AU746197B2 - Sucrose-N-alkyl-asparaginates, production and use thereof - Google Patents

Description

WO 99/48901 PCT/EP99/01619 Description Sucrose N-alkylaspartates, their preparation and use The invention relates to sucrose N-alkylaspartates of the formula (I) according to Fig. 1, and to the preparation and use thereof.

Sucrose is reacted, as hydrophilic component, with fatty acid derivatives by common processes to give the known sucrose fatty acid esters (Fig. 2), which, because of their amphiphilic properties, can be used as industrial auxiliaries and additives. The known compounds according to Fig. 2 are described as nontoxic, nonirritant to skin and readily biodegradable.

Sucrose acetates where R 1 OAc are used, for example, in detergents and bleach activators and with long-chain fatty acid radicals as interfaceactive compounds. Because of the very favorable physiological properties, other fields of use are in the food industry as emulsifiers, e.g. in bakery goods and chocolate, and in cosmetic formulations. Despite the advantages and although the compounds according to Fig. 2, in which up to 8 fatty acid radicals can be bonded directly to the OH groups of sucrose via ester bonds, have been known for some time, they are only used to a small extent as surface-active substances. They are preferably only used in the cosmetics, food, and pharmaceutical sector where specific dermatological and toxicological demands are made. The reason for this is, in particular, their complex and costly preparation, which prevent wider commercial exploitation. By contrast, the sorbitan fatty acid esters, which are accessible, for example, from the structurally more simple glucose in a manner which is technically more straightforward have carved out a niche in the market as emulsifiers for many years. For the broader commercial use of products obtainable from sucrose, which is particularly low-cost and available in large amounts, e.g. as cleaners or cosmetics for the consumer goods sector, a cost-effective preparation process thereof, in particular, is required.

The esters of sucrose according to Fig. 2 already known are prepared on an industrial scale namely by means of transesterification processes: In the solvent process, sucrose is reacted in the presence of a basic catalyst in a solvent such as dimethylformamide or dimethyl sulfoxide with fatty acid methyl esters R1COMe (JP 04,247,095). In the microemulsion WO 99/48901 PCT/E P99/01 61 9 2 process, the fatty acid ester is dispersed in a solution of the carbohydrate with the help of an emulsifier. The solvent is removed before the actual esterification takes places (EP 0254376). 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 another process, lipases are used (DE 3430944). Finally, the esterification of sucrose can also be carried out with carbonyl chlorides or carboxylic anhydrides. In processes which are less suitable for industrial productions, expensive auxiliary bases, such as, for example, pyridine or N,Ndimethylaminopyridine, are required for this (DE 19542303). In the lastmentioned laid-open specification, mixtures of oxidized sucroses, in particular of sucrose monocarboxylic acids are used, which for their part can be prepared in a complex oxidation process in low yield, e.g. as in DE 4307388.

The known transesterification processes are very complex both with regard to carrying out the process and also isolation of the product. The reaction parameters pressure and temperature have to be carefully controlled and, to isolate the sucrose ester, repeated extraction and distillation are required. In addition, the high reaction temperatures, in combination with the long reaction times, lead to discoloration of the products, which can only be reversed again by means of complex purification procedures. A further disadvantage of the compounds according to Fig. 2 is that although, as monoesters or as diesters, they exhibit surface-active properties, they can only be used as surfactants to a restricted extent because of their limited solubility in water. The monoesters dissolve sparingly in cold water, while the diesters are only emulsifiable in water. The multistage process mentioned in DE 19542303 attempts therefore to circumvent these problems by oxidatively introducing the additional carboxylate group in the sucrose molecule.

In EP 0324595 "aminofunctional compounds as builders/dispersants in cleaners" are described, which are obtained by addition of amino acids to maleate half-esters or polyols. The latter are obtained by reacting maleic anhydride, in particular with polyvinyl alcohol, sucrose also being cited.

Although the reaction of maleic anhydride with alcohols has been known for a long time, the subsequent reaction with amino acids is problematical since it requires a balance system of buffers and bases which suppresses k,) i WO 99/48901 PCT/EP99/01619 3 the alkaline back-reaction of the maleate half-ester. NaOH/Na 2

CO

3 is preferably added for this purpose. The excess bases have to be neutralized and the salts separated off as byproducts. Furthermore, complete purification steps are required and the yields are not quantitative since the maleate half-ester is of course cleaved off again with aqueous alkali metal hydroxides as a result of hydrolysis.

The maleate half-ester of sucrose according to Fig. 3 is described for example, as a builder (CO-/builder) in detergents (DE 2148279).

In DE 2739343 "basic" surface-active esters of aliphatic polyols are described, it also being possible to use sucrose as the polyhydroxy compound. Given as an acid component are compounds of the formula

R

8

-N(R

9 )-CH(R10)-CH(R11)-COOH, where R8 can be a C8-C22-alkyl or alkenyl radical, Rg and R 11 can, inter alia, also be hydrogen, and R10 can, S..i inter alia, also be a carboxyl group. However, "acidic esters" of this type can not be prepared by the multi-stage process described in DE 2739343 *because according to this only "basic esters" of sucrose are accessible, i.e.

completely esterified carboxylates in which the carboxyl group (radical is also present in esterified form, and not in protonated or anionic form.

It would therefore be desirable to provide novel derivatives of sucrose which can be prepared easily and which can be used as surface-active compounds.

Surprisingly, "acidic esters" of sucrose have the required properties.

The present invention therefore provides sucrose N-alkylaspartates of the formula (I)

OR,

RRIOO

OR,

R O ii ->-<A~VtXZhv t- WO 99/48901 PCT/EP9901619 4 in which R 1 independently of one another, identically or different is a group chosen from hydrogen, a compound of the formula (II): 0

OM

HN-R

2

(II)

where R 2 is CnH2n+1 or CnH2n, in which n is an integer from 2 to 28, preferably 6-22, especially 12-18, a compound of the formula (III) O 0,O"

M*

(III)..

(111) and/or a radical of the formula (IV) O=S-O M

(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 is a compound of the formula (II).

The compounds of the formula according to the invention cannot be prepared by the process described in DE 2739343 because for this, in an additional synthesis step, a chemoselective abstraction of the ester group designated by R10 has to be carried out. This is not, however, possible using known methods since in this case the ester bond just linked via the other carboxyl group in R8-N(R9)-CH(R10)-CH(R 11 )-COOH, would simultaneously be split back again. This hydrolysis occurs even at a mild pH below pH=10. In addition, the "basic esters" in DE 2739343 are

-II'

;F

21-02-2000 EP 009901619 WO 99/48901 PCT/EP99/01619 could have only led to 128 parts of the product. In actual fact, however, 189 parts of product were obtained. The difference can only be unreacted sucrose, S•which is clearly water-soluble and does not have a foaming action in water.

