WO1998034943A1

WO1998034943A1 - Surfactant amines and glycosides

Info

Publication number: WO1998034943A1
Application number: PCT/NL1998/000077
Authority: WO
Inventors: Piet Marc Paul Bogaert; Patrick Simon Georges Tassignon; Theodoor Maximiliaan Slaghek
Original assignee: Instituut Voor Agrotechnilogisch Onderzoek (Ato-Dlo)
Priority date: 1997-02-10
Filing date: 1998-02-10
Publication date: 1998-08-13
Also published as: NL1005244C2

Abstract

Surface-active amines are described having the formula (1): R?10R11R12N+-CHR2-A1-R1¿ wherein A1 represents a C¿7?-C11 alkylene group; R?1¿ represents hydroxymethyl, carbamoyl, carboxyl or (C¿1?-C4alkoxy)carbonyl; R?2¿ represents a C¿5?-C9 alkyl group; R?10 and R11¿ each represent hydrogen or a C¿1?-C4 alkyl group, or R?10 and R11¿ together with the nitrogen atom represent a pyrrolidino, piperidino or morpholino group; R12 represents a C¿1?-C20 alkyl, alkenyl, alkynyl, cycloalkyl(alkyl), aralkyl or acyl group, which group may be interrupted by one or more oxygen atoms or imino groups, a C1-C3alkyl or C2-C3 alkanoyl group substituted by a carboxyl, phospho and/or sulpho group, or a sugar residue; wherein, if R?10¿ represents hydrogen, the nitrogen atom may also be deprotonated. Surfactant alkylglycosides are also described. The compounds can be used as emulsifiers, in detergents and the like.

Description

Surfactant amines and glycosides

The invention relates to novel surface-active secondary amine compounds and glycosides.

GB 2237018 discloses the use of methyl 12- and 9-aminooctadecanoate as components of pharmaceutical compositions which modify the lipid structure of cell membranes. US patents 2,312,967 and 2,610,212 describe the preparation of 12-amino- octadecanoic acid by reductive amination of 12-oxo-octadecanoic acid. Alkyl glycosides having a long aliphatic chain are known from Biermann et al, Starch/Stάrke, 45 (1993) 281-288, Balzer, Tenside Surf. Det. 28 (1991) 419-427, and others. It has been found now that polar derivatives of certain secondary aminoalkyl compounds, as well as certain alkyl glycosides, have a more useful combination of surfactant properties and critical micelle concentration.

The novel secondary amine surfactant derivatives comply with formula 1

_R10_R11_R12_N+__CHR2__A1__R1 j wherein

A represents a Cγ-C^ alkylene group, in particular a decamethylene group;

R¹ represents hydroxymethyl, carbamoyl, carboxyl or Cγ-C alkoxycarbonyl;

R represents a C₅-C₉ alkyl group, in particular a hexyl group;

R and R each represent hydrogen or a C_j- t alkyl group, in particular a methyl group, or R¹⁰ and R¹¹ together with the nitrogen atom represent a pyrrolidino, piperidino or morpholino group; R can also be absent (neutral amine);

R represents a C^- _2Q alkyl, alkenyl, alkynyl, cycloalkyl(alkyl), aralkyl or acyl group, which group may be interrupted by one or more oxygen atoms or imino groups, or a

C_j-Cg alkyl or C₂-C₃ alkanoyl group substituted by a carboxyl, phospho and/or sulpho group. The symbol R¹² may also represent a group having the formula Sac-(Z-A )n-, wherein

A represents a C₂-C₆ alkylene group optionally substituted by hydroxy;

Z represents an oxygen atom or an imino group optionally substituted by a

alkyl, hydroxyalkyl or acyl group; n is an integer of 0-4; and

Sac represents a sugar residue.

These compounds can be cationic and anionic as well as non-ionic or zwitterionic. Examples of these surface-active amine compounds are 9- and 12-trimethyl- ammonio-, -benzyldimethylammonio-, -(carboxymethyl)dimethylammonio-, -(3- sulphopropyl)dimethylammonio-, -acetyldimethylammonio-, -phosphomethylamino- and -β-sulphosuccinoylamino-stearic acid and esters thereof, as well as analogues wherein one or more ethyleneimino groups are bound to the amine nitrogen, such as in

12-[(carboxymethyl)dimethylammonio-ethyleneamino]stearic acid, and corresponding derivatives of other C₁₄-C₂ fatty acids, esters, amides and alcohols. The sugar residue represented by Sac has the formula:

R⁶OCHR⁷-CHOR⁵-CHOR⁴-CHOR³-CHR⁸- wherein

R³, R⁴, R and R each represent hydrogen, a C_j-Cγ alkyl, alkenyl, aralkyl or acyl group or a C_j-03 alkyl or C₂-C alkanoyl group substituted by a carboxyl, phospho and/or sulpho group; R⁷ represents hydrogen, a carboxyl group or a group CH₂OR ; R⁸ represents hydrogen or together with one of the symbols R and R⁶ forms a direct bond; wherein one of the symbols R³, R⁴, R⁵ and R may also represent a sugar residue [R⁶OCHR⁷-CHOR⁵-CHOR⁴-CHOR³-CHR⁸-].

