FR2772031A1 - SALT OF ALKYL AMINO DEOXY GLYCONIC ACIDS, AMINO ACIDS, AMINE SALTS AND THE CORRESPONDING LACTONES, METHOD FOR PREPARATION AND USES - Google Patents

Abstract

The invention concerns compounds of formula (I) in which R1 represents a C7-C24 linear or branched, saturated or unsaturated alkyl radical; R2 represents a hydrogen atom or a methyl radical; M represents an alkaline or alkaline-earth metal, or a group of formula (a) in which R3, R4, R5 and R6, identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical; m is a whole number between 1 and 5. The invention also concerns amino acids, amine salts and lactones of formula (II) derived from compounds of said formula (I). Said compounds are used as surfactants in particular for hygienic and cosmetic purposes.

Description

DESCRIPTION
The present invention relates to glyconic alkyl amino deoxy acid salts and their derivatives such as amino acids, amine salts and corresponding lactones. It also relates to a process for the preparation of these compounds and their uses, especially as surface-active agents.

It is known that the grafting of substituents such as alkyl or acyl radicals on carbohydrates leads to compounds having surfactant properties which are often specific and which, in addition, are biodegradable. This is particularly the case of N-alkyl and N-acylamino sugars which, having a good safety vis-à-vis the skin, are widely used in the field of detergency and cosmetics (see Kellenberg H., Tens, Det, vol 25, pp. 8-13, 1988, and Koch,
Starch, vol. 45 (1), pp. 2-7, 1993).

 Surfactants based on neutral sugars having primary or secondary amine residues are known.

 N-alkyl aldonamides, especially N-alkyl lactobionamides and N-alkyl maltobionamides, obtained by opening the corresponding aldonolactone with a primary or secondary amine (see EP-A-550 106, EP-A550 278 and EP-A-550 281).

Bolaform surfactants of the bis-lactobionamide and bis-gluconamide type have also been described. These compounds are obtained respectively by lactobionic acid condensation reaction and a C6-C12 fatty α-diamine, and by opening of gluconolactone by said diamine (see Garelli-Calvet R. et al.,
Synthetic Communications, vol. 23 (1), pp. 35-44, 1993).

 In WO-A-92/06984 and WO-A-92/08687, N-alkyl polyhydroxy amides, in particular N-alkyl glucamides obtained by reductive amination of glucose with an amine, and acylation in the presence of an amine are described. fatty acid ester.

 In WO-A-95/19953 and WO-A-95/19954, polyamides obtained by reductive amination of glucose with a polyamine and amidation by reaction with a chloride or a fatty acid ester are provided.

 Biocompatible surfactants of the lactobionamide or maltobionamide type resulting from the condensation of lactonolactone or maltonolactone with an amino acid or a peptide are known (see Pucci B. et al., Bioorg Med Lett, vol.

3 (6), pp. 1003-1006, 1994 and WO-A-94/03468).

 It has also been proposed N-alkyl amino-1-deoxy alditols obtained by reductive amination of neutral sugars with a fatty amine. For example, mention may be made of lactylamines (see FR-A-2,661,413) and N-alkylamino-1-deoxy isomaltulitols (see Guderjahn L. et al., Tenside Surf, Det., Vol 31 (3), pp. 146-150, 1994).

 N-alkyl N-acetylosylamines (see EP-A-0 515 283) and N-alkyl N-acylamino-1-deoxy alditols are also known (see André-Barres C. et al., New J.

Chem. flight. 19, pp. 345-347, 1995).

 Finally, surfactants derived from uronic acid (see EP-A-0 550 276, EP-A-0 537 820 and EP-A-532 370) and uronamides have been proposed (see US 5412 118).

 It has now been found that compounds resulting from the reductive amination of uronic acids or uronolactones by fatty amines possess surface-active properties.

dans laquelle:
R1 représente un radical alkyle, linéaire ou ramifié, saturé ou insaturé, en
C7-C24
R2 représente un atome d'hydrogène ou un radical méthyle,
M représente un métal alcalin ou alcalino-terreux, de préférence Na ou K, ou un groupe de formule

dans laquelle R3, R4, R5 et R6, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C1-C6 ou un radical hydroxyalkyle en C1-C6,
m est un nombre entier de 1 à 5.The invention relates first of all to the compounds of the formula

in which:
R1 represents an alkyl radical, linear or branched, saturated or unsaturated, in
C7-C24
R2 represents a hydrogen atom or a methyl radical,
M represents an alkali or alkaline earth metal, preferably Na or K, or a group of formula

in which R3, R4, R5 and R6, which may be identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical,
m is an integer from 1 to 5.

