Reducing cosmetic composition for perming containing a derivative of a n-(mercapto-alkyl)succinamic acid or a n-(mercapto-alkyl)succinimid and its use in a process for permanent hair shaping

The subject of the present invention is a cosmetic reducing composition, for the first time in a permanent hair deformation operation, containing as reducing agent a derivative of N- (mercapto alkyl) succinamic acid or of N- (mercapto alkyl) succinimide or their counterparts and its use in a process of permanent deformation of the hair.

The technique for carrying out permanent deformation of the hair consists, firstly, in opening the disulphide bonds of the keratin (cystine) using a composition containing a reducing agent (reduction step), then, after having preferably rinsed the hair, to reconstitute in a second time said disulphide bonds by applying, to the hair under tension, an oxidizing composition, (oxidation step, also called fixing) so as to give the hair the desired shape. This technique makes it possible to carry out either the waving of the hair, or their straightening or their straightening.

The compositions for carrying out the first stage of a perming operation are generally in the form of lotions, creams, gels or powders to be diluted in a liquid support and contain, as reducing agent, preferably a mercaptan.

Among the latter, those commonly used are thioglycolic acid and thiolactic acid or a mixture of these acids as well as their esters, for example glycerol or glycol monothioglycolate.

These reducing agents are particularly effective in reducing the disulfide bonds of keratin, in particular thioglycolic acid which can be considered as the reference product in permanent form, and which leads to a reduction rate of approximately 50%.

These reducing agents have however a major drawback insofar as they give off bad odors, moreover specific to sulfur compounds which make permanent operations sometimes painful not only for the people who undergo them but also for the people who carry them out.

In order to remedy this drawback, use is generally made of a perfume making it possible to mask odors.

After extensive research, it has now been found, quite unexpectedly and surprisingly, that using a new class of N- (mercapto alkyl) succinamic acid derivatives or N- (mercapto alkyl) succinimides or their derivatives counterparts, it was possible to remedy certain drawbacks of the reducing agents of the prior art.

The reducing agents of the compositions according to the invention indeed have good reducing properties and are practically devoid of odor.

The present invention therefore relates to, as a new industrial product, a cosmetic composition for the first stage of a permanent hair deformation operation, containing, in a suitable cosmetic vehicle, as reducing agent, at least one derivative N- (mercapto alkyl) succinamic acid or N- (mercapto alkyl) succinimide or one of their counterparts having the following general formula:<chemistry id="chem0001" num="0001"><img file="EP0465342B1_D0001.tif" /></chemistry> in which :    n is 2 or 3    A represents a divalent radical chosen from:<ul id="ul0001" list-style="none"><li>(i) - (CH₂)_m-, m being 2 or 3,</li><li>(ii)<chemistry id="chem0002" num="0002"><img file="EP0465342B1_D0002.tif" /></chemistry> R₃ and R₄, identical or different, representing an alkyl radical having from 1 to 4 carbon atoms or R₃ and R₄ together form, with the adjacent carbon atoms, a cyclohexane ring, and</li><li>(iii)<chemistry id="chem0003" num="0003"><img file="EP0465342B1_D0003.tif" /></chemistry></li></ul>    R₅ and R₆, identical or different, representing a hydrogen atom, an alkyl radical having from 1 to 4 carbon atoms or R₅ and R₆ together form, with the adjacent carbon atoms, a benzene ring,    R₁ represents a hydrogen atom and    R₂ represents on hydroxy radical or    R₁ and R₂ taken together form a single bond, and the salts of an organic or mineral base of the said compounds in free acid form.

When the compounds of general formula (I) above are in the form of salts, it is more particularly an ammonium salt, a secondary or tertiary amine salt or else a salt of '' an alkali or alkaline earth metal.

In the general formula (I) above, when the radicals R₃ and R₄ form together with the adjacent carbon atoms a cyclohexane ring, the corresponding divalent radical is the radical 1,2-cyclohexylidene.

Furthermore, when the radicals R₅ and R₆ form together with the adjacent carbon atoms a benzene ring, the corresponding divalent radical is the o-phenylene radical.

By alkyl radical having 1 to 4 carbon atoms, is meant a methyl, ethyl, propyl, isopropyl or butyl radical.