Examples of the glycoside derivatives of the amine compounds include 12- and 9-(galactosylamino)stearic acid and 12- and 9-(glucosylamino)stearic acid and esters thereof and the corresponding stearic alcohol derivatives. Other possible sugar residues are described below. The sugar residue can be a reducing monosaccharide, disaccharide or oligosaccharide. Suitable sugars include the monosaccharides glucose (Glc), galactose (Gal), mannose (Man), fructose, xylose (Xyl) and arabinose, the disaccharides maltose (Glc-lα→4-Glc), isomaltose (Glc-lα→6-Glc), cellobiose (Glc-lβ→4-Glc), gentio- biose (Glc-lβ→6-Glc), laminaribiose (Glc-lβ→3-Glc), melibiose (Gal-l →6-Glc), lactose (Gal-lβ→4-Glc), epilactose (Gal-lβ→4-Man), primeverose (Xyl-1→6-Glu) and xylobiose (Xyl-lβ→4-Xyl) and the corresponding trisaccharides such as maltotriose, galactosyl-lactose and higher homologues. Di- and higher saccharides wherein the second sugar group is attached to the 2 position of the first sugar, such as kojibiose and sophorose, are somewhat less useful. Pentasaccharides and higher are also less important. Preference is given to aldoses, in particular non-expensive sugars such as glucose, galactose, lactose and maltose. Examples of groups forming part of the C_j-C^ alkyl groups interrupted by one

19 or more oxygen atoms or imino groups represented by R , and examples of the groups (Z-A²)_n, represented by R¹², include alkyleneoxy or alkyleneimino groups, such as ethyleneoxy, 1,2-propyleneoxy, 2-hydroxy- 1,3-propyleneoxy, 2,2-bis(hydroxy- methyl)- 1,3-propyleneoxy, ethyleneimino, 1,3-propyleneimino, hexamethyleneimino,

N-hydroxyethyl-ethyleneimino and oligomers thereof.

The secondary amines can be prepared from the corresponding unsaturated compounds, halogen compounds, ketones or alcohols. Thus, a mixture of methyl-9- and -10-aminooctadecanoic acid can be obtained by treatment of methyl oleate with 70% nitric acid and hydrogenation with Raney nickel, and 12-aminooctadecanoic acid can be obtained from 12-oxooctadecanoic acid by reductive amination with ammonia and a catalyst, of, advantageously, by oximation with anhydrous hydroxylamine in methanol followed by hydrogenation, such as illustrated in the examples. The same procedure can be followed for the corresponding 1-hydroxy compounds, starting from l-hydroxy-9- or -12-octadecanone, respectively.

The oximation of oxoalkanoic acids and oxoalkanols is preferably performed using neutral hydroxylamine in a C_j -C₃ alcohol, in particular methanol. The reduction thereof is preferably performed using mild temperatures, preferably about room temperature (10-30°C) and using hydrogen under a pressure of e.g. 1.5-5 bar in the presence of a transition metal catalyst, especially palladium on carbon. The same solvent

(e.g. methanol) can be used in the hydrogenation reaction and prior isolation of the oxime is not necessary.

The groups R¹⁰, R¹¹ and R¹² can be introduced in a manner known per se. If R¹⁰, R¹¹ (and R¹²) are alkyl groups, these can be introduced by reaction of the secondary amine with the corresponding alkyl halide, sύlphonate, sulphate or the like, such as methyl iodide, diethyl sulphate, butyl bromide. Similarly, groups such as alkenyl (e.g. allyl or octadienyl), alkynyl (e.g. propargyl), benzyl, cycloalkylalkyl, represented by R¹², can be introduced using the corresponding halide, (methane)sulphonate etc.. Hydroxy- alkyl groups can be introduced using halides or epoxides, such as epichlorohydrine. Acyl groups R such as acetyl are introduced using the appropriate acid anhydride or acid halide.

Alkyl or alkanoyl groups substituted by a carboxyl, phospho and/or sulpho group as R¹² include alkyl and alkanoyl groups substituted by one or more acid groups -COOH, -PO(R⁹)(OH), -PO(OR⁹)(OH), -OPO(R⁹)(OH), -OPO(OR⁹)(OH), -SO₃H or -OSO3H, while the group -PO(R⁹)(OH), -PO(OR⁹)(OH), -SO₃H can also be directly bound to the nitrogen atom. Herein R represents a hydrogen atom or a C_j-Cy hydrocarbon group, such as methyl, ethyl, allyl, butyl, phenyl, cyclohexyl or benzyl. The acid groups can of course be present in ionised form, and in particular as part of zwitter- ions. These compounds can be prepared for example by reaction of the amine, for example: a haloacetic acid resulting in a carboxymethyl derivative; acrylonitrile followed by saponification resulting in a carboxyethyl derivative; a halomethylphosphonic acid resulting in a phosphonomethyl derivative; formaldehyde and an alkylphosphinic acid resulting in an ethylphosphinicomethyl) derivative; hydroxymethylsulphonic acid resulting in a sulphomethyl derivative; chloroethanesulphonic acid resulting in a sulpho- ethyl derivative; ethyleneoxide and chlorosulphonic acid resulting in a sulphatoethyl derivative; chlorosulphonic acid or chlorophosphonic acid resulting in an sulphato or phosphato derivative; succinic anhydride resulting in a succinoyl derivative; or maleic anhydride and sulphite resulting in a β-sulphosuccinoyl derivative. Suitable derivatisation methods for introducing the acid groups have been described for example by Van

Haveren et al, NMR in Biomedicine, 8, 197-205 (1995), and O'Lenick et al, JAOCS, 73, 935-937 (1996).

The invention also relates to novel glycosides complying with formula 2,

Sac-(Z-A²)_n-Z-CH(R¹³R¹⁴) 2 wherein the symbols A², Z, n, Sac and R³ to R⁸ are as defined above and R¹³ and R¹⁴ are as defined in claim 6. The sugar residue Sac of the glycoside can be a reducing monosaccharide, disaccharide or oligosaccharide as described above.

