NL1002389C2 - Preparation of surfactant derivatives of galacto-oligosaccharide compounds - Google Patents

Abstract

Preparation of surfactant derivatives (X) of galacto-oligosaccharides such as lactose, comprises preparing an N-alkyl-galactoglycitylamine of formula Sar-NH-R1 (I) by reductively aminating the galacto-oligosaccharide with a 1-20C alkylamine and hydrogen in a single step in the presence of a transition metal catalyst. Sar = a reduced di- or oligo-saccharide residue containing \- 1 galactose unit and R1 = 1-20C alkyl. Also claimed are: (A) preparation of (X) which comprises preparing (I) by aminating the galacto-oligosaccharide with 1-20C alkylamine by reactive processing optionally with \~ 4 parts weight solvent containing carbon, hydrogen and/or oxygen atoms per weight oligosaccharide and reducing the obtained N-alkyl-galacto-glycosylamine; (B) preparation of (X) which comprises preparing an N-acyl-galactoglycosylamine of formula Sar-NR1'-CO-(NH)m-R2 (II) by aminating the galacto-oligosaccharide with ammonia or an amine of formula R1'-NH2 and acylating the obtained galactoglycosylamine with an anhydride or acid halide of formula R2-COX, or by amidating the galacto-oligosaccharide with urea or an amide of formula H2N-CO-(NH)m-R2 optionally with \~ 4 parts weight solvent containing C, H and/or O atoms per part weight galacto-oligosaccharide or galactoglycosylamine respectively, and optionally alkylating the obtained product with R1'X or R2Y; (C) preparation of (X) which comprises preparing a N-acyl-galactoglycosylamine of formula Sar-NR1-CO-R2 (III) which comprises reacting Sar-NHR1 with R2-COX in solvent containing C, H and/or O atoms, preferably a lower alcohol; (D) preparation of (X) which comprises oxidising an optionally N-acylated N-alkyl-galactoglycosylamine or -galactoglycitylamine to convert \- 2 (preferably 4-100) primary alcohol groups per 100 to a carboxylic acid and (E) preparation of (X) by converting an optionally N-acylated N-alkyl-galactoglycosylamine or -galactoglycitylamine with a haloalkyl-, hydroxyalkyl- or alkenyl-carboxylic acid, -phosphonic acid, -phosphate, alkylphosphinate, -phosphite, -sulphonic acid, -sulphate, or with a cyclic dicarboxylic anhydride, in particular with an ~a-haloalkanoate. m = 0 or 1; R1' = H or 1-20C alkyl; R2 = 1-19C alkyl; X = halo or acyloxy; Y = a leaving group.

Description

Preparation of lactose-based surfactants

The invention relates to a process for the preparation of surfactants based on aminated galactooligosaccharides such as lactose.

French patent application 2661413 discloses the preparation of N-alkyllactosyl-5 amines and N-alkyllactylamines. The N-alkyl lactosylamines are prepared by reacting lactose with an N-alkylaminc in water / 2-propanol. The amount of solvent is about 15 times the amount of lactose and the reaction takes about 24 hours. The yield is between 48 and 74%. The N-alkyllactylamines are prepared in a second step from the N-alkyllactosylamines, either by catalyzed hydrogenation (yield about 40%, incomplete conversion) or by reduction with sodium borohydride (yield 57-90%). The total conversion of lactose to alkyl lactylamine by this known method is about 25% for the catalyzed hydrogenation and 31-67% for the reduction with borohydride. This method has the drawback that low yields are obtained, especially if one does not work with expensive chemicals such as sodium borohydride.

FR-A-2661413 and EP-A-515283 also describe the preparation of N-acetyl-N-alkyl-lactosylamines by reaction of N-alkyllactosylamine with acetic anhydride. The reaction is carried out in a large amount (about 13 times the amount of lactosylamine) aprotic solvent such as dimethyl-20 formamide or dimethyl sulfoxide under argon. The yield is in the order of 35-50%. The disadvantage of this method is the low yield and the use of undesirable solvents, especially for food applications. A further drawback of the known processes for the preparation of lactose-derived amines is that they do not lend themselves to continuous operation.

The object of the inventions is to provide improved methods for the preparation of per se known surfactant, in particular detergent and / or emulsifying, lactose derivatives and to provide new surfactant derivatives of galactooligosaccharides.