In actual fact, also only a content of basic nitrogen of 1.4% was found, which would also have been expected if the substances had been merely :°.°.mixed together (calculated However, the predicted reaction product would have had a theoretical nitrogen content of Also, the value of 123, given as the saponification number does not permit inference to the formation of a reaction product because, from the stoichiometry, no change :in the saponification number can be expected, and because, from the 66 **.parts of the compound C12H 25 NH-CH(COOCH3)(CH2COOCH3) having the theoretical saponification number 122 used, in each case virtually the same saponification number must again be found. From this is drawn the conclusion that the reactions in DE 2739343 can not lead to the "acidic esters" according to the invention, do not describe a preparation, and thus do not represent prior art in this respect.

6 The present invention therefore provides new types of sucrose Nalkylaspartate of the formula which can be prepared surprisingly easily in high yields in a two-stage one-part process, and can be used as readily biodegradable, physiologically compatible and surface-active substances having a broad use. The compounds according to the invention are notable for the fact that at least one and up to eight radicals R 1 represents a 3- TAMENDED PAGE

AMENDEDIPAGE

7 w 7~ 21-02-2000 EP 009901619 WO 99/48901 PCT/EP99/01619 6 alkylamino-substituted half-ester radical of 1,4-butanedicarboxylic acid or salts thereof according to the formula (II).

To regulate the solubility of properties the compounds according to the invention can, in a preferred embodiment, also comprise one or more maleate radicals of the formula (III), in particular in accordance with the definition, given in Fig. 1, of the degree of substitution DS, which also includes fractions, where the total of the radicals II and III does not exceed the value DS 8.

In metal-free form (MO He), the compounds according to the invention as is typical in the case of amino acids can also be in the form of internal salts (betaines) with protonation of the amino function. Me is preferably an ion of the alkali metal and alkaline earth metals such as Nae, Lie, 2+ 2+ Mg Ca and NH4e, particularly preferably sodium or potassium ions, or Smixtures thereof.

22 Suitable alkylamino radicals NHR originate from primary a mines (monoalkylamines R2NH 2 of chain lengths C2 to C28, preferably from commercially available fatty amines having chain lengths from C6 to C22, in particular from C12 to C18, which are obtained from varyingly broad production cuts, including hydrogenated ones, for example from coconut, from palm, soya or tallow oil fats, especially from decyl-, dodecyl-, tetradecyl-, hexadecyl or octadecylamines or from radicals which are derived from coconut, palm, soya or tallow oil fat. Accordingly, the S compounds according to the invention can also carry different radicals.

Coconut fat generally comprises a mixture of hexanoic, octanoic, decanoic, lauric, myristic, palmitic, stearic, behenic, oleic and linoleic acid radicals.

Palm oil generally comprises a mixture of myristic, palmitic, stearic, oleic and linoleic acid radicals. Soya oil comprises, inter alia, radicals having a carbon chain length of 14, 16, 18, 20 and 22 carbon atoms, where, usually, C14 is unsaturated, C16 is monounsaturated and saturated, C18 is mono-, di- and triunsaturated and saturated, C20 is monounsaturated and saturated, and C22 is saturated. Tallow fat generally comprises radicals having 14, 16 and 18 carbon atoms.

AMENDED

PAGE

vs. V 21-02-2000 WO 99/48901 EP 009901619 PCT/EP99/01619 In a further preferred embodiment, one or more, preferably up to 2 radicals R can also be in sulfated form, where the sum of the radicals II, III and IV cannot of course exceed the numeral 8.

The present invention further provides a process for the preparation of a sucrose N-alkylaspartate of the formula where, in a first step, sucrose is acylated with maleic acid or a derivative of maleic acid, and 0O *e 0 0

S

S

0 *0Se 0

S

00e0 CS 0 AMENDED PAGE -I I I' WO 99/48901 PCT/E P99/01619 8 aqueous bases and buffer systems, for example as described in the application EP 0324595, which is therefore particularly advantageous.

In a further embodiment of the process according to the invention, the sucrose N-alkylaspartate are sulfonated, where, preferably, up to two radicals R are sulfonated by one of the methods for the functionalization of hydroxyl and amino groups which are known to the person skilled in the art. For this, following the above-described reactions, the reaction products are reacted in the same reaction vessel or following removal of the intermediates, with the calculated amount of a sulfonation reagent, optionally following the addition of an inert solvent, such as, for example, dichloromethane, tetrahydrofuran or dioxane. Suitable sulfonating reagents are, for example, SO3, CISO 3 H, DMF-S0 3 and/or pyridine-SO3.

The advantages of the process according to the invention compared with the known preparation processes are the high reactivity of the maleic anhydride and the nucleophilic attack of the fatty amine on the electrophilic CC double bond, as a result of which, for this reaction step, it is possible to dispense with further purification steps, expensive auxiliary bases or auxiliary reagents, such as, for example, catalysts. Through appropriate choice of the radicals R and the degree of substitution DS, the process further permits the provision of a high number of differently substituted compounds according to formula having tailored use properties and fields of use. In addition, the yields in the two-stage one-part process are greater than The process according to the invention for the preparation of compounds according to formula having a defined DS can, for example, be carried out as follows: Sucrose and the appropriately calculated amount of, for example, maleic anhydride and an amount, equivalent, for example, for this purpose, of a basic metal salt such as, for example, sodium hydrogencarbonate, sodium carbonate, sodium acetate, sodium formate, lithium acetate or potassium acetate, preferably sodium hydrogencarbonate, sodium carbonate or sodium acetate, is reacted without a diluent or in a suitable solvent, for example in N,N-dimethylformamide (DMF), N,NsT4 dimethylacetamide (DMA), dioxane, N-methylpyrrolidone (NMP), DMSO, (N M A I IA l< r\t\lA arlr\* r" /r rnf rr r A r rr VV 40I'O I r I Icr/ u1 Dl 9 tetrahydrofuron (THF), or in mixtures of these solvents, preferably in N,Ndimethylformamide, N-methylpyrrolidone, DMSO, dioxane or in mixtures of these solvents, at temperatures of 20 0 C up to the boiling point of the solvent in question or of the solvent mixture in question, preferably at temperatures in the range from about 20 to about 1400C, in particular at temperatures from about 40 to about 1200C.