The glycosides according to the invention are obtained from a secondary alcohol or a secondary amine. The secondary alcohol or the secondary amine which, together with the sugar, forms the surface-active glycoside according to the invention, contains at least 9, in particular 12-24 carbon atoms, the hydroxyl group and the amino group, respectively, being located at a distance of at least 4 atoms from the chain ends, such as in 9-octadecanol. The secondary alcohol can optionally contain a second, secondary hydroxyl group. Preferably, the secondary alcohol contains a carboxyl-derived function such as an alkyl ester, an amide or a mono- or di-alkylamide. Thus, one of the two groups R¹³ and R in the formulae 1 and 2 is preferably substituted in the manner as indicated, especially by carboxyl or alkoxycarbonyl. Examples of suitable hydroxy carboxylic acids are 10-hydroxyρalmitic acid, 9-hydroxystearic acid, 12-hydroxystearic acid, ricinoleic acid (12-hydroxyoleic acid) and dimoφhecolic acid (9-hydroxy-10,12-octadecadienoic acid). Most preferred are saturated acids such as the amino- and hydroxystearic acids. Starting materials that are most suitable are the alkyl esters and dialkylamides of the hydroxy acids. In this context, alkyl means C₁-C -alkyl, in particular methyl and ethyl. The esters and amides can be reduced afterwards to alcohols and amines, respectively, if desired.

The secondary amine can optionally also contain a hydroxyl group. Examples of suitable amines are 9- and 12-amino-octadecanoic esters and amides and 9- and 12- amino-octadecanol. The alcohols and amines can optionally contain one or more alkyleneoxy or alkyleneimino groups between the aliphatic residue and the sugar residue, as described above.

The novel alkyl glycosides can be prepared for example using the Koenigs- Knorr synthesis (Adv. Carbohydr. Chem. Biochem., 34 (1977) 243), starting with a glycosyl halide and the secondary alcohol in the presence of a heavy metal compound such as a silver or mercury compound, in particular a mercury(II) halide with a cata- lytically active amount of iodide ions in an anhydrous solvent such as dichloromethane and a water-binding agent such as molecular sieves. The other hydroxyl groups of the glycoside should be protected as an ester (for example an acetate) or ether (for example a benzyl ether). In an alternative embodiment, the process starts with an imidate ester of the sugar, in particular a trichloroacetic imidate, obtained by reaction of the sugar with trichloroacetonitrile (scc Angew. Chem., Int. Ed. Engl, 25 (1986) 212; Adv. Carbohydr. Chem. Biochem., 50 (1994) 21). The other hydroxyl groups of the glycoside can be protected herein as well. It has been found that the novel alkyl glycosides can be obtained in an advantageous manner by reaction of the glycosyl halide with a hindered amine, such as triethylamine or diisopropylamine, in a polar aprotic solvent such as acetonitrile, propiononitrile, tetrahydrofuran, nitromethane or dimethylformamide, in the presence of a water-binding agent. Yield in the order of 50% can be obtained in this way. Once the alkyl glycoside has been obtained, any protecting groups such as acetate groups or benzyl groups can be removed, if desired, by hydrolysis or reduction, in a manner known per se.

The amine can react with the sugar as such, producing a glycosylamine. Advantageously, this glycosylamine is reduced to the more stabile glycitylamine, the direct bond between R⁸ and R⁵/R⁶ in formula 2 being hydrogenated. The reduction can for example be performed with sodium borohydride or with hydrogen and a metal catalyst, such as nickel, palladium, platinum, ruthenium or another group VIII metal, optionally on a support such as carbon. The amination and reduction can be carried out in distinct steps. However, higher yields are obtained, when the reductive amination is carried out in a single step, preferably with hydrogen and a catalyst. Solvents to be used include, for example, water, an alcohol or an alcohol-water mixture. It was found that if a slightly less than equivalent amount of alkylamine with respect to sugar is used, the sugar is not reduced and thus the product can be further processed in a more simple manner.

The alkyl glycosylamine can also, advantageously, be acylated, resulting in more stabile derivatives, which moreover have useful surfactant properties; in formula 2, Z represents acylimino for these derivatives. The acylation can be effected by treating the alkylglycosylamine with a C_j-C₃ carboxylic acid anhydride or halide in a suitable solvent, preferably with a base.

The amination of the sugar and the acylation can also be performed by "reactive processing" (see e.g. Tomasik et al., Starch/Stάrke 47 (1995), 96-99, and Narkrugsa et al. Starch/Stάrke 44 (1992), 81-90), i.e. without or with low levels of solvents with mechanical agitation, for example in an extruder. Optionally one or more of the primary alcohol groups in the alkyl glycosides or alkyl glycosylamines can be converted to a carboxylic acid group, for example by oxidation with hypochlorite in the presence of 2,2,6,6-tetramethylpiperidine-l-oxyl (TEMPO), or by oxidation with oxygen and a transition metal catalyst.

A further aspect of the invention pertains to surfactant glycosyl amines and glycosides bearing an alkyl group or alkanoyl group having 1-4 carbon atoms substituted by one or more acid groups -COOH, -PO(R⁹)(OH), -PO(OR⁹)(OH), -OPO(R⁹)(OH), -OPO(OR⁹)(OH), -SO₃H or -OSO₃H on one or more of the oxygen- (and, if applicable, nitrogen) atoms, while the group -PO(R⁹)(OH), -PO(OR⁹)(OH), -SO₃H can also be directly bound to an oxygen atom. R represents hydrogen or a hydrocarbon group as defined above. These compounds can be prepared for example by reaction of a glycitylamine or glycosylamine as describe above with the reagents described above (a haloacetic acid etc.).