The compounds of formula (I) represent the basic form of s-amino acids of formula

Like all the compounds which contain an acid group (donor of H +) and a basic group (acceptor of H +), the s-amino acids of formula (Ia) give rise to different equilibria as a function of the pH of the solution which contains them. These balances can be summarized as follows:

The compound of formula (Ia) is predominantly in the form of the dipolar ion (zwitterion) resulting from the internal transfer of H + between the acid and basic functions. The equilibrium between the s-amino acid of formula (Ia) and its acid form of formula (I) or its basic form of formula (Ib) are dependent on the
pH, which is not the case of the equilibrium between the s-amino acid of formula (Ia) and zwitterion.

From the compound of formula (I), it is possible by controlled addition of an acid
obtain the compounds of formula (Ia), a mixture of the compounds of formulas (I) and
(la), a mixture of compounds of formulas (Ia) and (Ib), a mixture of the compounds of
formulas (Ia), (Ib) and (II), or compounds of formula (II).

The compounds of formulas (Ia), (Ib) and (II) which derive from
Formula (I) are also part of the present invention.

dans laquelle R1, R2 et m ont la signification donnée précédemment.The compounds (Ia) correspond to the formula:

in which R1, R2 and m have the meaning given above.

dans laquelle
R1, R2 et m ont la signification donnée précédemment,
X- représente l'an ion d'un acide.
Les composés (II) répondent à la formule:

dans laquelle
R1, R2 et X- ont la signification donnée précédemment,
n est un nombre entier compris entre 1 et m-2,
m est un nombre entier compris entre 3 et 5.The compounds (Ib) correspond to the formula:

in which
R1, R2 and m have the meaning given above,
X- represents the anion of an acid.
The compounds (II) correspond to the formula:

in which
R1, R2 and X- have the meaning given above,
n is an integer between 1 and m-2,
m is an integer from 3 to 5.

 By way of example of X- ions, mention may be made of halide anions, for example chloride, hydrogen sulfate anion, sulphate anion, alkyl sulphate anions, for example anion decyl sulphate or lauryl sulphate, anions sulphonates, for example benzyl sulphonate anion, paratoluene sulphonate or camphorsulphonate, alkylsulphonate anions, for example methanesulphonate anion, decyl sulphonate or lauryl sulphonate, sulphosuccinate anion, alkylsulphosuccinates anions, for example sulphosuccinate anion. Examples are: lecyl or lauryl, perhalohydrate anions, for example perchlorate anion, hydrogenphosphite anion, and mixtures of these anions. Preferably, X- is the chloride or methane sulphonate anion.

 The preferred compounds according to the invention are the compounds of formulas (I), (Ia), (Ib) and (II) in which m is equal to 4.

 By way of examples of the preferred compounds of formula (I), mention may be made of 6-alkylamino 6-deoxygluconates, 6-alkylamino 6-deoxy galactonates, 6-alkylamino 6-deoxymononates, 6- alkylamino 6-deoxygluconates, 6-alkylamino 6-deoxy idonates, and more preferably 6-alkylamino 6-deoxy L-gulonates, 6-alkylamino 6-deoxy L-galactonates, 6-alkylamino 6 deoxy dinonates, 6-alkyl amino 6-deoxy D-gluconates and 6-alkyl amino 6-deoxy L-idonates.

By way of examples of the preferred compounds of formula (II), mention may be made of 6-alkylammonium 6-deoxygulonolactones, 6-alkylammonium 6-leoxy-mannonolactones, 6-alkylammonium-6-deoxygluconolactones and 6-alkylammoniums. 6-deoxy idonolactones, more preferably 6-alkyl ammonium 6-deoxy L-gulonolactones, 6-alkyl ammonium 6-deoxy D-mannonolactones, 6-alkyl ammonium 6-deoxy
D-gluconolactones or 6-alkylammonium 6-deoxy L-idonolactones, and most preferably, 6-alkylammonium 6-deoxy L-gulofurano 1 (4) -lactones and 6-alkylammonium 6-deoxy D-mannofurano 1 (4) -lactones.

- et une amine de formule

dans lesquelles R1, R2, M et m ont la signification donnée précédemment,
pour former le composé de formule (I), et
b) à faire réagir le produit de l'étape précédente avec un acide pour former le composé de formule (II). Another subject of the invention relates to the preparation of the compounds of formula (I) and (II), where appropriate (Ia) and (Ib), according to a process which consists of
a) reacting, in the presence of a reducing agent,
a salt of glycuronic acid of formula

and an amine of formula

in which R1, R2, M and m have the meaning given above,
to form the compound of formula (I), and
b) reacting the product of the preceding step with an acid to form the compound of formula (II).

Retape a): Preparation of compounds of formula (I)
In the implementation of step a) of the process according to the invention, the preferred glycuronic acid salts of formula (III) are carboxylic acid salts derived from hexose (m = 4) such as guluronates. , galacturonates, mannuronates, glucuronates and iduronates, and more preferably L-guluronates, Dgalacturonates, D-mannuronates, D-glucuronates and L-iduronates. Advantageously, the compounds of formula (III) are in the form of sodium or potassium salts.

 The reduction carried out in step a) can be carried out according to two variants.

