examples of suitable monosaccharides are glucose, luctose, ribose, galactose, mannose, arabinose or xylo This is the base.

When using trisaccharides as carbohydrate X, sucrose, lactose, maltose , isomaltose and cellobiose.

In a preferred embodiment of the method of the present invention, the reaction between fatty acid (1) and glycoside (4) is actually Proceeds in a qualitatively non-aqueous medium. That is, the reaction is carried out in a suitable organic solvent (e.g. xane or acetonitrile) (or a particularly preferred embodiment). in the substantial absence of solvent, i.e. as a solvent for the glycoside. (a small amount of water is present bound to the enzyme and the enzyme is It should be noted that satisfactory reactivity may be ensured even if progress is made. good. by proceeding in a substantially non-aqueous medium, e.g. in the absence of a solvent, The equilibrium in the reaction between fatty acid ■ and glycoside ■ shifts toward the formation of the final product. In other words, the yield of compound (1) can be improved.

Although the pure α-anomer may be used in the method of the invention, surprisingly the β-anomer Since the mer form was found to be more reactive than the α-anomer in the method of the invention, At least a specific proportion of the glycoside moiety X-0CR is in the β-anomer form. was found to be advantageous. The higher reactivity of the β-anomer is due to the organic solvent analogy. This is believed to be due to the considerably higher solubility in fatty acids, resulting in more rapid A complete reaction was obtained and hence a higher yield of methyl glycoside ester was obtained. It will be done. In order to obtain advantageous effects involving the β-anomer, it can therefore be glycosylated. In a mixture of α- and β-anomeric forms of de ■ at least 10% by weight of the mixture It should preferably be present in an amount of at least 20% by weight, such as from 20 to 99% by weight. It is. Very satisfactory results are also obtained using the pure β-anomer (approximately 95% (see Example 1 for the yield of methyl glycoside ester).

R is preferably an alkyl group having 6 to 22 carbon atoms.

That is, R-Coo- is hexanoyl, heptanoyl, octanoyl, nonanoyl. yl, decanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, octane Tadecanoyl, eicosanoyl, docosanoyl, cis-9-octadecenoyl, cis, cis-9,12-octadecagenoyl or cis, cis, cis-9,1 Suitably it is selected from the group consisting of 2,15-octadecatrienoyl group. R -COO- further consists of arachinoyl, arachitonoyl and behenoyl groups can be selected from the group.

Therefore, the preferred compound (1) prepared by the method of the present invention is methyl 6-0-heta xanoyl glucoside, methyl 6-0-heptanoyl glucoside, methyl 6-0 -Octanoyl glucoside, methyl 6-0-nonanoyl glucoside, methyl 6- 0-decanoyl glucoside, methyl 6-0-dodecanoyl glucoside, methyl 6 -0-tetradecanoyl glucoside, methyl 6-0-hexadecanoyl glucoside methyl 6-0-octadecanoyl glucoside, methyl 6-0-eicosanoy luglucoside, methyl 6-0-docosanoylglucoside, methyl 6-0-cis- 9-octadecenoylglucoside, methyl 6-0-cis, cis-9,12-oc Tadecagenoyl glucoside and methyl 6-0-cis, cis, cis-9゜12 ．． 15-octadecatrienoyl glucoside.

Enzymes useful as catalysts in the method of the invention catalyze the hydrolysis of ester bonds. Hydrolase.

Such enzymes are lipases, esterases or proteases, especially esterases. Reactions involving ester bonds, such as hydrolysis, synthesis and/or exchange of ester bonds Lipase can be defined as an enzyme that catalyzes can be used in the method of the invention The lipase may be porcine pancreatic lipase or, for example, Aspergillus Enterobacterium (Enterobacterium) Chromobacterium, Geotricium (G eotricium) or Penicillium (p6nicillium) strains It is a microbial lipase produced by. Preferred lipases for use according to the invention Mucor (for example, Lipozyme@), Humicola ola), Pseudomonas or Candida (Ca. ndida) species.

Particularly preferred lipases are those produced by the following microbial strains; All of the Budapest Articles on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure In accordance with the terms of the Deutsche Samlung von Microorganismen utsche San+mlung von Mikroorganismen ) has been deposited at: Candida antarctica, 198 Deposited on September 29, 1986 and numbered DSM 3855, and filed on January 1, 1986. Entrusted with numbers DSM3908 and DSM3909 on February 8th.

Pseudomonas cephacia + Deposited on January 30, 1987 under number 3959.