The invention also relates to the use of the derivatives described above as an emulsifier in foodstuffs, as a detergent as an am emulsifier in washing compositions, dish-washing compositions, body care compositions, cosmetics, shampoos, or as a dis- persant for e.g. pesticides etc.

EXAMPLES General Methyl 9-hydroxyoctadecanoic acid was obtained by extraction of Dimorphoteca pluvialis seeds and transesterification and hydrogenation of the dimoφhecolic esters as described by Tassignon et al, Chem. Phys. Lipids 71 (1994) 187-196; Ind. Crops. Prod. 4 (1995) 121-125. 12-Hydroxyoctadecanoic acid is commercially available, but for the formation of the methyl ester an esterification step followed by crystallisation is advantageous. l-Hydroxy-9-octadecanone and l-hydroxy-12-octadecanone were prepared as described by Tassignon et al, Tetrahedron 51 (1995), 11863-11872.

Example 1: Methyl 12-(hydroxyimino)octadecanoate

Method 1 (using NH₂OH.HCl and Et^): 3.1 g (10 mmol) of methyl 12-oxo-octa- decanoate, 1.1 g (11 mmol) Et₃N and 0.75 g (11 mmmol) hydroxylamine-hydrochloride were dissolved in 27 ml of MeOH. This reaction mixture was refluxed for 2 hours and then transferred to a separatory funnel, containing 108 ml of water. The aqueous phase was extracted three times with hexane (50 ml). The organic layers were collected, washed with aq. HC1 (0.1N) until neutral pH of the organic phase, dried (MgSO₄), filtered, and evaporated to give 3.14 g (9.61 mmol, 96%) of product. Method 2 (using free NH₂OH): Prior to the condensation reaction of hydroxylamine and the keto function, 1.1 g (11 mmol) of Et₃N and 0.76 g (11 mmol) HONH₂.HCl were dissolved in 6 ml of CH₂C1₂. After 30 minutes, diethyl ether (30 ml) was added to the solution and triethylamine.hydrochloride crystals were formed. After filtration, the organic phase was transferred to a second flask in which 3.12 g (10 mmol) of methyl- 12-oxooctadecanoate in 30 ml of MeOH was dissolved. After 2 hours at reflux temperature, the solvents were evaporated and the crude oil was dissolved again in 2 ml of MeOH and 10 ml hexane and washed with two times 10 ml of water. The organic phase was dried (MgSO4) and the organic solvents were evaporated. Yield for the title compound: 3.17 g (96 %). 1H NMR (δ ppm; 400 MHz): 0.879 (t, 3 H, H-18, J_{18 17} = 6.9 Hz), 1.270-1.400 (m, 18 H, H-4, 5, 6, 7, 8, 9, 15, 16, 17), 1.497 (m, 4 H, H-10,

14), 1.622 (m, 2 H, H-3), 2.165 (t, 4H, H-ll, 13, J_{n l0} = 7.7 Hz, J_{13 14} = 7.7 Hz), 2.280-2.346 (m, 6 H, H-2, 11/13), 3.659 (s, 3 H, CH₃O); ¹³C NMR (δ ppm: 75 MHz): 14.13 (C-18), 22.66 (C-17), 25.71, 26.32, 26.44, 27.52, 27.58, 29.07, 29.16, 29.46, 29.74 and 29.98 (CH₂-alkyl), 31.89 and 31.95 (C-10, C-14), 34.07 and 34.13 (C-11, C-13), 51.44 ( CH₃O), 161.61 (C=N-OH, anti and syn), 174.30 (C-1); FT-IR (cm^-1): 1738.7 (C=O), 1658.5 (C=N-OH); M/e (%): 328 (M⁺+l,0.3), 310 (M⁺-OH,8), 242 (C₁₃H₂₄O₃N,15), 215(6), 199 (C₁₂H₂O₂, 23), 198 (21), 110 (7), 83 (12), 73 (C₃H₅O₂,100), 70 (15), 57 (35), 56 (12), 43 (58); Anal. Calc.(%) for C, H, N: 69.6, 11.3, 4.3; Found (%): 69.7, 11.2, 4.2.

Example 2: Methyl 9-(hydroxyimino)octadecanoate

The methods of example 1 were followed using methyl 9-oxo-octadecanoate. Yield: 3.17 g (97%). 1H and ¹³C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.

Example 3: l -Hydroxy-12-(hydroxyimino)octadecane

Similar reaction conditions were used as in example 1, using l-hydroxy-12- octanone. Yield: 2.79 g (93%). 1H and ¹³C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.

Example 4: l -Hydroxy-9-(hydroxyimino)octadecane

Similar reaction conditions were used as in example 1, using l-hydroxy-9- octanone. Yield: 2.83 g (94%). 1H and ¹³C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.