Among the compounds of formula (I) above in which R₁ represents a hydrogen atom and R₂ represents a hydroxy radical, the following may in particular be mentioned:    N- (2-mercapto ethyl) succinamic acid,    N- (3-mercapto-propyl) succinamic acid,    N- (2-mercapto-ethyl) hexahydrophthalamic acid,    N- (3-mercapto-propyl) hexahydrophthalamic acid,    N- (2-mercapto-ethyl) phthalamic acid,    N- (3-mercapto-propyl) phthalalamic acid,    N- (2-mercapto-ethyl) glutaramic acid,    N- (3-mercapto-propyl) glutaramic acid,    N- (2-mercapto-ethyl) maleamic acid.

Among the compounds of formula (I) above in which R₁ and R₂, taken together, form a single bond, the following may in particular be mentioned:    N- (2-mercapto-ethyl) succinimide,    N- (mercapto-3 propyl) succinimide,    N- (2-mercapto-ethyl) glutarimide,    N- (mercapto-3 propyl) glutarimide,    N- (2-mercapto-ethyl) hexahydrophthalimide,    N- (3-mercapto propyl) hexahydrophthalimide.

Some of the compounds of formula (I) are known and others are new and we will give below with regard to the latter various methods for obtaining them as well as several examples of preparation.

In the compositions according to the invention, the reducing agent of general formula (I) is generally present at a concentration of between 2 and 20% and preferably between 5 and 10% by weight relative to the total weight of the reducing composition.

The pH of the composition is preferably between 4.5 and 11, and more particularly between 6 and 10 and obtained using an alkaline agent such as for example ammonia, monoethanolamine, diethanolamine, triethanolamine , an alkali or ammonium carbonate or bicarbonate, an alkali hydroxide or using an acidifying agent such as for example hydrochloric acid, acetic acid, lactic acid, oxalic acid or l 'boric acid.

The reducing composition can also contain other known reducing agents such as for example thioglycolic acid, glycerol or glycol monothioglycolate, cysteamine and its acyl derivatives C₁-C₄ such as N-acetyl cysteamine or N-propionyl cysteamine , cysteine, N-acetylcysteine, N-mercaptoalkylamides of sugars such as N- (mercapto-2-ethyl) gluconamide, β-mercaptopropionic acid and its derivatives, thiolactic acid, thiomalic acid, pantethine, thioglycerol, sulfites and bisulfites of an alkali or alkaline earth metal, the N- (mercaptoalkyl) ω-hydroxyalkyl amides described in patent application EP 354 835, the N-mono or N, N dialkylmercapto 4-butyramides in patent application EP 368,763, and the aminomercaptoalkylamides described in patent application EP 403,267.

The reducing composition can also contain various ingredients such as for example cationic polymers such as those used in the compositions of French patents n ° 79.32078, 80.26421 and 89.16273 or also cationic polymers of the ionene type such as those used in the compositions of the French patent 82.17364, softening agents and in particular quaternary ammoniums derived from lanolin, protein hydrolysates, waxes, opacifying agents, perfumes, dyes, nonionic or cationic surfactants, treating agents or even penetrating agents such as urea, pyrrolidone or thiamorpholinone.

The reducing composition according to the invention can also be of the exothermic type, that is to say causing a certain heating during application to the hair, which brings pleasure to the person who undergoes the first time of the perm or straightening.

The vehicle for the compositions according to the invention is preferably water or an aqueous-alcoholic solution of a lower alcohol such as ethanol, isopropanol or butanol.

When the compositions are intended for a hair straightening or straightening operation, the reducing composition is preferably in the form of a cream so as to keep the hair as straight as possible. These creams are produced in the form of "heavy" emulsions, for example based on glyceryl stearate, glycol stearate, self-emulsifying waxes, fatty alcohol, etc.

It is also possible to use liquids or gels containing thickening agents such as carboxyvinyl polymers or copolymers which "stick" the hair and keep it in the smooth position during the setting time.

The compositions according to the invention can also be according to a particular embodiment in so-called "self-neutralizing" or even "self-regulated" form and in this case the reducing compound of formula (I) is associated with at least one disulfide either known for its use in a reducing composition for self-neutralizing perm, either derived from a compound of formula (I), which can be represented by the following general formula:<chemistry id="chem0004" num="0004"><img file="EP0465342B1_D0004.tif" /></chemistry> in which :    n, R₁, R₂ and A have the same meanings as those given for formula (I).