The reaction is complete when consumption of the sucrose is complete, which is readily detectable using thin layer chromatography. Then, the amount, calculated according to the desired DS, of the alkylamine R NH2 in question or of the alkylamine mixture is added, and the mixture is stirred in the same reaction vessel at temperatures of about 0°C to the boiling point of the solvent or of the solvent mixture in question, preferably at temperatures from about 20 to about 600C, until the reaction is, according to thin-layer chromatographic analysis, complete.

During the reaction, some of the end product precipitated out as a colorless solid, which can be filtered off with suction, washed and dried.

The majority of the solvent used is preferably distilled off, and the product is isolated by stirring with a low-boiling solvent. Alternatively, the product can also be precipitated out of the reaction solution by addition of the corresponding amount of solvent. Suitable solvents for the stirring-out and the precipitation process are ethyl acetate, hexane, methyl isobutyl ketone, acetone and the like. The solid end product is obtained following thorough vacuum drying as a colorless, odorless powder.

Depending on the nature of the metal salt MX used, the process gives the corresponding carboxylate salt as the end product, preference being given to the sodium or potassium salts or mixtures thereof. These can also be converted, using equivalent amounts of proton acids, into the free carboxylic acids (M H which, because of the secondary amine function present, are in equilibrium with the betaine form. By the careful addition of at most one further acid equivalent, the secondary amino group in the aspartic acid fraction can also be protonated, it being possible, for example, to use halocarboxylic acids, aliphatic and aromatic dicarboxylic acids and sulfonic acids. The negative counterion used has an effect, for example, on the surfactant properties of the compound according to the W/ invention. As a result of suitable choice of the counterion, for example a 77 7 Z 7, 7_ WO 99/48901 PCT/E P9901 61 9 paraffin sulfonate, it is thus possible, for example, to prepare tailored thickeners in formulations for shampoos and other cosmetic cleaners, and for liquid surfactant systems.

In a further embodiment, following the reaction described above, the products obtained are reacted, in the same reaction vessel or following removal of the intermediates, with the corresponding amount of the sulfonating reagent (preferably up to two mol equivalents of the sulfonating reagent, optionally with the addition of an inert solvent, such as, for example, dichloromethane, tetrahydrofuran or dioxane. Preferred sulfonating reagents are, for example, SO3, CISO 3 H, DMF-SO3 or pyridine-SO3.

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

The compounds according to the invention have excellent surface-active properties and can therefore be used diversely as industrial auxiliaries and additives, for example as surfactants, emulsifiers, stabilizers, emollients or solubility promoters. In addition, these compounds where DS 4 8 are suitable as low-calorie fat substitutes in foods.

In the case of degrees of substitution (DS) of from 1 to 7, as a result of reaction with, for example, MA, mixtures of substances are obtained, where predominantly the 3 primary OH groups react. Under specific conditions, the 2 OH group of the glucose can also be selectively acylated (FR 2670493), the yields being generally low, e.g. about 42% in the case of the selective enzymatic acylation of the 1'-OH group using vinyl methacrylate and subtilisin in DMF (Chan, A.W.Y. Ganem, B., Biocatalysis, 1993, 8, 163-169). Generally, there is a decreasing reactivity in the order HO-6 approx. HO-6' HO-1' HO-2 approx. HO-3'.

Compounds where DS=2 and DS=3, accordingly, have predominantly the constitution shown in Fig. 4.

-I-73, WO 99/48901 PCT/E P99/01 61 9 11 The addition of the alkylamine R NH2 to the sucrose maleate or to mixtures of intermediates which can comprise up to 8 radicals R 1 generally takes place stoichiometrically until complete reaction of the maleate CC double bond with a certain amine R 1

NH

2 The amine R 1 NH2 can, however, also be used in a substoichiometric amount, with retention of unsaturated maleate partial structures, for example in order to achieve a certain solubility of the products in water. Furthermore, it is also possible to use a mixture of two or more different alkylamines. Accordingly, the compounds according to the invention can also carry different radicals. The hydrophilicity to hydrophobicity ratio, which determines the surface-active properties of the compounds according to the invention, is adjusted by the 2 structure of the alkyl substituents R and their degree of substitution (DS).

The DS can be adjusted via the molar ratio of the alkylamine R2NH 2 to the sucrose.

The solubility of the compounds according to the invention in water can, if desired, also be adjusted via additional sulfonate groups, in that a higher number of N-alkylaspartate radicals can be compensated by, preferably, to two sulfonate groups.

The compounds according to the invention have in total up to eight radicals

R

1 the DS being between 1 and 8. As the DS increases, the lipophilicity of the compounds in principle increases, and their solubility in water decreases correspondingly sharply. At the same time, this effect can again be compensated by the carboxylate or sulfonate groups introduced. As already explained, the amphoteric character and the solubility of the surface-active substances in water can thus be modulated in a simple manner, which is important for the intended fields of use. Thus, for cosmetic applications, e.g. in shampoos or bath preparations, but also in household cleaners, such as, for example, in dishwashing detergents, good foaming ability and good foam stability are of importance. The amphoteric character of the compounds suggests a particular tolerability by the skin and a skin-protection action, in that a favorable interaction with the collagen of the skin can occur. In this connection, the formation of a protective layer can be reduced the excessive attack of surfactants on the upper layers of the skin and their strong degreasing and irritancy as a result of other anionic surfactants present in a formulation. Furthermore, the hydrophilic carboxylate groups of the asparagine partial structure or -o L

VT

WO 99/48901 PCTEP99/01619 12 optionally additional sulfonate groups ensure good wash-off from the skin, which is of particular importance for body cleansing.

For surface-active substances, surfactants and emulsifiers, the DS is therefore preferably about 1-3, in particular 5 3, and for low-calorie fat replacements for foods preferably about 3, in particular about 4-8. In the case of low-calorie fat replacements, melting points and taste sensations 2 can be controlled by the composition of the radicals R and the DS value: for example, only those fatty substances whose melting point is above body temperature and which are not liquid at room temperature produce a pleasant taste sensation. A tailored taste sensation, for example for a cocoa butter substitute, can be achieved by appropriate mixture of fatty amines of varying chain lengths, by using a C-12 (lauryl-), C-16 (palmityl-), (caprinyl-), C-14 (myristyl-) and C-18 (stearyl-)amines in matched ratios.

