WO1999056722A1

WO1999056722A1 - Alpha carboxylic acid (aha) derivatives

Info

Publication number: WO1999056722A1
Application number: PCT/FR1999/001044
Authority: WO
Inventors: Serge Petit
Original assignee: Ceca S.A.
Priority date: 1998-05-07
Filing date: 1999-05-03
Publication date: 1999-11-11
Also published as: FR2778405B1; FR2778405A1; EP1033968A1; AU3527099A

Abstract

The invention concerns the use of alpha hydroxy carboxylic acid (AHA) derivatives as washing and/or conditioning agents for the skin and the hair. The invention also concerns novel AHA derivatives, compositions, in particular cosmetic and hair compositions containing them, and methods for preparing them.

Description

ALPHA CARBOXYLIC ACID (AHA) DERIVATIVES

The invention relates to the use of derivatives of alpha hydroxy carboxylic acids as washing agents for human skin and / or for conditioning hair.

More specifically, the derivatives of alpha hydroxy carboxylic acids belong to the group consisting of N- (dialkylamino) alkyl alpha carboxamides and their derivatives obtained by acylation and / or quaternization reaction (s), by acylation reaction and betainization and by acylation and N-oxidation reaction. The subject of the invention is also derivatives of specific alpha hydroxy carboxylic acids, cosmetic or hair compositions containing said derivatives, and their methods of preparation.

Cationic, zwitterionic and N-oxide type surfactants are widely used in the field of cosmetics. Cationic surfactants are in particular sought after for their conditioning function of the skin and the hair. Thus, when applied to damp hair, the interactions between the hair are reduced and the disentangling during drying and combing is facilitated. These surfactants also make it possible to improve the texture and the softness of the hair, to prevent the formation of forks, to contribute to a better condition of the hair, to prevent damage due to external aggressions, and to reduce the effects of static electricity by neutralization of apparent anionic charges. This latter property can moreover be improved by the addition of a derivative of the N-oxide type.

Zwitterionic compounds are minimally irritating to the skin and mucous membranes, and reduce the irritation caused by anionic surfactants. They are also soluble in water and have good compatibility with other surfactants. In addition, like cationic compounds, they contribute to preserving the microbiological quality of the formulations by their bacteriostatic activity. Finally, being electrically neutral, they exhibit good insensitivity to variations in the ionic strength of the medium and their behavior is weakly dependent on temperature.

Compounds of the N-oxide type make it possible, like the zwitterionic compounds, to adjust the viscosity of the formulations. They can also be foam boosters, but their emollient properties are the most sought after.

We also know that alpha hydroxy carboxylic acids (AHA) have a beneficial action on the skin. Human skin is made up of the outer epidermis and the underlying dermis located above the fatty tissue.

The epidermis has four distinct layers: the stratum corneum, the stratum granulosum, the stratum spinosum and the basal stratum. The stratum corneum is the outer layer of the epidermis. It is composed of keratinocytes in the terminal differentiation phase (comeocytes) and lipids which fill the intercellular spaces.

On contact with AHAs, the cohesion of comeocytes in the stratum corneum is reduced, which has the effect of causing desquamation. The skin is thus smooth, soft and shiny.

The desired effect however requires the application of a composition with a relatively high AHA content (of the order of 2 to 15%), which causes unpleasant irritations and tingling in certain subjects.

There are already known uses of AHA derivatives. WO-A-95/05154 describes skin and hair washing compositions which contain a derivative of alpha hydroxy di- or tricarboxylic acid in which either the hydroxyl group is esterified by an acyl residue, or at least a carboxylate function is esterified by an alkyl group.

EP-A-0 327 379 describes humectants which can be used in cosmetic compositions which are amide derivatives obtained by reacting a carboxylic acid or an ester of this acid with an N, N-disubstituted alkyldiamine.

Seymour L. et al. (J.Am.Chem.Soc, vol. 81, pp.3083-3088, (1959)) describe the use of aminoalkylamides derived from glycolic, lactic and methyllactic acids as depressants of the central nervous system.

These compounds are prepared by reaction of the ethyl ester of the carboxylic acid with a dialkylamine, followed by a quaternization step.

In JP-A-06 234 714, amides of carboxylic acids, in particular glycolic acid, are used as activators for bleaching tissues with peroxides.

In US-A-5 456 846, it is proposed to soften the laundry by means of quaternary ammonium salts of amides or glyceric acid esters.

Finally, in JP-A-06 228 070, the use of carboxybetaines is described as humectants in cosmetic compositions. Carboxybetaines are derivatives of carboxylic and hydroxycarboxylic acids.

It goes without saying that there is a great need to seek to use products having surfactant properties and a low irritant power for cosmetic and hair applications. The present invention therefore proposes to use N- (dialkylamino) alkyl alpha hydroxy carboxamides and their derivatives as washing and / or conditioning agents for the skin and hair.

The invention relates firstly to the use, as agents for washing the human skin and / or conditioning the hair, of compounds belonging to the group consisting of:

(i) the compounds of formula:

H NH - (CH ₂ ) _F N m (I)

R-.

(ii) the compounds of formula

E_3 ^R 1 (5D

H NH - (CH ₂ 2) / p NR, nX (Il A) m

R.

(iii) the compounds of formula

(he b)

(iv) the compounds of formula

.-R. aD

R — C- NH - (CH ₂ ) _p - NR nX (III)

II O R. m

(v) the compounds of formula

R - c- NH - (CH ₂ ) _p - NR ₂ (IV)

II o (CH ₂ ) _r C0 ₂ m

(vi) the compounds of formula

R- (V)

formulas in which

Z represents the di- or polyvalent residue of an alpha hydroxy carboxylic acid,

R represents an aliphatic chain, linear or branched, saturated or unsaturated, in C1-C21,

R- | , R2 and R3, identical or different, represent an alkyl radical in C- | - C4,

X represents a halogen atom or a group of formula -SO3-O-R3, R3 having the meaning given above, m is an integer which can vary from 1 to 10, n, p and r, identical or different, are whole numbers that can vary from 1 to 4.

The preferred compounds which are suitable for use according to the invention are the compounds of formulas (I), (II A), (II B), (III), (IV) and (V) in which Z is a residue d alpha hydroxy carboxylic acid chosen from the residues of formula:

- o-c — c -

I II R ₅ O

in which: R4 and R5, identical or different, represent a hydrogen atom, a C-1-C4 alkyl radical, or a radical of formula:

in which Rg represents a hydrogen atom or -O-, and t is equal to 0, 1, 2 or

3.

By way of example of residue Z, there may be mentioned the residues of glycolic, lactic, 2-methyllactic, 2-hydroxybutanoic, 2-hydroxypentanoic, 2-hydroxy-hexanoic, malic, citramalic, tartaric, tartronic and citric acids. Even more advantageously, the compounds which can be used according to the invention are the compounds of formulas (I), (II A), (II B), (III), (IV) and (V) in which:

Z represents an alpha hydroxy carboxylic acid residue chosen from the residues of glycolic, lactic, 2-methyllactic, malic, tartaric, tartronic and citric acids, R represents a linear or branched, saturated or unsaturated, C -C2i aliphatic chain,

Rj, R2 and R3, identical or different, represent a methyl, ethyl or propyl radical, R * ι and R2 being preferably identical, X represents Cl, Br, I or a group of formula -SO3-O-R3, R3 having the meaning given above, m is an integer which can vary from 1 to 8, n is an integer which can vary from 1 to 3, p is equal to 3, r is equal to 1.

As examples of preferred acyl radicals of formula R-CO-, there may be mentioned the octanoyl, decanoyl, 10-undecenoyl, lauroyl, palmitoyl, stearoyl, oleoyl, eicosanoyl and behenoyl radicals.

A subject of the invention is also the preferred compounds of formula (III) and the compounds of formula (IV) and (V) described above.

Another subject of the invention relates to the compositions intended to be applied to the skin and the hair which comprise said compounds. These compositions are characterized in that they comprise:

- (A) at least one compound of formula (III), (IV) or (V), and - (B) a vehicle compatible with a topical application.

The content of compound (A) in the composition according to the invention can vary from 0.01 to 50% by weight of the composition, preferably 0.1 to 30% by weight and better still from 1 to 25% by weight.

The vehicle (B) is generally chosen from cosmetically acceptable vehicles well known to those skilled in the art. The vehicle facilitates the distribution of the compounds (A) to the surface of the skin or of the hair and also makes it possible to adjust the concentration of active material to the desired level.

The vehicle is generally water or an organic solvent compatible with topical application. By way of example, mention may be made of acetone, isopropyl alcohol, triglycerides of C -C 24 fatty acids, glycol ethers, esters of polyalkylene glycol and C 2 -C 4 acids, and volatile silicones.