By "galacto-oligosaccharides" here are meant reducing sugars and sugar derivatives containing at least one galactose unit with one or more further monosaccharide units bound thereto. The most important example of this is lactose, 1002389 2 (β-galactose-glucose: PGal-1,4-Glu). Other examples are lactose-based oligosaccharides to which one or more of the following galactose units are linked, for example, by reaction of lactose with a β-galactosidase (Gal (-Glu, n = 2-6)). Further examples are βθ3ΐ-1,6-θ3ΐ and melibiosis (aGal-1,6-Glu).

Accordingly, a galactoglycosylamine and a galactoglycitylamine are here understood to mean a galacto-oligosaccharide whose reducing hydroxyl group is not necessarily attached to the galactose unit, respectively. with reduction has been replaced by an amine group. The invention is explained in the following for the sake of convenience with reference to lactose and lact (os) ylamines, but 10 other galacto-oligosaccharides, as described above, are also used there. associated amines to be understood.

Where reference is made in this specification to a saturated or unsaturated C 1 -C 6 q or C 1 -C 6 Q alkyl group, a straight or branched chain alkyl, alkenyl, alkynyl, alkadienyl or alkapolyenyl group having 1-19 resp. 1-20 carbon atoms, in which an aromatic or alicyclic group may also be present. Random examples are methyl, propargyl, heptyl, isooctyl, undecyl, pentadecenyl, hexadecyl, octadecadienyl, nonadecatrienyl, 1-methylcyclohexyl, phenethyl and p-nonylphenyl.

In a first aspect, the invention relates to a process for the preparation of surfactant, detergent and / or emulsifying lactose derivatives, in which lactose is reductively aminated in a one-step process with a saturated or unsaturated C 1 -C 2 alkylamine and hydrogen in the presence of a transition metal catalyst.

The advantage of this method is that considerably higher yields are obtained than in the known two-step processes, and that no expensive reagents such as sodium cyanoborohydride are required.

This method preferably uses an equivalent amount, or a slight excess of alkylamine, in particular 1-1.5 equivalent. The transition metal known per se, such as nickel, palladium, platinum, ruthenium or other Group VIII metals, can be used as the transition metal. The transition metal may optionally be supported, such as carbon. As a solvent, for example, water, an alcohol or an alcohol-water mixture can be used.

In a second aspect, the invention relates to a process for the preparation of lactose surfactant derivatives in which lactose is reduced by reactive 1002389 processing with a C 1 -C 18 Q alkylamine, and the obtained N-alkyl lactosylamine obtained in a second step.

Here, "reactive processing" is understood to mean a reaction without or with small amounts of solvent, generally less than 4 parts by weight. and in particular less than 3 parts by weight. solvent per part by weight of lactose, under mechanical mixing. The mixing is such that a reaction occurs. Optionally, the reaction can be carried out under heating or in the melt. In particular, an extrusion process can be used. The reactive processing is known per se, for example for the preparation of starch derivatives (see e.g. Tomasik et al., 10 Starch / Starke 47 (1995), 96-99, and Narkrugsa et al. Starch / Starke 44 (1992), 81-90). The present process preferably uses moderate temperatures, for example between 10 and 100 ° C. As the solvent, water, alcohols such as isopropanol, or mixtures of water and an alcohol can be used. The reactive processing leads to high yields of alkyl lactosyl-15 amine in a short time (less than ½ hour). Important advantages of the reactive processing are that the reaction can be a continuous process, that the processes are more energetically favorable and that fewer or no solvents are used, so that fewer work-up steps are required.

The N-alkyl lactosylamine thus obtained is in itself less suitable for use because it is relatively labile. The N-alkyllactosylamine is therefore preferably reduced to an N-alkyllactylamine or acylated to an N-alkyl-N-acyllactosylamine. The reduction to N-alkyl lactylamine can be accomplished with hydrogen in the presence of a transition metal catalyst or with a hydride such as sodium borohydride. The catalyzed hydrogenation is preferably carried out at an elevated temperature, for example between 30 and 80 ° C. The reduction with sodium boron hydride can be carried out at room temperature. The reduction results in a yield of 70% or higher.

According to the aspects of the invention described above, N-alkyl-galactoglycitylamines of the formula: Sar-NH-R1 are thus prepared, wherein Sar represents the rest of a reduced di- or oligosaccharide containing at least one galactose unit and R1 represents a saturated or unsaturated C 1 -C 20 alkyl group. In view of the surfactant properties, preference is given to derivatives in which R 1 represents a Gj-C0 O group, especially a C10-C18 group, and especially a hexadecyl group.