Humicola Ianuginosa (Hua+1cola Ianuginosa) + 198 No. 3819 and 4109 dated 13th August and 4th May 2016, respectively. Deposited.

Humicola brevispora (Huwicola brevispora) + 1 It was deposited on May 4, 1987 under deposit number DMS4110.

Humicola brevi-s pora var, thermoideaL 19B Submitted on May 4, 2017 Deposited under deposit number DSM4111.

Humicola 1nsolens + 1981 It was deposited on October 1st under deposit number DSMI 800.

-i, the preferred lipase is Candida antarctica, DSM 3855.　 It is produced by DSM 3908 and DSM 3909. these The enzyme is produced by the method described in WO88102775. easy In other words, the Candida strain in question can be treated with assimilable carbon and nitrogen sources and essential It is a normal culture medium containing organic substances, elements of high concentration, etc., and is a practice established in the relevant technology. cultured under aerobic conditions. After culturing, e.g. preparing a liquid enzyme concentrate by removing insoluble material by filtration or centrifugation; The broth is then concentrated by evaporation or reverse osmosis. with salts or water-miscible solvents For example, by precipitating with ethanol or drying according to well-known methods. Solid enzyme formulations are prepared from concentrates, for example by spray drying.

In addition, lipase can also be obtained from the following strains, which are not subject to any restrictions: Centra Alprufurschimmerkulturen Cent with the following accession number: raalbureau voorSchi+u+elculturen (CB S) + American Type Culture Collection A + aerican Type eCu1ture Co11ection (ATCC) + Agricultural Tierra Research Culture Collection Agricul tural Re5ea rch Culture Co11ection (NRRL) and Inchite In5titude of Perme Cocaldida antarc publicly available from n-tation, Osaka (IFO) Tea Power, CBS 5955. ATCC34888, NRRL Y-8295, CB5667B, ATCC28323, CBS 6821 and NRRL Y -7954, Candida tsukubaens is+ CBS 6389+8TCC24555 and NRRL Y-7795 ; Candida auriculariae, CBS 6379+ ATTC24121 and IFo 1580; Candida fumicola , CBS 571. ATCC14438, IFO0760, CBS 2041 ゜ATCC9949, NRRL Y-1266, IFO0753 and IFO1 527i and Candtda foliorum, CB S5234 and ATCC18820° For example, recombinant DN as in EP 238023 or EP 305216. It is also known to produce lipases by the technique of A. Recombinant lipases are also included in the present invention. It can also be used for this purpose.

When used in the method of the invention, the enzyme may be in a soluble state.

However, recovery of methyl glycoside ester (1) prepared by the method of the present invention and better enzyme utilization as the immobilized enzyme is recycled. In order to achieve this, it is preferable to immobilize the enzyme. The immobilization method is well known (For example, Kay and Mosbach, Mo5bach, Immobilize Immobi] 1zed Enzymes”, Mary’s Inn Zymology Methods in Enzymology 4C Academic Press, New York, 1976L, which cross-links cell homogenates and removes insoluble molecules. Covalently bound to an organic or inorganic support, captured in a gel, and treated with an ion exchange resin or consists of adsorption onto another adsorbent. Coating on granular support (e.g. Nie, R., McCrae A. R., 11acrae and BiR, C, Hamorad R,C, Ha+u+ond, Biotechnology Iara. Dogenetic Engineering Revi s-3Biotechnology a nd Genetic Engineering Reviews 3, 1985 ．． p193 Suitable support materials for immobilized enzymes include, for example, plastics ( For example, polystyrene, polyvinyl chloride, polyurethane, latex, nylon Teflon, Dacron, polyvinyl acetate, polyvinyl alcohol or suitable copolymers of any of these), polysaccharides (e.g. agarose or xytran), ion exchange resins (both cation and anion exchange resins), with recon polymers (e.g. siloxane) or silicates (e.g. glass) be.

The enzyme can be adsorbed onto a resin or treated with glutaraldehyde or is an enzyme applied to an ion exchange resin by crosslinking it to the resin using other crosslinking agents. is preferably immobilized. Particularly preferred resins are weakly basic anion exchange resins. , for example polystyrene, polyacrylic acid or phenol-formaldehyde. It is a hydride type resin. An example of a commercially available polyacrylic acid type resin is Rewatit. (Lewati)■E1999/85 (manufactured by Bayer, Germany) ) and Duolite @ ES 568 (ROHMA, Germany) (manufactured by Ndohaas). Enzyme immobilization on this type of resin is described in EP No. 1405. This will be done in accordance with No. 42. Immobilization on phenol-formaldehyde type resin is carried out according to DK No. 85/878.