The compositions according to the invention may also contain:

- one or more other surfactants well known to those skilled in the art, for example anionic, cationic, amphoteric or nonionic surfactants. The amount of these surfactants can reach 49.99% by weight of the composition, preferably 20 to 49.90% by weight,

- additives capable of modifying the physical or chemical characteristics of the composition. Examples of such additives that may be mentioned: fatty substances such as natural or synthetic oils, thickeners and gelling agents, active materials such as hydrating agents, antioxidants, preservatives, perfumes, and dyes.

Depending on the nature of the vehicle and any additives, the compositions of the invention may have a solid, semi-solid or liquid appearance.

The solid compositions can be in the form of a stick, a cleaning bar, an impregnated pad or a hydrating mask.

The semi-solid compositions can be a milk obtained by dispersing a fatty phase in an aqueous phase or vice versa, or a suspension or an emulsion of soft consistency such as a cream, ointment or gel.

The liquid compositions can be a foaming or non-foaming lotion.

Mention may be made, as examples of cosmetic compositions, of foam baths, shower gels and mild liquid soaps. These compositions are also capable of having the properties of smoothing the skin, of giving it softness, shine, radiance and of contributing to its good health.

By way of example of hair compositions, mention may be made of shampoos, for example mild and for frequent use, conditioners which have in particular the property of conditioning the hair, lotions and emulsions intended to repair damaged hair.

The preparation of the compounds of formula (I), (II A), (II B), (III), (IV) and (V) is summarized in FIG. 1.

The processes which lead to their obtaining will be better understood in the light of the description which follows. These methods constitute another object of the invention.

A - Preparation of the compounds of formula (I)

The preparation process consists in reacting:

- an alkyl ester of alpha hydroxy carboxylic acid of formula:

H m: p- R. (VI) in which Z, m and n have the meaning given above and R7 represents a C-1-C4 alkyl radical;

- and an amine of formula:

R,

H ₂ N - (CH ₂ ) _p - N (VII)

R.

in which R- | , R2 and p have the meaning given above to form the compound of formula:

R ₁

H NH - (CH ₂ ) _ N m (I)

R-

The molar ratio of the amine of formula (VII) to the alkyl ester of alpha hydroxy carboxylic acid of formula (VI) is generally between 0.8n and 3n, preferably 1n and 2n, n being the total number of ester functions.

The reaction can be carried out in the presence of a solvent such as dimethylformamide or an alcohol containing up to 6 carbon atoms, for example methanol, ethanol, propanol or isopropanol. However, it is preferred to carry out the reaction in the absence of solvent.

The process is generally carried out at a temperature between 10 and 180 ° C, preferably 20 and 150 ° C, at atmospheric pressure and for a period which can vary from 1 hour to 5 days, preferably 3 to 24 hours.

At the end of the reaction, the reaction medium which contains the compound of formula (I) is recovered. The reaction medium can optionally undergo a concentration step, for example at a temperature which can vary from 50 to 200 ° C., and under a vacuum of between 0.007 and 101, 325 kPa.

The compound of formula (I) can be used as such or undergo an additional purification step, for example by distillation or recrystallization.

B - Preparation of the compounds of formula (II A)

The preparation process consists in reacting:

- the compound of formula:

in which Z, Rj, R2, m, n and p have the meaning given above, - and a quaternizing agent of formula: R ₃ X (VI II)

in which R3 and X have the meaning given above, to form the compound of formula:

The molar ratio of the compound of formula (I) to the quaternizing agent of formula (VIII) is generally between 1: 0, 80n and 1: 3n, preferably 1: 0, 9n and 1: 2n, n being the total number of tertiary amine functions to be quaternized.

The reaction can be carried out in the presence of a solvent chosen from alcohols such as methanol, ethanol, propanol, isopropanol, butanol or isobutanol, ethers-oxides such as tetrahydrofuran or ethylene glycol dimethyl ether, and halogenated hydrocarbons such as dichloromethane, dichloroethane or chloroform. Alcohols such as isopropanol, halogenated hydrocarbons and ethers are preferred.

Advantageously, the solvent for the reaction is anhydrous. It is generally used in an amount of 0.1 to 30 equivalents by weight, preferably 0.1 to 20 equivalents, per 1 equivalent by weight of the compound of formula (I).

The process is generally carried out at a temperature between 10 and 80 ° C, preferably 20 to 70 ° C, for a period which can vary from 0.5 to 48 hours.

At the end of the reaction, the reaction medium containing the compound of formula (II A) can optionally be treated with water in order to hydrolyze the excess of quaternizing agent. The reaction medium can undergo a concentration step, for example under a partial pressure of between 0.013 and 101, 325 kPa, preferably 0.013 and 4 kPa. The residue obtained can then be dissolved with deionized water and lyophilized, which has the effect of improving the appearance of the resulting solid.

It is possible that at the end of the reaction, a demixing of the reaction medium is observed. It then suffices to recover the compound of formula (II A) by decantation and, if necessary, to make it undergo a washing, for example by trituration in one of the abovementioned reaction solvents. C - Preparation of the compounds of formula (II B)

The preparation process consists in reacting: - the compound of formula:

R.

H NH - (CH ₂ ) _P N (I)

L J m

R

in which Z, R-j, R2, m, n and p have the meaning given above, - and an acylating agent of formula:

R - C - R, (IX) o in which R has the meaning given above, and Rs represents a halogen atom, preferably Cl, or a diglyceryl radical whose acyl residues, identical or different, contain from 2 to 22 carbon atoms, preferably 7 to 22 carbon atoms, a group -O-CO-Rg in which Rg represents a linear or branched hydrocarbon chain, saturated or unsaturated with C-1-C21, preferably C -C2, or a -OR-io group in which R-jn _. represents a C 1 -C ₄ alkyl radical. to form the compound of formula

When the acylating agent of formula (IX) is an acid anhydride, it is preferred that it be symmetrical (R = Rg).

When the acylating agent is an ester, the residues R and RJ Q. are preferably different. This agent may be prepared in particular from cuts aci ^¬ C 12-C14, C- | 6 / C- | 8 or C | -C-2 jβ-

The molar ratio of the compound of formula (I) to the acylating agent of formula (IX) and generally between 1: 095m and 1: 10m, preferably 1: 0.95m and

1: 6m, m being the number of total alcohol functions to be acylated. When the acylating agent is an acyl halide, a molar ratio varying from 1: 0.95m to 1: 2m is preferred.

The acylation reaction can be carried out in the presence of a solvent chosen from pyridine, ethers-oxides such as tetrahydrofuran or dimethyl ether of ethylene glycol, and halogenated hydrocarbons such as dichloro- romethane, dichloroethane or chloroform. Halogenated hydrocarbons are preferred.

The abovementioned solvent is advantageously anhydrous. It is generally used in an amount of 0.1 to 30 equivalents by weight, preferably 0.1 to 20 equivalents, per 1 equivalent by weight of the compound of formula (I).

The acylation reaction can also be carried out in the presence of a carbonate or a hydrogen carbonate of an alkali or alkaline earth metal, for example potassium carbonate, sodium carbonate, potassium hydrogen carbonate and the sodium hydrogencarbonate. The molar ratio of carbonate or hydrogen carbonate to the compound of formula (I) is generally between 0.4m and 10m, preferably 0.4m and 2m, m being the total number of alcohol functions to be esterified.

When the acylating agent is an acid anhydride or an acyl halide, the reaction is carried out at a temperature between -10 ° C and + 60 ° C, preferably -5 and + 30 ° C, and at atmospheric pressure.

When the acylating agent is an ester, the reaction is carried out at a temperature between 60 and 180 ° C, preferably 70 and 160 ° C, and at a pressure between 0.013 and 101, 325 kPa, preferably 0.013 and 10 kPa.

The reaction time can vary from 1 to 120 hours, preferably 2 to 48 hours.

During the reaction, it is possible to add a phase transfer catalyst chosen from nonionic, cationic or anionic surfactants, for example amines and compounds containing ammonium or phosphonium ions, crown ethers, cryptands, aminopolyethers, phosphorylsulphoxides and esters of glycol or sorbitan.

By way of example of compounds of the ammonium type, mention may be made of hexadecyl trimethyl ammonium chloride, benzyl trimethyl ammonium chloride, trioctyl methyl ammonium chloride, tricapryl methyl ammonium chloride, tetrabutyl ammonium acid sulfate and tetrabutyl ammonium chloride or bromide. Preferably, hexadecyl trimethyl ammonium chloride, tricapryl methyl ammonium chloride and tetrabutyl ammonium chloride or bromide are used.

The content of phase transfer catalyst is generally between 0.01 n and 1n% by weight of compound of formula (I), n being the total number of alcohol functions to be esterified.