The present invention therefore further provides for the use of a sucrose Nalkylaspartate according to the invention as surface-active compounds, in particular the use of one or more sucrose-N-alkylaspartates according to the invention as additives in hygiene compositions, cleaners, cosmetics, foods and/or medicaments, or in pesticides or for the prevention and/or control of contaminations of water by chemicals and/or oil, for example as additive in soaps, scouring agents, all-purpose cleaners, dishwashing detergents, laundry detergents, shampoos, universal detergents and/or bath preparations, where the degree of substitution DS of at least one sucrose N-alkylaspartate is preferably between 1 and about 4.

In a particular embodiment, the sucrose-N-alkylaspartate is used together with at least one other surface-active substance (cosurfactant), the cosurfactant is preferably chosen from alkyl polyglycosides, alkyl glycosides, alcohol ether sulfates or alkyl glucamides.

The present invention further relates to the use of a sucrose Nalkylaspartate according to the invention as low-calorie fat replacement, where the degree of substitution DS of at least one sucrose Nalkylaspartate is preferably between about 4 and 8.

WO 99/48901 PCT/E P99/01 61 9 13 In another subject-matter of the present invention, the sucrose Nalkylaspartate according to the invention is in the form of an aqueous solution, an emulsion, a suspension, a gel, a cream, a paste or a powder.

The surface-active properties of the compounds according to the invention thus open up a large number of use possibilities. The use examples below serve to illustrate the diverse possible fields of use and do not signify a limitation on these examples.

In the case of washing and cleaning, the reduction in surface tension brings about easier soil detachment from the fibers and stabilization of the soil constituents in the wash liquor. In the textile industry, the wash, dyeing and finishing operations are improved and accelerated with the help of surfactants. During wool dyeing, for example, the pore damage caused by the dyeing process is reduced, the surfactants have a stabilizing action in hydrogen peroxide bleaching baths, and the dispersion effect for textile dyes facilitates the dyeing process. In the leather industry, during the preparation of the hide, and in the paper industry, surfactants are important auxiliaries. They are added to car and engine oils to form uniform, nonbreaking lubricating films. In paints and surface coating they improve the wetting and, as a result of their dispersing action, also delay the settling out of the color pigments whilst the paints are standing. In cosmetics, in the food industry, in medicine, in disinfectants and in the case of pest control, the distribution of the active ingredients in a liquid phase or its adhesion to a surface is achieved. They can also be used as emulsifiers for bakery goods and ice cream. Floor treatments, furniture and car polishes, and paint strippers typically likewise comprise surfactants. During the recovery of ores, coal and potash, the solid substances are slurried by the surfactant coupling them to air bubbles (flotation). On the other hand, other surfactants can be influenced in their foaming ability as a result of the action of the surface-active substances, in that the ascension and bursting of the gas bubbles is promoted (defoaming). Such foam-control agents are used in particular in the case of dishwashing detergents and in many industrial processes, such as the production of paper and sugar. The low toxicity and biocompatibility known of other sugar radicals and of biosurfactants means that the compounds according to the invention also have similarly favorable properties. These advantages can, for example, "-,also be utilized for fighting tanker accidents at sea and, generally, for -0 .LL WO 99/48901 PCT/EP99/01619 14 fighting oil contamination in water, in that the oil is more rapidly dispersed, without the disadvantages of an additional burden on rivers and lakes occurring as a result of the aid.

In the pharmaceutical sector, biocompatible surfactants are used, for example, as auxiliaries in the preparation of vaccines, more specifically for the isolation of purification of bacterial polysaccharides as vaccines (see e.g. W097/30171).

Depending on the intended use, in detergents, surfactants constitute about 10-40% of the total amount. The typical composition of a universal detergent can comprise e.g. 5-15% of a compound according to the invention, 3-5% of another foam regulator (soap or silicone oil), 30-40% of a builder zeolite, polycarboxylate), 20-30% of a bleach sodium perborate), 0-10% of an extender sodium sulfate), 1.5-4% of a bleach activator tetraacetylethylenediamine), 0.2-2% of a stabilizer for perborate EDTA, Mg silicate), 0.3-1% of an enzyme a protease), 0.5-1% of an antiredeposition agent carboxymethylcellulose), 0.1- 0.3% of an optical brightener a stillbene or pyrazoline derivative) and 0.1-0.2% of a fragrance.

The invention relates in particular to aqueous solutions, soaps, cleaners, such as scouring agents, all-purpose cleaners, dishwashing detergents or laundry detergents, shampoos, universal detergents, bath preparations, foods, cosmetics, emulsions, suspensions, jellies, face cleansers, coldwave and fixing compositions, surfactant preparations for babies, creams, pastes and powders which comprise at least one of the compounds according to the invention or else mixtures thereof with other surface-active substances (cosurfactants), for example alkyl polyglycosides (APGs), monoester alkyl glycosides (Biosurf@ grades from Novo Nordisk), alcohol ether sulfates (AEs), or alkylglucamides.

The betaine structure of the N-alkylaspartate given above in the compounds according to the invention is structurally very similar to the aspartic acid which occurs naturally in proteins. It is therefore to be assumed that the tendency, discussed e.g. in the case of purely nonionic amphiphilic compounds, such as the N-alkylglucamines, towards the formation of carcinogenic N-nitrosamines does not exist.

WO 99/48901 PCT/EP9901619 In the pharmaceutical industry, surface-active compounds are used in formulations for active ingredients, with which improved active-ingredient uptake is said to be achieved (drug delivery systems). Cyclosporin, for example, is formulated as a "microemulsion preconcentrate". Also in the case of vitamins, such as vitamins A and K, there are solubilizing formulations in micellar form. However, there are only very few suitable surface-active substances which on the one hand have a good capacity for the sufficiently stable inclusion of active ingredients, and which on the other hand have zwitterionic properties at a low critical micell concentration, and have low toxicity. In particular, the ability to form stable vesicles is desirable. For this, surface-active substances with short hydrophilic head groups and with long hydrophobic chains are required, as are present, for example, in the phosphatidylcholines. Similarly to the substances, the compounds according to the invention, having, for example, 2 long alkane chains (DS about have structural prerequisites for the formation of stable vesicles. For example, mixing 4 g of a 2 compound according to the invention where DS 2 and R dodecyl in a liter of water gives a homogeneous, opaquely milky phase which remains stable and unchanged at pH 5-7 over 8 weeks.

The observed light scattering is presumably caused by microvesicles, for which a minimal structure section is illustrated, for example, in Fig. Alternatively, it is also possible to formulate larger structures according to the scheme K1-S1'-S2-K2-S2'-S3-K3-S3' etc., where K1 is "head group molecule S1 is "tail group molecule S1' is "a further tail group of molecule 1" etc. It is possible to incorporate pharmaceutical or cosmetic active ingredients into such vesicles which can lead to an improved presentation of the active ingredients. Suitable active ingredients are also therapeutic genes, antisense oligonucleotides or retroviral expression vectors, for whose application so-called transfection reagents are required.