Example 5: Methyl 12-aminooctadecanoate

Methyl 12-(hydroxyimino)-octadecarioate (example 1) (3.27 g) was hydrogenated during 48 hours in methanol (100 ml) with 10% palladium on activated coal (200 mg), at room temperature and 2.1-2.8 bar of hydrogen pressure. Then the catalyst was removed from the reaction mixture by filtration over Celite . The Celite layer was washed with a total of 150 ml warm (50°C) methanol, and the filtrate was evaporated to dryness. The residue was redissolved in 30 ml hot methanol and this solution was added to 120 ml of distilled water. Methyl 12-aminooctadecanoate was extracted from the aqueous methanol phase with a total of 150 ml of hexane. The organic phase was dried (MgSO₄), filtered, and the solvent was evaporated, yielding the title product (3.0 g, 95%). 1H NMR (δ ppm; 300 MHz): 0.879 (t, 3H, H-18, J_{18 17} = 6.9 Hz), 1.270-1.400 (m, 18H, H- 4, 5, 6, 7, 8, 9, 15, 16, 17), 1.497 (m, 4H, H-10, 14), 1.624-1.973 (m, 2H, H-3), 2.179 (t, 2H,J₂₎₃ = 7.7 Hz), 2.280-2.346 (m, 4H, 11/13), 3.212 (s, 1H, H-9), 3.663 (s, 3H, CH₃O); ¹³C NMR (δ ppm: 75 MHz): 13.52 (C-18), 22.06 (C-17), 23.34, 24.44, 24.86, 28.49, 28.64 (CH₂-alkyl, with overlap), 31.04 and 32.17 (C-10, C-14), 33.58 (C- 11, C-13), 50.96 (CH₃O), 52.08 (C-12) 173.65 (C-1); FT-IR (cm^-1): 3402.1-3014.2

(NH^, 1746.2 (C=O); M/e (%): 314 (M⁺, 0.1), 242 (3), 228 (C₁₃H₂₆O₂N, 52), 196 (8), 128 (5), 114 (C₇H₁₆N,100), 81 (2); Anal. Calc.(%) for C, H, N: 72.7, 12.4, 4.5; Found (%): 72.6, 12.5, 4.4.

Example 6: Methyl 9-aminooctadecanoate The methods as described in example 5 were used starting with the 9-oxime of example 2. Yield: 3.0 g (96%). 1H (3.150 s, 1H, H-9) and ¹³C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.

Example 7: l -Hydroxy-12-aminooctadecane

Similar reaction conditions were used as in example 5 using the compound of example 3. Yield: 2.66 g (94%). 1H (3.125 m, 1H, H-9) and ¹³C NMR, FT-IR, MS spectral and analysis data are in accordance with the structure.

Example 8: 1 -Hydroxy -9-aminooctadecane

Similar reaction conditions were used as in example 5, using the compound of example 4. Yield: 2.75 g (97%). 1H (δ ppm; 300 MHz): 0.879 (t, 3H, H-18, J_{18 17} = 6.6 Hz), 1.210-1.456 (m, 24H, H-3,4,5,6,7,11, 12,13,14,15,16,17), 1.560 m, 2H, H-2), 2.13

(1-OH, NH^, 2.371 (2*t, 4H, H-8, 10, J_{8 7} = 7.6 Hz, J_{lo n} = 7.6 Hz), 3.231 (m, 1H, H-9), 3.621 (t, 2H, H-l, J_1>2 = 6.6 Hz); ¹³C (d ppm; 75 MHz): 13.92 (c-18), 22.78 (C- 17), 25.16, 25.29 25.56, 27.56, 29.00, 29.59, 29.84, 31.50, 32, 31 (CH₂-alkyl), 32,12, 33.18 (C-2, 16), 42.12 (C-9, 10), 52.39 (C-9), 62.78 (C-1); FT-IR: (cm^-1): 3600-3040 (OH, NH₂), 1703.8, 1610.2; M/e (%): 285 (M⁺+l, 3), 268 (M⁺-NH₂, 8), 267 (M⁺-OH,

4), 157 (C₉H₁₉ON, 26), 155 (C_ιrjH₂₁N, 26), 131 (12), 127 (8), 97 (94), 81 (40), 69 (53), 57 (29), 55 (100); Anal. Calc.(%) for C, H, N: 76.1, 12.4, 4.9; Found (%): 76.0, 12.4, 5.0.

Example 9: 1 -Hydroxy -9- (trimethylammonio)octadecane The product of example 8 is dissolved in dichloromethane and reacted with methyl iodide (6 equivalents) to produce the title product after evaporation.

Example 10: Methyl 12-(peracetylgalactosylamino)stearate via Koenings -Knorr reaction

In a 250 ml flask (dried at 105°C) 2.47 g (7.9 mmol) of methyl 12-aminostearate (example 5) and 2.85 g (7.9 mmol) of mercury(II) bromide are added to 100 ml dry dichloromethane. About 10 g of molecular sieves (4) are also added and the flask is equipped with a calcium chloride tube. The mixture is cooled at 0°C in an ice bath, and 3.37 g (7.9 mmol) of peracetylgalactosyl bromide is added after 1 h. The mixture is stirred overnight at 0 °C. The molecular sieves and the mercury bromide are filtered off, the residue is washed with 150 ml of dichloromethane. The dichloromethane phase is consecutively washed with 100 ml of saturated sodium bicarbonate solution and 100 ml of brine (twice). After the washings the dichloromethane phase is dried overnight on magnesium sulphate. The magnesium sulphate is filtered off and the dichloromethane layer is evaporated on a rotary film evaporator. Of the crude product (4.96 g), 2.0 g is brought on a silica gel column with 35/65 ethyl acetate/n-hexane as eluent. The yield of methyl 12-(peracetylgalactosyl)stearate is 0.81 g (36%).

1H-NMR: (δ in ppm; 400 MHz): 0.8834 (H-18, t, J=5.24 Hz), 1.2618-1.5999 (alkyl, m), 1.9889-2.1799 (CH₃, m, acetyl), 2.3329 (H-2, t, J=7.5 Hz), 3.4856 (H-12, q, J=22 Hz), 3.6712 (OCH₃), s), 3.9319 (H-5', m), 4.1139-4.1873 (H-6',m), 4.4053 (HI', J=7.96 Hz), 5.0202 (H-3', J=5.3 Hz), 5.2023 (H-2', dd, Jab=6.5 Hz; Jac=7.46 Hz), 5.3974 (H-

4', t, J=3.32 Hz).

