DE19812661A1 - Sucrose-N-alkyl asparaginates, their preparation and use - Google Patents

Abstract

The invention relates to sucrose-N-alkyl aspartate of the formula (I) DOLLAR F1 and the preparation and use thereof.

Description

The invention relates to sucrose-N-alkylasparaginates of the formula (I) according to FIG. 1, their preparation and use.

Sucrose is used as a hydrophilic component with fatty acid derivatives by conventional methods to give the known sucrose fatty acid esters ( FIG. 2), which can be used as industrial auxiliaries and additives due to their amphiphilic properties. The known compounds according to FIG. 2 are described as non-toxic, non-irritating to the skin and readily biodegradable. Sucrose acetate with R ¹ = OAc are e.g. B. used in detergents as bleach activators and with longer chain fatty acid residues as surface-active compounds. Due to the very favorable physiological properties, there are further areas of application in the food industry as emulsifiers, for. B. in baked goods and chocolate as well as in cosmetic formulations. Despite these advantages and although the compounds according to FIG. 2, in which up to 8 fatty acid residues can be bonded directly to the OH groups of sucrose via ester bonds, have long been known, they are only used to a small extent as surface-active substances. They are preferably only used in the cosmetics, food and pharmaceutical sectors, where special dermatological and toxicological requirements are made. The reason for this is, in particular, their complex and expensive production, which stand in the way of wider commercial use. In contrast, z. B. sorbitan fatty acid esters, which are accessible from the structurally simpler glucose in a technically simpler manner, have conquered a market as emulsifiers for many years. For the broader commercial use of products that are available from the particularly inexpensive and available in large quantities sucrose, for. B. as a cleaning agent or Kos metika for the consumer goods sector, especially an inexpensive manufacturing process of the same is required.

The known esters of sucrose according to FIG. 2 are produced on an industrial scale mainly by means of transesterification processes:
In the solvent process, sucrose is reacted with fatty acid methyl esters R ¹ COMe in the presence of a basic catalyst in a solvent such as dimethylformamide or dimethyl sulfoxide (JP 04,247,095). In the microemulsion process, the fatty acid ester is dispersed in a solution of the carbohydrate using an emulsifier. The solvent is removed before the actual esterification takes place (EP 0 254 376). In the solvent-free process, the so-called direct process, the fatty acid methyl ester is reacted in the melt with sucrose and a basic catalyst (GB 1399053). In other processes, lipases are used (DE 34 30 944). Finally, the esterification of sucrose can also be carried out with carboxylic acid chlorides or anhydrides. In processes unsuitable for large-scale technical productions, expensive auxiliary bases such as B. pyridine or N, N-dimethylaminopyridine required (DE 195 42 303). In the latter publication, mixtures of oxidized sucrose, in particular sucrose monocarboxylic acids, are used, which in turn are used in a complex oxidation process in low yield, e.g. B. according to DE 43 07 388 can be produced.

The known transesterification processes are very expensive both in terms of their process control and product isolation. The reaction parameters pressure and temperature must be carefully checked and the Sucro seester must be extracted and distilled several times to obtain it. In addition, the high reaction temperatures in combination with the long reaction times lead to discoloration of the products, which can only be reversed using complex cleaning processes. A further disadvantage of the compounds according to FIG. 2 is that they are used as monoesters. as diesters show surface-active properties, but because of their limited solubility in water they can only be used to a limited extent as surfactants. The monoesters dissolve poorly in cold water, while the diesters are only emulsifiable in water. The above-mentioned multi-stage process according to DE 195 42 303 therefore tries to circumvent this problem by introducing the additional carboxylate group into the sucrose molecule by oxidative means.

EP 0 324 595 describes "amino-functional compounds as builders / dispersants in cleaning agents" which are obtained by adding amino acids to maleate half-esters of polyols. The latter are obtained in particular by reaction of maleic anhydride with polyvinyl alcohol, with sucrose also being listed. Although the reaction of maleic anhydride with alcohols has been known for a long time, the subsequent reaction with amino acids is problematic, since this requires a balanced system of buffers and bases which suppresses the alkaline back reaction of the maleate half-ester. NaOH / Na ₂ CO ₃ is preferably added here. The excess bases must be neutralized and the salts separated as by-products. In addition, complex cleaning steps are required and the yields are not quantitative, since the maleate half-ester is naturally split off again by saponification with aqueous alkali metal hydroxide solution.

The Maleathalbester of sucrose according to FIG. 3 is, for. B. as a builder (CO / builder) in detergents (DE 21 48 279).

DE 27 39 343 describes "basic" surface-active esters of aliphatic polyols, it also being possible to use sucrose as the polyhydroxy compound. Compounds of the general formula R ₈ -N (R ₉ ) -CH (R ₁₀ ) -CH (R ₁₁ ) -COOH are specified as an acid component, where R _{8 is} a C ₈ -C ₂₂ -alkyl or alkenyl radical, R ₉ and R _{11 can} also mean hydrogen and R _{10 can} also mean a carboxyl group. However, such "acid esters" cannot be produced by the multi-stage process described in DE 27 39 343, because only "basic esters" of sucrose are then available, ie completely esterified carboxylates in which the carboxyl group (R ₁₀ radical) is also esterified , but not in protonated or anionic form.

The object of the present invention was therefore to prepare new derivatives of sucrose deliver that are easy to manufacture and ver as surface-active compounds can be applied.

Surprisingly, "acid esters" of sucrose have the required properties. The present invention therefore relates to sucrose-N-alkylasparagina te of the formula (I)

wherein R ^1, independently of one another, identically or differently, selects a group from hydrogen, a compound of the formula (II)

where R ² is C _n H _{2n + 1} or C _n H _2n , where n is an integer from 2-28, preferably from 6-22, especially from 12-18, a compound of the formula (III)

and / or a radical of formula (IV)

and M ⁺ is hydrogen, an alkali metal ion and / or an alkaline earth metal ion, preferably a sodium, potassium, lithium, magnesium, calcium and / or ammonium ion, with the requirement that at least one radical R ^{1 is} a compound of the formula (II) is.

The compounds of the formula (I) according to the invention cannot be prepared by the process described in DE 27 39 343, because a chemoselective cleavage of the ester group denoted by R ₁₀ would have to be carried out in an additional synthesis step. However, this is not possible with known methods, since at the same time the ester bond just linked via the other carboxyl group in R ₈ -N (R ₉ ) -CH (R ₁₀ ) -CH (R ₁₁ ) -COOH would be cleaved again. This saponification occurs even at mild pH values below half pH = 10. In addition, the "basic esters" in DE 27 39 343 are described as clearly water-soluble, resinous and little or practically non-foaming. In contrast, the "acid esters" of the formula (I) according to the invention are partially crystalline but amorphous solids with only limited solubility in water, very stable, well-foaming emulsions being formed. This is particularly surprising because aliphatic esters of carboxylic acids are generally less water-soluble than their salts.