Among the known disulfides, mention may in particular be made of dithioglycolic acid, dithioglycerol, cystamine, N, N-diacetyl-cystamine, cystine, pantethine and the disulphides of the N- (mercaptoalkyl) ω-hydroxyalkylamides described in the application. EP 354 835, the disulphides of N-mono or N, N-dialkylmercapto 4-butyramides described in patent application EP 368 763 and the disulphides of aminomercaptoalkylamides described in patent application EP 403 267.

Among the disulfides of formula (II), the following may be mentioned in particular:    bis [N- (3-carboxypropionyl) N-ethyl] disulfide,    bis [N- (2-carboxy cyclohexane carbonyl) N-ethyl] disulfide,    bis [N-ethyl succinimide] disulfide.

The disulfide is generally present in the compositions in a molar proportion relative to the thiol of formula (I) ranging from 0.5 to 2.5 and preferably from 1 to 2 (see US Patent 3,768,490).

The present invention also relates to a process for permanent deformation of the hair consisting, in a first step, in reducing the disulphide bonds of the keratin by application, for approximately 5 to 60 minutes, of a reducing composition as defined above. then in a second step to reform said bonds by applying an oxidizing composition or optionally by allowing the oxygen in the air to act.

The present invention also relates to a hair waving process in which a reducing composition as defined above is applied to wet hair previously rolled on rollers having from 4 to 20 mm in diameter, the composition possibly being able to be applied as the hair is rolled up; the reducing composition is then left to act for a time of 5 to 60 min, preferably from 5 to 30 min, then it is rinsed thoroughly after which is applied, to the coiled hair, an oxidizing composition making it possible to reform the disulfide bonds of the keratin for an exposure time of 2 to 10 min. After removing the rollers, rinse the hair thoroughly.

The oxidation or oxidizing composition is of the type commonly used and contains, as oxidizing agent, hydrogen peroxide, an alkali bromate, a persalt, a polythionate or a mixture of alkali bromate and parsley. This oxidation can be immediate or delayed. The concentration of hydrogen peroxide can vary from 1 to 20 volumes and preferably from 1 to 10, the concentration of alkali bromate from 2 to 12% and that of parsley from 0.1 to 15% by weight relative to the total weight of the oxidizing composition. The pH of the oxidizing composition is generally between 2 and 10.

The present invention also relates to a process for straightening or straightening the hair in which a reducing composition according to the invention is applied to the hair and then the hair is subjected to mechanical deformation which makes it possible to fix them in their new shape, by a hair straightening operation with a wide tooth comb, with the back of a comb or by hand. After an exposure time of 5 to 60 min, in particular 5 to 30 min, we then proceed to a new smoothing, then rinse thoroughly and apply the oxidizing or fixing composition which is left to act for 2 to 10 min approximately. then rinse the hair thoroughly.

The compounds of general formula (I) are prepared according to methods known per se.

The N- (mercapto alkyl) succinamic acid derivatives or their counterparts, that is to say the compounds of formula (I) in which R₁ = H and R₂ = OH, are obtained by reacting a mercaptoalkylamine (<u style="single">1</u>) on an anhydride of formula (<u style="single">2</u>) according to the following reaction scheme:<chemistry id="chem0005" num="0005"><img file="EP0465342B1_D0005.tif" /></chemistry>

The mercapto alkylamines (<u style="single">1</u>) used are either mercapto-2 ethylamine or cysteamine (n = 2) or mercapto-3 propylamine (n = 3).

Anhydrides (<u style="single">2</u>) are succinic anhydride, maleic anhydride, 1,2 cyclohexane dicarboxylic anhydride, phthalic anhydride, methyl succinic anhydride, glutaric anhydride.

The opening reaction of the anhydride (<u style="single">2</u>) is generally carried out under an inert atmosphere in an alcohol such as methanol, ethanol, isopropanol or butanol, and depending on the boiling point of the latter and the ease with which the acids of formula (Ia) cyclize , at a temperature between 0 and 110 ° C.

