FR2669329A1 - Aminomercaptoalkylamides, process for their preparation and their use in a reducing (reductive) cosmetic composition in the permanent deforming (waving) of hair - Google Patents

Abstract

New aminomercaptoalkylamides corresponding to the following general formula (IV): in which: A represents the -(CH2)n- divalent radical, n being an integer between 2 and 5, or the -(CH2)2-O-(CH2)2- divalent radical, m is 0 or an integer between 1 and 4, (i) when m is O, R1 represents a hydrogen atom, a methyl radical, an ethyl radical, an isopropyl radical, an isobutyl radical, a 2-methylbutyl radical, a benzyl radical, a 4-aminobutyl radical, a 3-guanidinopropyl radical, a 2-(methylthio)ethyl radical, a carboxymethyl radical or a 2-carboxyethyl radical, (ii) when m is an integer from 1 to 4, R1 represents a hydrogen atom or a lower alkyl radical having from 1 to 5 carbon atoms, with the exclusion of the compounds in which: (i) A represents -(CH2)2- and m is 0 or 1, and R1 represents a hydrogen atom, a linear or branched alkyl radical having from 1 to 5 carbon atoms, a benzyl radical or a 2-carboxyethyl radical, (ii) A represents -(CH2)3- and m is 1, and R1 represents a hydrogen atom, and the salts of the said compounds of formula (IV) and their corresponding disulphides. Use in cosmetics in reducing compositions for the first step of a permanent deforming operation of hair.

Description

 The present invention relates to a reducing composition, for the first time of a permanent hair deformation operation, containing as reducing agent an amino mercaptoalkylamide or one of its cosmetically acceptable salts, and its use in a process of permanent deformation of the hair.

The technique for carrying out the permanent deformation of the hair consists, in a first step, in opening the disulfide bonds of keratin (cystine) with a composition containing a reducing agent (reduction step), and then, after having preferably rinsed the hair, to reconstitute in a second time said disulfide bonds by applying, on the hair under tension, an oxidizing composition (oxidation step, also called fixation) so as to give the hair the desired shape.This technique allows indifferently to achieve either the waving of the hair, or their straightening or their decribing. :
The compositions for performing the first time of a permanent operation are generally in the form of lotions, creams, gels or powders for dilution in a liquid carrier and preferably contain a mercaptan as the reducing agent.

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

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

 These reducing agents however have a major disadvantage insofar as they give off bad odors.

 In order to remedy this, it is generally used a perfume for masking odors.

 After extensive research, it has now been found, quite unexpectedly and surprisingly, that using a new family of amino mercaptoalkylamides or their cosmetically acceptable salts, it was possible to overcome the disadvantages of the reducing agents of the the technique.

 The reducing agents of the compositions, according to the invention, not only have the advantage of being substantially odorless but also allow for greater yield, crispness and beauty of crimping than those obtained according to the state of the art in the art. using for example thioglycolic acid.

The subject of the present invention is therefore, as a new industrial product, a cosmetic composition for the first time of a permanent hair deformation operation, containing, in a suitable cosmetic vehicle, as reducing agent, at least one amino mercaptoalkylamide corresponding to the following general formula (I)

in which
A represents the divalent radical - (CH2) n-, n being an integer between 2 and 5, or the divalent radical -iCH2) 2-0- (CH25-2,
m is 0 or an integer from 1 to 4,
(i) when m is 0, R1 represents a hydrogen atom, a methyl radical, an ethyl radical, an isopropyl radical, an isobutyl radical, a methyl-2-butyl radical, a benzyl radical or a 4-butyl radical; a 3-guanidinopropyl radical, a 2-methylthiethyl radical, a carboxymethyl radical or a 2-carboxyethyl radical,
(ii) when m is an integer from 1 to 4, R 1 represents a hydrogen atom or a lower alkyl radical having from 1 to 5 carbon atoms, provided that when m is I and A represents the divalent radical - ( CH2) 2-, R1 is other than a hydrogen atom, and the salts of said compounds of formula (I).

 Among the cosmetically acceptable salts of the compounds of formula (I), those which are particularly preferred are hydrochlorides, hydrobromides, citrates and oxalates.