In addition, it can be concluded from the stoichiometry of the reactions described in the examples of DE 27 39 343 that the "basic esters" described are mixtures of sucrose with the reaction components of the formula R ₈ -N (R ₉ ) -CH ( R ₁₀ ) -CH (R ₁₁ ) -CO ₂ CH ₃ . For example, in Example 6 of DE 27 39 343 137 parts of sucrose were reacted with 66 parts of a compound of the empirical formula C ₁₂ H ₂₅ NH-CH (COOCH ₃ ) (CH ₂ COOCH ₃ ). In purely arithmetical terms, this implementation could only have resulted in 128 parts of the product. In fact, 189 parts of product were obtained. The difference can only be unreacted sucrose, which is clearly water-soluble and does not form a foam in water. In fact, only a basic nitrogen content of 1.4% was found, which would be expected even if the substances were only mixed (calculated 1.4%). The predicted reaction products would, however, have a theoretical nitrogen content of 2.2%. Even the value of 123 given as the saponification number does not allow any conclusion to be drawn about the formation of a reaction product because no change in the saponification number can be expected from the stoichiometry, and because from the 66 parts of the compound C ₁₂ H ₂₅ NH-CH (COOCH _{3 used} ) (CH ₂ COOCH ₃ ) with the theoretical saponification number 122 in almost every case the same saponification number must be found again. It can be concluded from this that the reactions in DE 27 39 343 cannot lead to the "acidic esters" according to the invention, do not describe a preparation and therefore do not constitute prior art in this regard.

The present invention therefore provides novel sucrose-N-alkylasparaginates of the formula (I) which can be prepared surprisingly smoothly in high yields by a two-stage one-pot process and as a readily biodegradable, physiologically tolerable and surface-active substance with a broad application can be used. The compounds according to the invention are distinguished in that at least one and up to eight R ₁ radicals represent a 3-alkylamino-substituted half-ester radical of 1,4-butanedicarboxylic acid or its salts according to the formula (II).

To regulate the solubility properties, the compounds according to the invention can, in a preferred embodiment, also contain one or more ma residue of the formula (III), in particular according to the definition of the degree of substitution DS given in FIG. 1, which also includes non-integer intermediate values, the sum of the Residues A and B do not exceed the value DS = 8.

In metal-free form (M ^⊕ = H ^⊕ ), the compounds according to the invention - as is typical for amino acids - can also be present as internal salts (betaines) with protonation of the amino function. M ^⊕ is preferably an ion of the alkali and alkaline earth metals such as Na ^⊕ , K ^⊕ , Li, Mg ²⁺ , Ca ²⁺ and NH ₄ ^⊕ , particularly preferably sodium or potassium ions or mixtures thereof.

Suitable alkylamino radicals NHR ² come from primary amines (monoalkylamines R ² NH ₂ ) of chain lengths C ₂ to C ₂₈ , preferably from commercially available fatty amines with chain lengths from C ₆ to C ₂₂ , in particular from C ₁₂ to C ₁₃ , which consist of more or less wide production cuts, also hydrogenated, for example from coconut, palm, soy or tallow oil fats, especially from decyl, dodecyl, tetradecyl, hexadecyl or octadecylamines or from residues derived from coconut, palm -, soybean or tallow oil fats are derived. Accordingly, the compounds according to the invention can also carry different radicals.

Coconut fat generally contains a mixture of hexane, octane, decane, lauric, myristic, palmitic, stearic, behen, oil and linoleic acid residues. Palm oil generally contains a mixture of myristic, palmitic, stearic, oil and linoleic acid residues. Soybean oil contains, inter alia, residues with a carbon chain length of 14, 16, 18, 20 and 22 carbon atoms, usually C ₁₄ unsaturated, C ₁₆ monounsaturated and saturated, C ₁₈ mono-, di- and tri-unsaturated and saturated, C ₂₀ single unsaturated and saturated and C _{22 is} saturated. Tallow fat generally contains residues with 14, 16 and 18 carbon atoms.

In a further preferred embodiment, one or more, preferably up to 2, radicals R ^{1 can} also be present in sulfated form, the sum of the radicals A, B and C naturally not being able to exceed the number 8.

Another object of the present invention is a process for the preparation of a sucrose-N-alkyl aspartate of formula (I), wherein
in a first step sucrose is acylated with maleic acid or a derivative of maleic acid, and
in a second step one to eight molar equivalents of amine of the formula R ² NH ₂ with R ² equal to C _n H _{2n + 1} , where n is an integer from 2-28, preferably 6-22, especially 12-18 the maleate sucrose formed in the first step is added.

The method according to the invention consists in the acylation of the sucrose preferably maleic anhydride (MSA) and the subsequent addition of fet tamines to the CC double bond of the intermediate maleat sucrose preferably without isolation or purification of the intermediate. Another a suitable acylating agent is maleic acid chloride. The fatty acid residue will not introduced directly by acylation of the OH groups of sucrose, but indirectly about the addition of the fatty amines to the intermediate, which is preferably not isolated dukt. This creates an N-alkylated aspartic acid, which acts as a linker group for the lipophilic alkyl radical acts. Both steps are largely stoichiometric trical in the sense of additions without the formation of stoichiometric amounts of salt as By-products.  

In a preferred embodiment, the acylation is carried out in the presence of a Catalyst, preferably in the presence of a basic metal salt, in particular those of a carbonate, bicarbonate, acetate and / or formate leads. Usually one equivalent of a basic metal salt is consumed that as a catalyst in the acylation with MSA and to neutralize the ge formed carboxylates acts. By-products are simple, depending on the metal salt separable acetic acid or carbon dioxide. At the same time prevents the formation of the Carboxylate salt advantageously the consumption of a salt-bound fat tamine equivalent, which is then no longer for the subsequent addition to the CC Double bond would be available. The carboxy formed in the first step lat group additionally improves the hydrophilic properties and the water solubility of the surfactants. Surprisingly the process comes entirely without the addition of aqueous bases and buffer systems , for example as described in the application EP 0 324 595, which is therefore particularly important is advantageous.

In a further embodiment of the process according to the invention, the sucrose-N-alkylaspartate is sulfonated in a further step, preference being given to sulfonating up to two radicals R ¹ by one of the methods familiar to the person skilled in the art for the functionalization of hydroxyl and amino groups. For this purpose, following the reactions described above, the reaction products are reacted in the same reaction vessel or after separation of the intermediates with the calculated amount of a sulfonation reagent, if appropriate after adding an inert solvent such as dichloromethane, tetrahydrofuran or dioxane. Suitable sulfonating reagents are e.g. B. SO ₃ ClSO ₃ H, DMF-SO ₃ and / or pyridine-SO ₃ .