As a rule, lipids, such as, for example, DOTAP or DC cholesterol (SIGMA, Saint Louis, MO) are used for this purpose, or mixtures of neutral and cationic lipids. The cationic structural element promotes the complexation of the DNA, and the lipid fraction promotes integration into the cell membrane. These structural prerequisites also relate to the compounds according to the invention, which, as amino acids, can be in the .t WO 99/48901 PCTEP99/01619 16 physiologically protonated form. In particular, the compounds according to the invention can therefore be used for the invitro or invivo transfection of cells, in particular skin cells, in order, for example, to heal genetic skin disorders. The transfection of skin cells with retroviral expression vectors is described, for example, in Deng., H. et al., Nature Biotechnology, 1997, Vol. 15, 1388-1391.

The present invention thus further provides for the use of the sucrose Nalkylaspartate according to the invention as transfection reagent. The compounds according to the invention can be used in a variety of application forms (formulations), for example in the food, medicament or hygiene sector. The application form is adapted to the respective field of application.

The figures and examples below serve to illustrate the invention in more detail without limiting it: Description of the figures Fig. 1 shows diagrammatically the preparation of the sucrose Nalkylaspartates 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 maleate half-ester of sucrose.

Fig. 4 shows examples of compounds where DS 2 and DS 3. Further maleate groups, of which up to 6 can be present if DS 2 and up to 7 can be present if DS 3, and also sulfonate groups, of which, preferably, up to 2 groups can be present, are not shown in the formulae. The exact position of the substituents can vary and deviate from the representation shown here.

Fig. 5 shows a minimum structural section of a microvesicle.

Fig. 6 shows, in graph form, the results of comparative experiments relating to foam stability.

Fig. 7 shows, in graph form, the results of comparative experiments relating to the dispersing action.

WO 99/48901 PCT/E P99/01 61 9 17

EXAMPLES

Example 1: Synthesis using sodium acetate in DMF: DS 2.0, R dodecyl, 30.0 g (87.6 mmol) of sucrose, 15.8 g (192.6 mmol, 2.2 equiv.) of sodium acetate and 18.9 g (192.8 mmol, 2.2 equiv.) of maleic anhydride were stirred in 150 ml of dry N,N-dimethylformamide at 50 0 C for 3 hours.

According to the thin layer chromatogram, all of the sucrose had then reacted. 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 0

C.

During the reaction, some of the product precipitated out as a colorless solid. Most of the solvent was distilled off under reduced pressure, and replaced by ethyl acetate, with stirring. The product was filtered off, washed with ethyl acetate and dried under reduced pressure at 70 0

C.

Yield: 83.9 g. Based on a composition where DS=2 of the empirical formula

C

44

H

7 8Na 2 N2017 (953 g/mol), the yield was 100%. The H-NMR assignment (in CDCI3/CD 3 0D) gave a DS of about 2.0: 6 1.85 Me), 1.25 C9H18), 2.6-3.3 CH 2 NCHCH2), 2.30-5.40 (sucrose CHO).

[Assignment compared with the N-dodecylaspartate C12H2 5 NHCH(COONa)CH2COOCH 3 as a result of the micell or vesicle formation, line broadenings and deviating shifts occurred, e.g. CH2COO sucrose can also be assigned to the broad multiplett at 6 1.95. In the case of the N-dodecylaspartate C12H25NHCH(COONa)CH 2

COOCH

3 the corresponding CH 2 signal is at 8 2.4 (CDC13).] Elemental analysis: N (found) (N calculated for DS 2.0: Na (found) 4.2% (Na calculated for DS 2.0: Mass spectrum (electrospray, ESI-MS): [M1-H 624 (M1 C28H51N014; 625); [M21- 908 (M2 C44H80N2017; 908); [(M1-2H++Na+) 2 1272; in the positive mode: 626 (M1 C28H 5 1NO14; 625); [Mi+Na+] 648; [M 2 907; 1252.

Example 2: Synthesis using sodium carbonate in DMF: DS 2.1, R dodecyl 30.0 g (87.6 mmol) of sucrose, 10.2 g (96.2 mmol, 2.2 equiv. of Na of sodium carbonate and 18.9 g (192.8 mmol, 2.2 equiv.) of maleic anhydride WO 99/48901 PCT/EP99/01619 18 were reacted for 2 hours at 800C and then for a further 3 hours at 1000C in 150 ml of dry N,N-dimethylformamide with stirring. According to the thin layer chromatogram, the sucrose had then completely reacted. 37.6 g (203 mmol, 2.32 equiv.) of 1-dodecylamine were added, and the mixture was stirred for a further 3 hours at 500C and for a further 2 hours at 700C.

During the reaction, some of the product precipitated out as a colorless solid. Most of the solvent was distilled off under reduced pressure, and replaced by ethyl acetate, with stirring. The product was filtered off as colorless solid, washed with ethyl acetate and dried under reduced pressure at 700C. Yield: 82.9 g (96% based on product where DS 2.1 (C4 5 6 H80.

8 Na 2 1

N

2 1 0 17 3 983.6 g/mol). 1H-NMR (CDCI 3

/CD

3 0D) gave a DS 1.9-2.2 (assignment see Example Elemental analysis: N (found) N (calculated for DS 2.1: Na (found) Na (calculated for DS 2.0: Mass spectrum (electrospray, ESI-MS): [M 1 624 (M1 C 28

H

5 1NO1 4 625); 907 (M2 C 44 H80N201 7 908); [2M1-H 1249; [2M1+Na+-2H+]- 1271; in the positive mode: 626 (M1 C28H51NO 14 625); [M 1 648; 907; 1252.

Example 3: Synthesis using sodium carbonate in DMSO: DS 1.9, R 2 dodecyl 30.0 g (87.6 mmol) of sucrose, 5.1 g (48.1 mmol, 1.1 equiv. of Na of sodium carbonate and 9.5 g (96.9 mmol, 1.1 equiv.) of maleic anhydride were reacted for 2 hours at 300 in 100 ml of dry DMSO with stirring. After the addition of a further 5.1 g (48.1 mmol, 1.1 equiv. Of Na of sodium carbonate and 9.5 g (96.9 mmol, 1.1 equiv.) of maleic anhydride, the mixture was stirred for a further 8 hours at 300 and a further 2 hours at C. According to the thin layer chromatogram, all of the sucrose had then reacted. 35.7 g (193 mmol, 2.2 equiv.) of 1-dodecylamine were added, and the mixture was stirred for 3 hours at 300C and for 2 hours at C. During the reaction, some of the product precipitated out as a colorless solid. Most of the solvent was distilled off under reduced pressure, and replaced by ethyl acetate with stirring. The product was filtered off as a colorless solid, washed with ethyl acetate and dried under reduced pressure at 700C. Yield: 75.4 g (93% for DS 1.9).