 By lower alkyl radical having from 1 to 5 carbon atoms, is meant a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-methylbutyl or pentyl radical.

Among the preferred compounds corresponding to the general formula (I), mention may be made in particular
2-amino-N- (2-mercaptoethyl) acetamide,
2-amino-N- (3-mercaptopropyl) acetamide,
2-amino-N- (5-mercapto-pentyl) acetamide,
2-amino-N - [(2-mercaptoethoxy) -2-ethyl] acetamide,
2-amino-N- (2-mercaptoethyl) propionamide,
2-amino-N- (3-mercaptopropyl) propionamide,
2-amino-N- (5-mercaptopentyl) propionamide,
2-amino-N- (2-mercapto-ethoxy-2'-ethyl) propionamide,
3-amino-N- (3-mercaptopropyl) propionamide,
1-amino-Sx- (5-mercapto-pentyl) propionamide,
3-amino-NE (2-mercaptoethoxy) -2'-ethylpropionanide,
2-amino-N- (2-mercaptoethyl) methyl-3-butanamide,
2-amino-N- (2-mercaptoethyl) methyl-4-pentanamide,
Amino N- (2-mercaptoethyl) hydrocinnamide,
4-amino-amino [(2-mercaptoethyl) amino] -5-oxo-pentanic acid,
4-amino-N- (2-mercaptoethyl) butanamide,
4-amino-N- (3-mercaptopropyl) butanamide,
4-amino-N- (5-mercapto-pentyl) butanamide,
4-amino-N- (2-mercaptoethoxy) -2-ethyl] butanamide, and
6-amino-N- (2-mercaptoethyl) hexanamide,
as well as their hydrochlorides.

 The compounds of general formula (I), some of which are known, are prepared according to methods known per se which will be mentioned below and which depend on the different substituents, the raw materials used and their ease of use.

dans laquelle
A, R1 et m ont les mêmes significations que ci-dessus pour la formule générale (I) et,
X est C1 ou Br.The compounds according to the invention can in particular be prepared via thioesters of general formula (II)

in which
A, R1 and m have the same meanings as above for the general formula (I) and,
X is C1 or Br.

 These thioesters are obtained either by condensation of an aminothiol on an amino acid acid halide as described for example by Th.

WIELAND et al, Justus Liebigs Annalen der Chemie, 576, 20, (1952), or by hydrolysis of a substituted thiazoline, which is obtained by reaction of an aminonitrile on an aminothiol such as cysteamine, as described in Japanese patent applications 66/22389, 75/62931 and 75/62932 of the company DAICHI SEYAKU Company.

 The thioesters of general formula (II) are rearranged to amino mercaptoalkylamides of general formula (I) by treatment with a base.

This reaction is carried out in a hydroalcoholic medium at room temperature in the presence of at least 1 equivalent of a base such as ammonia, alkali metal hydroxides or a tertiary amine such as triethylamine or triethanolamine according to the following reaction:

<tb><SEP> base
<tb> ff-AS-CO-ICH- (CE2) m-Ni2 <SEP> 2EK
<tb><SEP> R1
<tb><SEP> (II)
<tb> HS-A-NH-CO-CH <SEP> s <SEP> HX
<tb><SEP> I '<SEP> m
<tb><SEP> (I)
<Tb>
The compounds according to the invention may also be prepared in a more conventional manner by condensation of an N-protected amino acid with a
S-acylaminothiol in the presence of a peptide synthesis activating agent such as for example dicyclohexylcarbodiimide.

 The thiol and amine functions are then deprotected by acid or basic hydrolysis, as described for example by M. FATBPp4 et al.

Eur. J. Med. Chem., 23, (1988), 257-266 or by J. OIRY et al., J.

Med. Chem., 29 (11), 2217-25, (1986).

 In the compositions according to the invention, the reducing agent of general formula (I) is generally present in a concentration of between 2 and 30% and preferably between 5 and 25% by weight relative to the total weight of the reducing composition.