The advantages of the process according to the invention compared to the known production processes are the high reactivity of the maleic anhydride and the nucleophilic attack of the fatty amine on the electrophilic CC double bond, which means that for this reaction step on further purification steps, expensive auxiliary bases or auxiliary reagents such as e.g. B. catalysts can be dispensed with. Through the choice of the radicals R ¹ and the degree of substitution DS, the process also makes it possible to provide a large number of differently substituted compounds of the formula (I) with tailored application properties and areas of use. In addition, the yields in the two-stage one-pot process are over 90%.

The inventive method for the preparation of compounds according to For mel (I) with a defined DS can, for example, be carried out as follows:

Sucrose and the correspondingly calculated amount of, for example, maleic acid hydride and an equivalent amount of a basic metal salt, for example zes (MX), such as sodium bicarbonate, sodium carbonate, natri umacetat, sodium formate, lithium acetate or potassium acetate, preferably natri umhydrogencarbonate, sodium carbonate or sodium acetate, is in substance or in a suitable solvent, for example in N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), dioxane, N-methylpyrrolidone (NMP), DMSO, Tetrahydrofuron (THF) or in mixtures of these solvents, preferably in N, N-dimethylformamide, N-methylpyrrolidone, DMSO, dioxane or in mixtures this solvent, at temperatures from 20 ° C to the boiling point of the concern the solvent or the relevant solvent mixture, preferably in Temperatures in the range of approx. 20 to approx. 140 ° C, especially at temperatures from approx. 40 to approx. 120 ° C.

The reaction is complete after the sucrose has been completely consumed, which is easily detectable by thin layer chromatography. Then the corresponding DS calculated amount of the relevant alkylamine R ² NH ₂ or the alkylamine mixture is added and in the same reaction vessel at temperatures from about 0 ° C to the boiling point of the solvent or the solvent mixture concerned, preferably at Temperatures of about 20 to about 60 ° C stirred until the reaction is complete after analysis by thin layer chromatography.

The end product partially precipitated out as a colorless solid during the reaction can be suctioned off, washed and dried. Preferably the Most of the solvents used are distilled off and the product is eliminated stir isolated in a low boiling solvent. Alternatively, the product also from the reaction solution by adding the appropriate amount of solvent be canceled. Suitable solvents for the stirring and precipitation processes are ethyl acetate, hexane, methyl isobutyl ketone, acetone and the like. The solid end product is after thorough vacuum drying as a colorless, ge nefarious powder obtained.

Depending on the nature of the metal salt MX used, the process provides the corresponding carboxylate salt as the end product, preferably the sodium or potassium salts or mixtures thereof. These can be also with equivalent quantities of proton acids to the free carboxylic acids (M = H ^{⊕ ⊕)} via lead are present, the secondary amine function due to the presence in equilibrium with the betaine. By carefully adding a maximum of another acid equivalent, the secondary amino group in the aspartic acid part can be protonated, for example halogen carboxylic acids, aliphatic and aromatic carboxylic acids and sulfonic acids can be used. The negative gene used affects, for example, the surfactant properties of the compound according to the invention. The suitable selection of the counterion, for example a paraffin sulfonate, makes it possible, for example, to produce tailor-made thickeners in formulations for shampoos and other cosmetic cleaning agents and for liquid surfactant systems.

In a further embodiment, following the reaction described above, the products obtained are given in the same reaction vessel or after separation of the intermediates with the appropriate amount of the sulfonating reagent, preferably up to 2 molar equivalents of the sulfonating reagent, if after adding an inert solvent such as dichloromethane , Tetrahydrofuran or dioxane. Preferred sulfonating reagents are e.g. B. SO ₃ ClSO ₃ H, DMF-SO ₃ or pyridine-SO ₃ .

The compounds of the formula (I) obtained by the process according to the invention are characterized by means of analytical and spectroscopic methods such as TLC, ¹ H NMR and mass spectroscopy and elemental analysis. The DS of the products can be determined by means of the proton ratio (integration of the ¹ H NMR signal) and by means of elemental analysis.

The compounds of the invention have excellent surfactants Properties and are therefore diverse as industrial auxiliaries and additives, for example as surfactants, emulsifiers, stabilizers, plasticizers or solvents usability mediator. These compounds with DS = 4-8 are also suitable as low-calorie fat substitutes in food.

At degrees of substitution (DS) from 1 to 7 are by reaction with z. B. MSA substance mixtures obtained, predominantly the 3 primary OH groups react. Under special conditions, the 2-OH group of glucose is selectively acylatable (FR 2670493), the yields being generally low, for. B. approx. 42% in the selective enzymatic acylation of the 1'-OH group with methacrylic acid vinyl ester and subtilisin in DMF (Chan, AWY & Ganem, B., Biocatalysis, 1993, 8, 163-169). In general, there is a decreasing reactivity in the order HO-6 approx. = HO-6 '<HO-1'<HO-2 approx. = HO-3 '. Connections with DS = 2 and DS = 3 therefore predominantly have the constitution shown in FIG. 4.

The addition of the alkylamine R ² NH ₂ to the sucrose maleates or to mixtures of intermediates, which can contain up to 8 radicals R ¹ , is generally carried out stoichiometrically until the maleate-CC double bond is completely reacted with a certain amine R ¹ NH ₂ . However, the amine R ¹ NH ₂ can also be used substoichiometrically while maintaining unsaturated maleate substructures, for example in order to achieve a certain water solubility of the products. In addition, a mixture of several different alkylamines can also be used. Accordingly, the compounds according to the invention can also carry different radicals. The ratio of hydrophilicity to hydrophobicity, which determines the surface-active properties of the compounds according to the invention, is adjusted via the structure of the alkyl substituents R ² and their degree of substitution (DS). The DS can be adjusted via the molar ratio of the alkylamine R ² NH ₂ to sucrose.

The water solubility of the compounds according to the invention can optionally also Be adjusted via additional sulfonate groups by adding a higher number N-alkyl aspartate residues by preferably up to two sulfonate groups can be penalized.

The compounds according to the invention have a total of up to eight radicals R ¹ , the DS being between 1 and 8. As the DS increases, the lipophilicity of the compounds increases and their water solubility decreases accordingly. At the same time, this effect can be compensated for by the carboxylate or sulfonate groups introduced. As already explained, the amphoteric character and the water solubility of the interfacially active substances can be modulated in a simple manner, which is significant for the intended areas of use. So for cosmetic applications such. B. in shampoos or baths, but also in household cleaning agents, such as. B. in dishwashing agents, a good foaming ability and good foam stability of importance. The amphoteric character of the compounds suggests a special skin compatibility and skin protection effect, since a favorable interaction with the collagen of the skin can occur. Here, the formation of a protective layer, the excessive attack of surfactants on upper skin layers and their strong degreasing and irritation can be reduced by other anionic surfactants contained in a formulation. In addition, the hydrophilic carboxylate groups of the asparagine substructure or, if appropriate, additional sulfonate groups ensure good washability from the skin, which is particularly important for body cleansing.