¹³C-NMR: (δ in ppm; 400 MHz) 11.09 (C-18, CH₃); 20.60, 20.67, 20.82, 21.07 (acetyl, CH₃); 22.59, 22.66, 23.69, 24.98, 25.41, 25.68, 26.51, 27.17, 28.95, 29.05, 29.11, 29.19, 29.29, 29.37, 29.70, 31.59, 34.18 (alkyl, CH₂) 42.83, ( ); 51.56 (OMe, CH₃); 54.61, 57.00 (α and β CH-N); 61.34 (C-6', CH^, 66.19, 67.13 (α and β C-4'); 67.57, 68.16

(α and β C-2'); 68.19, 68.84 (α and β C-3'); 70.65, 71.01 (α and β C-5'); 97.21, 102.08 ( and β C-1^*); 169.54, 170.21, 170.29, 170.47 (acetyl, C=O); 174.60 (C-1, C=O). IR (cm^-1): 2935 (s,w): 2855 (s,w); 1783 (s,w); 1517 (s); 1455 (s).

Example 11: Methyl 12-galactosylaminostearate The product of the previous example is deacetylated with sodium methoxide in methanol with reflux for 4 h. IR (cm^-1): 3365 (w); 2936 (s); 2359 (s); 2337 (s); 1651 (s); 1447 (s,w); 1354 (s). Examples 12-15: 1 -0-(ll -Methoxycarbonyl-1 -hexylundecyl) -β-D-glucose,

-galactose, -lactose and -maltose

1, 2, 3, 4, 6-Penta - O -acetyl -β -D -glucopyranose

In a porcelain mortar 4 g (48 mmol) of anhydrous sodium acetate and 5 g (27.4 mmol) dry α-D-glucose are milled, the powder mixture is transferred to a round-bottomed flask of 200 ml and 7 g (25 ml, 0.26 mol) of acetic anhydride is added. The mixture is refluxed (120°C) and occasionally shaken until a clear solution is obtained. After another two hours of heating the reaction mixture is poured onto 250 ml of ice. Na 1 The crystals are filtered off after 1 h, washed with cold water and recrystallised from ethanol. Yield 6.2 g (56%). Galactose, lactose and maltose are acetylated in the same way yields of 57%, 76%, and 74%, respectively. 2, 3,4,6- Tetra - O -acetyl -a-D-glucopyranosyl bromide

To a solution of 1,2,3,4,6-penta-O-acetyl-β-D-glucopyranose (3.90 g, 10 mmol) in dichloromethane (9 ml), 33% HBr in glacial acetic acid (9 ml) is added at 0°C. The mixture is stirred until thin layer chromatography (ethyl acetate/dichloromethane: 1/1;

Rf= 0.56) shows that the bromination is completed (Rf= 0.57). The mixture is poured onto ice, taken up in dichloromethane (50 ml), washed with water (50 ml), saturated NaHCO₃ solution (50 ml) and again with water (2x 50 ml). The organic phase is dried on MgSO , filtered concentrated. The residue (oil) is dissolved in ether and stored at 4°C. Crystals appear after several hours; yield 3.83 g (93%). The same method is followed for the bromination of galactose, lactose and maltose (yields 93%, 93%, and 95%, respectively).

2,3,4,6-Tetra-O -acetyl- l-O- (11 -methoxycarbonyl-1 -hexylundecyl) -β-D-glucose Method 1: To a mixture of 0.628 g (2 mmol) methyl 12(R)-hydroxyoctadecanoate, 0.72 g (2 mmol) HgBr₂ and 6 g molecular sieves' (4A), 0.1 g KI in 24 ml dry dichloromethane is added. The reaction mixture is stirred at room temperature for 1 h. Finally, 0.82 g (2 mmol) of 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide is added. After overnight stirring at 0°C, the mixture is extracted with 150 ml of dichloromethane, and the organic layer is washed twice with 40 ml of an aqueous 5% (w/v) KI solution, then with saturated NaHCO₃ (25 ml) and finally twice with water (40 ml). The organic phase is dried on MgSO₄, filtered, and evaporated. The residue is purified with column chromatography (R_f = 0.33; ethyl acetate/hexane: 35/65). Yield 0.45 g (35%). The corresponding galactose, lactose and maltose derivatives are prepared in a similar manner; yields 15%-40%. Method 2: To a mixture of 0.628 g (2 mmol) methyl 12-hydroxy-octadecanoate (in 50 ml acetonitrile) and 6 g molecular sieves (4A), 0.404 g (4 mmol) Et₃N is added. The reaction mixture is stirred at room temperature for 1 h. Then 0.82 g (2 mmol) of 2,3,4,6- tetra-O-acetyl-α-D-glucopyranosyl bromide is added and the mixture is refluxed for 24 h. When the mixture does no longer show any reaction, (check with TLC; ethyl acetate/hexane: 35/65; R_f value 0,33), the molecular sieves are filtered off and the filtrate is then concentrated. The residue (oil) is dissolved in ether, the mixture is filtered and the organic phase is purified by column chromatography (R_f = 0.33; ethyl acetate/hexane: 35/65). Yield 0.54 g (42%). The corresponding galactose, lactose and maltose derivatives are prepared following the same method; yields 41-51%. The ¹H NMR, ¹³C NMR and

IR data of these compounds confirm their structure. 1 -0-(ll -Methoxycarbonyl-1 -hexylundecyl) -β-D-glucose

In a 100 ml flask 0.45 g of the acetylated product described above is refluxed in 30 ml of a mixture of methanol and dichloromethane (60/40, v/v). After 10 minutes 1 g of sodium (5 times 0.2 g) is added in a period of 10 minutes. After standing at 82°C for another 15 h the crystals formed were filtered off, washed twice with dichloromethane (30 ml), dissolved in 20 ml of water and washed with dichloromethane (30 ml). 60 ml of methanol was added to the water phase and then the product crystallises. Yield 0.27 g (94%). The corresponding galactose, lactose and maltose derivatives are prepared by the same method; yields 93-97%. The IR data are presented in table 1. The CMC values and surface tensions are presented in table 2.