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

 The reducing composition may also contain other known reducing agents such as, for example, thioglycolic acid, glyceryl or glycol monothioglycolate, cysteamine and its C 1 -C 4 acyl derivatives, such as N-acetylcysteamine or N-propionyl. cysteamine, cysteine, N-acetylcysteine, N-mercaptoalkylamides of sugars such as N- (mercapto-2-ethyl) gluconamide, R-mercaptopropionic acid and its derivatives, thiolactide acid, pantethine, thioglycerol , sulfites or bisulfites of an alkali or alkaline earth metal and the thiols described in European Patent Applications EP 354,835 and EP 368,763.

 The reducing composition may further contain various ingredients such as, for example, cationic polymers such as those used in the compositions of French Pat. Nos. 79,32078 and 80,26421, or cationic ionic polymers such as those used in the compositions of French Pat. "82.17364, softening agents and especially quaternary ammonium lanolin derivatives, protein hydrolysates, waxes, opacifying agents, perfumes, dyes, nonionic or cationic surfactants, alcohols such as methanol, propanol, isopropanol, 1,2-propanediol, 1,2-butanediol or glycerol, treating agents or penetration agents such as urea, pyrrolidone or thiamorpholinone.

 The reducing composition according to the invention may also be of the exothermic type, that is to say causing a certain heating during application to the hair, which gives an approval to the person who undergoes the first stage of the permanent or straightening.

 The vehicle of the compositions according to the invention is preferably water or a hydroalcoholic solution of a lower alcohol such as ethanol, isopropanol or butanol.

 When the compositions are intended for 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-emulsifiable waxes, fatty alcohols, etc.

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

According to a particular embodiment of the invention, the reducing compounds of general formula (I) can be formed in situ at the time of use from their thioester precursors corresponding to the following general formula (II)

in which
A, R1 and m have the same meanings as above for the general formula (I), and
X is C1 or Br.

 It has indeed been found that in the presence of a base such as ammonia, monoethanolamine, diethanolamine, triethanolamine, sodium hydroxide or potassium hydroxide, these thioester precursors were transformed almost instantaneously and quantitatively into thiols corresponding to the general formula (I).

 The thioester precursor of formula (II) is generally present in a concentration of between 2 and 30% and preferably between 5 and 25% by weight relative to the total weight of the composition.

 According to this embodiment, the precursor thioester in the solid state, preferably in the form of a powder, is mixed at the time of use with a basic aqueous solution of pH of between 8 and 10, optionally containing various ingredients such as those mentioned above.

 The pH of the composition is then adjusted, if necessary, with an alkaline agent or an acidifying agent such as those mentioned above.

Among these thioesters there may be mentioned the following compounds
the dihydrochloride of 2-aminoethyl thioglycinate,
the dihydrochloride of 2-aminoethyl thioalaninate,
2-amino-2-amino-2-thiobutyrate dihydrochloride,
the dihydrochloride of 2-aminoethyl thiovalinate,
the dihydrochloride of 2-aminoethyl thioleucinate,
2-amino-3-phenylthioalaninate dihydrochloride,
the dihydrochloride of thiomethioninate of 2-aminoethyl,
the dihydrochloride of 3-aminopropyl thioglycinate,
5-amino-thioglycinate dihydrochloride,
the dihydrochloride of (2-amino-ethoxy) -Z-ethyl thioglycinate,
3-aminopropylamino-3-thiopropionate dihydrochloride,
5-Amino-5-pentylamino-3-thiopropionate dihydrochloride,
2- (2-amino-ethoxy) -2-ethylamino-3-thiopropionate dihydrochloride
2-amino-4-aminobutyrate thiobutyrate dihydrochloride,
3-amino-4-aminopropylamino-4-thiobutyrate dihydrochloride,
5-aminopropylamino-4-thiobutyrate dihydrochloride,
2- (2-amino-ethoxy) -2-amino-thiobutyrate dihydrochloride
ethyl,
- 2-amino-6-amino-thiocaproate dihydrochloride,
the dihydrochloride of the thioalaninate of 3-aminopropyl,
5-amino pentyl thioalaninate dihydrochloride, and
- (2-amino-ethoxy) -2-ethyl thioalaninate dihydrochloride.