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A further aspect of the invention relates to a process for preparing lactose surfactant derivatives by acylating a lactose-derived lactosyl amine with a C 1 -C 2 Q carboxylic anhydride or halide by reactive processing.

This acylation by reactive processing preferably takes place by means of reactive extrusion, at elevated or not elevated temperatures, such as 10-100 ° C. It is preferred to work without a solvent, especially if the carboxylic anhydride or halide is liquid. Furthermore, a base is added to bind acid formed. Preferably, a solid base such as potassium carbonate or sodium bicarbonate is used, or optionally a liquid base such as triethylamine. The reactive processing can advantageously be carried out continuously.

An important advantage of the acylation by means of reactive processing is that no nuisance solvents, such as DMF, DMSO or pyridine, which are undesirable for food use need to be used. Furthermore, high to quantitative yields are obtained.

The lactosylamine, which is the starting material for the above-described acylation, can be obtained by reacting lactose with ammonia or a C 1 -C 18 alkyl amine in a manner known per se. This amination can be carried out in water and / or an alcohol, such as isopropanol, as a solvent, for example at a temperature of 30-70 ° C. The lactosylamine can also be obtained by reactive processing in the manner described above.

In addition to sequential amination and acylation, as described above, the acylated lactosylamines can also be prepared by amidation of lactose. This amidation is carried out with a C 1 -C 6 o -acylamine or with urea or an alkyl urea by reactive processing as described above for the acylation. In the case of amidation of lactose with urea, an alkylation can then be carried out, for example with an alkyl halide, acetate, benzoate or sulfonate, in order to introduce the alkyl group required for the surfactant properties.

In this aspect of the invention, N-acyl-galactoglycosyl amines of the formula Sac-NR ^ CO ^ NH ^ -R2 are prepared, wherein Sac represents the remainder of a reducing di-or oligosaccharide containing at least one galactose unit , m represents 1002389 5 number O or 1, R 1 represents hydrogen or an unsaturated or saturated alkyl group of 1 to 20 carbon atoms and R 2 hydrogen represents a saturated or unsaturated alkyl group of 1 to 19 carbon atoms. Preferably, at least one of the groups R and R contains at least 7 and more preferably at least 10 carbon atoms. In particular, when m is equal to 0 and R2 is a methyl group, or when R2 is a hydrogen atom, R1 preferably contains at least 12 carbon atoms.

According to the invention, it is also possible to prepare N-alkyl-N-acyllactylamines by either acylating an N-alkyllactylamine obtained in the manner described above, for example by means of reactive processing, or an N-10alkyl-N- reduce acyl-lactosylamine, for example with hydrogen / palladium or sodium borohydride. Thus, N-acyl-galactoglycitylamines of the formula Sar-NR1-CO- (NH) m-R2 are prepared, wherein Sar represents the remainder of a reduced di- or oligosaccharide containing at least one galactose unit, m the number 0 or 1, R 1 represents hydrogen or an unsaturated or unsaturated alkyl group of 1-20 carbon atoms, and R 2 hydrogen represents an unsaturated or unsaturated alkyl group of 1-19 carbon atoms. Again, at least one of the groups R 1 and R 2 preferably contains at least 7 and more preferably at least 10 carbon atoms.

In a further aspect, the invention relates to a process for the preparation of surfactant oxidized lactose derivatives, in which an N-alkyllactosyl-20 amine, N-alkyllactylamine, N-alkyl-N-acyl-lactylamine or N-alkyl-N-acyl-lactosyl -amine oxidizes such that at least a portion of the primary alcohol groups are converted into a carboxylic acid. In particular, the aminated lactose derivatives are oxidized such that per 100 primary alcohol functions, at least two are converted to a carboxylic acid group. Since the aminated lactose derivatives contain two primary alcohol functions per molecule, this yields a product consisting of at least about 4 mol% carboxylated compounds. If desired, all primary alcohol functions can also be oxidized to carboxylic acid functions, but in general it is sufficient for an effective surfactant action if some of the functions are oxidized. The advantage of partially oxidized lactylamines is that they have an increased water solubility or lead to a reduced precipitation. In particular, 4 to 50% of the primary alcohol groups are oxidized to a carboxylic acid.