For surface-active substances, surfactants and emulsifiers, the DS is therefore preferably approximately 1-3, in particular ≦ 3, and for low-calorie fat substitutes for foods, preferably approximately <3, in particular approximately 4-8. In the case of low-calorie fat substitutes, melting points and taste sensations can be controlled via the composition of the radicals R ² and the DS value: only those fatty substances that have a melting point above body temperature and that are not liquid at room temperature give a pleasant taste sensation. A coordinated taste sensation, for example for a substitute for cocoa butter, can be achieved by a corresponding mixture of fatty amines of different chain lengths, by C-12 (lauryl-), C-16 (palmityl-), C-10 (caprinyl-), C- 14 (myristyl) and C-18 (stearyl) amines can be used in coordinated proportions.

Another object of the present invention is therefore the use of a sucrose-N-alkyl aspartate according to the invention as a surface-active Ver Binding, in particular the use of one or more inventions Sucrose-N-alkylasparaginate as an additive in hygiene, cleaning, cosmetic, le pharmaceuticals and / or pharmaceuticals or in pesticides or for prevention and / or be fighting water pollution from chemicals and / or oil, for example as an additive in soaps, abrasives, all-purpose cleaners, dishes detergents, detergents, shampoos, heavy duty detergents and / or baths substitute, the degree of substitution DS of at least one sucrose-N alkyl aspartate is preferably between 1 to about 4.  

In a particular embodiment, the sucrose-N-alkyl aspartate is added together with at least one other surface-active substance (co- Surfactant) is used, wherein the co-surfactant is preferably selected from Alkyl polyglycosides, 6-0-monoesteralkyl glycosides, alcohol ether sulfates or Al kylglucamide.

Another object of the present invention is the use of a Sucrose-N-alkyl asparaginates according to the invention as a low-calorie fat substitute substance, the degree of substitution DS of at least one sucrose-N-alkylasparagi nates is preferably between about 4 and 8.

Another object of the present invention is the fiction moderate sucrose-N-alkyl aspartate in the form of an aqueous solution, an emulsion, a suspension, a jelly, a cream, a paste or a powder.

The surfactant properties of the compounds of the invention thus open up a multitude of possible uses. The following Application examples serve to illustrate the many possible options Areas of application and mean no limitation to these examples.

When washing and cleaning, the surface tension is reduced easier removal of dirt from the fiber and stabilization of the dirt ingredients in the wash liquor. In the sub-industry, washing, coloring and equipment processes with the help of surfactants improved and accelerated. At wool dyeing becomes, for example, the wool caused by the dyeing process Damage reduced, the surfactants work in hydrogen peroxide bleach baths stabilizing and the dispersing effect for textile dyes makes dyeing easier process. In the leather industry, in fur preparation and in the paper industry are important tools. Car and machine oils become bil added even, non-tearing lubricating films. In paints and an  Coating agents improve wetting and delay their dispersion effect at the same time the deposition of the color pigments when the color is standing. In the Cosmetics, in the food industry, in medicine, in disinfectants and in pest control, the distribution of active ingredients in a liquid Phase or its adhesion to a surface is reached. They can also be used as Emulsifiers can be used for baked goods and ice cream. With floor care Tel, furniture and car polish and paint strippers typically contain also surfactants. When mining ores, coal and potash, the up is floating of the solids causes the surfactant to adhere to air bubbles couples (flotation). On the other hand, other surfactants can by the action of this surface active substances are influenced in their foaming power, by promoting the rising and bursting of the gas bubbles (defoaming mung). Such anti-foaming agents are used especially in dishes detergents and in many technical processes such as paper and sugar position used. The one known from other sugar residues and biosurfactants low toxicity and biocompatibility shows that the invention Compounds have similarly favorable properties. These advantages can be found at for example, to combat tanker gaps at sea and in general Combating oil pollution of water can be used by the oil is distributed more quickly without the disadvantages of additional water pollution occur through the excipient.

In the pharmaceutical sector, biocompatible surfactants are used, for example, as auxiliary substances used in vaccine production for the isolation and purification of bacterial polysaccharides as vaccines (see, for example, WO 97/30 171).

In detergents, tensides make up approx. 10-40% of the total depending on the intended use crowd out. The typical composition of a universal detergent can e.g. B. 5-15% of a compound according to the invention, 3-5% of another foam regulator tors (soap or silicone oil), 30-40% of a builder (e.g. zeolite, polycarboxy lat), 20-30% of a bleaching agent (e.g. sodium perborate), 0-10% of a setting agent  (e.g. sodium sulfate), 1.5-4% of a bleach activator (e.g. tetraacetylethylenedia min), 0.2-2% of a stabilizer for perborate (e.g. EDTA, Mg silicate), 0.3-1% an enzyme (e.g. a protease), 0.5-1% of a graying inhibitor (e.g. Car boxymethylcellulose), 0.1-0.3% of an optical filler (e.g. a stilbene or Pyrazoline derivative) and 0.1-0.2% of a fragrance.

The invention particularly relates to aqueous solutions, soaps, cleaning agents such as abrasives, all-purpose cleaners, dishwashing detergents or detergents, hair detergents, heavy duty detergents, bath additives, food, cosmetics, emul sions, suspensions, jellies, facial cleansers, cold wave and fixatives, ten Sid preparations for babies, creams, pastes and powders that contain at least one of the inventions compounds of the invention or mixtures thereof with other above surface-active substances (co-surfactants), for example alkyl polyglycosides (APGs), 6-O-monoesteralkyl glycosides (Biosurt® types from Novo Nordisk), Al Contain alcohol ether sulfates (AEs), or alkyl glucamides.

The betaine structure of the N- In terms of structure, alkyl asparaginates comes naturally to those found in proteins Aspartic acid very close. It can therefore be assumed that the z. B. at purely nich ionic amphiphiles, such as the N-alkylglucamines, discussed tendency to Bil there is no carcinogenic N-nitrosamine.

In the pharmaceutical industry, surface-active compounds are used in formulations for active substances with which an improved active substance uptake is to be achieved (drug delivery systems). Cyclosporin e.g. B. is formulated as a "microemulsion preconcentrate". Vitamins such as vitamins A and K also have solubilizing formulations in micellar form. However, there are very few suitable surface-active substances which on the one hand have a good ability to contain active substances in a sufficiently stable manner and on the other hand have zwitterionic properties with a low critical micelle concentration and low toxicity. In particular, the ability to form stable vesicles is desirable. This requires surface-active substances with short, hydrophilic head groups and with long, hydrophobic chains, such as those found in phosphatidylcholines. Similar to these substances, the compounds according to the invention, for example with 2 long alkane chains (DS approx. 2), have structural prerequisites for the formation of stable vesicles. If, for example, 4 g of a compound according to the invention with DS = 2 and R ² = dodecyl are mixed in one liter of water, a homogeneous, opaque milky phase is obtained which remains stable and unchanged for 8 weeks at pH 5-7. The light scattering observed is presumably caused by microvesicles, for which a minimal structural detail is shown in FIG. 5, for example.