At the end of the reaction, the reaction medium containing the compound of formula (II B) can optionally undergo one or more stages of filtration and / or washing and / or removal of the solvent or excess reagent. The compound of formula (II B) can also be subjected to additional purification, for example by distillation, in particular under reduced pressure, by chromatography on a silica column or by recrystallization.

D - Preparation of the compounds of formula (III)

The compounds of formula (III) can be prepared according to two embodiments.

In the first mode, the compound of formula (MA) is subjected to an acylation reaction. More specifically, the method consists in reacting:

- the compound of formula:

_H ^R 1 aD

H NH - (CH ₂ ) _p - N - R ₂ nX (I l A) m

R,

in which Z, R-j, R2, R3, X, m, n and p have the meaning given above, - and an acylating agent of formula:

in which R and Rβ have the meaning given above.

The reaction conditions are the same as those described above for the preparation of the compounds of formula (II B). The value of the weight ratio or of the molar ratio must be understood as referring to the compound of formula (II A).

The reaction can be carried out in the absence of any basic compound, that is to say a base, a solvent or a base precursor. In this case, an exchange of contrion is likely to occur partially or totally. Thus, starting from an acid chloride, the compound of formula (III) obtained will be in the form of methane sulfate, chloride or a mixture of these two forms.

In the second embodiment, the compound of formula (II B) is subjected to a quaternization reaction.

More specifically, the process consists in reacting: - the compound of formula:

in which Z, R, R-j, R2, m, n and p have the meaning given above, - and a quaternizing agent of formula:

R ₃ x (VIII)

in which R3 and X have the meaning given above.

The reaction conditions are the same as those described above for the preparation of the compounds of formula (II A). The value of the weight ratio or of the molar ratio indicated should be understood as referring to the compound of formula (II B).

At the end of one or other of the above embodiments, the compound of formula is recovered:

R— (III)

E - Preparation of the compounds of formula (IV)

The preparation process consists in reacting - the compound of formula:

in which Z, R, R <| , R2, m, n and p have the meaning given above, - and a compound of formula:

Y - (CH ₂ ) _r - CO-OR 11 (X)

in which R11 represents a hydrogen atom or an alkali metal, Y represents a halogen atom, preferably Cl or Br, and r has the meaning given above,

- In a solvent chosen from water, C- | -Cg alcohols and hydroalcoholic mixtures, to form betaine of formula: R.

R- C NH - (CH ₂ 2) / p NR. (IV) aD

II o (CH ₂ ) _r C0 ₂ m

The molar ratio of the compound of formula (II B) to the compound of formula (X) is generally between 1: 0, 95n and 1: 1 On preferably 1: 1n and 1: 2n, n being the number of tertiary amine functions to betainize.

The amount of solvent is generally chosen so as to obtain a final concentration of betaine of between 1 and 50%, preferably 5 and 40% of the total weight of the solution or of the dispersion obtained at the end of the reaction.

The process is generally carried out at a temperature between 20 and 110 ° C, preferably 60 and 100 ° C. The pH of the reaction medium is generally maintained between 6 and 11, preferably 6.5 and 8, for example by means of an alkali hydroxide such as sodium or potassium hydroxide, preferably in aqueous solution whose concentration is between 30 and 50% by weight. The reaction can be carried out in the presence of a salt resulting from the combination of a halide ion and an alkaline ion, for example Kl, and / or a phase transfer catalyst, for example tetrabutyl bromide ammonium.

The reaction time can vary from 1 to 24 hours, preferably 2 and 12 hours.

The betaine of formula (IV) thus formed can be used as it is or undergo one or more subsequent treatments, for example a concentration step.

(removal of the solvent under reduced pressure, lyophilization, etc.) or a purification step (filtration of the salts formed or added to facilitate precipitation, chromatography on a silica column, etc.).

F - Preparation of the compounds of formula (V) The preparation process consists in reacting:

- the compound of formula:

R — c - NH - (CH ₂ ) N (I l B)

I I R. O m

in which Z, R, R- | , R2, m, n and p have the meaning given above,

- and an oxidant,

in a solvent chosen from water, C- | -Cg alcohols and hydroalcoholic mixtures, - optionally in the presence of a complexing agent to form the compound of formula:

By way of example of the oxidant, mention may be made of hydrogen peroxide and the compounds generating hydrogen peroxide. Hydrogen peroxide is preferred. Hydrogen peroxide is generally used in the form of an aqueous solution having a concentration by weight of between 5 and 70%, preferably 8 and 60%.

The molar ratio of the compound of formula (II B) to the oxidant is generally between 1: 0, 95n and 1: 1, 25n, preferably 1: 1 n and 1: 1, 15n, n being the total number of amino functions to N-oxidize.

The preferred solvent for the reaction is water. The amount of solvent used is generally chosen so as to obtain a final concentration of compound of formula (V) of between 1 and 50%, preferably 5 and 35% of the total weight of the solution or of the dispersion obtained at the end of the reaction. .

The complexing agent is generally chosen from derivatives of the carboxy methyl amino type, such as nitrilotriacetic acid (NTA) and ethylenediamine tetraacetic acid (EDTA), alpha hydroxy carboxylic acids such as those defined above by Z , more particularly glycolic acid, lactic acid, malic acid, tartaric acid and citric acid, and dicarboxylic acids such as succinic acid and maleic acid. EDTA and alpha hydroxy carboxylic acids are preferred.

The weight ratio of the complexing agent to the compound of formula (II B) is generally between 10 ^_ 2n: 1 and 10 ^_ 5n: 1, preferably 10 ^_ 3n: 1 and 10 ^_ 4n: 1. The process is generally carried out at a temperature between 20 and 100 ° C, preferably 50 and 90 ° C. The pH of the reaction medium is maintained between 6 and 10, preferably 6 and 9, for example by means of an alkali hydroxide such as sodium or potassium hydroxide, preferably in aqueous solution whose concentration is between 30 and 50% by weight.

The reaction is carried out at atmospheric pressure. It is optionally possible to operate under an inert atmosphere, for example under argon or nitrogen. The reaction time can vary from 0.5 to 24 hours, preferably 1 to 12 hours.

The compound of formula (V) thus formed can be used as it is or undergo an additional step of concentration of the solvent, for example by evaporation under reduced pressure or by lyophilization, or a purification step, for example by chromatography on a silica column. .

The compounds of formula (I), (II A), (II B), (III), (IV) and (V) thus obtained have washing and / or conditioning properties for the skin and the hair. The following examples illustrate the invention. In these examples, the following methods of analysis are used.

Thin-layer chromotography

The Rp is measured by thin layer chromatography on silica (Alugram; Ref. 818133; MACHEREY-NAGEL). The migration solvent is methanol and the migration spots are revealed by spraying a 0.5% ninhydrin solution in n-butanol and heating at 120 ° C for 2 minutes.

Nuclear magnetic resonance (NMR)

Spectra are made using a BRUCKER AC device

200 multi-cores, at 200.13 MHz ( ¹ H) and 50.32 MHz ( ¹³ C) in deuterated chloroform for the compounds of formula (I), (MB) and (III), in deuterated dimethyl sulfoxide for the compounds of formula (MA) and in deuterated methanol for the compounds of formula (IV) and (V).

The internal reference is tetramethylsilane. The chemical shifts are expressed in ppm. Infrared spectrography (IR)

The spectra are carried out by means of a PERKIN ELMER 1720X apparatus with Fourier transform, on film between two NaCI pellets for the liquid compounds or in dispersion in KBr (2% tablet) for the solid compounds.

The values are expressed in number of waves per centimeter. Melting temperature

It is measured on a BIICHI device, and expressed in ° C (not corrected).

Water surface tension (y)

The surface tension of the water is measured by tensiometry according to ISO standard 304 modified in that the dimensions of the rectangular plate are 25 mm × 5 mm × 0.1 mm. The surface tension γ is expressed in mN / m. Foaming power

The foaming power is measured by bubbling nitrogen at a constant flow rate (100 ml / min.) Through a frit (water permeability: 60 ml / h at atmospheric pressure) placed at the base of a graduated cylinder (320 mm x 70 mm) and thermostatically controlled containing 100 ml of aqueous surfactant solution. The foaming power is defined by the minimum concentration of surfactant which makes it possible to produce a volume of foam of 400 ml.