\ro WO 99/48901 PCTEP99/01619 19 Example 4 Synthesis using sodium acetate in DMSO: DS 2.2, R 2 dodecyl 30.0 g (87.6 mmol) of sucrose, 15.8 g (192.6 mmol, 2.2 equiv.) of sodium acetate and 18.9 g (192.8 mmol, 2.2 equiv.) of maleic anhydride were reacted for 2 hours at 50*C in 100 ml of dry dimethyl sulfoxide with stirring.

According to the thin layer chromatogram, all of the sucrose had then reacted. 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 0 C and for a further 2 hours at 70 0 C. During the reaction, some of the product precipitated out as a colorless solid. Most of the solvent was distilled off under reduced pressure, and replaced by ethyl acetate with stirring. The product was filtered off as a colorless solid, washed with ethyl acetate and dried under reduced pressure at 70 0

C.

Yield: 81.5 g (92% for DS The DS was determined by means of 1 integration of the H-NMR spectrum from the ratio of the sucrose CHO signals and the N-dodecylaspartate signals.

Example 5: Synthesis using sodium acetate in DMSO: DS 1.0, R dodecyl 30.0 g (87.6 mmol) of sucrose, 15.8 g (192.6 mmol, 2.2 equiv.) of sodium acetate and 18.9 g (192.8 mmol, 2.2 equiv.) of maleic anhydride were reacted for 2 hours at 50 0 C in 100 ml of dry dimethyl sulfoxide with stirring.

According to the thin layer chromatogram, the sucrose had then completely reacted. 17.9 g (96.4 mmol, 1.1 equiv.) of 1-dodecylamine were added, and the mixture was stirred for a further 6 hours at 20 0 C. Most of the solvent was distilled off under reduced pressure, and replaced by ethyl acetate with stirring. The product was filtered off as a colorless solid, washed with ethyl acetate and dried under reduced pressure at 70 0

C.

Yield: 66.3 g The DS was determined by means of integration of the H-NMR spectrum from the ratio of the CHO, maleate and N-dodecyl signals as about 1.0 (C28H50NaNO1 4 647.7 g/mol).

Example 6: Synthesis using sodium carbonate in DMSO and coconut fatty amine C12: R dodecyl WO 99/48901 PCTEP99/01619 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 reacted for 3 hours at 500C in 100 ml of dry dimethyl sulfoxide with stirring. According to the thin layer chromatogram, the sucrose had then completely reacted.

40.0 g of Genamin® 12R100D [from coconut fat, average empirical formula CH3(CH 2 1 2.

3 NH2] were added, and the mixture was stirred for a further 3 hours at 40 0 C. During the reaction, some of the product precipitated out as a colorless solid. Most of the solvent was distilled off under reduced pressure, and replaced by ethyl acetate with stirring. The product was filtered off as a colorless solid, washed with ethyl acetate and dried under reduced pressure at 70 0 C. Yield: 78.0 g (89% for DS 2.2).

Example 7: Synthesis using sodium acetate in DMF: DS 8, R 2 dodecyl 10.0 g (29.2 mmol) of sucrose, 21.6 g (263 mmol, 9 equiv.) of sodium acetate and 25.8 g (263 mmol) of maleic anhydride were stirred for 3 hours at 400C in 150 ml of dry N,N-dimethylformamide. The 1 H-NMR analysis of a sample in D20 shows only small amounts of maleic anhydride (6 6.30 ppm) and the formation of the oleofinic maleate protons at 8 6.70 ppm and 6 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 for 14 h at 200C. Most of the solvent was distilled off under reduced pressure, and replaced by ethyl acetate with stirring. The product was filtered off, washed with ethyl acetate and dried under reduced pressure at 700C. Yield: 73.0 g Example 8: Synthesis using sodium acetate in DMF: DS 8, R dodecyl/hexadecyl/octadecyl (35/60/5%) 10.0 g (29.2 mmol) of sucrose, 21.6 g (263 mmol, 9 equiv.) of sodium acetate and 25.8 g (263 mmol) of maleic anhydride were dried for 3 hours at 400C in 150 ml of dry N,N-dimethylformamide. A mixture comprising 17.1 g (92.0 mmol) of 1-dodecylamine, 38.1 g (157.8 mmol) of 1-hexadecylamine and 3.5 g (13.1 mmol) of 1-octadecylamine was added, and the mixture was stirred for 14 h at 200C. Most of the solvent was distilled off under reduced pressure, and replaced by ethyl acetate with stirring. The product was filtered off, washed with ethyl acetate and dried under reduced pressure at 700C. Yield: 90.0 g. 3

J

WO 99/48901 PCT/E P99/01 61 9 21 Example 9: Synthesis of without the use of solvent 30.0 g (87.6 mmol) of sucrose, 15.8 g (192.6 mmol, 2.2 equiv.) of sodium acetate were stirred for 20 minutes at a bath temperature of 195 0 C under reduced pressure (about 20 torr). The mixture was cooled to 175 0 C (bath temperature) at atmospheric pressure, and 18.9 g (192.8 mmol, 2.2 equiv.) of molten maleic anhydride were slowly added dropwise thereto minutes). The mixture turned brown, started to foam, and was cooled after 2 minutes to 1250C with stirring. 1H-NMR analysis of a sample in revealed only small amounts of maleic anhydride (8 6.30 ppm) and the formation of the oleofinic maleate protons at 8 6.70 ppm and 6 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 for minutes at 1250C, and then ethyl acetate was added with evaporative cooling and stirring. The product was filtered off, washed with ethyl acetate and dried under reduced pressure at 700C.

Example 10: Monosulfonation using chlorosulfonic acid g (6.0 mmol) of the product from Example 1 (RS 786) were suspended in 50 ml of dichloromethane and 1 ml of dimethylsulfoxide. Over the course of 1 hour, 0.4 ml (6.0 mmol) of chlorosolfonic acid in 25 ml of dichloromethane were added dropwise at room temperature. The mixture was stirred for a further 3 hours at room temperature, to give a clear solution. The solvent was stripped off under reduced pressure. The product was then washed by stirring with ethyl acetate, filtered off with suction and dried under reduced pressure at 600C. This gave 4.6 g of a colorless solid (RS 814).