 In the first variant, the reduction is carried out catalytically. It is generally carried out in the presence of a metal catalyst in an alcoholic medium in an autoclave under a hydrogen pressure which can vary from atmospheric pressure up to 6000 kPa, preferably 4000 to 5000 kPa, and at a temperature of 20 ". C at 100 C, preferably 40 to 50 ° C.

 As an example of a metal catalyst, mention may be made of palladium on carbon and Raney nickel.

 In the second, preferred variant, the reduction is carried out chemically by means of a metal hydride in a solvent.

 By way of example of metal hydride, mention may be made of lithium aluminum hydride, sodium or lithium cyanoborohydride, sodium borohydride and diborane. Preferably, sodium cyanoborohydride or sodium borohydride is used.

 The reaction solvent is generally chosen from water, alcohols such as methanol, ethanol, isopropanol or butanol, ether oxides such as tetrahydrofuran, dioxane and ethylene dimethyl ether. glycol or diethylene glycol, halogenated hydrocarbons such as dichloromethane, dichloroethane or chloroform, amides such as N-methylformamide or N, N-dimethylformamide, and mixtures of these compounds. Water, alkcols and hydroalcoholic mixtures are preferred.

 The reaction may be conducted in the presence of a weak organic acid such as propanoic acid.

 The conditions for carrying out the reduction step may vary substantially depending on the preferred hydride used.

When the hydride is sodium cyanoborohydride, the step is advantageously carried out by mixing the glucuronic acid salt of formula (III),
The amine of formula (IV), the hydride, the weak acid and the solvent.

 The molar ratio of amine to glycuronic acid salt is between 0.8 and 5, preferably 1 and 2.

 The molar ratio of hydride to glycuronic acid salt is between 0.8 and 1.5, preferably 1 and 1.2.

 The molar ratio of the acid to the glycuronic acid salt is between 0.4 and 6, preferably 0.5 and 3.

 The weight ratio of the solvent to the glycuronic acid salt is between 1 and 50, preferably 5 and 25. The preferred solvent is a methanol-water mixture.

 The reaction is carried out at a temperature between 0 and 1200C, preferably 20 and 100 "C, for a period ranging from 1 to 48 hours, preferably 5 to 24 hours, with a stirring whose speed can vary from 100 to 1000 rpm, preferably 300 to 700 rpm.

 At the end of the reaction, the stirred medium is cooled to a temperature ranging from 0 to 50 ° C, preferably 10 to 40 ° C. After removal of the supernatant fluid phase, the viscous precipitate formed is taken up in a solvent as defined above, preferably an alcohol such as methanol or ethanol.

 The weight ratio of the solvent to the glycuronic acid salt is between 1 and 100, preferably 10 and 30.

 The salt of the alkyl amino deoxy glyconic acid of formula (I), crystallized, is filtered, for example on sintered glass n ° 3 or 4, and, if appropriate, is washed with a solvent and dried.

 The washing solvent is generally chosen from the solvents of the reaction as defined above, ketones such as dimethyl ketone, diethyl ketone or diisopropyl ketone esters such as ethyl acetate, propyl acetate or propylene glycol. butyl acetate, and mixtures of these solvents. Preferably, the solvent is an alcohol such as methanol or ethanol, an ether ether such as diethyl ether oxide, a ketone such as dimethyl ketone, or a mixture of these solvents.

 When the hydride is sodium borohydride, the reaction is advantageously carried out in two stages: in the first step, the corresponding imine is formed, optionally isolated, and in the second step it is reacted with the hydride.

 The preparation of the imine is carried out by reacting the glycuronic acid salt of formula (III) and the amine of formula (IV) in the presence of the solvent.

 The molar ratio of amine to glycuronic acid salt is between 0.8 and 5, preferably 1 and 2.

 The weight ratio of the solvent to the glycuronic acid salt is between 1 and 50, preferably 5 and 20. The preferred solvent is an isopropanol-water mixture.

 The formation of the imine is carried out at a temperature between 0 and 60 ° C, preferably 20 and 40 ° C, for a period of time ranging from 1 to 48 hours, preferably 12 to 36 hours, with stirring The speed can vary from 100 to 1000 rpm, preferably 300 to 700 rpm. It is followed by additional heating in the range of 50 to 100 ° C, preferably 60 to 80 ° C, for 15 minutes to 2 hours, preferably 30 minutes to 1 hour.

Although the imine can be used as it is in the second reaction step with the hydride, however, it is preferred to purify it. The purification can be carried out by proceeding as follows:
1 - removal of the solvent under reduced pressure (0.013-101.325 kPa, preferably 0.013-4 kPa),
2 - recovery of the residue in a solvent, with stirring,
3 - filtration of the precipitate obtained, for example on sintered glass n ° 3 or 4,
4 - washing the precipitate with a solvent,
Solubilization of the precipitate in the reaction solvent.