EXAMPLES 1 to 5: Preparation of the compounds of formula (I) (p = 3, R-j = R2 = CH3)

1 mole of the following hydroxy hydroxy acid alkyl ester is introduced into a 1 liter reactor:

- ethyl glycolate (104.11 g; Ref. 36,484-3; ALDRICH): example 1

- ethyl lactate (118.13 g; Ref. E3.410-2; ALDRICH): example 2 - dimethyl malate (162.14 g; Ref. 37,431-8; ALDRICH): example 3

- diethyl tartrate (206.19 g; Ref. 21, 396-9; ALDRICH): example 4

- triethyl citrate (276.29 g; Ref. 10.929-0; ALDRICH): example 5

- and 3-dimethyl aminopropylamine (Ref. D14,500; ALDRICH):

- 1.5 moles (188.75 ml; 153.27 g): examples 1 and 2 - 3 moles (377.51 ml; 306.54 g): examples 3 and 4

- 4.5 moles (566.27 ml; 459.81 g): example 5 After 24 hours (examples 1, 2 and 4) or 72 hours (stirring at examples 3 and 5), the residue is recovered. compound of formula (I) by concentration under reduced pressure (2.4 kPa / 30 ° C, then 2.4 kPa / 60 ° C and 7 Pa / 60 ° C). The compounds according to Examples 1, 2 and 4 are purified by distillation

(examples 1 and 2) and by recrystallization (example 4).

The characteristics of this compound are given below: • Example 1: N- (3-dimethyl aminopropyl) glycolamide

- Yield: 91.7% - Melting point: 54-55 ° C (Hexane)

- Distillation: 155-160 ° C under 7 Pa

- IR: 3293, 2947, 1652, 1539, 1464, 1263, 1159, 1079, 1040, 822

- NMR

6 2 1 3 4 5 CH3

HO - CH ₂ - C - NH - CH ₂ - CH ₂ - CH ₂ - N i) ^CH 3 H: 7.46 (NH); 6.05 (OH); 3.95 (H2); 3.28 (H3); 2.29 (H5); 2.16 (H6);

1.64 (H4) ³ C: 172.703 (C1); 61.951 (C2); 57.172 (C5); 45.159 (C6); 37.338 (C3); 26.895 (C4).

• Example 2: N- (3-dimethyl aminopropyl) lactamide

- Yield: 91.9% - Distillation: 144-148 ° C at 7 Pa

- IR: 3299, 2942, 2861, 2776, 1656, 1533, 1463, 1366, 1314, 1263, 1157, 1126, 1075, 1041, 972, 843

- NMR

7 2 1 4 5 6 ^CH 3

HO-CH - C-NH - CH - CH - CH, - N i l! CH

3 CH ₃ O ^OM 3 ¹ H: 7.50 (NH); 5.13 (OH); 4.13 (H2); 3.28 (H4); 2.33 (H6); 2.20 (H7);

1.67 (H5); 1.35 (H3)

¹³ c: 175.395 (C1); 67.774 (C2); 57.101 (C6); 45.036 (C7); 37.379 (C4); 26.720 (C5); 21.095 (C3).

• Example 3: N- (3-dimethyl aminopropyl) malamide - Yield: 81.4%

- IR: 3304, 3084, 2944, 2862, 2819, 2779, 2361, 1708, 1651, 1538, 1464, 1374, 1309, 1264, 1183, 1101, 1040, 975, 839.

- NMR

8 2 1 5 6 7, ^CH 3

HO-CH-

₃ CH ₂

H: 7.68 (NH); 4.31 (H2); 3.27 (H5); 2.44-2.72 (H3); 2.26-2.35 (H7);

2.18 (H8); 1.63 (H6) ³ C: 173.019 (C1); 171.759 (C4); 69.306 (C2); 57.657 (C7); 45.384 (C8); 39.295 (C3); 38.009 (C5); 26.924 (C6).

• Example 4: N- (3-dimethyl aminopropyl) tartramide - Yield: 71.3%

- Melting point: 119-120 ° C (ethyl acetate)

- NMR 8 CH-

HO - CH - C - NH - CH ₂ ^~ CH ₂ ^~ CH ₂ N

CH-

O CH-

HO - CH - C - NH - CH ₂ - CH ₂ - CH ₂ - N

² f] 5 6 7 _{CH 3}

8H: 7.70 (NH); 6.6-6.5 (OH); 4.41 (H2); 3.24 (H5); 2.26 (H7); 2.12 (H8) ¹ 3c: 173.029 (C1); 72.208 (C2); 57.342 (C7); 45.247 (C8); 37.835 (C5); 26.912 (C6).

• Example 5: N- (3-dimethyl aminopropyl) citramide

- Efficiency: 95%

- IR: 3301, 3102, 2945, 2764, 1653, 1539, 1461, 1373, 1262, 1186, 1100, 1041,975,908,842.

- NMR

8

H: 7.80 (NH-C9); 7.56 (NH-C5); 3.17 (H5 + H9); 2.65-2.42 (H2); 2.24 (H7 + H11); 2.13-2.12 (H8 + H12); 1.56 (H6 + MO).

¹³ C: 173.855 (C4); 170.574 (C1); 75.383 (C3); 57.852 (C7); 57.768 (C11); 45.522 (C12); 45.415 (C8); 42.795 (C2); 38.470 (C5 + C9); 26.718 (C10); 26.606 (C6).

EXAMPLES 6 to 9: Preparation of the compounds of formula (HA) (p = 3, R <[= R ₂ = R3 = CH ₃ , X = CH3OSO3)

0.1 mol of the alpha hydroxy carboxamide of formula (I) is introduced into a 500 ml reactor

- example 1 (16.3 g) example 6 - example 2 (17.5 g) example 7 - example 3 (30.3 g) example 8 - example 4 (31, 9 g) example 9 200 ml of anhydrous dichloromethane and, drop by drop, with stirring of dimethyl sulphate (Ref. D18,630-9; ALDRICH):

- 0.11 mole (10.40 ml; 13.87 g): examples 6 and 7

- 0.22 mole (20.81 ml; 27.75 g): examples 8 and 9 After two hours of stirring at 25 ° C, the biphasic reaction medium obtained is decanted and the oily residue in the minority (upper phase in the examples 6, 7 and 8; lower phase in Example 9) is washed with chloroform (by trituration) then concentrated in vacuo (2.4 kPa / 50 ° C; Examples 6 and 7) or taken up with 200 ml of methanol, concentrated under vacuum (2.4 kPa / 30 ° C), taken up again with 200 ml of dichloromethane, decanted and concentrated again under vacuum (2.4 kPa / 50 ° C - examples 8 and 9).

The compound of formula (MA) which has the following characteristics is recovered:

• Example 6: methyl sulfate of N- (3-trimethyl ammonium propyl) glycolamide

- Efficiency: 85%

- IR: 3359, 2949, 1669, 1541, 1482, 1345, 1226, 1059, 1009, 913, 755, 667, 610

H: 7.90 (NH); 3.81 (H2); 3.41 (H7); 3.28 (H5); 3.25 (H3); 3.05 (H6);

1.86 (H4)

• Example 7: N- (3-trimethyl ammonium propyl) lactamide methyl sulfate

- Efficiency: 80% - IR: 3360, 2950, 1652, 1539, 1483, 1370, 1250, 1222, 1125, 1060,

- NMR

2 1 4 5 6 Ξf ³ 8 <_ty

HO -CH -C- NH - CH ₂ - CH ₂ ^~ CH ₂ - N -CH ₃ CH ₃ OS0 ₃

I II I 7

3 CH ₃ O CH ₃

¹ H: 7.86 (NH); 5.43 (OH); 3.98 (H2); 3.43 (H8); 3.29 (H6); 3.16 (H4); 3.07 (H7); 1.87 (H5); 1, 23 (H3) • Example 8: N- (3-trimethyl ammonium propyl) malamide methyl sulfate

- Efficiency: 75%

- IR: 3323, 3039, 2950, 2836, 1651, 1538, 1485, 1368, 1224, 1059, 1009, 971, 915, 755, 611, 580.

- NMR 8

H

¹ H: 7.98; 7.95 (NH); 5.69 (OH); 4.23 (H2); 3.41 (H9); 3.26 (H7); 3.14 (H5); 3.05 (H8); 2.49; 2.37 (H3); 1.85 (H6). ³ C: 173.589 (C1); 170.143 (C4); 68.557 (C2); 63.340 (C7); 52.989 (C9); 52.144 (C8); 40.713 (C3); 35.397; 35.266 (C5); 22.829 (C6).

• Example 9: N- (3-trimethyl ammonium propyl) tartramide methyl sulfate

- Efficiency: 60%

- IR: 3347, 3041, 2950, 1651, 1539, 1487, 1256, 1134; 1060, 1008, 914,821,760. - NMR

2 1 5 6 7 [5) ^CH 3 9 φ

HO - CH - C - NH - CH ₂ - CH ₂ - CH ₂ - N - CH ₃ CH ₃ OS 0 ₃

0 ^X CH ₃

1 5 6 7 E) ^CH 3 9 ( ^* * £) HO - CH - C NH - CH ₂ - CH ₂ - CH ₂ - N - CH ₃ CH ₃ OS0 ₃

? He \

O 8 CH ₃ H: 7.95 (NH); 5.63 (OH); 4.26 (C2); 3.405; 3,400 (C9); 3.23 (C7); 3.16 (C5); 3.04 (C8); 1.87 (C6).