Example 11: Monosulfonation using pyridine-S03 complex g (6.0 mmol) of the product from Example 1 (RS 786) were stirred into ml of dimethylformamide at 700C until virtually all of the solid had dissolved. The mixture was then left to cool to 300C, and 1.0 g of sulfur trioxide-pyridine-complex were added. The mixture was stirred for 3 hours at 300C and for 1 hour at 600C. The solvent was stripped off under -3 reduced pressure. The product was then washed by stirring with ethyl If~, o^ WO 99/48901 PCTEP99/01619 22 acetate, filtered off with suction and dried under reduced pressure at 60 0

C.

This gave 4.3 g of a colorless solid (RS 825).

Example 12: Determination of the surface tension The compounds according to the invention, in particular those having 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 micell concentration (CMC) and the lowering of the surface tension (amin) were measured using a tensiometer (Lauda, model TD1, water double-distilled, omin 71.8 mN/m) at 25 0 C. For this, the concentration was increased up to the minimum force to be applied in order to obtain the CMC and amin values.

Product from Example 1: C44H7 8 Na 2 017 953 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): C44H 7 8 Na 2

N

2 02 0 S 1033 g/mol Table 1: CMC and amin values CMC [mol/I] a[mN/m] C12H2 5 NaSO4 8.6 x 10 3 37.4

(SDS)

RS 786 1.0 x 10 3 29.7 RS 795 4 3 x 10 4 36.5 RS 814 1.4 x 10 3 21.2 The results in Table 1 illustrate the very good surfactant properties of the compounds according to the invention, which, for example, are superior to a commercially used standard surfactant (SDS).

Example 13: Measurement of the foam height and foam stability In certain fields of application, e.g. for dishwashing detergents, highfoaming surfactants are required. Data on the foaming properties is obtained, for example, according to the Ross Miles method (ASTM D1173- 53, Oil Soap 62, 1260, 1958). According to this, 200 ml of the surfactant solution are run in, via a pipette having an internal diameter of 2.9 mm, 'ver a 90 cm drop, into a measuring cylinder containing 50 ml of the same l L WO 99/48901 PCT/E P99/01 61 9 23 surfactant solution. The foam height was read off immediately (t 0, IFH initial foam height) and then at given points in time. Using this experimental arrangement, the foam heights at 25 0 C and using a 0.1% concentration of the novel product in question from Example 1: RS 786; product from Example 5: RS 795 were [lacuna]. Surprisingly, the substance RS 795, which was still clearly soluble up to 20 g/l, showed, after a slight drop in foam height within the first 5 minutes, virtually no further drop over a period up to 2 hours. Even the less readily soluble substance RS 786, which can dissolve clearly in water only up to 4 g/l, showed, after an initial drop, excellent foam stability. By contrast, the foam of SDS disappeared virtually completely within about 100 minutes (see Fig. The foam stability of the sulfonate prepared as in Example 10 was likewise excellent: the foam height dropped here from 33 mm (product from Example 10) to 24 mm over the course of 2 hours in the same test procedure.

Example 14: Dispersing action To determine the solubilization of Sudan Red B in water using the compounds according to the invention, 12.5 mg of Sudan Red B were added in each case to solutions of varying concentrations (0.075 g, 0.150 g and 0.300 g in 25 ml of water). The dye was dispersed using ultrasound.

The suspension was then centrifuged at 7500 rpm for 70 min and filtered through a membrane. The absorbance of the supernatant clear solution was measured photometrically at a wavelength of 516 nm (cell length 1 cm). The blank used was the solution of Sudan Red B in water (12.5 mg in 25 ml). The compound named "caprylate" is a caprylate of the oxidized sucrose from Example 10 in DE 19542303. This comparison compound is accordingly significantly less effective than, for example, the compound from Example 1. The same applies in the case of low concentrations up to 0.3% by weight to the less substituted compound from Example 5 (see Tab. 2, Fig. 7).

Tab. 2 UV absorbance Cone. Caprylate* 1 1 by wt.) (Example 1 (Example RS 783 =RS 795 0.0 0.0001 0.0002 0.0001 0.3 0.0096 0.0495 0.0253

RA

WO 99/48901 PCT/EP99/01619 0.6 0.0654 0.0997 0.0571 1.2 0.1513 0.1603 0.1003 These measured results show that the compounds according to the invention have excellent solubilizing properties. The compounds are therefore suitable, for example, for laundry detergents, dishwashing detergents and cleaners, and as formulation auxiliaries in the pharmaceutical sector and in the agricultural sector.

Example 15: Solubilization of an active ingredient Pharmaceutical active ingredients and food additives for which no suitable presentation is obtainable can be better solubilized in water or incorporated into other formulations. Obvious examples for improving effectiveness are, for example, Doxorubicin (tumor therapy), Amphotericin (treatment of mycoses) and vitamins (additive). In the present example, 50 mg of vitamin E (tocopherol) were smoothly absorbed by only 150 mg of compound from Example 1 without the addition of solvent (see Tab. A dispersion experiment in water (25 ml) was carried out analogously, as described in Example 14: Tab. 3 Vitamin E Comp. 1 UV (mg) (mg) absorbance (290 nm) 12.5 0 0.0115 12.5 75 0.6997 12.5 150 0.9005 12.5 300 0.9819 Example 16: Preparation of active ingredient formulations for cropprotection agents and for the treatment of seed Fungicides and insecticides which are sparingly soluble in water in foliar sprays or in seed dressing treatments can be better formulated using additives of the compounds according to the invention. A typical -o _7 J ;7 y z" WO 99/48901 PCT/EP99/01619 formulation is, for example, prepared from 20-600 g of a fungicide or 500 g of an insecticide, 50-150 g of a frost-protection agent, such as ethylene glycol or propylene glycol, 2-10 g of an antifoam, 2-100 g of a compound according to the invention and water (to top up to give a 1 liter formulation).

Example 17: Hand washing experiment on healthy and on sensitive/diseased skin 2 g of the product from Example 2 form, at 200C in 100 ml of water, a colorless, finely-pored-foaming emulsion of PH about 9. This emulsion was adjusted, using citric acid, to the physiological PH of healthy skin, which is about 5.5. Handwashing experiments using this solution gave, on healthy and also on stressed skin, sensitive skin and skin suffering from chronic dermatosis, a subjectively pleasant, irritation-free feel on the skin, and an excellent cleansing effect. A comparable treatment with conventional soap lead in the case of the test persons to a itchy skin reddening within about minutes, which then had to be treated with a corticosteroid ointment. The formulations comprising compounds according to the invention are therefore suitable particularly for frequent washing, showering and bathing in cases of sensitive or diseased skin, and also for the cleansing, in particular, of teenager's skin. The subjectively mild character evidently imparts an effect to the compounds which stabilizes the protective acid mantel of the skin.