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Depending on the method of oxidation, in addition to the primary alcohol functions, secondary alcohol functions can also be oxidized, whereby ketone groups and, optionally, with the breaking of a carbon-carbon bond, dialdehyde groups or dicarboxylic acid groups are formed. These functions too can contribute to the desired surfactant properties of the derivatives.

The oxidation can be carried out, for example, with molecular halogen (Cl2 or ΒΓ2) or with a hypohalite (usually NaOCl or NaOBr). This oxidation can be performed in water or a water / alcohol mixture at a pH of 8-10. In addition to conversion of primary alcohol groups, oxidation of C2-C3-10 diol groups can also occur during this oxidation.

More selective oxidation of the animated lactose derivatives can be achieved by carrying out the oxidation with a hypohalite in the presence of a di-tertiary nitroxyl compound as a catalyst.

The di-tertiary-alky 1-nitroxyl compound can be, for example, di-tert-butyl-nitroxyl 15, but is in particular a cyclic compound such as an N-oxyl-pyrrolidine, -piperidine or -morpholine compound, the carbon atoms in addition to the nitroxyl group are methylated, and which may further contain, for example, methyl or methoxy substituents. 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO) is preferably used. The di-tert-alkyl-nitroxyl can optionally be prepared in the reaction medium, for example, by oxidation of the corresponding di-tert-alkyl-amine with hydrogen peroxide and tungstate.

A catalytic amount of nitroxyl is understood to mean an amount which, after conversion of the nitroxyl radical to the corresponding nitrosonium ion, is less than 10% of the amount required for oxidation of all primary hydroxyl groups to carboxyl groups. Preferably, the catalytic amount of nitroxyl to the carbohydrate monomer is 0.1-2 mol%.

Furthermore, the oxidation of the lactosamine derivatives can be carried out with oxygen in the presence of a transition metal catalyst. Thus, the oxidation with, for example, platinum on carbon has been found to lead to a selective oxidation of the primary alcohol groups. This oxidation can also be carried out in water or a water / alcohol mixture, whereby the pH can for instance be kept between 7 and 10.

1002389 7

Advantageously, the oxidation can also be carried out enzymatically, in particular with galactose oxidase (EC 1.1.3.9). Here the primary alcohol group of the galactose unit is selectively oxidized and an oxidation degree between 0 and 100% can be obtained.

The above-mentioned oxidations can be carried out both with the N-alkyl lactyl amines obtained, for example, by reductive amination, and with N-alkyl-N-acyl lactosyl amines. In both cases, a product with good surfactant properties is obtained.

The invention also relates to the oxidized lactose-10 amine derivatives thus obtainable, in particular those of which at least 2%, more in particular at least 4% of the primary alcohol groups have been converted into a carboxylic acid group.

Furthermore, the invention relates to the use of the above-described derivatives as an emulsifying agent in foodstuffs, as a cleaning agent or as an emulsifying agent in washing agents, dishwashing detergents, body care agents, beauty agents, shampoos, or as a dispersing agent, inter alia for pesticides, etc.

Example 1. One step procedure for the synthesis of N-octyllactylamine.

Lactose (10.26 grams, 30 mmol) was dissolved in 10 ml of warm water. To this was added 4.65 grams of octylamine (36 mmol, 1.2 eq.) In 70 ml of 2-propanol and 750 mg of 10% Pd / C. The reaction mixture was hydrogenated in a Parr apparatus (3.5 bar, 50 ° C) overnight. A sample was taken by filtering a few ml of the reaction mixture over celite and evaporating. 13 C-NMR showed that the lactose was 60-70% converted to the N-octyllactylamine, with lactose, octyl-lactosylamine and possibly lactitol as the other ingredients. 13 C-NMR (DMSO-d6) δ (ppm); 104.3 (Cl, gal), 80.9, 76.3, 73.9, 71.8, 71.5, 70.4, 69.5, 69.1 (C2-C5 gal and glu unit), 63, 4, 63.0, 25 61.86, 61.4 (C6 gal, glu), 52.7 and 50.1 (CH 2 -N-Cl glu and Cl octylamine), 32.1, 29.7, 29, 5, 27.6, 25.9, 22.9, 14.7 (C 2 -C 8 octyl chain).

Example 2. Synthesis of hexadecyllactosylamine by reactive processing.