¹ 3c: 172.248 (C1); 72.785 (C2); 63.456 (C7); 52.891 (C9); 52.213 (C8); 35.273 (C5); 22.896 (C6).

EXAMPLES 10 to 12: Preparation of the compounds of formula (IIB) (p = 3, i = R2 = CH ₃ )

A - Process using acyl chloride a- preparation of O-dodecanoyl N- (3-dimethyl aminopropyl) glycolamide (example 10)

0.1 mole of the alpha hydroxy carboxamide according to Example 1 (16.3 g), 350 ml of chloroform, 0.13 mole (17.96 g) of potassium carbonate are introduced into a 1 liter reactor. (Ref. 20,961-9; ALDRICH) and, drop by drop, 0.12 mole of dodecanoyl chloride (26.26 g; Ref. 15,693-0; ALDRICH).

After 8 hours of stirring at 25 ° C., the reaction medium is filtered through sintered glass No. 3 and the filtrate is washed successively with an aqueous solution of sodium hydrogen carbonate at 10% by mass (80 ml x 3) and with water (80 ml x 3). The organic phase is recovered, dried (anhydrous magnesium sulfate), and concentrated (2.4 kPa / 40 ° C) and purified by distillation.

O-dodecanoyl N- (3-dimethyl aminopropyl) glycolamide having the following characteristics is recovered:

- Efficiency: 63%

- Distillation: 190-200 ° C under 7 Pa

- IR: 3302, 3084, 2931, 2856, 2817, 2767, 1749, 1669, 1540, 1465, 1378, 1262, 1157, 1115, 1041, 722

- NMR

6 2 1 3 4 5 CH ₃ O CH ₂ —C— NH —CH ₂ —CH ₂ —CH ₂ —N

O ^CH 3

2 Z 4 5 6 1 8 9 10 '1 l' 12 '

C CH ₂ CH ₂ CHo CH CH CHo CHo CHo CHo CHo HH: 7.45 (NH); 4.49 (H2); 3.35 (H3); 2.36 (H5); 2.31 (H2 '); 2.19 (H6); 1.63 (H4); 1.60 (H3 ¹ ); 1.32 (H4 '); 1.21 (H5'-H11 '); 0.83 (H12 ') ³ C: 172.286 (C1'); 167.070 (C1); 62.871 (C2); 58.876 (C5); 45.450 (C6); 39.296 (C3); 33.974 (C2 '); 31, 893 (C10 ');29.577; 29.428 (C6'-C8 ');29.308; 29.246 (C5 '+ C9'); 29.147 (C4 '); 25.668 (C4); 24.788 (C3 '); 22.665 (C11 '); 14.088 (C12 '). b- preparation of O-alkanoyl N- (3-dimethyl aminopropyl) lactamide (examples 11 and 12).

The procedure is carried out under the conditions of Example 10 above modified in that the alpha hydroxy carboxamide according to Example 2 (17.5 g), undecenoyl chloride (24.33 g; Ref. 16,166-7; ALDRICH; example 11) or oleoyl chloride (36.11 g; Ref. 36,785-0; ALDRICH; example 12) and stirred for

16 hours at 30 ° C.

The O-alkanoyl N- (3-dimethyl aminopropyl) lactamide recovered has the following characteristics:

• Example 11: O-undecenoyl N- (3-dimethyl aminopropyl) lactamide

- Yield: 71.6%

- Distillation: 200-210 ° C at 134 Pa

- IR: 3306, 2980, 2930, 2859, 2818, 2767, 1743, 1664, 1536, 1460, 1372, 1242, 1160, 1100, 1041, 995, 910, 862.

- NMR 7

2 1 5 6 CH-

O-CH-C NH - CH- CH- CH- N

3CH ₃ O CH-

5 6 10 '11

C CHo CH CH ^* CH- CH CH- CH- CHo CH - CHo

OH: 7.63 (NH); 5.81 (MO '); 5.20 (H2); 4.94 (H11 '); 3.36 (H4); 2.40 (H6); 2.36 (H2 '); 2.24 (H7); 2.04 (H9 '); 1.67 (H5); 1.64 (H3 '); 1.45 (H3); 1.30 (H4'-H8 ^* ). ³ C: 172.274 (C1 '); 170.413 (C1); 139.115 (C10 '); 114.191 (C11 '); 70.357 (C2); 58.842 (C6); 45.461 (C7); 39.306 (C4); 34.306; 33.769 (C9 '+ C2');29.274;29.199;29.104;29.034; 28.877 (C4'-C8 '); 25.754 (C5); 24.838 (C3 '); 18.062 (C3).

• Example 12: O-oleoyl N- (3-dimethyl aminopropyl) lactamide

- Efficiency: 83%

- Distillation: 200-220X under 7 Pa

- IR: 3309, 2927, 2854, 1744, 1666, 1536, 1461, 1374, 1260, 1100, 1041,863,722

- NMR

7

2 1 4 CH- CH C NH CH- CHo CH- N

CH-

3 CH ₃ O 2 2 9

C CH CHv ^" CH2 Crin ^" CH ^• 2- CHo CHo CH

CH π CHπ 'v C_ »πHo ₂ - v C_-πHo- CH ₂ - CH

1δ '17'

1133 '' 12 '11' 10 '

¹ H: 7.62 (NH); 5.35 (H9 '+ H10'); 5.20 (H2); 3.37 (H4); 2.41 (H6): 2.37 (H2 '); 2.25 (H7); 2.10 (H8 '+ H11'); 1.68 (H5); 1.65 (H3 '); 1.46 (H3); 1.31-1.27 (H4'-H7 \ H12'-H17 '); 0.88 (H18 "). ³ C: 172.223 (C1 '); 170.401 (C1); 130.018; 129.675 (C9' + C10 '); 70.298 (C2); 58.643 (C6); 45.326 (C7); 34.245 ( C2 '); 39,144 (C4); 31,875 (C16');29,731;29,655;29,490;29,285;29,149; 29,066 (C4'-C7 \ C12'-C15 ');27,188; 27,124 (C8' + C11 '); 25.707 (C5); 24.803 (C3 '); 22.646 (C17'); 18.009 (C3); 14.074 (C18 '). Β - Process using a methyl ester

34.435 mmol (6 g) of the alpha hydroxy carboxamide according to the example are introduced into a 100 ml reactor fitted with a mechanical stirring device, a descending cooler and a 50 ml recovery flask. 1,169.65 mmol (33.7 g; 37.8 ml; 4.92 molar equivalents) of undecylenate methyl (ELF ATOCHEM), 34.73 mmol (4.8 g) of potassium carbonate and 0.219 mmol (88.4 mg; 0.1 ml) of tricapryl methyl ammonium chloride (Aliquat 33; Ref. 20,561-3; ALDRICH).

After partial vacuum (2.4 kPa), the reaction medium is heated to 100 ° C for 24 hours, filtered through a celite cake and concentrated in vacuo (0.9 kPa / 95 ° C).

The residue is chromatographed on a silica column (230-400 Mesh ASTM; eluent: ethyl acetate then methanol).

O-undecenoyl N- (3-dimethyl aminopropyl) lactamide is recovered with a yield of 85.3%. This compound has the same characteristics as in Example 11.

EXAMPLES 13 to 16: Preparation of the compounds of formula (III) (p = 3, Ri = R ₂ = R ₃ = CH3 and X = CH3OSO3 or CH3OSO3 / CI) A - By acylation of a compound of formula (II A)

0.01 mol (3 g) of N- (3-trimethyl ammonium propyl) lactamide methyl sulfate according to Example 7 and 0.012 mol of dodecanoyl chloride (2.62 g; 2) are introduced into a 100 ml reactor. , 78 ml; Ref. 15,693-0; ALDRICH).

After 72 hours of stirring at 25 ° C., 100 ml of chloroform are added to the reaction medium and filtered through sintered glass No. 3. The filtrate is concentrated under vacuum (2.4 kPa / 40 ° C) and the residue is purified by rapid chromatography on a silica column (230-400 Mesh ASTM; eluent: methanol).

Recovering the methyl sulfate / O-dodecanoyl chloride N- (3-trimethyl ammonium propyl) lactamide (Example 8) which is predominantly in the chloride form, the additional contrion being the methyl sulfate form. This compound has the following characteristics:

- Efficiency: 65%

- IR: 3294, 2920, 1733, 1668, 1548, 1484, 1467, 1374, 1102, 1042, 969

- NMR

CH

2 1 4 5 6 H | ³ 8 SD SD

O - CH - C - NH - CH ₂ - CH ₂ - CH ₂ N - CH ₃ CH ₃ OS0 ₃ / Cl

3 CH ₃ O CH ₃

1

C CHo CHo CHo CHo CHo CHo CHo CHo CH CH CH ₃

Q 2 ^' 3 ^' 4 ^' 5 ^' 6 '7' 8 '9' 10 '11' 12 ^' H: 8.62 (NH); 4.99 (H2); 3.53 (H6); 3.39 (H8); 3.31 (H4); 3.21 (H7); 2.34 (H2 '); 2.02 (H5); 1.56 (H3 '); 1.23 (H4'-H11 '); 1.42 (H3); 0.85 (H12 ').