It may be advantageous to use salts of the mercapto alkylamines (<u style="single">1</u>) in particular the hydrochlorides, and in this case the preferred solvent is ethanol and the base used to release the amine is a tertiary amine. It may be advantageous to add an excess of amine, this in order to salify the acid (Ia) formed progressively and thus limit the cyclization.

When the mercapto alkylamines (<u style="single">1</u>) are in free amine form, it may be advantageous not to use a solvent and to mix in stoichiometric proportions the mercapto alkylamine and the anhydride, and to bring the mixture to a temperature of between 20 and 100 ° C.

When the mercapto alkylamine is cysteamine, it is desirable to operate in an autoclave this in order to eliminate the problems of sublimation.

The progress of the reaction is monitored by assaying the unprocessed mercapto alkylamine. When the reaction time is too long, it may be advantageous to use an excess of the mercapto alkylamine which is eliminated at the end of the reaction by filtration of the mixture on an acid sulphonic resin.

The derivatives of N- (mercapto alkyl) succinimide or their homologs, that is to say the compounds of formula (I) in which R₁ and R₂, taken together, form a single bond, are obtained by dehydration of the succinamic acids of formula ( Ia).

In order to carry out the dehydration reaction, an aromatic solvent preferably forming an azeotrope is chosen with the water formed during the reaction, having a sufficiently high boiling point such as toluene or xylene. In this case, a water separator (Dean Stark) is used and it is then easy to follow the progress of the reaction by measuring the volume of water removed.

The N- (mercapto alkyl) succinimides or their counterparts, can also be obtained from mercapto alkylamine (<u style="single">1</u>) and anhydride (<u style="single">2</u>) in the presence or absence of solvent, without intermediately isolating the succinamic acid derivative (Ia), the cyclization being carried out by prolonged heating by placing the mixture under reduced pressure when no reaction solvent is used.

If during the reactions a certain amount of thiol is oxidized to the corresponding disulfide, the reaction mixture is then diluted by twice its volume of water and is stirred in the presence of a mixture of sulfonic resin and zinc powder for 3 to 10 hours.

The majority of the disulfide being reduced, the mixture is then filtered and a solution of the expected compound is obtained which can be used directly.

In the case of self-neutralizing compositions, the reaction mixture containing a certain quantity of thiol oxidized to disulfide can be used without proceeding with the reduction of the disulfide.

In some cases, depending on the nature of the anhydride (<u style="single">2</u>) used, the succinamic acids (Ia) are easily cyclized and a mixture of the corresponding acid and imide can be obtained.

The disulfides (II) according to the invention can be obtained by oxidation of the compounds of formula (I) either in the open air or preferably by using, for example, hydrogen peroxide in the possible presence of ferrous ions.

The disulfides (II) can also be obtained by reaction of a disulfide of formula (<u style="single">3</u>) on an anhydride (<u style="single">2</u>) according to the following reaction scheme:<chemistry id="chem0006" num="0006"><img file="EP0465342B1_D0006.tif" /></chemistry>

The disulfides (IIa) lead by prolonged heating to the disulfides of formula (IIb).

The subject of the present invention is also, as new industrial products, the compounds corresponding to the following general formulas (III) and (IV):<chemistry id="chem0007" num="0007"><img file="EP0465342B1_D0007.tif" /></chemistry> in which :    n is 2 or 3, and    B represents a divalent radical taken from the group consisting of:<ul id="ul0002" list-style="none"><li>(i) - (CH₂) ₃-</li><li>(ii) 1,2-cyclohexylidene, and</li><li>(iii) -CH = CH- when in the latter case n is 3 and their corresponding disulfides.</li></ul><chemistry id="chem0008" num="0008"><img file="EP0465342B1_D0008.tif" /></chemistry> in which : n is 2 or 3<ul id="ul0003" list-style="none"><li>(a) when n is 2 Z represents the 1,2-cyclohexylidene radical</li><li>(b) when n is 3 Z is a divalent radical chosen from the group consisting of:<ul id="ul0004" list-style="none"><li>(i) - (CH₂)_m-, m being 2 or 3,</li><li>(ii) -CH = CH-</li><li>(iii) 1,2-cyclohexylidene, and</li><li>(iv) o-phenylene,</li></ul> and their corresponding disulfides, as well as the corresponding disulfide when n is 2 and Z represents an o-phenylene radical.</li></ul>

We will now give by way of illustration several examples of preparation of the compounds of formulas (I) and (II) as well as several examples of the reducing compositions according to the invention and their use in a process for permanent deformation of the hair.