 The solvent of steps 2 and 4 is chosen from the washing solvents described above. Preferably, an alcohol such as methanol, ethanol or isopropanol is used in step 2, and an alcohol such as ethanol or an ether ether such as diethyl ether oxide in step 4.

 The preferred solvent of step 5 is water or an alcohol.

 The weight ratio of the solvent of step 2 or 5 to the starting glycuronic acid salt varies from 1 to 50, preferably 10 to 30.

The reaction of imine with sodium borohydride is carried out as follows:
The solution of imine, crude or preference purified, is brought to a temperature between -10 ° C and +20 ° C, preferably 0 and +10 ° C, stirred, and brought into contact with a quantity of hydride such that the molar ratio of hydride to imine is between 0.8 and 1.5, preferably 1 and 1.2. After 15 minutes to 2 hours, preferably 15 minutes to 1 hour, the reaction medium is brought to a temperature of the order of 20 to 60 ° C, preferably 20 to 40 ° C, for 1 to 24 hours, preferably 1 to 12 hours.

 At the end of the reaction, the solvent is removed, for example by lyophilization or by concentration under reduced pressure (0.013-101.325 kPa). The residue obtained is taken up in methanol and coevaporated at atmospheric pressure. After a renewal of the operation from 2 to 10 times, the salt of the alkylamino deoxy glyconic acid of formula (I) is recovered.

 The latter, whether it is obtained according to one or other of the aforementioned variants, can undergo an ultimate purification step, for example by washing with a washing solvent as defined above or by chromatography on a silica column.

Retape b) Preparation of the compounds of formula (II)
In step b) of the process according to the invention, any organic or inorganic acid known to those skilled in the art can be used. By way of example, mention may be made of hydrohalic acids such as hydrochloric acid, sulfuric acid, alkylsulphuric acids such as decylsulphuric acid or laurylsulphuric acid, and sulphonic acids such as benzenesulphonic acid. Para-toluenesulfonic acid or camphorsulfonic acid, alkylsulfonic acids such as methanesulfonic acid, decylsulfonic acid or laurylsulfonic acid, sulfosuccinic acid or an alkylsulphosuccinate, for example decyl or lauryl sulphosuccinate, perhalohydric acids such as perchloric acid or hypophosphorous acid, and mixtures of these compounds.

 Any compound or mixture of compounds capable of forming an acid may also be used. By way of illustration, mention may be made of the mixture of an organic acid chloride and an alcohol, for example acetyl-methanol chloride, which generates hydrochloric acid.

 Preferably, hydrochloric acid, methanesulfonic acid or acetyl chloride-methanol mixture is used.

 The molar ratio of the acid to the compound of formula (I) is generally between 1 and 30, and preferably 5 and 20.

 The compound of formula (I) obtained in step a) is used in solution in a reaction solvent as defined above, the solvent preferably being anhydrous. An alcohol is preferably used and advantageously methanol or ethanol.

 The weight ratio of the solvent to the compound of formula (I) is generally between 1 and 200, and preferably 1 and 100.

 The reaction is generally carried out at a temperature of between 0 and 1500 ° C., preferably between 0 ° and 100 ° C., for a period which can vary from 1 to 48 hours, preferably 1 to 12 hours, with stirring of the order of 100 to 100 ° C. 800 rpm, preferably 200 to 600 rpm.

 At the end of step b), the reaction solvent is removed, for example by concentration under a pressure of the order of 0.013 to 101.325 kPa and preferably 0.013 and 4 kPa.

 The residue obtained can be taken up in a washing solvent as defined above. The preferred solvent is an ether ether such as diethyl ether, a ketone such as dimethylketone, or a mixture of these solvents.

 During the solubilization, the weight ratio of the solvent to the residue containing the compound of formula (II) ranges from 1 to 50, preferably 5 to 30.

 Preferably, the residue is stirred for 30 minutes to 24 hours, more preferably 30 minutes to 12 hours, and at a temperature of from -20 ° C to +100 ° C, more preferably 0 to + 60 ° C. This stirring step is intended to pre-crystallize the reaction product.

 The crystalline compound of formula (II) is generally separated from the reaction medium by filtration, for example on sintered glass n ° 3 or 4, and washed with a washing solvent as defined above.This compound may optionally be purified, for example by column chromatography, and dried.

dans laquelle m a la signification générale ou préférée donnée précédemment,
ou de la glycosiduronolactone correspondante, lorsqu'elle existe,
- et d'une base
- dans un solvant.Preparation of compounds of formula (III)
The glycuronic acid salts of formula (III) required for the synthesis of the compounds according to the invention may be prepared by reaction
a glycosiduronic acid of formula

in which my general or preferred meaning given previously,
or the corresponding glycosiduronolactone, when it exists,
- and a base
in a solvent.

dans laquelle R3, R4, R5 et R6 ont la signification donnée précédemment. As an illustration of the base, mention may be made of compounds of formula M (OH) x in which M represents an alkali metal or alkaline earth metal and x is the valence of the metal, and the ammonium hydroxides of formula

in which R3, R4, R5 and R6 have the meaning given above.