13c: 173.700 (C1 '); 171.966 (C1); 70.390 (C2); 64.321 (C6); 53.174 (C7); 50.290 (C8); 36.004 (C4); 34.212 (C2 '); 31.934 (C10 ');29.671;29.571; 29.369; 29.218 (C4'-C9 '); 24.967 (C3 '); 23.043 (C5); 22,700 (C11 '); 17.914 (C3); 14.118 (012 ").

B - By quaternization of a compound of formula (IIB) a- preparation of O-dodecanoyl methyl sulfate N- (3-trimethyl ammonium propyl) glycolamide (example 14)

0.01 mol (3.41 g) of O-dodecanoyl N- (3-dimethyl ammonium propyl) glycolamide according to Example 10 is introduced into a 100 ml reactor, 50 ml of dichloromethane and, drop by drop, under stirring, 0.012 mole (1.08 ml; 1.51 g) dimethyl sulfate. After 6 hours of stirring at 30 ° C, the reaction medium is concentrated

(101, 325 kPa / 40 ° C and 67 Pa / 70 ° C).

The O-dodecanoyl N- (3-trimethyl ammonium propyl) glycolamide methyl sulfate is recovered having the following characteristics:

- Yield: 62% - IR: 3359, 2949, 1669, 1541, 1482, 1345, 1226, 1059, 1009, 913, 755,

667.610.

- NMR

6

0 -

C CHp CHp CHp CHp CHp CHp CHp CHp CHp CHo ^ - ^, '' Q '2 3 4 5 6 1 8' 9 '10' 1 1 '12'

¹ H: 7.71 (NH); 4.48 (H2); 3.90 (H7); 3.61 (H7); 3.44 (H5); 3.31 (H3); 3.11 (H6); 2.36 (H2 '); 1.99 (H4); 1.54 (H3); 1.25 (H4'-H11 '); 1.18 (H5'-H10 '); 0.80 (H12 ').

¹³ C: 173.587 (C1 '); 168.445 (C1); 62.656 (C2); 64.435 (C5); 54.456 (C7); 53.162 (C6); 35.918 (C3); 33.896 (C2 '); 31, 890 (C10 ¹ ); 29.614; 29.520; (C6'-C8 ');29.321; 29.321 (C5 '+ C9'); 29.154 (C4 '); 24.852 (C3 '); 23.033 (C4); 22.659 (C11 '); 14.090 (C12 '). b- preparation of O-undecenoyl methyl sulfate N- (3-trimethyl ammonium propyl) lactamide (example 15)

The process is carried out under the conditions of Example 14 above modified in that the O-undecenoyl N- (3-dimethyl aminopropyl) lactamide according to Example 11 is used.

The O-undecenoyl N- (3-trimethyl ammonium propyl) lactamide methyl sulfate obtained has the following characteristics:

- Efficiency: 70% - IR: 3480, 2927, 2856, 1738, 1673, 1546, 1483, 1462, 1388, 1225, 1101, 1061, 1009,912,831,756.

- NMR

7

CH

2 1 4 5 6 Ξj

Φ

CH - C- NH- -CH ₂ - -CH ₂ -CHp - N- CH- CH ₃ OS0 ₃

! II IlI CH ₃ 0 CH

C-CH- CH ₂ CH- CHo CH- CH- CH- CH- CH = CH-

O 3 '10' 11

H: 7.77 (NH); 5.80 (MO '); 4.96 (H2 + H11 '); 3.68 (H8); 3.47 (H6); 3.28 (H4); 3.18 (H7); 2.39 (H2 '); 2.03 (H5 = H9 '); 1.57 (H3 '); 1.28 (H4'-H8 '); 1.43 (H3).

¹³ C: 173.649 (C1 '); 172.165 (C1); 139.154 (C10 '); 114.207 (C11 '); 70.454 (C2); 64.430 (C6); 54.641 (C8); 53.221 (C7); 35.853 (C4); 34.10; 33.790 (C2 '+ C9');29.344;29.258;29,117;29.084; 28.910 (C4'-C8 '); 24.880 (C3 '); 23.080 (C5); 17.739 (C3). c- preparation of methyl sulfate of O-oleoyl N- (3-trimethyl ammonium propyl) lactamide (Example 16) The procedure is carried out under example 14 above modified in that the O-oleoyl N is used - (3-dimethyl aminopropyl) lactamide according to Example 12, 0.015 mole (1.36 ml; 1.89 g) of dimethyl sulphate and the reaction medium is stirred for 48 hours at 40 ° C.

The O-oleoyl N- (3-trimethyl ammonium propyl) lactamide methyl sulfate obtained has the following characteristics:

- Efficiency: 68%

- IR: 3302, 2921, 1740, 1671, 1546, 1466, 1374, 1217, 1008, 969, 853,

752.

NMR

CH-

2 1 4 5 6 [__ ⁸ Φ

O-CH-C NH-CHp - CHp - CHp - -CH CH ₃ OS0 ₃

I II ^{ll λ} I ^to

3CH ₃ O CH ₃

2 '3' 4 '5' 6 '7' 8 '

1

C CHo CH ₂ CH ₂ CHp CHp CH CH ₂ o

9 CH

Ii

10 'CH

H C CHp CHp CHp CHp CHp CHp CHp

18 '17' 16 '15' 14 '13' 12 '11' ¹ H: 7.83 (NH); 5.26 (H9 '+ H10'); 4.94 (H2); 3.67 (H8); 3.42 (H6); 3.25 (H4); 3.11 (H7); 2.35 (H2 '); 2.1-1.9 (H5 + H8 '+ H11').

EXAMPLES 17 to 21: Preparation of the compounds of formula (IV) (p = 3, r = 1 and Ri = R2 = CH ₃ )

20 mmol of O-acyl N- (3-dimethyl aminopropyl) carboxamide of formula (II B) are introduced into a 100 ml three-necked flask equipped with magnetic stirring, a pH probe and an ascending condenser. identified as follows:

- O-undecenoyl N- (3-dimethyl aminopropyl) glycolamide (6.53 g) prepared under the conditions of Example 11 modified in that the alpha hydroxy carboxamide of Example 1 is used: Example 17

- O-dodecanoyl N- (3-dimethyl aminopropyl) glycolamide (6.85 g) according to Example 10: Example 18

- O-undecenoyl N- (3-dimethyl aminopropyl) lactamide (7.10 g) according to Example 11: Example 19

- O-dodecanoyl N- (3-dimethyl aminopropyl) lactamide (7.13 g) prepared under the conditions of Example 10 modified in that the alpha hydroxy carboxamide of Example 2 is used: Example 20

- O-oleoyl N- (3-dimethyl aminopropyl) lactamide from Example 12: Example 21.

30 ml of demineralized water are then introduced and the reaction medium is heated to 75 ° C. 21 mmol (2.45 g) of sodium chloroacetate (Ref. 29,113-7; ALDRICH) are added and the medium is heated at 90 ° C for 7 hours.

The solution is lyophilized and the betaine of formula (IV) is recovered. The characteristics of betaine are presented below:

• Example 17: O-undecenoyl N- (3-dimethyl ammonium methane carboxy propylate) glycolamide

- Yield: 75% - NMR

6

CHo

2 1 3 4 5 E) ^J 7 8 ^

- CHp - C - NH - CHp - CHp - CHp - N - CHp - COp II I ^ ^/

O CH ₃

C CHp CHo CHp CHp CHp CH ₂ CH ₂ CH ₂ CH - CH ₂

O 2 3 4 5 6 1 8 '9' 10 '1 l' H: 4.96 (H11 '); 5.81 (MO '); 4.56 (H2); 3.83 (H7); 3.64 (H5); 3.34 (H3); 3.26 (H6); 2.47 (H2 '); 2.05 (H9 '); 2.00 (H4); 1.64 (H3 '); 1, 33 (H4'-H8 '). ¹³ C: 176.447 (C1 '); 172.212 (C1); 170.416 (C8); 141, 714 (C10 '); 116.336 (C11 '); 66.630 (C7); 65.206 (C2); 65.010 (C5); 53.439 (C6); 38.646 (C3); 36.462 (C9 '); 36.196 (C2 ');32.005; 31, 951; 31, 852; 31, 744; 31, 678 (C4'-C8 '); 27.417 (C3 '); 25.734 (C4).