Lactose (53 grams, 147 mmol) was placed in a Haacke Rheocord 50 kneader together with hexadecylamine (57 grams, 183 mmol), 46 grams of water and 64 grams of 2-propanol. The mixture was heated to 68 ° C and then kneaded at 33 rpm for 15 minutes at 1002389. Analysis (13 C solid NMR) showed that 60-70% of the lactose had been converted to hexadecyllactosylamine.

Example 3. Synthesis of N-acetyl-N-hexadecyllactosylamine by reactive processing.

Hexadecyllactosylamine was processed at a flow rate of 2 kg / h on a Wemer and Pfleiderer ZKS 25 rotating twin screw extruder. Water was injected on the extruder at a flow rate of 1.3 kg / hour. The total length of the extruder was 28D at a diameter D of 25 mm. At a distance of 12D, acetic anhydride was added at a flow rate of 0.55 kg / h and sodium bicarbonate at a flow rate of 0.45 kg / h. A speed of 50 rpm was used. An average residence time of the product in the extruder of approx. 3 minutes was determined using dye. The set temperature profile across the extruder was 40-60-60-70-70 ° C. A material temperature of 72 ° C was measured at the extruder head. Analysis by 13 C-NMR showed complete conversion to N-acyl-N-hexadecyllactosylamine.

Example 4. Oxidation of dodecyllactylamine with bleach.

Dodecyllactylamine (0.5 grams, 0.98 mmol) was dissolved in 50 ml of water. 0.4 ml (0.21 mmol) of a sodium hypochlorite solution with 4% active chlorine was adjusted to pH 9 and added to the dodecyllactylamine solution, after which the pH was kept at 9 with 1 M 20 NaOH. After the oxidation reaction was completed, the reaction mixture was neutralized and evaporated. 13 C-NMR showed that a partially oxidized alkyl lactylamine had evolved, with primary alcohol groups also oxidized and charge built into the molecule.

Example 5. Oxidation of dodecyllactylamine with hypochlorite / hypobromite and TEMPO. Dodecyllactylamine (0.5 gram, 0.98 mmol), TEMPO (1 mg, 0.007 mmol) and 78 mg (0.38 mmol) NaBr were dissolved in 50 ml of water. 1.9 ml of sodium hypochlorite solution with 4% active chlorine was brought to pH 7 and added to the dodecyllactylamine solution, after which the pH was kept at 7 by adding 1 M NaOH using a pH state. After the oxidation reaction was finished, the reaction mixture was evaporated. 13 C-NMR showed that an oxidized dodecyllactylamine had been obtained, with the oxidation taking place mainly on the primary alcohol groups of the dodecyllactylamine.

Example 6. Oxidation of dodecyllactylamine with PtIC and oxygen. s 0.1 gram of 5% Pt / C was dissolved in 25 ml H 2 O. Dodecyllactylamine (0.5 gram, 0.98 mmol) was dissolved in 30 ml H 2 O and added to the Pt / C. The reaction mixture was brought to pH 9 and oxygen was passed through the mixture. After completion of the reaction, the catalyst was filtered off and the reaction mixture was evaporated to dryness. 13 C-NMR showed that an oxidized dodecyllactylamine had been obtained, with the oxidation taking place mainly on the primary alcohol groups of the dodecyllactylamine.

Example 7: Enzymatic oxidation of decyl lactylamine.

Decyl lactylamine (10.0 mg, 0.21 mmol) was dissolved in 5 ml of 10 mM phosphate buffer (pH = 7.0) and to this were added 30 mg of galactose oxidase (EC 1.1.3.9) and 125 µ of catalase 15. The mixture was incubated at 37 ° C for 24 hours, after which the mixture was centrifuged off and the supernatant was evaporated. 13 C-NMR showed that the decyl lactylamine had been converted to about 50%, with the primary alcohol group of the galactose unit being selectively oxidized.

Example 8. Critical Micelle Concentrations Table 1 below lists the critical micelle concentrations (CMC) of some alkyl lactylamines prepared according to the invention. Table 2 lists the surface tension (ST) depending on the concentration of hexadecyllactylamine.