Other materials convenient for enzyme immobilization are inorganic supports such as silicates. enzyme is described, for example, in Kay and Mosbach, Mo5-bach, supra. It is attached to the support by adsorption or covalent coupling so as to

The method of the invention may be performed at low pressures, such as less than about 0.05 bar, especially about 0.01 bar. Advantageously, the process proceeds at pressures below 100 ml. The reaction temperature is about 20-100°C, preferably It is in the range of about 30-80°C.

Upon completion of the reaction, compound (I) is recovered by filtering off the (immobilized) enzyme and and remove excess fatty acids, for example by short bath distillation in a manner known per se. do.

Surprisingly, when included in personal care compositions according to the present invention, surfactant compounds (I) is particularly useful in imparting favorable foaming properties to such compositions. It has been found that it exhibits advantageous properties. In particular, R in the formula (■) has 7 to 10 carbon atoms. an alkyl group, in particular R-COO is an octanoyl group, and/or Preference is given to personal care compositions when the carbohydrate High foaming properties are created during use. That is, for inclusion in the composition of the present invention An example of a preferred compound (1) is methyl 6-0-octanoyl glucoside. transformation Compound (I) is prepared by the method described above, and as described above, α- and β- - May be present as a mixture of anomers.

Examples of personal care compositions of the invention include shampoos, toothpastes, shaving creams. a group of products in which foaming is considered important; For example, the Journal Opthe Society of Cosmetic Chemistry Journal al of the 5ociety of Cosmetic Chemist s, 10.1960. Compare p. 390-414.

The shampoo composition (eg hair or body shampoo) of the present invention comprises or may contain methyl glucoside ester (1) as a sole surfactant. , in which case it is usually present in an amount of 1 to 25% by weight of the composition. however, The composition further comprises an anion in an amount of 5 to 35%, especially 10 to 25% by weight of the composition. It may contain a surfactant.

Examples of suitable anionic surfactants for inclusion in shampoos include alkyl ethers. sulfonates, alkyl sulfates (e.g. 10-carbon atoms in the alkyl chain) 22), alkyl polyethoxysulfonates (e.g. 1O-18 carbon atoms), α-olefin sulfonates (e.g. 1O-18 carbon atoms), O-24), α-sulfocarboxylate (e.g. 6-20 carbon atoms) and esters (e.g. prepared using alcohols containing 1 to 14 carbon atoms), alkyl glyceryl ether sulfonates (e.g. 1 carbon atom in the alkyl chain) O-18), fatty acid monoglyceride sulfates and sulfonates, alkyl Phenol polyethoxy ether sulfate (e.g. carbon atom in the alkyl chain) Number of molecules 8-12L 2-acyloxy-1-sulfonate (e.g. in the acyl chain 2-9 carbon atoms and 9-22 carbon atoms in the alkane moiety) and β-alkyl 1-3 carbon atoms in the alkyl group and and the number of carbon atoms in the alkane moiety is 8-20).

When an anionic surfactant is included in the composition of the present invention, compound (1) is included in the composition. Suitably it is present in an amount of 1 to 20% by weight.

The shampoo composition of the present invention may further include a foam enhancer, such as a sialicyl fatty acid. amide, N-acylamino acid or betaine derivative in an amount of 0.1 to 20% by weight of the composition. It may be contained in an amount of %.

If a higher viscosity shampoo composition is desired, e.g. carboxymethylcellulose may contain suitable thickening agents such as In the case of kill ether sulfonates, salts such as NaCl! , using viscosity may be adjusted.

According to the present invention, a typical shampoo composition is formulated as follows: Methyl glycoside ester 1-20% Anionic surfactant 10-20% Foaming enhancer 0.1-10% Salt 0-5% Thickener 0-5% Acid (for pH adjustment) pH 4-7 Fragrance (appropriate amount) Preservative appropriate amount water balance When the composition of the present invention is a toothpaste composition, compound (I) is added in an amount of 1 to 20% by weight. It may also contain the usual ingredients such as gelling agents, thickeners, abrasives, bulking agents, etc. It may also contain agents etc.

When the composition of the present invention is a liquid soap composition, the amount of surfactant compound (I) is 1 to 20%. % and may further contain conventional ingredients such as anionic surfactants, foam enhancers, etc. It may also contain promoters and the like.

Similarly, the shaving cream composition of the present invention contains methyl glycosyl, in addition to the usual ingredients. It may contain 1 to 20% by weight of side ester (■).