• Example 18: O-dodecanoyl N- (3-dimethyl ammonium methane carboxy propylate) glycolamide

Yield: 74% NMR

6 CHo

SD

CH ₂ - C - NH - CH ₂ - CH ₂ - CH ₂ - N - CH ₂ - C0 ₂

CH-

C CHp CHp CHp CHp CHp CHp CH CH- CH- CH- CH ₃

2 3 4 5 6 7 8 9 10 '1 1 12

¹ H: 4.55 (H2); 3.81 (H7); 3.62 (H5); 3.34 (H3); 3.25 (H6); 2.46 (H2 '); 1.98 (H4); 1.65 (H3 '); 1.30 (H4'-H11 '); 0.91 (H12 ').

¹³ C: 174.779 (C1 '); 170.570 (C1); 168.781 (C8); 64.874 (C7); 63.527 (C2); 63.290 (C5); 51, 593 (C6); 36.958 (C3); 34.530 (C2 '); 33.019 (C10 ');30.693;30.588;30.573;30.422; 30.391 (C5'-C9 '); 30.143 (C4 '); 25.778 (C3 '); 24.070 (C4); 23.690 (C11 '); 14.435 (C12 ').

• Example 19: O-undecenoyl N- (3-dimethyl ammonium methane carboxy propylate) lactamide

Yield: 85% NMR

7

O - CH - C - NH - CH- CHp CHp

³ CHo O

1

CHo CHo CH p CπHpp CπH- v CHHp- C Hp CHp CH - CHp

2 3 4 5 5 '66' 77 8 9 10 '11 OH: 5.80 (MO'); 4.97 (H2); 4.95 (H11 '); 3.82 (H8); 3.61 (H6); 3.32 (H4); 2.42 (H2 '); 2.02 (H9 '); 1.99 (H5); 1.61 (H3 '); 1.43 (H3); 1.32 (H4'-H8 '). ³ C: 174.655 (C1 '); 173.862 (C1); 168.648 (C9); 139.940 (C10 '); 114,723 (C11 "); 71,529 (C2); 64,964 (C8); 63,309 (C6); 51,660 (C7); 36,881 (C4); 34,738 (C9 '); 34,669 (C2');30,288;30,222;30,016; 30,016 (C5'-C8 '); 29,941 (C4'); 25,720 (C3 '); 23,990 (C5); 18,050 (C3). • Example 20: O-dodecanoyl N- (3-dimethyl ammonium methane carboxy propylate) lactamide

Yield: 83% NMR

7

CH

2 1 4 5 6 Ξ | 3 ₈ g ^

O-CH - C - NH - CHp - CHp - CHp - N - CHp - COo

: | || 2 d 2

3 CH ₃ O CH ₃

C CHp CH ₂ CH ₂ CHp CHp CHp CHp CHp CHp CHp CH

Q 2 '3' 4 '5' 6 '7' 8 '9' 1θ '11' 12 '

¹ H: 4.96 (H2); 3.81 (H8); 3.60 (H6); 3.31 (H4); 3.25 (H7); 2.42 (H2 '); 1.98 (H5); 1.62 (H3 '); 1.43 (H3); 1.29 (H4'-H11 '); 0.89 (H12 ').

¹³ C: 176.483 (C1 '); 175.706 (C1); 170.395 (C9); 73.294 (C2); 66.638 (C8); 65.060 (C6); 53.405 (C7); 38.612 (C4); 36.408 (C2 '); 34.668 (C10 ');32.336;32.336;32.218;32.066; 32.024 (C5'-C9 '); 31.790 (C4 '); 27.474 (C3 '); 25.738 (C5); 25.340 (C11 '); 19.727 (C3); 16.095 (C12 ').

• Example 21: O-oleoyl N- (3-dimethyl ammonium methane carboxylate propyl) lactamide

Yield: 86% - NMR

7 CHo

2 1 4 5 6 Hj 8 9

O-CH-C-NH-CHp - CHp - CHp - N-CHp - CO,

! Il 2 2 j 2 2

3 CH ₃ O CH ₃

2 3 '4 5' 6 '7' δ '

1

C CHo CHo CH- CHo CH 'CH- CH-

//

10 CH

HoC CHp CHp CHp CHp CHp CHp CHp

18 '17' 16 '15' 14 '13' 12 '11'

¹ H: 5.33 (H9 '+ H10'); 4.97 (H2); 3.82 (H8); 3.60 (H6); 3.31 (H4); 3.25 (H7); 2.42 (H2 '); 2.02 (H5 + H8 '+ H11'); 1.62 (H3 '); 1.43 (H3); 1.33-1.29 (H4'-H7'- H12'-H17 '); 0.89 (H18'). C: 176.405 (C1 '); 175.658 (C1); 170.424 (C9); 132.522; 132.418 (C9 + C10 '); 73.287 (C2); 66.680 (C8); 65.068 (C6); 53.438 (C7); 38.634 (C4) 36.445 (C2 '); 34.703 (C16 ');32.488;32.466;32.261;32.095;31.995; 31,865 31,823; 31.688; 29.904; 29.804 (C4'-C8 ';C11'-C15')); 27.503 (C3 '); 25.745 (C5) 25.386 (C17 '); 19.802 (C3); 16.199 (C18 '). EXAMPLE 22 Preparation of a compound of formula (V) (p = 3, Rj = R2 = CH3)

20 mmoles (7.13 g) of O-dodecanoyl N- (3 mm) -dimethyl aminopropyl) lactamide (prepared under the conditions of Example 10 modified in that the alpha hydroxy carboxamide of Example 2 is used). Then 20 ml of water, 5 mg of EDTA (Ref. E2, 628-2; ALDRICH) are introduced and, with stirring, the reaction medium is heated to 70 ° C. 6.9 g of a 10% by mass aqueous solution of hydrogen peroxide (0.75 g; 22 mmol) containing 5 mg of EDTA are poured in dropwise.

After 5 hours of stirring at 70 ° C., the reaction medium is lyophilized and the O-dodecanoyl N- (3-dimethylamine N-propyl oxide) lactamide is recovered. The characteristics of this compound are presented below: - Yield: 70%

- Rp = 0.41

- NMR

7 _π CHo

2 1 4 5 6 Ξ | ^{• ***} _T)

O - CH - C - NH - CHp - CHp - CH ₉ - N 0

III ^zz I

3 CH ₃ O CH ₃

1

C CHp CHp CHp CHp CHp CHp CHp CHp CH ₂ CH ₂ CH

0 2 3 4 5 6 7 8 9 10 1 1 12 H: 4.96 (H2); 3.35-3.26 (H4 + H6); 3.16; 3.15 (H7); 2.41 (H2 '); 2.04 (H5); 1.62 (H3 '); 1.42 (H3); 1.29 (H4'-H11 '); 0.90 (H12 ').

¹³ C: 174.953 (C1 '); 174.256 (C1); 71.852 (C2); 69.652 (C6); 58.920 (C7); 37.730 (C4); 35.026 (C2 '); 33.354 (C10 ');31.016;31.016;30,890;30,751;30.699; 30.461 (C4'-C9 '); 26.126 (C3 '); 25.098 (C5); 24.019 (C11 '); 18.380 (C3); 14.740 (C12 ').

EXAMPLE 23 Lowering of the surface tension of water

Surface tension (γ) (mN / m) Example 13 27 (80 mg / l) 26 (100 mg / l)

Example 21 33 (20 mg / l)

ORAMIX-NS-10 26 (330 mg / l)

(APG; SEPPIC)

MIRANOL 33 (200 mg / l) (cocoamphodiacetate; Rhône-Poulenc)

GENAPOL ZRO 27 (100 mg / l)

(lauryl ether sulfate 3OE; HOECHST) 26 (115 mg / l)

EXAMPLE 24 Foaming Power

Minimum concentration

(mg / l)

Example 20 40

Example 21 32

ORAMIX-NS-10 40

(APG; SEPPIC)

MIRANOL 65

(cocoamphodiacetate; Rhône * -Poulenc)

Claims

1. Use as washing and / or conditioning agents for the skin and hair of compounds belonging to the group consisting of: (i) the compounds of formula:

R.

H NH - (CH ₂ ), N m (I)

R.

(ii) the compounds of formula:

(He has)

(iii) the compounds of formula

R.

R - C- Z NH— (CH ₂ ). N (Il B)

II o R-. m

(iv) the compounds of formula:

^ Φ

Rc ZH-NH - (CH ₂ ) _p -NR ₂ nX (lll)

II o R, m

(v) the compounds of formula

_R.