EXAMPLE I

Preparation of N- (2-mercapto-ethyl) succinamic acid

at)

From cysteamine hydrochloride

114 g of cysteamine hydrochloride are introduced into an reactor under an inert atmosphere to which 133 cm³ of triethanolamine dissolved in 180 cm³ of absolute ethanol are added dropwise, with mechanical stirring and at room temperature. A slight exotherm is observed and 100 g of succinic anhydride are then introduced so as to maintain the medium at a temperature in the region of 40 ° C. The mixture is then stirred for 3 hours at room temperature and left overnight under an inert atmosphere. The transformation of the anhydride is followed by vapor phase chromatography (CPV) and that of the starting amine by assaying the amount of remaining amine. After 3 hours of reaction, there is practically no more starting material. The salt is removed by filtration and the filtrate is concentrated under reduced pressure. 170 g of a crude product are obtained, which crystallizes in the form of a pasty solid at ordinary temperature. This product is stirred under an inert atmosphere in 200 cc of 1,2-dichloroethane which is gradually brought to the boil. After returning to ambient temperature, two liquid phases are observed and the mixture is cooled to 0 ° C. for 4 hours. The solid formed is drained, washed three times with 100 cm³ of ethyl ether and then dried under reduced pressure. 125 g of a white powder are obtained which are recrystallized from hot ethyl acetate. After cooling, spinning and drying under vacuum at 45 ° C., 110 g of N- (mercapto-ethyl) succinamic acid are obtained in the form of a white solid with a melting point of 82 ° C. The 250 MHz 1 H NMR spectrum conforms to the expected structure. The dosages of the thiol and carboxylic acid functions are greater than 95% of the theory.

Elementary analysis: C₆H₁₁NO₃S<tables id="tabl0001" num="0001"><img file="EP0465342B1_D0009.tif" /></tables>

b)

From cysteamine

A mixture of 5 g of cysteamine and 6 g of succinic anhydride is stirred under an inert atmosphere at a temperature of about 100 ° C. The transformation of the starting materials is practically complete half an hour after the start of the reaction. The mixture is dissolved in 50 cc of water to which 5 g of acid sulfonic resin and 3 g of zinc powder are added with stirring to transform the disulfide present in the mixture. The resin is removed by filtration and the filtrate is concentrated under reduced pressure. After drying, 9 g of N- (2-mercapto-ethyl) succinamic acid are obtained, the characteristics of which are identical to those of the acid obtained according to procedure (a) above.

EXAMPLE II

Preparation of N- (2-mercapto-ethyl) succinimide

at)

From cysteamine

A stirred mixture of 5 g of cysteamine and 6 g of succinic anhydride is gradually brought under an inert atmosphere for 6 hours at a temperature of approximately 130 ° C. About half an hour is necessary for the total transformation of succinic anhydride (CPV). At this stage, to facilitate the cyclization reaction, the reaction medium is placed under reduced pressure and the evolution of the reaction mixture is monitored by acidimetric determination of the unconverted N- (2-mercapto-ethyl) acid succinamic acid. At the end of the reaction, the mixture is cooled and 7 g of crude product are obtained which are dissolved in 50 cm³ of water to which 10 g of acid sulfonic resin are added with stirring. After one hour of stirring, the resin which has fixed the traces of cysteamine or unreacted cystamine is removed by filtration. To reduce any disulfide present, 10 g of sulfonic resin and 3 g of zinc powder are added to the stirred filtrate. After 3 hours the mixture is filtered and the filtrate is concentrated under reduced pressure. After drying, 5 g of N- (2-mercapto-ethyl) succinimide are obtained in the form of a white powder, with a melting point of 45 ° C. The ¹H and ¹³C NMR spectra conform to the expected structure.