Apart from this, it has been found that compounds of general formula I exhibit good leaning properties. It was. In particular, surprisingly, monoesters of fatty acids and methyl glycosides are surfactants in cleaning compositions, especially compositions for removing fatty stains. It was found to be very effective. Therefore, the present invention provides a general formula R-Coo-X-OCH3(1') (wherein R and X are as defined above) The present invention relates to a cleaning composition comprising an effective amount of a surfactant. Preferably a compound (1') is one in which X is a monosaccharide.

The monosaccharide in the glycoside moiety may be a pentose or hexose, but is preferred. Preferably, it is a monohexose. For economic considerations, monohexoses are Preferably, glucose, galactose or fructose, i.e. the glycoside is Preferably it is a coside, a galactoside or a fructoside. Monosaccharide X is the above-mentioned as in the furanose or pyranose form. Most available due to ease of preparation Easier isomers are preferred, such as glucopyranoside, galactopyranoside or or fructofuranoside.

When the monosaccharide X' is a monohexose, the group R-Coo- is added to the monohexose. The connecting ester bond is preferably connected to the 6-position of the monohexose.

The cleaning compositions of the present invention may be prepared in any convenient form such as powder, liquid, etc. and then blended. Representative examples of cleaning compositions according to the invention include laundry detergents , dishwashing detergent and hard surface cleaner. A more specific example is liquid heavy duty detergent. (with or without phosphate builders) and powdered heavy duty detergents (with or without phosphate builders) (with or without the builder).

The surfactants in the cleaning compositions of the present invention are primarily of non-ionic type (e.g. (at least 80% by weight of nonionic surfactants) or of nonionic type (such as 20-80% by weight) and another type of surfactant (e.g. anionic, cationic). (20-80% by weight of surfactant) Good too. An example of an anionic surfactant is linear alkylbenzenesulfone+-(L AS), fatty alcohol sulfate, fatty alcohol ether sulfate ( AES), α-olefin sulfonate (AO3) and soap.

The nonionic surfactant in the cleaning composition of the present invention is mainly used as a medicinal surfactant as described above. methyl glycoside monoester (1') (e.g. at least 80% by weight) or methyl glycoside monoester (1') (e.g. 20-80% by weight) ) and one or more other nonionic surfactants. Other non- Examples of ionic surfactants are alkyl polyethylene glycol ethers or nonionic surfactants. polyethylene glycol ether.

Liquid and powder detergents according to the invention (in Western Europe, Japan and the United States, respectively) (suitable for popular washing conditions) is “Frame Formulations”. Aliquid/Powder Heavy Duty Detergents Frame formu ations forliquid/powder heavy-duty detergents” (JE, Falbe J, Falbe: Surf Aku 5 urfactans in Consum er Products, Theory, Chikunoroshi and Application Th eory, Technology and Application, Subu Springer-Verlag 1987) All or part (e.g. 50%) of the non-ionic surfactant, as shown in Substituted with one or more alkyl glycoside mono-esters (I) as described above By this, it is substantially blended.

Therefore, as described in J. Falbe, supra, the liquid heavy duty cleaning according to the present invention Agents include anionic surfactants, nonionic surfactants, foaming regulators, foaming enhancers, Enzymes, builders, formulation aids, optical brighteners, stabilizers, fabric softeners, fragrances, dyes and and water. Similarly, the powdered heavy duty detergent according to the invention comprises anionic surfactants, Nonionic surfactants, foam regulators, foam enhancers, chelating agents, ion exchange agents , alkaline agent, cobuilder, bleach, bleach activator, bleach stabilizer, textile softener, anti- Redepositing agents, enzymes, optical brighteners, anti-corrosion agents, fragrances, dyes and blue tints, formulation aids , filler and water.

The invention will be further illustrated in the following example, which illustrates the use of the invention to claim protection. It is not intended to limit the scope in any way.

example General method Satisfactory 1H and CNMR spectra were obtained for all compounds. Ta. Bruker in organic solvent using TMS as an internal control. Spectra were recorded on a WM400 spectrometer. In DzO δ= The water signal at 4.8 was used as an internal standard. Mercuricrosolp (Mer ck LiChrosorb) N Hz-column and 96% ether as eluent. Shimadzu L C-4A device (refractive index detection) using tanol HPLC-analysis was carried out in a vessel). Preparative liquid chromatography, eluate in SiO□ using a gradient of n-pentane, ethyl acetate and methanol as It was carried out in