1002389 10 {

Table I

CMC values and associated surface tension (ST) of alkyl lactylamines

compound CMC (mM) CMC (g / 1) ST at CMC

(mN / m) 5 octyllactylamine 42 19.1 31.2 decyllactylamine 37 18.9 38.0 dodecyllactylamine 9.8 4.7 35.4 hexadecyllactylamine 1.3 0.71 37.3

TabeL2 10 ST of hexadecyllactylamine depending on the concentration log (concentration, M) ST (mN / m) -4.0 58 -3.3 46 -3.0 39 15 -2.7 38 -2.3 38

Preparation Example 1. Synthesis of dodecyllactosylamine.

10.76 g (30.0 mmol) of lactose was dissolved in 60 ml of H 2 O with heating (to 50 ° C). A solution of 9.25 g of dodecylamine (49.9 mmol, 1.66 equivalent) in 100 ml of 2-20 propanol was added to this. The clear solution was stirred at room temperature overnight and then heated to 60 ° C for 30 minutes. The solution was evaporated on a rotary evaporator. The residue was taken up in 40/20 (v / v) ethanol / toluene and evaporated again to completely remove the water. The product was crystallized from 100 ml of ethanol and washed with diethyl ether. The product was obtained with a yield of 90%. From the 13 C-NMR spectrum (DMSO-d6) it appears that in a DMSO solution the dodecyllactosylamine is present in a ring-closed form due to the chemical shift of the Cj atom of the glucose unit (6 = 90.7 1002389 11 ppm). Furthermore, it appears that the product has probably crystallized in only one anomeric form (probably the β-νοπη), because only one signal from the Cj atom of the glucose unit is present in the spectrum.

13 C-NMR (DMSO-d6, ref. (CD3) 2SO 6 = 39.5 ppm): 6 103.9 ppm (Cl, gal), δ 90.7 5 ppm (Cl, glu), δ 81.4 - 68.3 ppm (C2 - C5), δ 60.0 and 60.5 ppm (C6), δ 45.7 ppm (HN-CH ^, δ 31.3 - 22.1 (C2-C11, dodecyl tail), δ 13.9 (CH3).

Preparation Example 2. Reduction of dodecyllactosylamine with NaBH4 4.03g (21.7mmol) of dodecyllactosylamine was dissolved in 150ml of methanol with heating to 50 ° C. After the solution cooled to room temperature, 1.08 g (28.5 mmol) of NaBH4 were added in portions. After stirring overnight at room temperature, the clear solution was acidified with 1 M HCl to pH 2 and the solution was evaporated. The solution was then evaporated from methanol four more times to completely remove the boric acid. The 13 C-NMR spectrum shows that the dodecyllactosylamine is completely reduced. Moreover, it appears that no lactitol has been formed, in contrast to the reduction reaction in aqueous solution.

Preparation Example 3. Reduction of dodecyllactosylamine with Pd / C.

1.03 g (2.02 mmol) of dodecyllactosylamine was dissolved in 250 ml of ethanol. 104 mg of 10% Pd / C was added to this solution. After 21 hours at 50 ° C under 2.8 bar hydrogen pressure in a Parr apparatus, the reaction was stopped. After working up, a light yellow solid was obtained. The 13 C-NMR spectrum shows that the reduction has progressed for about 75%.

1002389

Claims (10)