Alternatively, larger structures can also be created according to the scheme K1-S1'-S2-K2- Formulate S2'-S3-K3-S3 'etc., whereby K1 "head group molecule 1", S1 "Tail group of molecule 1", S1 '"further tail group of molecule 1" etc. means. Pharmaceutical or cosmetic effects can be found in such vesicles Incorporate substances that lead to an improved dosage form of the active ingredients can. Therapeutic genes, antisense Oligonucleotides or retroviral expression vectors come into question for their Application so-called transfection reagents are required. Usually are lipids such. B. DOTAP or DC cholesterol (SIGMA, Saint Louis, MO) or mixtures of neutral and cationic lipids. The Cationic structural element promotes the complexation of the DNA and the lipid part integration into the cell membrane. Meet these structural requirements also to the compounds of the invention, which as amino acids in the physiologically protonated form can be present. In particular, the inventions Compounds according to the invention therefore for in vitro or in vivo transfection of Cells, especially skin cells, are used to, for example, genes to heal table-related skin diseases. The transfection of skin cells with retroviral expression vectors is e.g. B. in Deng., H. et al., Nature Biotechno logy, 1997, vol. 15, 1388-1391.  

Another object of the present invention is therefore the use of Sucrose-N-alkyl asparaginates according to the invention as a transfection reagent. The Compounds according to the invention can be in various application forms (Formulations) for example in food, pharmaceutical or hygiene be used richly. The application form is the respective An application range adapted.

The following figures and examples are intended to explain the invention in greater detail, without it to restrict:

Description of the figures

Fig. 1 shows schematically the production of the sucrose-N-alkyl asparaginates according to the invention and the calculation of the degree of substitution DS.

Fig. 2 shows known sucrose fatty acid esters.

Fig. 3 shows a male half-ester of sucrose.

Fig. 4 shows examples of compounds with DS = 2 and DS = 3. Further maleate groups, of which up to 6 at DS = 2 and up to 7 at DS = 3, and sulfonate groups, of which preferably up to 2 groups may not be present in the formulas. The exact position of the substituents can vary and deviate from the illustration shown here.

Fig. 5 shows a detail of a minimum structural Mikrovesikels.

Fig. 6 shows graphically the results of comparative experiments on foam stability.

Fig. 7 shows graphically the results of comparative experiments on the dispersing effect.

EXAMPLES example 1 Synthesis with sodium acetate in DMF: DS = 2.0, R ² = dodecyl

30.0 g (87.6 mmol) sucrose, 15.8 g (192.6 mmol, 2.2 equiv.) Sodium acetate and 18.9 g (192.8 mmol, 2.2 equiv.) Maleic anhydride were 3 hours at 50 ° C in 150 ml of dry N, N-dimethylformamide. After the thin-layer chromatogram, the sucrose was then converted quantitatively. 35.7 g (193 mmol, 2, 2 equiv.) Of 1-dodecylamine (laurylamine) were added and the mixture was stirred at 50 ° C. for a further 3 hours. During the reaction, some of the product precipitated out as a colorless solid. The solvent was largely distilled off in vacuo and replaced with ethyl acetate with stirring. The product was filtered off, washed with ethyl acetate and dried in vacuo at 70 ° C. Yield: 83.9 g. Based on a composition with DS = 2 of the sum formula C ₄₄ H ₇₈ Na ₂ N ₂ O ₁₇ (953 g / mol), the yield was 100%. The ¹ H NMR assignment (in CDCl ₃ / CD ₃ OD) gave DS approx. 2.0: δ = 1.85 (t, Me), 1.25 (m, C ₉ H ₁₈ ), 2.6- 3.3 (m, CH ₂ NCHCH ₂ ), 2.30-5.40 (sucrose-CHO). [Assignment compared to the N-dodecyl aspartate C ₁₂ H ₂₅ NHCH (COONa) CH ₂ COOCH ₃ ; due to the micelle or vesicle formation, line broadening and deviating shifts occurred, e.g. B. CH ₂ COOSucrose can also be assigned to the broad multi plett at δ = 1.95. In the case of N-dodecylasparaginate C ₁₂ H ₂₅ NHCH (COONa) CH ₂ COOCH ₃ , the corresponding CH ₂ signal is at δ = 2.4 (CDCl ₃ ).] Elemental analysis: N (found) 2.7%, (N calculated for DS = 2.0: 2.9%), Na (found) 4.2% (Na calculated for DS = 2.0: 4.8%). Mass spectrum (electrospray, ESI-MS): [M ₁ -H ⁺ ] ^- = 624 (M ₁ = C ₂₈ H ₅₁ NO ₁₄ ; 625); [M ₂ ] ^- = 908 (M ₂ = C ₄₄ H ₈₀ N ₂ O ₁₇ ; 908); [(M ₁ -2H ⁺ + Na ⁺ ) ₂ ] ^- = 1272; In positive mode: [M + H ⁺ ] ⁺ = 626 (M ₁ = C ₂₈ H ₅₁ NO ₁₄ ; 625); [M ₁ + Na ⁺ ] ⁺ = 648; [M ₂ + H ⁺ ] ⁺ = 907; [(M ₁ + H ⁺ ) ₂ ] ⁺ = 1252.

Example 2 Synthesis with sodium carbonate in DMF: DS = 2.1, R ² = dodecyl

30.0 g (87.6 mmol) sucrose, 10.2 g (96.2 mmol, 2.2 equiv. Na ^⊕ ) sodium carbonate and 18.9 g (192.8 mmol, 2.2 equiv.) Maleic anhydride 2 hours at 80 ° C and then 3 hours at 100 ° C in 150 ml of dry N, N-dimethylformamide with stirring. According to the thin layer chromatogram, the sucrose then reacted completely. 37.6 g (203 mmol, 2.32 equiv.) Of 1-dodecylamine were added and the mixture was stirred for a further 3 hours at 50 ° C. and for a further 2 hours at 70 ° C. During the reaction, some of the product precipitated out as a colorless solid. The solvent was largely distilled off in vacuo and replaced with ethyl acetate with stirring. The product was filtered off as a colorless solid, washed with ethyl acetate and dried in vacuo at 70.degree. Yield: 82.9 g (96% based on product with DS = 2.1 (C _45.6 H _80.8 Na _2.1 N _2.1 O _17.3 = 983.6 g / mol). ¹ H NMR ( CDCl ₃ / CD ₃ OD) gave DS = 1.9-2.2 (assignment see example 1). Elemental analysis: N (found) 2.7%, N (calculated for DS = 2.1: 3.0%) , Na (found) 4.8%, Na (calculated for DS = 2.0: 4.9%) Mass spectrum (electrospray, ESI-MS): [M ₁ -H ⁺ ] ^- = 624 (M ₁ = C ₂₈ H ₅₁ NO ₁₄ ; 625); [M ₂ -H ⁺ ] ^- = 907 (M ₂ = C ₄₄ H ₈₀ N ₂ O ₁₇ ; 908); [2M ₁ -H ⁺ ] ^- = 1249; [2M ₁ + Na ⁺ -2H ⁺ ] ^- = 1271. In positive mode: [M + H ⁺ ] ⁺ = 626 (M ₁ = C ₂₈ H ₅₁ NO ₁₄ ; 625); [M ₁ + Na ⁺ ] ⁺ = 648; [M ₂ + H ⁺ ] ⁺ = 907; [(M ₁ + H ⁺ ) ₂ ] ⁺ = 1252.