Example 1 Preparation of methyl 6-0-dodecanoyl β-D-glucopyranoside Methyl-β-(D)-glucopyrano in a stirred batch reactor at 80°C cid (400 g, 2.06 mol, Sigma Chemical) and dodecanoic acid (620 g, 3. Candida antarctica (20 g, 88102775, prepared as described in Examples 1 and 19). was added. Continue stirring under reduced pressure (0,01 bar) to proceed with the ester synthesis. was monitored by HPLC. After 21 hours, the enzyme was filtered off (at 80°C). . The synthesis of the title compound is shown schematically in the accompanying Diagram 1. Repeated cycles to remove excess fatty acids When removed by short bath distillation (105°C, 4.10-2 mbar), 5 75% (580g) with %β-(D)-glucopyranoside and 20% diester ) A crude product was obtained (HPLC analysis). Purify the crude product by chromatography. It was prepared and identified by NMR spectroscopic analysis.

Example 2 Preparation of methyl 6-0-decanoyl-D-glucopyranoside methyl-D-glucopyranoside Ranoside (19.8 g, 0.10 mol, methyl α-(D)-glucopyranoside) and methyl β-(D)-glucopyranoside, both with Sigma Chemica For example, using 3 g of immobilized lipase (derived from Candida antarctica). ester using dodecanoic acid (31 g, 0.15 mol) according to the procedure described in 1. It became. The reaction was completed in 24 hours (HPLC showed >90% conversion) and the enzyme was filtered off. Purification by chromatography yields the title compound as a crystalline powder. Obtained with a yield of 79% (30 g); show.

Example 3 Preparation of methyl 6-0-decanoyl-D-glucopyranoside methyl-D-glucopyranoside Ranosside (2:3 mixture of α- and β-anomers) (24 g, 0.12 mol, Prepared according to Example 6), immobilized lipase (from Candida antarctica) with decanoic acid (43 g, 0.25 mol) by the procedure described in Example 1 using 2.4 g. Esterified. After 17 hours, the enzyme was filtered off (at 80°C). H of crude product PLC analysis shows 77% title compound, 15% diester, methyl-D-glucopyramid. It showed 8% noside. Purification of a portion of the crude product by chromatography yields the standard 39.4 g (59%) of the title compound were obtained, which was identified by NMR spectroscopy. Ta.

Example 4 Preparation of methyl 6-0-octanoyl-α-D-glucopyranoside Methyl α-D-glucopyranoside (20.0 g, 0.10 mol, according to example 6) 6. Prepared by using a method of immobilized lipase (derived from Candida antarctica) as a catalyst. Octanoic acid (29.7 g, 0.21 mol) by the procedure described in Example 1 using 0 g It was esterified with. After 36 hours, HPLC analysis showed 77% conversion (65% monoester). 12% diester). The reaction was stopped by filtering off the enzyme. . A portion of the crude composition was purified by chromatography to yield 10.7 g of the title compound ( 32.4%), which was identified by NMR spectroscopy.

Example 5 Preparation of methyl 6-0-dodecanoyl-D-glucopyranoside Stir at 80'C Methyl-D-glucopyranoside (2 α and β anomers) in a batch reactor :3 mixture) (150 g + o, 77 mol, prepared according to example 6) and Immobilized lipase (10 g, derived from Candida antarctica) was added.

Stirring was continued under reduced pressure (0,01 bar) and the progress of the ester synthesis was monitored by HPLC. I tarred.

After 18 hours, methyl-α-D-glucopyranoside (64 g.

0.33 mol, prepared according to Example 6), dodecanoic acid (90 g, 0.45 mol) and 6g lipase were added. After a further 22 hours, the enzyme was filtered off and the product was collected in Example 1. When finished by short bath distillation according to the method, 84% 6-0-dodecanoyl -D-glucopyranoside Contains 9% methyl-D-glucoside and 7% diester A crude product was obtained. A portion of the product was purified by chromatography and analyzed by NMR Spectroscopic analysis confirmed the identity of the title compound (approximately 1:1 mixture of anomers).

Example 6 Preparation of methyl D-glucopyranoside α-D-glucose (500 g, ’2.78 mol) and strong acid cation exchange Resin (100g Amberlis) 15. BDH Chemicals) to methanol (150 0d! , 37.1 mol). The mixture was stirred for 68 hours at 65°C. . Progress of the reaction was monitored by HPLC. 'HNMR analysis of the reaction mixture revealed that α- and the l:1 ratio of the β-anomer. Filter off the ion exchange resin and cool the solution at 4°C. It was cooled to C. 230 g of crystalline methyl α-D-glucopyranoside was removed by filtration. , 43%) and evaporation of the mother liquor under reduced pressure yielded crude methyl D-glucopyranoside (30 4 g, 57%) was obtained as a thick syrup ('HN MR is α- and The β-anomer ratio was shown as 2/3).