Elementary analysis: C₆H₁₁NO₃S<tables id="tabl0002" num="0002"><img file="EP0465342B1_D0010.tif" /></tables>

b)

From N- (2-mercapto-ethyl) succinamic acid

In a 100 cm³ reactor fitted with a water separator (Dean Stark), a mixture, stirred under an inert atmosphere, of 20 g of N- (2-mercapto-ethyl) succinamic acid in 50 cm³ of xylene is brought to a temperature of 140 ° C. After approximately 5 hours of reaction, the theoretical amount of water (2 cm³) is eliminated. The xylene is then distilled under reduced pressure. The crude product is dried and 18 g of a pasty product are obtained which slowly crystallizes at room temperature, its characteristics are the same as those of the product prepared according to procedure (a) above.

EXAMPLE III

Preparation of bis [N- (3-carboxypropionyl) N-ethyl] disulfide

A solution of 3.7 g of cysteamine and 2 g of succinic anhydride in 80 cm³ of ethanol is brought, with stirring, to the boiling point of ethanol for 10 hours, after which time all the anhydride is transformed. The mixture is left overnight and the following day, air is bubbled at ordinary temperature in the solution until all of the thiol is converted into disulfide. The mixture is concentrated to mid-volume and then cooled to O ° C. The crystallized disulfide is drained and dried. 2 g of bis N- (3-carboxy-propionyl) N-ethyl disulfide are obtained in the form of a white powder with a melting point: 141 ° C.

Elementary analysis: C₁₂H₂₀N₂O₆S₂<tables id="tabl0003" num="0003"><img file="EP0465342B1_D0011.tif" /></tables>

EXAMPLE IV

Preparation of bis [(N-ethyl succinimide)] disulfide

15.9 g (0.1 mol) of N- (2-mercapto-ethyl) succinimide, described in group II, are dissolved in approximately 200 cm³ of ethanol and 200 cm³ of water. Cool to a temperature between 15 and 20 ° C, add a few drops of 20% ammonia to make the pH alkaline, then drop by drop hydrogen peroxide at 110 volumes until complete transformation of thiol into disulfide iodine dosage).

The solution is clarified by filtration on sintered glass and then concentrated under reduced pressure to approximately 100 cm³. After cooling to 0 ° C., the white solid is drained and then dissolved again in the minimum amount of ethanol. The solution is filtered and then concentrated under vacuum until crystallization begins. Cool to + 5 ° C, drain the crystals and dry under vacuum at 60-70 ° C. 12.8 g of bis (N-ethyl succinimide) disulfide are obtained in the form of a white solid with a melting point of 119 ° C.

The NMR¹H 80MHz spectrum conforms to the expected structure.

Elementary analysis: C₁₂H₁₆N₂O₄S₂<tables id="tabl0004" num="0004"><img file="EP0465342B1_D0012.tif" /></tables>

EXAMPLE V

Preparation of N- (mercapto-2ethyl) hexahydrophthalamic acid

To a solution of 7.72 g (0.1 mole) of cysteamine in 40 cc of methanol, maintained under an inert atmosphere and cooled to a temperature between 0 and 5 ° C., 15.43 g (0, 1 mole) of hexahydrophthalic anhydride. After 7 hours of stirring at this temperature, only traces of starting cysteamine remain. The solution is evaporated to dryness under reduced pressure at room temperature. 23 g of N- (2-mercapto-ethyl) hexahydrophthalamic acid are obtained in the form of a colorless oil.

The 80 H NMR¹H spectrum corresponds to the expected structure.

EXAMPLE VI

Preparation of N- (2-mercapto-ethyl) hexahydrophthalimide

15.43 g (0.2 mole) of cysteamine, 100 cm³ of toluene and 30.83 g (0.2 mole) of hexahydrophthalic anhydride are introduced into a reactor equipped with a Dean-StarK. heated to reflux with stirring with distillation of the water formed. After 4 hours of reflux, the reaction is complete. It is evaporated to dryness under reduced pressure. The white solid obtained is purified by recrystallization from ethyl acetate. After drying under vacuum at 70 ° C., 37.5 g of N- (2-mercapto-ethyl) hexahydrophthalimide are obtained in the form of a white solid with a melting point of 79-80 ° C.

The 80 MHz 1 H NMR spectrum conforms to the expected structure.