Example 3 Synthesis with sodium carbonate in DMSO: DS = 1.9, R ² = dodecyl

30.0 g (87.6 mmol) sucrose, 5.1 g (48.1 mmol, 1.1 equiv. Na ⁺ ) sodium carbonate and 9.5 g (96.9 mmol, 1.1 equiv.) Maleic anhydride Reacted for 2 hours at 30 ° in 100 ml of dry DMSO with stirring. After adding a further 5.1 g (48.1 mmol, 1.1 equiv. Na ⁺ ) sodium carbonate and 9.5 g (96.9 mmol, 1.1 equiv.) Maleic anhydride, the mixture was stirred for a further 8 hours at 30 ° and more 2 hours at 60 ° C stirred. According to the thin layer chromatogram, the sucrose was then fully implemented. 35.7 g (193 mmol, 2, 2 equiv.) Of 1-dodecylamine were added and the mixture was stirred for 3 hours at 30 ° C. and 2 hours at 40 ° C. During the reaction, some of the product precipitated out as a colorless solid. The solvent was largely distilled off in vacuo and replaced with ethyl acetate with stirring. The product was filtered off as a colorless solid, washed with ethyl acetate and dried in vacuo at 70 ° C. Yield: 75.4 g (93% for DS = 1.9).

Example 4 Synthesis with sodium acetate in DMSO: DS = 2.2, R ² = dodecyl

30.0 g (87.6 mmol) sucrose, 15.8 g (192.6 mmol, 2.2 equiv.) Sodium acetate and 18.9 g (192.8 mmol, 2.2 equiv.) Maleic anhydride were 2 hours at 50 ° C in 100 ml of dry dimethyl sulfoxide with stirring. According to the thin-layer chromatogram, the sucrose then reacted completely. 35.7 g (193 mmol, 2.2 equiv.) Of 1-dodecylamine (laurylamine) were added and the mixture was stirred for a further 3 hours at 50 ° C. and for a further 2 hours at 70 ° C. During the reaction, some of the product precipitated out as a colorless solid. The solvent was largely distilled off in vacuo and replaced with ethyl acetate while stirring. The product was filtered off as a colorless solid, washed with ethyl acetate and dried at 70 ° C. in vacuo. Yield: 81.5 g (92% for DS = 2.2). The DS was determined by integrating the ¹ H NMR spectrum from the ratio of the sucrose CHO signals and the N-dodecyl aspartate signals.

Example 5 Synthesis with sodium acetate in DMSO: DS = 1.0, R ² = dodecyl

30.0 g (87.6 mmol) sucrose, 15.8 g (192.6 mmol, 2.2 equiv.) Sodium acetate and 18.9 g (192.8 mmol, 2.2 equiv.) Maleic anhydride were 2 hours at 50 ° C in 100 ml of dry dimethyl sulfoxide with stirring. According to the thin-layer chromatogram, the sucrose then reacted completely. 17.9 g (96.4 mmol, 1.1 equiv.) Of 1-dodecylamine were added and the mixture was stirred at 20 ° C. for a further 6 hours. The solvent was largely distilled off in vacuo and replaced with ethyl acetate with stirring. The product was filtered off as a colorless solid, washed with ethyl acetate and dried in vacuo at 70 ° C. Yield: 66.3 g (98.6%). The DS was determined by integrating the ¹ H NMR spectrum from the ratio of the CHO, maleate and N-dodecyl signals to approximately 1.0 (C ₂₈ H ₅₀ NaNO ₁₄ = 647.7 g / mol).

Example 6 Synthesis with sodium carbonate in DMSO and coconut fatty amine C ₁₂ : R ² = dodecyl

30.0 g (87.6 mmol) of sucrose, 10.2 g (96.4 mmol) of sodium carbonate and 18.9 g (192.8 mmol, 2.2 equiv.) Of maleic anhydride were mixed in 100 at 50 ° C. for 3 hours ml of dry dimethyl sulfoxide reacted with stirring. According to the thin-layer chromatogram, the sucrose then reacted completely. 40.0 g of Genamin® 12R100D [from coconut fat, average molecular formula CH ₃ (CH ₂ ) _12.3 NH ₂ ] were added, and the mixture was stirred at 40 ° C. for a further 3 hours. During the reaction, some of the product precipitated out as a colorless solid. The solvent was largely distilled off in vacuo and replaced with ethyl acetate with stirring. The product was filtered off as a colorless solid, washed with ethyl acetate and dried in vacuo at 70.degree. Yield: 78.0 g (89% for DS = 2.2).

Example 7 Synthesis with sodium acetate in DMF: DS = 8, R ² = dodecyl

10.0 g (29.2 mmol) sucrose, 21.6 g (263 mmol, 9 equiv.) Sodium acetate and 25.8 g (263 mmol) maleic anhydride were dissolved in 150 ml dry N, N at 40 ° C for 3 hours -Dimethylformamide stirred. The ¹ H NMR analysis of a sample in D ₂ O shows only small amounts of maleic anhydride (δ = 6.30 ppm) and the formation of the olefinic maleate protons at δ = 6.70 ppm and δ = 5.90 ppm in the expected integration ratio . 48.7 g (263 mmol, 9 equiv.) Of 1-dodecylamine were added and the mixture was stirred at 20 ° C. for 14 h. The solvent was largely distilled off in vacuo and replaced with ethyl acetate with stirring. The product was filtered off, washed with ethyl acetate and dried in vacuo at 70 ° C. Yield: 73.0 g. (96%).

Example 8 Synthesis with sodium acetate in DMF: DS = 8, R ² = dodecyl / hexadecyl / octadecyl (35/60/5%)

10.0 g (29.2 mmol) sucrose, 21.6 g (263 mmol, 9 equiv.) Sodium acetate and 25.8 g (263 mmol) of maleic anhydride were dry for 3 hours at 40 ° C. in 150 ml nem N, N-dimethylformamide stirred. A mixture of 17.1 g was added (92.0 mmol) 1-dodecylamine, 38.1 g (157.8 mmol) 1-hexadecylamine and 3.5 g (13.1 mmol) 1-octadecylamine and the mixture was stirred at 20 ° C. for 14 h. The Lö Medium was largely distilled off in vacuo and with vinegar stirring Acid ethyl ester replaced. The product was filtered off with ethyl acetate washed and dried in vacuo at 70 ° C. Yield: 90.0 g. (99%).  