Example 7 foaming In this example, methyl-D-glucoside ester was prepared according to Example 4.

AES (alkyl ether sulfate) is sodium lauryl ether sulfate Fate (Berol 452, Berol Chemie Bee Berol Kemi AB+ (Sweden). CDE is coconut acid jetano Ruamide (Empilan CDE, Albright and Will, Ri (Albright & Wilson, UK).

Three commercially available sucrose esters from Mitsubishi Kasei Foods Company, Japan were used. this The following composition is known from the catalog: Ryoto L595 95 %Dodecane 30% 70%-L1570 70%-70% 30%-L16 95 95%-80% 20% foaming measurement As follows, L-Moldovanyi+Daplu , Hungerbihler W, Hungerbihler, B., Lande B., Lan. ge: Cosmetica Kos+wetika, Vol, 5+ p, 37 42 Foaming was measured by the method of (1977). In this method, air is introduced into the test solution. and record the time it takes to fill a certain volume with foam. i.e. shorter Filling time indicates better foaming properties.

The detailed conditions were as follows. -Air flow rate 151/min -Capacity of test solution 500d -Inner diameter of air introduction tube 5nm -Volume of collected foam 21 Inner diameter of one foam tube 26M Foaming of one surfactant Foaming was measured in a 2% solution (as active substance).

The results are shown below: ) Measurement was not possible because the surfactant was not sufficiently dissolved.

The compound of the present invention is more effective than AES, a surfactant commonly used in shampoos. It is clear that it exhibits excellent foaming properties.

Commercially available sucrose esters are produced by prior art techniques that are very similar to the esters of the present invention. represents the carbohydrate esters of Poo and for the higher esters of the monoesters. were chosen to represent the various ratios that can occur. Sucrose ester used in prior art The foamability of the methyl glucoside ester of the present invention is much lower than that of the methyl glucoside ester of the present invention. it is obvious.

Example 8 washing experiment All glycolipids used in this example were prepared by a similar procedure to Example 3 and therefore It was about a 2:3 mixture of α- and β-anomers. Methyl 6-0-coconut Coconut fatty acid mixture for preparing fatty acyl-D-glucosides contains 1% Decanoic acid, 51% dodecanoic acid, 24% tetradecanoic acid, 5% cis-9-octade Contains senic acid and 2% cis, cis, 9-12-octadecadienoic acid. Ta.

A heavy duty powder detergent with or without phosphate virgoo was formulated as follows: : Basic phosphate-containing detergent (without surfactant): IJ Umtripolyphosphene 415g of salt, 95g of sodium metasilicate, carboxymethyl cellulose (CMC) 12g, EDTA 2.4g, sodium sulfate 475g (amounts are basic (expressed as g per kg of detergent).

Basic phosphate-free detergent without surfactants: 265 g Zeolite A, Nit 106 g of lilotriacetic acid, 85 g of sodium metasilicate, 11 g of CMC SE 2.1 g of DTA, 425 g of sodium sulfate.

Add surfactant (nonionic/LAS 33:67 ratio) to the basic detergent and make the final concentration. 12.5% (w/w) phosphate-containing detergent and 11.3% phosphate-free detergent And so. Detergents were applied at concentrations of 4.8 g/l and 5.3 g/f, respectively.

The washing experiment was carried out using a torque-autometer Terg-0-tome under the following conditions. Performed in ter: Temperature: 25°C Time: 20 minutes Water = 9°dH (German hardness) pH: 9.5 Test sample: EMPAI 12 (7x7cm) Foaming ratio: Laundry foaming 700 7 samples per i) EMPAI 12 samples (available from EMPA in Switzerland) ) is contaminated with coconut coir, milk fat and sugar.

The amount of fat remaining after washing was measured after Soxhlet extraction and was calculated as the fat weight % of the sample product. It was expressed as

I got the following result: Berol 160 1.96 1.97 Hodag CB -61,971,95 o -/l/160 Swedish company Alcohol ethoxylates commercially available from Berol AB Yes, the chain length in the fatty alcohol moiety with 12 to 14 carbon atoms and 6E○ It has a degree of ethoxylation. This is a widely used non-fat removal effect that has good fat removal effect. This is an example of an ionic surfactant.