Examples 16-19: 1 -O- (8 -Methoxycarbonyl-1 -nonylundecyl)-β-D-glucose, -galactose, -lactose and -maltose

These compounds are prepared following the methods of examples 1-4, however starting with methyl 9-hydroxyoctadecanoate in stead of methyl 12-hydroxyoctadecanoate. The

1H NMR, ¹³C NMR and IR data of the peracetyl compounds confirm their structure. The IR data of the deacetylated compounds are summarised in table 1 and the CMC values and surface tensions are given in table 2.

Example 20: Methyl 12-maltosylstearate Methyl 12-(peracetylmaltosyl)stearate is dissolved in a small amount of methanol. After addition of sodium, the solution is refluxed for 4 hours. The product precipitates and is filtered. Yield: 80.7%. IR methyl 12-(peracetylmaltosyl)stearate: 3582-2524 (NH); 2926; 1728,5 (C=O); 1612;

1237; 1040 cm -1.

IR methyl 12-maltosylstearate: 3309 (OH); 2925; 2853; 1604; 1444; 1315; 1049 cm -l

TABLE 1 FT-IR data for the compounds of examples 12-19

Sugar side chain IR (cm^-1) residue position glucosyl 12- 3641-3030 (OH); 2788; 2700 1080 galactosyl 12- 3683-3095 (OH); 2801; 2701 1102 lactosyl 12- 3680-3080 (OH); 2802; 2713 1132 maltosyl 12- 3640-3085 (OH); 2803; 2715 1141 glucosyl 9- 3651-3072 (OH); 2809; 2708 1081 galactosyl 9- 3672-3042 (OH); 2819; 2712 1041 lactosyl 9- 3700-3080 (OH); 2820; 2717 1125 maltosyl 9- 3680-3071 (OH); 2821; 2714

1105

TABLE 2 Critical micelle concentrations (CMC) and surface tensions in Milli-Q water of the compounds of examples 12-19

Compound CMC (mol/1) YCMC (mN/m)

Methyl 12-glucosyl-stearate 3.0 x 10^-3 32.8

Methyl 9-glucosyl-stearate 2.8 x 10^-3 32.2

Methyl 12-galactosyl-stearate 1.2 x 10^-3 34.5

Methyl 9-galactosyl-stearate 8.3 x 10^-4 33.6

Methyl 12-lactosyl-stearate 5.2 x 10^-3 36.8

Methyl 9-lactosyl-stearate 3.1 x 10^-3 36.1

Methyl 12-maltosyl-stearate 6.1 x 10^-3 38.1

Methyl 9-maltosyl-stearate 4.8 x 10^-3 37.2

Claims

1. A surfactant amine compound having formula 1,

_R10_R11_R12_N+__CHR2__A1__R1 j wherein

A¹ represents a Cy-C^ alkylene group;

R represents hydroxymethyl, carbamoyl, carboxyl or ( ^^ alkoxy)carbonyl;

R² represents a C₅-C₉ alkyl group;

R and R¹¹ each represent hydrogen or a C_j- ^ alkyl group, or R and R together with the nitrogen atom represent a pyrrolidino, piperidino or mo╧åholino group;

R¹² represents a CJ-C^_Q alkyl, alkenyl, alkynyl, cycloalkyl(alkyl), aralkyl or acyl group, which group may be interrupted by one or more oxygen atoms or imino groups, a C_j-0₃ alkyl or C₂-C₃ alkanoyl group substituted by a carboxyl, phospho and/or sulpho group, or a group having the formula Sac-(Z-A )n-;

A represents a C₂-C₆ alkylene group optionally substituted by hydroxy;

Z represents an oxygen atom or an imino group optionally substituted by a CJ-CJ alkyl, hydroxyalkyl or acyl group; n is an integer of 0-4;

Sac represents a sugar residue; wherein, if R¹⁰ represents hydrogen, the nitrogen atom may also be deprotonated.

2. An amine compound according to claim 1, wherein A represents a decamethylene group and R² represents a hexyl group.

3. An amine compound according to claim 1 or 2, wherein R and/or R represent a methyl group.

4. An amine compound according to any one of claims 1-3, wherein Sac represents a sugar residue having the formula R⁶OCHR⁷-CHOR⁵-CHOR⁴-CHOR³-CHR⁸- wherein

R³, R⁴, R⁵ and R⁶ each represent hydrogen, a C₁-C₇ alkyl, alkenyl, aralkyl or acyl group or a C_j-C₈ alkyl or C₂-C₃ alkanoyl group substituted by a carboxyl, phospho and/or sulpho group;

R represents hydrogen, a carboxyl group or a group CH₂OR ; R⁸ represents hydrogen or together with one of the symbols R⁵ and R⁶ forms a direct bond; wherein one of the symbols R³, R⁴, R⁵ and R⁶ may also represent a sugar residue

[R⁶OCHR⁷-CHOR⁵-CHOR⁴-CHOR³-CHR⁸-]; and Sac is preferably glucosyl or galactosyl.