A process for preparing surfactant derivatives of galacto-oligosaccharides, such as lactose, using an N-alkyl-galactoglycitylamine of the formula Sar-NH-R1, wherein Sar is the rest of a reduced, at least one galactose unit-containing di- or oligosaccharide and R 1 represents an unsaturated or unsaturated C 1 -C 20 alkyl group prepared by reacting the galacto oligosaccharide with a C 1 -C 2 alkyl alkyl, characterized in that either: (1) the galacto-oligosaccharide is reductively aminated in a one-step process with the alkylamine and hydrogen in the presence of a transition metal catalyst, or (2) the galacto-oligosaccharide without reactive processing or with at most 4 parts by weight of solvent per part by weight of oligosaccharide amines with the alkylamine, and the resulting N-alkyl-galactoglycosylamine is reduced. 2. A process for the preparation of surfactant derivatives of galacto-oligo-15-saccharides, in which an N-acyl-galactoglycosylamine of the formula Sac-NR ^ CO ^ NH ^ -R2, in which Sac is the remainder of a reducing, at least one galactose unit containing di- or oligosaccharide, m represents the number 0 or 1, R1 is hydrogen or an unsaturated or saturated alkyl group with 1-20 carbon atoms and hydrogen is an unsaturated or unsaturated alkyl group with 1-19 carbon atoms is; prepared by aminating the galacto-oligosaccharide with ammonia or an amine of the formula R1-NH2 and acylating the resulting galactosylglycosylamine with an anhydride or acid halide of the formula R2-COX, wherein X represents a halogen atom or an acyloxy group, or the amidate galacto-oligosaccharide with urea or an amide of the formula H 2 N-CO- (NH) m-R 2, characterized in that the amination and / or acylation, or the amidation is carried out by means of reactive processing without solvent or with up to 4 parts by weight of solvent per part by weight of galactooligosaccharide or. galactoglycosylamine, and the product obtained, if desired, alkylates with a compound of the formula R * X or R2Y, wherein Y represents a leaving group. 1002389 Process for the preparation of surfactant derivatives of galacto-oligosaccharides, characterized in that an N-alkyl-galactoglycosylamine, an N-alkyl-galactoglycitylamine or N-alkyl-N-acyl-galactoglycosylamine is oxidized, wherein at least 2, in particular 4-50, primary alcohol groups per 100 are converted into a 5 carboxylic acid. The process according to claim 3, wherein the amine is oxidized with a hypo-halogenite, optionally in the presence of a di-tertiary nitroxyl compound. The process of claim 3, wherein the amine is oxidized with oxygen in the presence of a transition metal catalyst. The method of claim 3, wherein the amine is oxidized in the presence of a galactose oxidase. N-Hexadecyl-galactoglycitylamine of the formula Sar-NH-C16H33 wherein Sar represents the remainder of a reduced di- or oligosaccharide containing at least one galactose unit, and in particular a lactyl group. 8. N-Acyl-galactoglycosylamine of the formula Sac-Ni ^ -CO ^ NH ^ -R2, wherein: Sac represents the remainder of a reducing di-or oligosaccharide containing at least one galactose unit, m the number 0 or 1 represents, R 1 represents hydrogen or an unsaturated or saturated alkyl group of 1 to 20 carbon atoms and R hydrogen represents a saturated or unsaturated alkyl group of 1 to 19 carbon atoms, provided that if R 2 is methyl and m is 0, R * is at least 12 carbon atoms. 1002389 N-Acyl-galactoglycitylamine of the formula Sar-NR1-CO- (NH) m-R2, wherein: Sar represents the rest of a reduced di- or oligosaccharide containing at least one galactose unit, 5. the number 0 or 1 represents R 1 represents hydrogen or an unsaturated or unsaturated alkyl group of 1 to 20 carbon atoms and R 2 hydrogen represents an unsaturated or unsaturated alkyl group of 1 to 19 carbon atoms. 10. Partially oxidized derivative of a galacto-oligosaccharide of the formula Sax-NR-Z-R2, wherein Sax represents the remainder of a reducing or reduced, at least one galactose unit containing di- or oligosaccharide, R1 hydrogen or an al or unsaturated alkyl group of 1-20 carbon atoms, R2 hydrogen represents a saturated or unsaturated alkyl group of 1-19 carbon atoms and Z represents a direct bond, a carbonyl group or a carbonylamino group, with at least 2 per 100 primary alcohol groups in a carboxylic acid group 20 have been converted. 1002389 REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE <· "" LOENTIFIKATlE OF OE NATIONAL APPLICATION Characteristic of applicant ol v »n β · gemacnagoe NO 40430 TM INeoenanoaa application no. ATO-DLO) Submitted request for an unclear type of survey type By ee m * an »e for intemate size Unquestion (ISA) atri request for an inquiry of type memo type eegekeno no. SN 27143 NL. CLASSIFICATION OF THE SUBJECT (with oe patang of a deendlenoe rtattiilcaeet. All etaasificaotymboien tasks) tolgare oe mamaoonate «attrticaue (IPC) Int.Cl.6; C 07 H 15/04, C 07 H 15/12. FIELDS OF OE TECHNOLOGY INVESTIGATED Unsourced minimum documentation Classification system Classifications __j Int.Cl.6; C 07 H laarzeen »anoere ooeumenaoe aan oe mntnutn ooeumenaoe insofar as there are a number of documents on the basis of the sentence Qinomm ^« u ». III.! ! NO INQUIRY FOR CERTAIN CONCLUSIONS (comments on supplement olafl) IV.! _ 1 LACK OF UNIT OF INVENTION (comments on supplement olafl) j 2ö = orm PCT /; SA / 231iaiC £