Example 9 Synthesis of (I) without the use of solvents

30.0 g (87.6 mmol) sucrose, 15.8 g (192.6 mmol, 2.2 equiv.) Sodium acetate were stirred for 20 minutes at a bath temperature of 195 ° C. under vacuum (approx. 20 torr). The mixture was cooled to 175 ° C. (bath temperature) at atmospheric pressure and 18.9 g (192.8 mmol, 2.2 equiv.) Of molten maleic anhydride were slowly added dropwise (5 minutes). The mixture turned brownish, started to foam and was cooled to 125 ° C. after 2 minutes with stirring. The ¹ H NMR analysis of a sample in D ₂ O showed only small amounts of maleic anhydride (δ = 6.30 ppm) and the formation of the olefinic maleate protons at δ = 6.70 ppm and δ = 5.90 ppm in the expected integration ratio . 35.7 g (193 mmol, 2.2 equiv.) Of 1-dodecylamine (laurylamine) were added, the mixture was stirred at 125 ° C. for 20 minutes and then treated with ethyl acetate with boiling cooling and stirring. The product was filtered off, washed with ethyl acetate and dried in vacuo at 70 ° C.

Example 10 Monosulfonation with chlorosulfonic acid

5.0 g (6.0 mmol) of product from Example 1 (RS 786) were in 50 ml of dichloromethane and 1 ml of dimethyl sulfoxide. 0.4 ml (6.0 mmol) of chlorosolonic acid in 25 ml of dichloromethane was added dropwise at room temperature. The mixture was stirred for a further 3 hours at room temperature. Then you got a clear one Solution. The solvent was removed under vacuum. Then was with Stirred ethyl acetate, suction filtered and dried under vacuum at 60 °. 4.6 g of colorless solid (RS 814) were obtained.

Example 11 Monosulfonation with pyridine-SO ₃ complex

5.0 g (6.0 mmol) of product from Example 1 (RS 786) were in 50 ml of dimethyl form Amide stirred at 70 ° C until the solid had almost completely dissolved. Then let  cooled to 30 ° C and added 1.0 g of sulfur trioxide-pyridine complex. Man stirred for 3 hours at 30 ° C and 1 hour at 60 ° C. The solvent was under Vacuum removed. The mixture was then stirred with ethyl acetate, suction filtered and dried under vacuum at 60 ° C. 4.3 g of colorless were obtained Solid (RS 825).

Example 12 Determination of the surface tension

The compounds according to the invention, in particular those with a degree of acylation up to DS = 3, had excellent surface-active properties. Table 1 shows that the compounds according to the invention reduce the surface tension of water. The critical micelle formation concentration (CMC) and the reduction in surface tension (σ _min ) were measured with a tensiometer (company Lauda, type TD1, water distilled twice, σ _min = 71.8 mN / m) at 25 ° C. The concentration was increased to the minimum force to obtain the CMC and σ _min values.
Product from Example 1: C ₄₄ H ₇₈ Na ₂ N ₂ O ₁₇ = 953 g / mol (RS 786)
Product from Example 5: C ₂₈ H ₅₀ NaNO ₁₄ = 647.7 g / mol (RS 795)
Product from Example 10: (RS 814): C ₄₄ H ₇₈ Na ₂ N ₂ O ₂₀ S = 1033 g / mol

Table 1

CMC and σ _min values

The very good surfactant properties of the Compounds (1) according to the invention which, for example, a commercially used Standartensid (SDS) surpass.

Example 13 Measurement of foam height and foam stability

In special application areas, e.g. B. for dishwashing detergent, good foaming surfactants are required. Data about the foam properties are obtained e.g. B. according to the Ross Miles method (ASTM D1173-53, Oil & Soap 62, 1260, 1958). Thereafter, 200 ml of the surfactant solution are run into a measuring cylinder with 50 ml of the same surfactant solution via a pipette with an inner diameter of 2.9 mm and a height of 90 cm. The foam height was read off immediately (t = 0, IFH = initial foam height) and then at given times. With this experimental setup, the foam heights were measured at 25 ° C. and with a 0.1% concentration of the compounds according to the invention in comparison to a standard surfactant (SDS). Product from Example 1: RS 786; Product from Example 5: RS 795. The substance RS 795, which was still clearly soluble at up to 20 g / l, surprisingly showed practically no more waste in a period of up to 2 hours after a slight drop in foam height within the first 5 minutes. Even the less readily soluble substance RS 786, which could only be clearly dissolved in water up to 4 g / l, showed excellent foam stability after the initial drop. In contrast, the foam from SDS practically completely disappeared within about 100 minutes (see FIG. 6). The foam stability of the sulfonate produced according to Example 10 was also excellent: the foam height dropped here from 33 mm (product from Example 10) to 24 mm within 2 hours using the same test method.

Example 14 Dispersing effect

To determine the solubilization of Sudan Red B in water with the compounds according to the invention, solutions of various concentrations (0.075 g, 0.150 g and 0.300 g in 25 ml of water) were each treated with 12.5 mg of Sudan Red B. The dye was dispersed by ultrasound. The suspension was then centrifuged at 7500 rpm for 70 min and membrane filtered. The extinction of the supernatant clear solution was measured photometrically at a wavelength of 516 nm (cuvette length 1 cm). A solution of Sudan Red B in water (12.5 mg in 25 ml) served as the zero sample. The compound referred to as "caprylate" is a caprylate of the oxidized sucrose from Example 10 in DE 195 42 303. This comparison compound is therefore significantly less effective than e.g. B. the compound from Example 1. The same applies to the lower substituted compound from Example 5 at low concentrations up to 0.3% by weight (see Table 2, Fig. 7).

These measurement results show that the compounds of the invention have drawn solubilization properties. The connections are suitable therefore, for example for detergents, dishwashing detergents and cleaning agents as well as a formulation aids in pharmaceuticals and agriculture.  

Example 15 Solubilization of an active ingredient

Active pharmaceutical ingredients and food additives for which no suitable Pharmaceutical form is available, can be better solubilized in water or in other re formulations are incorporated. Obvious examples of effectiveness Proof of safety includes doxorubicin (tumor therapy), amphotericin (treatment of mycoses) and vitamins (additive). In the present example, 50 mg of vitamin E (tocopherol) of only 150 mg of the compound from Example 1 without Solvent additive absorbed smoothly (see Tab. 3). An attempt at dispersion in water (25 ml) was carried out analogously to that described in Example 14:

Tab. 3

Example 16 Manufacture of active ingredient formulations for plant protection products and for the treatment of seeds

Few water-soluble fungicides and insecticides in spray liquors (foliar sprays) or in seed dressings (seed treatment) with additives of the invention Connections are better formulated. A typical wording is at for example from 20-600 g of a fungicide or 10-500 g of an insecticide, 50-150 g an antifreeze such as ethylene glycol or propylene glycol, 2-10 g of a Ent foamer, 2-100 g of a compound according to the invention and water (filling on 1 liter of formulation).  