 Any compound or mixture of compounds capable of generating such a base, for example an alkali or alkaline earth metal carbonate or hydrogencarbonate, may also be used.

 Preferably, sodium or potassium hydroxide is used.

 The solvent is generally chosen from the reaction solvents as defined above. Water, alcohols or hydroalcoholic mixtures are preferred.

 The molar ratio of the base to the glycosiduronic acid or to the starting lactone is between 0.8 and 2, preferably 1 and 1.2.

 The weight ratio of the solvent to the glycosiduronic acid or to the starting lactone can vary from 1 to 20.

 The reaction is generally carried out at 0 to 100 ° C, preferably 10 to 30 ° C, and for a period of time ranging from 30 minutes to 10 hours, preferably 1 to 5 hours.

 At the end of the reaction, the glucuronic acid salt of formula (III) is recovered by filtration, optionally after the addition of a solvent chosen from the reaction solvents when it does not precipitate spontaneously in the reaction medium. .

 The salt obtained may, if appropriate, be washed with a solvent selected from washing solvents as defined above, and dried.

 The preferred washing solvent is an alcohol such as methanol, a ketone such as dimethyl ketone, or an ether ether such as diethyl ether.

 The compounds according to the invention of formulas (I), (Ia), (Ib) and (II), alone or as a mixture, exhibit surface-active properties, in particular solubilizing, emulsifying, foaming and dispersing properties.

 In addition, these compounds have the property of not attacking the skin and the mucous membranes, which makes them particularly suitable for the preparation of hygiene compositions such as, for example, shampoos, hair or cosmetic compositions such as ointments, creams and beauty milks.

 Because of their foaming power and their ability to soften the skin, the compounds according to the invention can also be used in compositions for the bath (bubble bath) or for the shower (shower gel) as well as in soaps, in particular Syndet type ("Synthetic Detergent" in English).

 The following examples illustrate the invention without limiting it.

In these examples, the following methods of analysis are used:
Nuclear Magnetic Resonance (NMR)
The chemical shifts are expressed in ppm and the coupling constants (J) in Hz.

 1 H NMR: carried out at 300 MHz in DMSO-d6 at 50-80 C.

 13 C NMR: carried out at 50 or 75 MHz in DMSO-d6 at 50 ° C. (Examples 13 and 14), 60 ° C. (Example 11) or 80 ° C. (Example 12).

Mass spectrometry (MS)
The mass spectra are obtained after FAB + ionization. The values are expressed in units of atomic mass (z / e).

Infrared Spectrography (IR)
The measurements are carried out on a KBr 1% pellet. The values are expressed in cm-1.

Thin-layer chromotography
The RF is measured by thin layer chromatography of silica (film thickness: 200 μm, particle size: 5-10 μm, Kieselgel 60F254 sold by Merck). The migration solvent of the compounds of Examples 2 to 10 is a mixture of acetic acid / butanol / water 1/1/1 (v / v / v) and the migration spots are revealed by spraying sulfuric acid at 50% by volume in Ibau and heating (120 C, 2 minutes)
The migration solvent of the compounds of Examples 11 to 14 is a 7/3 (v / v) chloroform / methanol mixture and the migration spots are evidenced by spraying a 2% ninhydrin solution in acetone and heating.

Fusion point
It is not corrected and is expressed in degrees Celsius.

EXAMPLE 1 Preparation of sodium D-glucuronate
To 17.62 g (0.1 mole) of Dglucuronoyl-3-lactone in suspension in 30 ml of water is added, with stirring at 0 ° C., 4 g (0.1 mole) of sodium hydroxide. solution in 20 g of water and, after 3 hours, 300 g of methanol. Stirring is maintained for 4 hours. The sodium D-glucuronate which is filtered is formed (sintered glass n 4), washed successively with methanol (100 g), acetone (50 g) and diethyl ether (50 g), and dried ( 40 C, 0.2 kPa). 16.9 g of sodium dglucuronate (a yield of 78.3%) are recovered having the following characteristics:
Melting point: 1 37 C
IR: 3604-3155 (γOH); 1603 (γ C = O)
EXAMPLES 2 TO 10 Preparation of sodium 6-alkylamino 6-deoxy L-gulonate
A - PROCESS USING SODIUM CYANOBOROHYDRIDE
To 21.61 g (0.1 mole) of sodium D-glucuronate according to Example 1, 100 g of methanol, 160 g of water and 7.4 g (0.1 mole) of propanoic acid are added. (ref.

 40.297 to 7; ALDRICH) and 6.3 g (0.1 mole) of sodium cyanoborohydride (Ref 15, 615-9, ALDRICH) previously solubilized in 150 g of methanol.