Hodag CB-6 is a mixture of methyl glucoside esters based on fatty acids from coconut oil. This is a specific It is a mixture of mono-, di-, and tri-esters.

From the table, the diester and Hodag C to which the monoester of methyl glycoside corresponds It is clear that it shows a better fat removal effect than B-6.

Ward - table - top international search report 111,,lA,111.1. -Toba IK 9010O04Q International Investigation Report

Claims (49)

[Claims] 1. General formula I (RCOO)n -X-OCH3 (In the formula, R may be optionally substituted with a hydroxy group or a halogen atom. is an alkyl group having 4 to 24 carbon atoms, and X is a carbohydrate consisting of 1 to 3 monosaccharide units. and n is 1, 2 or 3). Therefore, the method is based on the general formula II R-COOR1 (wherein R is as defined above and R1 is H or a lower alkyl group) The acid or ester represented by the general formula as defined above in the presence of an enzyme catalyst is IIIX-OCH3 a compound of formula I, which comprises reacting with a glycoside of formula I; Preparation method. 2. 2. A method according to claim 1, wherein n is 1. 3. Each monosaccharide unit is a hexose or bentose, especially a furanose or a pyrase. 2. A method according to claim 1, which is in the north shape. 4. The glycoside moiety X-OCH3 is in α- or β-anomeric form or 4. A method according to any one of claims 1 to 3, wherein the method is present in a mixture. 5. Glycoside moiety X-OCH3 exists in a mixture of α- or β-anomeric forms and the β-anomer accounts for at least 10% by weight of the mixture, preferably at least 20% by weight of the mixture. % by weight, such as from 20 to 99 % by weight. Law. 6. 4. The method according to claim 1 or 3, wherein X is a monosaccharide. 7. Monosaccharides include glucose, fructose, ribose, galactose, and arabinose glucose, xylose and mannose, preferably glucose and galactose 7. The method according to claim 6, wherein the method is selected from the group consisting of: 8. X is sucrose, lactose, maltose, cellobiose and isomal The method according to claim 1, wherein the disaccharide is selected from the group consisting of toses. 9. Claims 1 to 8, wherein R is an alkyl group having 6 to 22 carbon atoms. The method described in any of the following. 10. R-COO- is hexanoyl, heptanoyl, octanoyl, nonanoyl , decanoyl, dodecanoyl, tetradecanoyl, hexadecanoyl, octade Canoyl, eicosanoyl, docosanoyl, cis-9-octadecanoyl, cis , cis-9,12-octadecanoyl or cis, cis, cis-9,12,15 - from octadecatrienoyl, arachinoyl, arachinoyl and behenoyl 10. The method according to claim 9, wherein the method is selected from the group consisting of: 11. Methyl 6-O-hexanoylglucoside, methyl 6-O-heptanoylglucoside rucoside, methyl 6-O-octanoyl glucoside, methyl 6-O-nonanoyl glucoside, methyl 6-O-decanoyl glucoside, methyl 6-O-dodecanoyl luglucoside, methyl 6-O-tetradecanoyl glucoside, methyl 6-O-he Xadecanoyl glucoside, Methyl 6-O-octadecanoyl glucoside, Methi Methyl 6-O-eicosanoyl glucoside, Methyl 6-O-docosanoyl glucoside , methyl 6-O-cis-9-octadecenoyl glucoside, methyl 6-O-cis , cis-9,12-octadecadienoyl glucoside and methyl 6-O-cis , cis, cis-9,12,15-octadecatrienoyl glucoside 11. A method according to claim 10 for preparing a compound selected from: 12. Any one of claims 1 to 11, wherein the enzyme catalyst is a hydrolase. Method described. 13. Claims where the hydrolase is a lipase, esterase or protease The method according to scope item 12. 14. Lipase Mucor, Humicola, Pseudo Produced by Monas Pseudomonas or Candida species 14. The method of claim 13, wherein the method is one of: 15. Lipase is produced by Candida antarcti ca, DSM3855, DSM3908 or DSM3909, Pseudomonas Cephasia Pseudomonas cephacia, DSM3959, Fumi Humicola lanuginosa, DSM3819 is DSM4109, Humicola brevispo ra, DSM4110, Humicola plebis var. Thermoidia Humicola brevis var. thermoidea, DSM4111, or Fumi Humi-cola insolens, by DSM1800 15. The method according to claim 14, wherein the method is made by: 16. The method according to claim 1, wherein the enzyme is an immobilized enzyme. 17. The reaction between fatty acid or ester (II) and glycoside (III) is substantial. 2. A method according to claim 1, wherein the method proceeds in a non-aqueous medium. 18. The reaction between fatty acid or ester (II) and glycoside (III) occurs in the solvent. 18. The method according to claim 17, which proceeds in the absence of the presence of a molecule. 