5. A process for preparing a surfactant amino compound according to any one of claims 1-5, wherein R may also represent hydrogen, comprising reacting a keto compound having the formula R -CO-A¹-R¹, wherein A¹, R¹ and R² are as defined in claim 1, with hydroxylamine, and hydrogenating the oxime obtained, followed, if desired, by reacting the amine obtained with one or halides having the formulae R¹⁰X, RⁿX and R¹²X, wherein X represents a halogen atom.

6. A surface active glycoside having formula 2,

R⁶OCHR⁷-CHOR⁵-CHOR⁴-CHOR³-CHR⁸-(Z-A²)_n-Z-CH(R¹³R¹⁴) 2

wherein

R³, R⁴, R⁵ and R⁶ each represent hydrogen, a C^Cy alkyl, alkenyl, aralkyl or acyl group or a Cy-C^- alkyl or C₂-C₃ alkanoyl group substituted by a carboxyl, phospho and/or sulpho group; R represents hydrogen, a carboxyl group or a group CH₂OR ; R⁸ represents hydrogen or together with one of the symbols R⁵ and R⁶ forms a direct bond; wherein one of the symbols R³, R⁴, R⁵ and R⁶ may also represent a sugar residue

[R⁶OCHR⁷-CHOR⁵-CHOR⁴-CHOR³-CHR⁸-]; R¹³ and R¹⁴ each represent a C₄-C₁₅ alkyl or alkenyl group optionally substituted by hydroxy, alkoxycarbonyl, amino, (di)alkylamino, carbamoyl or (di)alkylcarbamoyl; A² represents a C₂-C₆ alkylene group optionally substituted by hydroxy; Z represents an oxygen atom or an imino group optionally substituted by a C_j-C₈ alkyl, hydroxyalkyl or acyl group; n is an integer of 0-4.

7. A glycoside according to claim 6, wherein R represents an C₇-C alkyl group substituted by hydroxy or alkoxycarbonyl and R¹⁴ represents a C₅-C₉ alkyl group;

8. A glycoside according to claim 6 or 7, wherein R³, R⁴, R⁵ and R⁶ each represent hydrogen, wherein one of the symbols R⁴, R and R⁶ may also represent a glucosyl or galactosyl group, and R⁸ may also form a direct bond with one the symbols R⁵ and R⁶.

9. A glycoside according to claim 8, which is a ╬▓-glucoside or ╬▓-galactoside.

10. A glycoside according to any one of claims 6-9, wherein Z represents an oxygen atom; n equals 0 and

R⁸ together with one of the symbols R and R forms a direct bond.

11. A process for preparing a glycoside according to any one of claims 6-10, comprising reacting a glycosyl halide having the formula 3,

R⁶OCHR⁷-CHOR⁵-CHOR⁴-CHOR³-CHR⁸-X 3 wherein R³, R⁴, R⁵ and R each represent hydrogen, a C_j-C₇ alkyl, alkenyl, aralkyl or acyl group; R represents hydrogen or a group CH₂OR ;

R⁸, together with one of the symbols R⁵ and R , forms a direct bond; wherein one of the symbols R³, R⁴, R⁵ and R⁶ may also represent an alkylated or acylated sugar residue, X is a halogen atom, with a secondary alcohol or a amine having formula 4,

HZ-(A²-Z)-CHR¹³R¹⁴ 4 wherein

R¹³ and R¹⁴ each represent a C₄-C₁₅ alkyl or alkenyl group optionally substituted by alkoxycarbonyl, carbamoyl or (di)alkylcarbamoyl, a secondary carbon atom of which being optionally substituted by hydroxy or amino or (di)alkylamino,

A², Z and n are as defined in claim 6, in a manner known per se, optionally followed by substituting alkyl and acyl groups of R³ to R⁶ by hydrogen atoms by reduction or hydrolysis, and optionally reducing an alkoxycarbonyl or carbamoyl group in R .

12. A process for preparing a glycoside according to any one of claims 5-10, comprising reacting a glycosyl halide having formula 3,

R⁶OCHR⁷-CHOR⁵-CHOR⁴-CHOR³-CHR⁸-X 3 wherein

R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are as defined in claim 6,

X is a halogen atom, wwiitthh aa sseeccoonnddaarryy aallceohol having formula 4, wherein R and R are as defined in claim 6, in the presence of a hindered amine in an aprotic solvent, optionally followed by substituting alkyl and acyl groups of R to R by hydrogen atoms by reduction or hydrolysis, and optionally reducing an alkoxycarbonyl or carbamoyl group in R¹³.

13. A process according to claim 11 or 12, wherein R³ is an acetyl group.

14. A process according to any one of claims 11-13, wherein Z represents oxygen and n equals 0.

15. A process for preparing a glycoside according to any one of claims 6-10, comprising reacting a glycose having formula 3,

R⁶OCHR⁷-CHOR⁵-CHOR⁴-CHOR³-CHR⁸-X 3

wherein

R³, R⁴, R⁵, R⁶, and R⁷ are as defined in claim 1 R⁸ and X together form an optionally acetalised oxo group, with an amine having formula 4,

HZ-(A²-Z)_n-CHR¹³R¹⁴ 4 wherein

R¹³, R¹⁴, A² and n are as defined in claim 1 and Z represents an imino group, optionally in the presence of a reducing agent.

16. A detergent and/or emulsifying composition containing a surface-active compound according to any one of claims 1-10.