With stirring (500 rpm) at 20 ° C., 0.2 mole of the following fatty amine is cast in 45 minutes:
23.4 g of heptylamine (Ref 12,680-2, ALDRICH): Example 2
25.8 g of octylamine (Ref 0.580-2, ALDRICH): Example 3
28.6 g of nonylamine (Ref N3, 100-1, ALDRICH): Example 4
31.4 g of decylamine (Ref D240-4 and Aldrich): Example 5
34.2 g of undecylamine (Ref U140-0, ALDRICH): Example 6
- 33.8 g of undecenylamine prepared according to VIG OP et al. (Indian Journal of Chemistry, 21B, pp. 784-786, 1982): Example 7
37.7 g of dodecylamine (Ref 32,516-3 and Aldrich): Example 8
42.7 g of tetradecylamine (Ref T1, 020-0, ALDRICH): Example 9
48.3 g of hexadecylamine (Ref H740-8, ALDRICH): Example 10
The reaction medium is heated at 80 ° C. for 9 hours. After cooling to 25 ° C., the lower viscous phase is solubilized in 400 g of methanol and stirred for 3 hours at 500 rpm. The crystallized alkyl amino gluconate obtained is filtered (sintered glass n 4) and washed successively with methanol (100 g), diethyl ether (100 g) and acetone (50 g), and dried (40 ° C. 0.2 kPa).

The characteristics of the 6-alkylamino 6-deoxy L-sodium gluconates obtained are presented below:
# Example 2
Yield: 41.2%
RF. 0.42
IR 3200-3600 (vN-H and vO-H); 2927-2857 (v CH) 1600 (vC = 0 and 8 NH); 1467-1417 (CH)
# Example 3
Yield: 51.4%
RF. 0.42
IR 3200-3600 (v NH and OH); 2958, 2927, 2857 (v C
H); 1603 (v C = O and 8 NH); 1467, 1421, 1379 (6 CH)
MS:
anionic form: C14H28NO6Na; molecular weight: 329.36
zwitterionic form: C14H29NO6: molecular weight: 307.38; 308.4 (M + H) +; 330.4 (M + Na) +; 352.4, (M-H + 2Na) +
# Example 4
Yield: 58%
RF. 0.42
IR # 3200-3600 (v NH and OH); 2958, 2927, 2855 (v C
H); 1605 (v C = O and 8 NH); 1468, 1422, 1379 (# CH)
# Example 5
Yield: 65%
RF. 0.43
IR 320
RF: 0.44
IR # 3200-3600 (v NH and OH); 2973-2936 (v CH); 1599 (v C = O and 8 NH); 1465, 1430, 1417 (6 CH)
MS:
anionic form: C20H40No6Na; molecular mass: 413.53
zwitterionic form: C20H41NO6; molecular weight: 391.54; 392.6 (M + H) +
Example 10
Yield: 77%
RF. 0.44
IR 3200-3600 (v NH and OH); 2957, 2917, 2851 (v C
H); 1597 (v C = O and 6 NH); 1469, 1413 (# CH)
SM
anionic form: C22H44NO6Na; molecular weight: 441.58
zwitterionic form: C22H45NO6; molecular mass: 419.60420.6 (M + H) +; 442.5 (M + Na) +; 466.8 (M + H + 2Na) +
B - PROCESS USING SODIUM BOROHYDRIDE
32.4 g (0.15 mole) of sodium dglucuronate prepared according to Example 1 are added, 250 g of water and 0.2 mole of the fatty amine as defined in the aforementioned method A, said amine being solubilized beforehand in 250 g of isopropanol.

 The reaction mixture is stirred (500 rpm) for 24 hours at 25 ° C. and then for 30 minutes at 65 ° C. and concentrated in a rotary evaporator (2.5 kPa, 60 ° C.) The residue obtained is then added to 500 g of dichloromethane. The ethanol is stirred (700 rpm, 30 minutes, 25 ° C.), filtered (sintered glass No. 4) and washed with 100 g of absolute ethanol and 200 g of diethyl ether.

The residue obtained is solubilized in 500 g of water maintained at 5 ° C. and 6.8 g (0.18 mol) of sodium borohydride (Ref 19.807-20;
ALDRICH) dissolved in 150 g of water. The reaction medium is stirred (500 rpm) for 30 minutes at 5 ° C. and 6 hours at 25 ° C. and then concentrated in a rotary evaporator (2.5 kPa, 60 ° C.) in the absence of any additional solvent for a first time. cycle and in the presence of methanol during the next 5 cycles.

 The thus obtained 6-alkyl-6-deoxy-sodium gluconate is washed successively with methanol (150 g), diethyl ether (100 g) and acetone (100 g).