Example 18: Preparation of a shampoo To prepare 1 kg of a shampoo, 60 g of the compound according to the invention from Example 130 g of cocamidopropylbetaine, 15 g of NaCI, 1.5 g of preservative potassium sorbate and/or sodium benzoate), 0.5 g of allantoin, 2 g of sodium formate, 7 g of sodium citrate and 1 g of perfume oil are mixed and made up to 1 kg with water. This gives a skin-and hair-compatible, highly effective shampoo.

Example 19: Preparation of a scouring agent To prepare 1 kg of a scouring agent, 30 g of the compound according to the invention from Example 20 g of octadecyl polyethylene glycol :ilT "ii WO 99/48901 PCT/EP99/01619 26 ether, 45 g of pentasodium triphosphate and 2 g of fragrance are mixed and made up to 1 kg with quartz powder.

Example 20: Preparation of a laundry detergent To prepare 1 kg of a laundry detergent, 150 g of the compounds according to the invention from Example 200 g of complexing agent, e.g.

zeolite, 30 g of laundry detergent protease, 35 g of sodium citrate, 80 ml of ethanol and optionally fragrances and dyes are mixed and made up to 1 kg with water.

Example 21: Preparation of a bath preparation To prepare 1 kg of a bath preparation, 20 g of the compound according to the invention, from Example 45 kg of coconut fatty acid ethanolamine, 50 g of almond oil, 10 g of sodium chloride, 3.5 g of preservative, 10 g of hexadecanol and 10 g of perfume are mixed and e made up to 1 kg with water.

Example 22: Testing the biodegradability According to OECD 301 B, substances can be classified as readily biodegradable if at least 60% of the carbon has been mineralized to carbon dioxide following contact with an activated sludge mixed population for 28 days. In this test, a compound according to the invention (sample from Example 1) had metabolized to 60.3% after just 18 days. The substance is 099* accordingly very readily biodegradable.

99 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers or steps but not the exclusion of any other integer or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that the prior art FS 7 t~rms part of the common general knowledge in Australia.

Y -OFF\O«'

Claims (16)

1. A sucrose N-alkylaspartate of the formula (I) OR, RiOi RIO 0 1 i OR, R 1 0 (I) in which R 1 independently of one another, identically or different is a group chosen from hydrogen, a compound of the formula (II): 0O M HN -R (II) where R 2 is CnH2n+1 or CnH2n, in which n is an integer from 2 to 28, preferably 6-22, especially 12-18, a compound of the formula (III) and/or a radical of the formula (IV) 4,RP -M 7 'C L i o WO 99/48901 PCT/E P99/01 6 1 28 0=S-O M (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 is a compound of the formula (II).

2. A sucrose N-alkylaspartate as claimed in claim 1, wherein the degree of substitution of the radical R (DS) is defined by the following formula: DS n x [radical of the formula [0 to x [radical of the formula (III)] (0 to m) x [radical of the formula where m 2 when n 1-6, and m 1 when n 7 and n 8.

3. A sucrose N-alkylaspartate as claimed in claim 1 or 2, wherein R 2 is a decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radical, or a radical derived from coconut, palm, soya or tallow oil fats, or mixtures thereof.

4. A process for the preparation of a sucrose N-alkylaspartate of the formula which comprises, in a first step, acylating sucrose with maleic acid or a derivative of maleic acid, and, in a second step, adding one to eight mole equivalents of amine of the formula R NH2 where R is CnH2n+1 or CnH2n, in which n is an integer from 2 to 28, preferably 6-22, especially 12-18, to the maleate sucrose formed in the first step. The process as claimed in claim 4, wherein the acylating reaction is carried out in the presence of a catalyst.

6. The process as claimed in claim 5, wherein the catalyst is a basic metal salt, preferably a carbonate, hydrocarbonate, acetate and/or formate. WO 99/48901 PCT/EP99/01619 29

7. The process as claimed in one of claims 4-6, wherein, in a further step, the resulting sucrose N-alkylaspartate is sulfonated.

8. The process as claimed in claim 7, wherein up to two radicals R are sulfonated.

9. The process as claimed in claim 7 or 8, wherein the sulfonation is carried out with S03, CISO3H, DMF-S03 and/or pyridine-SO3. The use of a sucrose N-alkylaspartate as claimed in one of claims 1-3 as surface-active compound.

11. The use of one or more sucrose N-alkylaspartates as claimed in one of claims 1-3 as additive in hygiene compositions, cleaners, cosmetics, foods and/or medicaments or in pesticides or for the prevention and/or control of contamination of water by chemicals and/or oil.

12. The use as claimed in claim 11 as additive in soaps, scouring agents, all-purpose cleaners, dishwashing detergents, laundry detergents, shampoos, universal detergents and/or bath preparations.

13. The use as claimed in claim 11 or 12, wherein the degree of substitution DS of at least one sucrose N-alkylaspartate is between 1 and about 4.

14. The use as claimed in one of claims 10-13, wherein the sucrose N- alkylaspartate is used together with at least one other surface-active substance (cosurfactant). The use as claimed in claim 14, wherein the cosurfactant is chosen from alkyl polyglycosides, 6-O-monoester alkyl glycosides, alcohol ether sulfates or alkyl glucamides.

16. The use of a sucrose N-alkylaspartate as claimed in one of claims 1-3 as low-calorie fat substitute. WO 99/48901 PCT/EP99/01619

17. The use as claimed in claim 16, wherein the degree of substitution DS of at least one sucrose N-alkylaspartate is between about 4 and 8.

18. The use of a sucrose N-alkylaspartate as claimed in one of claims 1-3 as transfection reagent.

19. A sucrose N-alkylaspartate as claimed in one of claims 1-3 in the form of an aqueous solution, emulsion, suspension, gel, cream, paste or powder. Sucrose N-alkylaspartate of the formula processes for its preparation or uses thereof, substantially as hereinbefore described with reference to the Examples. DATED this 31st day of January, 2002 AVENTIS RESEARCH TECHNOLOGIES GMBH CO. KG By its Patent Attorneys DAVIES COLLISON CAVE 0e S. S S r *S S S SS w S. *I S C S SS S S. SS S S S CSG I