R - c- NH- (CH ₂ ) _p -NR ₂ aD (IV)

II o (CH ₂ ) _r -C0 ₂ m

(vi) the compounds of formula:

formulas in which Z represents the di- or polyvalent residue of an alpha hydroxy carboxylic acid,

R represents an aliphatic chain, linear or branched, saturated or unsaturated, in C-1-C2, R- | , R2 and R3, identical or different, represent a C- ^* alkyl radical |

C4.

X represents a halogen atom or a group of formula -SO3-O-R3, R3 having the meaning given above, m is an integer which can vary from 1 to 10, n, p and r, identical or different, are whole numbers which can vary from

1 to 4.

2. Use according to claim 1, in which the residue Z is chosen from the residues of formula:

R,

-o-c — c-

R ₅ O

in which :

R4 and R5, identical or different, represent a hydrogen atom, a C1-C4 alkyl radical, or a radical of formula:

in which RQ represents a hydrogen atom or -O-, and t is equal to 0, 1, 2 or 3.

3. Use according to claim 2, in which Z is chosen from the residues of glycolic, lactic, 2-methyllactic, 2-hydroxybutanoic, 2-hydroxypentanoic, 2-hydroxyhexanoic, malic, citramalic, tartaric, tartronic and citric acids.

4. Use according to claim 3, in which:

Z represents an alpha hydroxy carboxylic acid residue chosen from the residues of glycolic, lactic, 2-methyllactic, malic, tartaric, tartronic and citric acids, R represents a linear or branched, saturated or unsaturated, C6-C21 aliphatic chain,

R-1, R2 and R3, identical or different, represent a methyl, ethyl or propyl radical, R * ι and R2 being preferably identical,

X represents Cl, Br, I or a group of formula -SO3-O-R3, R3 having the meaning defined above, m is an integer which can vary from 1 to 8, n is an integer which can vary from 1 to 3, p is 3, r is 1.

5. Use according to one of claims 2 to 4, in which the radical R-CO- is chosen from the octanoyie, decanoyie, 10-undecenoyl, lauroyl, palmitoyl, stearoyl, oleoyl, eicosanoyl and behenoyl radicals.

6. Compound of formula:

in which

Z represents the di- or polyvalent residue of an alpha hydroxy carboxylic acid of formula:

in which :

R4 and R5, identical or different, represent a hydrogen atom, a C-1-C4 alkyl radical, or a radical of formula:

in which RQ represents a hydrogen atom or -O-, and t is equal to 0, 1, 2 or 3, R represents an aliphatic chain, linear or branched, saturated or unsaturated, in C1-C2,

R- | , R2 and R3, identical or different, represent a C ^< | - alkyl radical

C4.

X represents a halogen atom or a group of formula -SO3-O-R3, R3 having the meaning given above, m is an integer which can vary from 1 to 10, n and p, identical or different, are whole numbers that can vary from 1 to 4.

7. Compounds according to claim 6, in which Z represents a residue chosen from the residues of glycolic, lactic, 2-methyllactic, 2-hydroxybutanoic, 2-hydroxypentanoic, 2-hydroxyhexanoic, malic, citramalic, tartaric, tartronic and citric acids.

8. Compounds according to claim 7, in which:

Z represents an alpha hydroxy carboxylic acid residue chosen from the residues of glycolic, lactic, 2-methyllactic, malic, tartaric, tartronic and citric acids,

R represents a linear or branched, saturated or unsaturated, C6-C21 aliphatic chain,

Ri, R2 and R3, identical or different, represent a methyl, ethyl or propyl radical, R- ^* | and R2 being preferably identical,

X represents Cl, Br, I or a group of formula -SO3-O-R3, R3 having the meaning given above, m is an integer which can vary from 1 to 8, n is an integer which can vary from 1 to 3, p is equal to 3.

9. Compounds according to one of claims 6 to 8, in which the radical R-CO- is chosen from the octanoyie, decanoyie, 10-undecenoyl, lauroyl, palmitoyl, stearoyl, oleoyl, eicosanoyl and behenoyl radicals.

10. Formula compounds

OR

in which :

Z represents the di- or polyvalent residue of an alpha hydroxy carboxylic acid,

R represents an aliphatic chain, linear or branched, saturated or unsaturated, at C-1-C2,

R- | and R2, which are identical or different, represent a C1-C4 alkyl radical, m is an integer which can vary from 1 to 10, n, p and r, which are identical or different, are whole numbers which can vary from 1 to 4.

11. Compounds according to claim 10, in which the residue Z is chosen from the residues of formula:

- o-c-c -

R ₅ O

in which :

in which Rβ represents a hydrogen atom or -O-, and t is equal to 0, 1, 2 or 3.

12. Compounds according to claim 11, in which Z is chosen from the residues of glycolic, lactic, 2-methyllactic, 2-hydroxybutanoic, 2-hydroxypentanoic, 2-hydroxyhexanoic, malic, citramalic, tartaric, tartronic and citric acids.

13. Compounds according to claim 12, in which:

Z represents a residue of alpha hydroxy carboxylic acid chosen from the residues of glycolic, lactic, 2-methyllactic, malic, tartaric, tartronic and citric acids, R represents a linear or branched, saturated or unsaturated, C6- aliphatic chain C21,

Ri and R2, identical or different, represent a methyl, ethyl or propyl radical, R- | and R2 being preferably identical, m is an integer which can vary from 1 to 8, n is an integer which can vary from 1 to 3, p is equal to 3, r is equal to 1.

14. Compounds according to one of claims 10 to 13, in which the radical is chosen from the octanoyie, decanoyie, 10-undecenoyl, lauroyl, palmitoyl, stearoyl, oleoyl, eicosanoyl and behenoyl radicals.

15. Compositions, in particular cosmetic and hair, which comprise: - (A) at least one compound according to claims 6 and 10, and

- (B) a vehicle compatible with a topical application.

16. Compositions according to claim 15, in which the content of compound (A) varies from 0.01 to 50% by weight of the composition.

17. Compositions according to claim 16, in which the content of compound (A) varies from 0.1 to 30% by weight of the composition.

18. Compositions according to one of claims 15 to 17, in which the vehicle (B) is water or an organic solvent such as acetone, isopropyl alcohol, triglycerides of fatty acids C6- C24, glycol ethers, polyalkylene glycol esters of C2-C4 acids, and volatile silicones.

19. Composition according to one of claims 15 to 18 which also contains one or more other surfactants and / or additives.

20. Compositions according to claim 19, in which the surfactant content can reach 49.99% by weight of the composition.

21. Process for preparing the compounds according to claim 6, which consists in reacting:

- the compound of formula:

R ₃ x (lll)

in which R3 and X have the meaning given above.

22. The method of claim 21, wherein the molar ratio of the compound of formula (II B) to the quaternizing agent of formula (Vlll) is between 1: 0, 80n and 1: 3n.

23. Process for the preparation of the compounds of formula

R- (III)

which consists in reacting the compound of formula

(He has)

and an acylating agent of formula

R - C - R "(IX) formulas in which Z, R, R <| , R2, R3, X, m, n and p have the meaning given above, and Rg represents a halogen atom, a diglyceryl radical whose acyl residues, identical or different, contain 2 to 22 carbon atoms, a group - O-CO-Rg in which Rg represents a linear or branched hydrocarbon chain, saturated or unsaturated in CJ-C21, or a group -ORI Q in which R- | rj represents an alkyl radical in C1-C4.

24. The method of claim 23, wherein the molar ratio of the compound of formula (II A) to the acylating agent of formula (IX) is generally between 1: 0.95m and 1: 10m.

25. Process for the preparation of the compounds of formula:

.R.

R - C NH - (CH ₂ ) N R- (IV)

II Φ o (CH ₂ ) _r - C0 ₂ m

which consists in reacting:

- the compound of formula:

R.

R- C NH - (CH ₂ ) _F (I l B)

H R O m

and a compound of formula:

Y - (CH ₂ ) _r - CO -O -R ^ (X)

- in a solvent chosen from water, C-J-CR alcohols and hydroalcoholic mixtures, formulas in which Z, R, R-j, R2, m, n, p and r have the meaning given above, R "| - | represents a hydrogen atom or an alkali metal, and Y represents a halogen atom.

26. The method of claim 25, wherein the molar ratio of the compound of formula (II B) to the compound of formula (X) is generally between 1: 0.95n and 1: 1 On.

27. Process for the preparation of the compounds of formula

R— c- NH - (CH ₂ ) _p - NR ₂ (V)

I I o m φ

which consists in reacting:

- the compound of formula:

in which Z, R, R- | , R2, m, n and p have the meaning given above,

- and an oxidant,

- in a solvent chosen from water, C-J-CR alcohols and hydroalcoholic mixtures,

- optionally in the presence of a complexing agent.

28. The method of claim 27, wherein the molar ratio of the compound of formula (II B) to the oxidant is generally between 1: 0, 95n and 1: 25n.