Elementary analysis: C₁₀H₁₅NO₂S<tables id="tabl0005" num="0005"><img file="EP0465342B1_D0013.tif" /></tables>

EXAMPLE VII

Preparation of N- (3-mercapto-propyl) glutaramic acid

8.56 g (0.075 mole) of glutaric anhydride by keeping the temperature of the medium below 40 ° C. After 6:30 of stirring the reaction is complete. The solution is evaporated to dryness under reduced pressure. It is then dried under vacuum at a temperature below 60 ° C. and 19.5 g of N- (3-mercapto-propyl) glutaramic acid are obtained in the form of a colorless oil.

The 80 MHz 1 H NMR spectrum conforms to the expected structure.

COMPOSITION EXAMPLES

EXAMPLE 1

:

A reducing composition for permanent deformation of the hair is prepared according to the invention by mixing the following ingredients:<img file="EP0465342B1_D0014.tif" />

This composition is applied to wet hair previously wound on styling rollers. After having left the composition to act for approximately 15 min., Rinse thoroughly with water and then apply the following oxidizing composition:<img file="EP0465342B1_D0015.tif" />

The oxidizing composition is left to act for approximately 10 min., Then the rollers are removed and the hair is thoroughly rinsed with water.

After drying under a helmet, the hair has beautiful curls.

In this example, the oxidizing composition can be replaced by the following:<img file="EP0465342B1_D0016.tif" />

EXAMPLE 2

According to the same embodiment as in Example 1, the hair was permanently deformed using the following reducing and oxidizing compositions:<ul id="ul0005" list-style="none"><li>AT. <u style="single">Reducing composition</u><img file="EP0465342B1_D0017.tif" /></li><li>B. <u style="single">Oxidizing composition</u><img file="EP0465342B1_D0018.tif" /><img file="EP0465342B1_D0019.tif" /></li></ul>

EXAMPLE 3

:

<ul id="ul0006" list-style="none"><li>AT. <u style="single">Reducing composition</u><img file="EP0465342B1_D0020.tif" /></li><li>B. <u style="single">Oxidizing composition</u><img file="EP0465342B1_D0021.tif" /></li></ul>

EXAMPLE 4

<ul id="ul0007" list-style="none"><li>AT. <u style="single">Reducing composition</u><img file="EP0465342B1_D0022.tif" /></li><li>B. <u style="single">Oxidizing composition</u><img file="EP0465342B1_D0023.tif" /></li></ul>

EXAMPLE 5

<ul id="ul0008" list-style="none"><li>AT. <u style="single">Reducing composition</u><img file="EP0465342B1_D0024.tif" /></li><li>B. <u style="single">Oxidizing composition</u><img file="EP0465342B1_D0025.tif" /></li></ul>

EXAMPLE 6

:

<ul id="ul0009" list-style="none"><li>AT. <u style="single">Reducing composition</u><img file="EP0465342B1_D0026.tif" /></li><li>B. <u style="single">Oxidizing composition</u><img file="EP0465342B1_D0027.tif" /></li></ul>

EXAMPLE 7

<ul id="ul0010" list-style="none"><li><u style="single">A. Reducing composition</u><img file="EP0465342B1_D0028.tif" /></li><li><u style="single">B. Oxidizing composition</u><img file="EP0465342B1_D0029.tif" /></li></ul>

EXAMPLE 8

<ul id="ul0011" list-style="none"><li><u style="single">A. Reducing composition</u><img file="EP0465342B1_D0030.tif" /></li><li><u style="single">B. Oxidizing composition</u><img file="EP0465342B1_D0031.tif" /></li></ul>

EXAMPLE 9

<ul id="ul0012" list-style="none"><li><u style="single">A. Reducing composition</u><img file="EP0465342B1_D0032.tif" /></li><li><u style="single">B. Oxidizing composition</u><img file="EP0465342B1_D0033.tif" /></li></ul>

EXAMPLE 10

<ul id="ul0013" list-style="none"><li><u style="single">A. Reducing composition</u><img file="EP0465342B1_D0034.tif" /></li><li><u style="single">B. Oxidizing composition</u><img file="EP0465342B1_D0035.tif" /></li></ul>

EXAMPLE 11

<ul id="ul0014" list-style="none"><li><u style="single">A. Reducing composition</u><img file="EP0465342B1_D0036.tif" /></li><li><u style="single">B. Oxidizing composition</u><img file="EP0465342B1_D0037.tif" /></li></ul>