EXAMPLES 11 TO 14: Preparation of 6-alkyl ammonium 6-deoxy L-gluconolactones
To 17.3 g (0.22 mol) of acetyl chloride, 170 g of anhydrous methanol are added, with stirring, at 0 ° C., over a period of 30 minutes. After 30 minutes, 0.03 mol of sodium 6-alkyl-6-deoxy-L-gulonate, dissolved in 300 ml of anhydrous methanol, is rapidly run in at 25 ° C., ie:
10.3 g of sodium 6-nonylamino 6-deoxy L-gulonate prepared according to Example 4: Example 11
11.14 g of sodium 6-undecyl amino 6-deoxy L-gulonate prepared according to Example 6: Example 12
11.08 g of sodium 6-undecenyl amino 6-deoxy L-gulonate prepared according to Example 7: Example 13
11.56 g of sodium 6-dodecylamino 6-deoxy L-gulonate prepared according to Example 8: Example 14

 After refluxing for 6 hours, the reaction medium is concentrated in a rotary evaporator (2.5 kPa, 25 ° C.). The viscous liquid obtained is solubilized in 200 g of diethyl ether and stirred (500 rpm) for 30 minutes at 25 ° C. and 12 hours at 5 ° C. The reaction medium is filtered (sintered glass n 4) washed with 50 ° C. g of diethyl ether and dried (2 kPa, 25 ° C.).

# Exemple 11
Rendement: 49 %
RF . 0,52
IR 3479, 3348, 3155 (v N-H et v O-H); 2927, 2855 (v C
H); 1776 (v C = O et # N-H); 1470 (# C-H)
RMN1H 8 4,42 (H2); 4,31 (H3) ; 4,27 (H4) ; 4,16 (H5) ; 3,17 (H6); 2,94 (H6'); 2,9 (CH2-N); 1,69 (CH2-CH2N); 1,27 ((CH2)p); 0,87 (CH3) 9,00-5,81-5,73 (OH) ; J2,3 = 4,5 ; J3,4 = 2,8 ; J4,5 = 7,9 ; J5,6 = 2K7 ; J5,6' 9 9 ; J6,6' = 12,9
RMN 13C## 175,4 (C1); 70,4 (C2) ; 68,8 (C3) ; 80,5 (C4); 65,4 (C5) ; 47,8 (C6) ; 47,1 (C1') ; 13,7 (CH3) ; 31,1-30,4-28,6-28,4-25,9-24,9-21,9(C2' à
C8').The characteristics of the 6-alkylammonium 6-deoxy L-gulonolactones obtained are presented below:

# Example 11
Yield: 49%
RF. 0.52
IR 3479, 3348, 3155 (v NH and OH); 2927, 2855 (v C
H); 1776 (v C = O and # NH); 1470 (# CH)
1 H NMR 4.42 (H2); 4.31 (H3); 4.27 (H4); 4.16 (H5); 3.17 (H6); 2.94 (H, 6 '); 2.9 (CH2-N); 1.69 (CH2-CH2N); 1.27 ((CH 2) p); 0.87 (CH 3) 9.00-5.81-5.73 (OH); J2,3 = 4.5; J, 3.4 = 2.8; J4.5 = 7.9; J5.6 = 2K7; J5.6 9 9; J6.6 '= 12.9
13C NMR ## 175.4 (C1); 70.4 (C2); 68.8 (C3); 80.5 (C4); 65.4 (C5); 47.8 (C6); 47.1 (C1 '); 13.7 (CH3); 31,1-30,4-28,6-28,4-25,9-24,9-21,9 (C2 'to
C8 ').

# Example 12
Yield: 67%
RF. 0.60
IR 3158 (v NH and OH); 2923, 2863 (v CH); 1775 (v C = O and # NH); 1470 (# CH)
1 H NMR # 4.43 (H2); 4.33 (H3); 4.27 (H4 + H5); 3.17 (H6); 2.94 (H, 6 '); 2.90 (CH2-N); 1.69 (CH2-CH2N); 1.28 ((CH 2) p); 0.87 (CH2); 9.038.06-5.54 (OH); J2,3 = 4.6; J4.5 = 7.8; NMR13C. # 175.8 (C1); 70.3 (C2); 68.6 (C3); 80.8 (C4); 65.4 (C5); 47.5 (C6); 47.1 (C1 '); 13.8 (CH3); 31.3-30.6-28.9-28.6-28.5-28.3-25.8-25.121.9 (C2 'to C10').

# Example 13 '
Yield: 72%
RF. 0.53
IR # 3600-3200 (v NH and OH); 2926, 2854 (v CH); 1776 (v C = O and # NH); 1642 (v C = C); 1470 (# CH)
1 H NMR # 4.43 (H2 + H3); 4.25 (H4); 4.14 (H5); 3.17 (H, 6 '); 2.96 (H, 6 '); 2.89 (CH 2 -N); 1.67 (CH2-CH2N); 1.28 ((CH 2) p); 5.79 (H10 '); 4.95 (H11 '); 9.03-5.63 (OH); J2,3 = 4.3; J4.5 = 8; J5.6 '= 8.16; J6.6 '= 12.9.