Example 17 Try hand washing on healthy and sensitive / diseased skin

2 g of the product from Example 2 at 20 ° C in 100 ml of water form a colorless, fine-pored foam-forming emulsion with a pH of approx. 9. This emulsion was adjusted to the physiological pH of healthy skin with citric acid, which is around 5.5. Hand washing attempts with this solution turned out to be more healthy and also on stressed, sensitive and by chronic dermatosis a subjectively pleasant, irritation-free skin feeling as well as a excellent cleaning effect. A comparable treatment with ordinary Soap resulted in a test person within about 5 minutes severe itchy reddening of the skin, which is subsequently treated with a corticosteroid ointment had to be delt. Formulation containing the compounds according to the invention Stanchions are therefore particularly suitable for frequent washing, showering and bathing for sensitive or sick skin, and also for cleaning especially the youthful skin. The subjectively mild character often gives the connections obviously an effect stabilizing the protective acid mantle of the skin.

Example 18 Manufacture of a shampoo

To produce 1 kg of a shampoo, 60 g of the inventive moderate compound (e.g. from Example 1), 130 g cocamido-propyl-betaine, 15 g NaCl, 1.5 g preservative (e.g. potassium sorbate and / or sodium benzoate), Mixed 0.5 g allantoin, 2 g sodium formate, 7 g sodium citrate and 1 g perfume oil and made up to 1 kg with water. It contains a skin and hair compatible very effective shampoo.  

Example 19 Manufacture of an abrasive

To produce 1 kg of an abrasive, 30 g of the invention compound (e.g. from Example 2), 20 g octadecyl polyethylene glycol ether, 45 g Pentasodium triphosphate and 2 g fragrance mixed and with quartz flour to 1 kg replenished.

Example 20 Manufacture of a detergent

To produce 1 kg of a detergent, 150 g of the invention Compounds (e.g. from Example 3), 200 g complexing agents, e.g. B. zeolite, 30 g Detergent protease, 35 g sodium citrate, 80 ml ethanol and possibly fragrance and dyes mixed and made up to 1 kg with water.

Example 21 Manufacture of a bath additive

To produce 1 kg of a bath additive, 20 g of the invention moderate compound (e.g. from Example 3), 45 g coconut fatty acid ethanolamide, 50 g Almond oil, 10 g sodium chloride, 3.5 g preservative, 10 g hexadecanol, and 10 g of perfume mixed and made up to 1 kg with water.

Example 22 Testing biodegradability

According to OECD 301 B, substances can be classified as readily biodegradable if, after 28 days of contact with an activated sludge mixed population mineralizing at least 60% of the carbon to carbon dioxide. In this A compound according to the invention (sample from Example 1) has already been tested metabolized to 60.3% after 18 days. The substance is therefore very light biodegradable.

Claims (19)

1. Sucrose-N-alkyl aspartate of the formula (I)
wherein R ^1, independently of one another, identically or differently, is a group selected from hydrogen, a compound of the formula (II):
where R ² is C _n H _{2n + 1} or C _n H _2n where n is an integer from 2-28, preferably 6-22, especially 12-18, a compound of the formula (III)
and / or a radical of formula (IV)
and M ⁺ is hydrogen, an alkali metal ion and / or an alkaline earth metal ion, preferably a sodium, potassium, lithium, magnesium, calcium and / or ammonium ion with the proviso that at least one radical R ^{1 is} a compound of the formula (II) is. 2. Sucrose-N-alkyl aspartate according to claim 1, characterized in that the degree of substitution of the radical R ¹ (DS) is determined by the following formula:
DS = n × [rest of formula (II)] + [0 to (8-n)] × [rest of formula (III)] + (0 to m) × [rest of formula (IV)], where m = 2 for n = 1-6 and m = 1 for n = 7 and n ≦ 8. 3. Sucrose-N-alkyl aspartate according to claim 1 or 2, characterized in that R ² is a decyl, dodecyl, tetradecyl, hexadecyl or octadecyl residue or a residue derived from coconut, palm, soy or tallow oil fats , or mixtures thereof. 4. A process for the preparation of a sucrose-N-alkyl aspartate of the formula (I), characterized in that sucrose is acylated with maleic acid or a derivative of maleic acid in a first step, and in a second step one to eight molar equivalents of amine of the formula R. ² NH ₂ with R ² equal to C _n H _{2n + 1} or C _n H _2n , where n is an integer from 2-28, preferably 6-22, especially 12-18, to the maleate sucrose formed in the first step is added. 5. The method according to claim 4, characterized in that the Acylierungsre action is carried out in the presence of a catalyst. 6. The method according to claim 5, characterized in that the catalyst basic metal salt, preferably a carbonate, hydrogen carbonate, acetate and / or formate. 7. The method according to any one of claims 4-6, characterized in that in a further step sulfonates the sucrose-N-alkylaspartate obtained becomes. 8. The method according to claim 7, characterized in that up to two radicals R ^{1 are} sulfonated. 9. The method according to claim 7 or 8, characterized in that the sulfonation is carried out with SO ₃ , ClSO ₃ H, DMF-SO ₃ and / or pyridine-SO ₃ . 10. Use of a sucrose-N-alkyl aspartate according to one of the claims 1-3 as a surface-active compound. 11. Use of one or more sucrose-N-alkylasparaginates according to one of claims 1-3 as an additive in hygiene, cleaning, cosmetics, food and / or pharmaceuticals or in pesticides or for prevention and / or loading  fighting water pollution by chemicals and / or Oil. 12. Use according to claim 11 as an additive in soaps, abrasives, general purpose cleaner, dishwashing detergent, detergent, shampoo, heavy-duty detergent and / or bath additives. 13. Use according to claim 11 or 12, characterized in that the Degree of substitution DS of at least one sucrose N-alkyl aspartate between 1 to about 4. 14. Use according to any one of claims 10-13, characterized in that the sucrose N-alkyl aspartate along with at least one other surface-active substance (co-surfactant) is used. 15. Use according to claim 14, characterized in that the co- Surfactant is selected from alkyl polyglycosides, 6-0-monoesteralkylglykosi de, alcohol ether sulfates or alkyl glucamides. 16. Use of a sucrose-N-alkyl aspartate according to one of the claims 1-3 as low-calorie fat substitute. 17. Use according to claim 16, characterized in that the substitute degree DS of at least one sucrose-N-alkyl aspartate between approx. 4 and is 8. 18. Use of a sucrose-N-alkyl aspartate according to one of the claims 1-3 as a transfection reagent.   19. Sucrose-N-alkyl aspartate according to any one of claims 1-3 in the form of a aqueous solution, emulsion, suspension, jelly, cream, paste or powder.