19. The reaction of the fatty acid or ester (II) is carried out at low pressure, e.g. about 0.05 bar. Claim 1 carried out at a pressure below, in particular at a pressure below about 0.01 bar. The method described in. 20. General formula I (R-COO)n-X-OCH3 (wherein R, X and n are as defined above) Human care composition. 21. Claim 20, wherein R is an alkyl group having 7 to 10 carbon atoms. Composition. 22. 22. The composition according to claim 21, wherein R-COO is an octanoyl group. 23. 21. The composition of claim 20, wherein X is a monosaccharide. 24. 24. The composition of claim 23, wherein X is glucose. 25. Compound (I) is prepared by the method according to any one of claims 1 to 19. 21. The composition of claim 20, which is a compound made by 26. Claims in which compound (I) is present in a mixture of α- and β-anomers The composition according to any one of items 20 to 25. 27. Claim 20, wherein the compound is methyl 6-O-octanoyl glucoside The composition according to any one of Items 1 to 26. 28. Shampoo, toothpaste, shaving cream or liquid soap The composition according to any one of claims 20 to 27. 29. A shampoo composition in which compound (I) is present in an amount of 1 to 25% by weight The composition according to any one of items 20 to 28. 30. Further, an anionic surfactant is added in an amount of 5 to 35% by weight of the composition, preferably 10 to 35% by weight of the composition. A composition according to claim 29 containing in an amount of 25% by weight. 31. Anionic surfactants include alkyl ether sulfonates and alkyl sulfates. alkyl polyethoxy sulfonate, α-olefin sulfonate, α- Sulfocarboxylate and its esters, alkyl glyceryl ether sulfo phonates, fatty acid monoglyceride sulfates and sulfonates, alkylphs Enol polyethoxy ether sulfate, 2-acyloxy-2-sulfone selected from the group consisting of A composition according to claim 30. 32. Provided that the amount of compound (I) present in the composition is 1 to 20% by weight of the composition. The composition according to claim 30. 33. Furthermore fatty acid dialkanolamide, N-acyl amino acid or betaine Claims 28 to 3 containing the derivative in an amount of 0.1 to 20% by weight of the composition The composition according to any one of Item 2. 34. A toothpaste composition in which compound (I) is present in an amount of 1 to 20% by weight. The composition according to claim 28. 35. Shaving cream composition in which compound (I) is present in an amount of 1 to 20% by weight 29. The composition according to claim 28, which is a product. 36. A liquid soap composition in which compound (I) is present in an amount of 1 to 25% by weight. The composition according to claim 28. 37. Single stage I' R-COO-X-OCH3(I') (wherein R and X are as defined above) A cleaning composition comprising an effective amount of a surfactant. 38. 38. A composition according to claim 37, wherein X is a monosaccharide, especially a monohexose. 39. If the monohexose is glucose, galactose or fructose, The composition according to claim 38. 40. Claim 38 or wherein the R-COO- group is connected to the 6-position of the monohexose is the composition according to item 39. 41. The amount of alkyl glycoside monoester (I) is the total amount of nonionic surfactant. According to any one of claims 37 to 40, the amount is at least 80% by weight of Composition of. 42. The amount of alkyl glycoside monoester (I) is the total amount of nonionic surfactant. The composition according to any one of claims 37 to 40, which is 20 to 80% by weight of thing. 43. The amount of nonionic surfactant is at least 80% by weight of the total amount of surfactant. The composition according to any one of claims 37 to 42. 44. Make sure that the amount of nonionic surfactant is 20 to 80% by weight of the total amount of surfactant. The composition according to any one of items 37 to 42. 45. Additionally, anionic, cationic and/or Zwitter ionic surfactants are added. According to claim 44, the surfactant is contained in an amount of 20 to 80% by weight of the total amount of the surfactant. Composition of. 46. The amount of surfactant is 1 to 70% by weight of the total composition, preferably 4 to 50% by weight. A composition according to any one of claims 37 to 45. 47. Claims 37 to 46 in liquid or powder form Composition. 48. The laundry detergent is preferably a heavy or light detergent.Claims 37 to 4 The composition according to any one of Item 7. 49. Claims 37 to 4 which are dishwashing detergents or hard surface cleaners The composition according to any one of Item 7.