 13 C NMR 175.5 (C1); 70.4 (C2); 68.8 (C3); 80.5 (C4); 65.4 (C5); 47.8 (C6); 47.1 (C1 '); 33, 0-28.6-28.4-28.3-28.2-25.9-25.0 (C2 'to C9'); 138.7 (C10 '); 114.5 (C11 ').

# Example 14
Yield: 71%
RF. 0.61
IR 3600-3200 (v NH and OH); 2920, 2852 (v CH); 1785 (v C = O and # NH); 1471 (6 CH)
1H NMR 4.44 (H2); 4.26 (H3); 4.23 (H4); 4.12 (H5); 3.18 (H6); 2.92 (H, 6 '); 2.89 (CH 2 -N); 1.66 (CH2-CH2N); 1.26 ((CH 2) p); 0.87 (CH3); 8.86-5.88-5.81 (OH);
13 C NMR # 176.3 (C1); 71.0 (C2); 69.3 (C3); 81.3 (C4); 65.9 (C5); 47.6 (C6); 47.2 (C1 '); 14.5 (CH3); 22.6-25.7-26.6-29.1 -29.2-29.3-29.5-29.6-31.8 (C2 'to C11');
EXAMPLES 15 TO 17: Preparation of sodium 6-alkylamino 6-leoxy L-galactones
Sodium D-galacturonate is prepared from D-galacturonic acid (Ref 85-728-9, ALDRICH) under the conditions described in Example 1.

Under the conditions of process A of Examples 2 to 10, 21.61 g (0.1 mole) of the sodium D-galacturonate thus obtained and 0.2 mole of amine are reacted as follows:
-25.8 g of octylamine (Ref.0,508-2; ALDRICH): Example 15
31.4 g of decylamine (Ref D2404, ALDRICH): Example 16
37.7 g of dodecylamine (Ref 32,516-3, Aldrich): Example 17
The characteristics of the sodium 6-alkylamino 6-deoxy L-galactonates obtained are presented in the following table:

<tb><SEP> EXAMPLE <SEP> YIELD <SEP> (%) <SEP> IR <SEP> (cm-1)
<tb> 15 <SEP> 43 <SEP> 3326, <SEQ> 3166, <SEP> 2920, <SEQ> 2852, <SEP> 2340, <SEP> 2172, <SEP> 1614, <SEP> 1470,
<tb><SEP> 1418, <SEQ> 1378, <SEQ> 1332, <SEQ> 1246, <SEQ> 1104, <SEQ> 1036, <SEQ> 840, <SEP> 722,684 <SEP>
<tb> 16 <SEP> 84 <SEP> 3403, <SEP> 2923, <SEQ> 2853, <SEP> 1615, <SEQ> 1468, <SEQ> 1417, <SEP> 1082, <SEP> 971
<tb><SEP> 17 <SEP> 91 <SEP> 3397, <SEP> 2923, <SEQ> 2853, <SEP> 1599, <SEP> 1468,1417, <SEP> 1082, <SEP> 968,
<tb><SEP> 722
<Tb>

Claims (15)

 m is an integer from 1 to 5.  in which R3, R4, Rivet R6, identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical,

 M represents an alkali or alkaline earth metal, or a group of formula  R2 represents a hydrogen atom or a methyl radical, C7-C24  R1 represents an alkyl radical, linear or branched, saturated or unsaturated, in  in which

 1. Compounds of formula  2. Compounds of formula

 in which R1, R2 and mount the meaning given above.  3. Compounds of formula

 in which  R1, R2 and m have the meaning given above,  X- represents the anion of an acid.  4. Compounds of formula

 in which  R1, R2 and X- have the meaning given above,  n is an integer between 1 and m-2,  m is an integer from 3 to 5.  5. Compounds according to one of claims I to 4, characterized in that m is equal to 4.  6. Compounds according to claim 1 or 5, characterized in that M represents a sodium or potassium atom.  7. Compounds according to one of claims 3 to 5, characterized in that X is the chloride anion or methane sulfonate.  8. Process for the preparation of the compounds according to claim 4 or 7, which consists  a) reacting, in the presence of a reducing agent,  a salt of glycuronic acid of formula

 and an amine of formula

 in which R1, R2, M and m have the meaning given above,  to form the compound of formula (I), and  b) reacting the product of the preceding step with an acid to form the compound of formula (II).  9. The method of claim 8, characterized in that step a) is carried out catalytically in the presence of hydrogen and a metal catalyst.  10. Process according to claim 9, characterized in that the catalyst is palladium on carbon or Raney nickel.  11. The method of claim 8, characterized in that step a) is carried out chemically by means of a metal hydride.  12. The method of claim 11, characterized in that the hydride is sodium borohydride or sodium cyanoborohydride.  13. Method according to one of claims 8 to 12, characterized in that the glucuronic acid salt is selected from guluronic acid, galacturonic acid, mannuronic acid, glucuronic acid and iduronic acid.  14. Use of the compounds according to one of claims 1 to 7 as surfactants.  15. Hygiene composition containing at least one compound according to one of claims 1 to 7.