dans laquelle
A, R1 et m ont les mêmes significations que ci-dessus pour la formule générale (I)
Ce disulfure peut également se présenter sous forme d'un sel cosmétiquement acceptable.The compositions according to the invention can also be in the so-called "self-neutralizing" or "self-regulated" form and in this case, the compound of general formula (I) is associated with at least one disulfide known for its use in a reducing composition for permanent self-neutralizing either derived from a compound of general formula (I) or from one of its salts and corresponding to the following general formula (III)

in which
A, R1 and m have the same meanings as above for the general formula (I)
This disulfide may also be in the form of a cosmetically acceptable salt.

 Among the known disulphides, mention may in particular be made of dithioglycolic acid, dithioglycerol, cystamine, N, N'-diacetyl-cystamine, cystine, pantethine, and the disulfides described in European Patent Applications EP 354,835 and EP 368,763.

Among the disulphides deriving from a compound of general formula (I) and corresponding to general formula (III), mention may be made of
N, N '- (2-dithiodiethanediyl) bis-2-aminoacetamide,
N, N '- (2-dithiodiethanediyl) bis-2-aminopropionamide,
N, N'-dithiobis (trimethylene) bis-2-vinylpropionamidea,
N, N '- (dithiodiethanediyl-2,1) bis [α] -amino benzene propionamide,
N, N '- (dithiodiethanediyl-2,1) bis [2-amino-4-methylpentanamide],
N, N '- (dithiodiethanediyl-2,1) bis-4-amino butanamide),
N, N '[dithiobis (trimethylene)] bisramino-3 propionamidi
[dithiobis (ethanediylamino-2,1)] -5,5'bis [amino-4]
5-oxo-pentanoic],
N, N- [dithio (trimethylene)] bis [2-aminoacetamide],
N, N'-Cdithiobis (pentamethylenebis-2-aminoacetamid)
N, N 'raithiobis (penramethylene bis-4-butanamide),
N, N'-ithiobis (2-ethyloxyethyl) 7-bis-2-aminoacetamide, and
N, N '- (dithiodiethanediyl-2,1)] bis-6-aminohexanamido.

In self-neutralizing compositions, the disulfide is generally present in a molar ratio of 0.5 to 2.5 and preferably
I to 2 relative to the compound of general formula (I) or its salts (see US Patent 3,768,490).

 The disulphides of general formula (III) are obtained by oxidation of the compounds of general formula (I) either with air or using known oxidants such as, for example, hydrogen peroxide in the presence, if appropriate, of metal salts such as, for example, salts ferrous.

dans laquelle
A, R1 et m ont les mêmes significations que données ci-dessus pour la formule générale (I) à l'exclusion des composés dans lesquels
(i) A représente (CH2)2 et m est 0 ou 1, et R1 représente un atome d'hydrogène, un radical alkyle, linéaire ou ramifié, ayant de 1 à atomes de carbone, un radical benzyle ou un radical carboxy-2 éthyle,
(ii) A représente (CH2)3 et m est 1, et R1 représente un atome d'hydrogène, et les sels desdits composés de formule (IV).The subject of the present invention is also, as new industrial products, the amino-mercaptoalkylamides corresponding to the following general formula (IV)

in which
A, R1 and m have the same meanings as given above for the general formula (I) excluding compounds in which
(i) A represents (CH 2) 2 and m is 0 or 1, and R 1 represents a hydrogen atom, a linear or branched alkyl radical having from 1 to carbon atoms, a benzyl radical or a carboxy-2 radical; ethyl,
(ii) A represents (CH2) 3 and m is 1, and R1 represents a hydrogen atom, and the salts of said compounds of formula (IV).

 The compounds of formula (IV) are prepared according to the methods mentioned for the preparation of the compounds of general formula (I).

Among the amino-mercaptoalkylamides of general formula (IV), mention may especially be made of
2-amino-N- (3-mercaptopropyl) acetamide,
2-Amino-N- (5-mercapto-pentyl) acetamide,
2-amino-N - [(2-mercaptoethoxy) -2-ethyl] acetamide,
2-amino-N- (3-mercaptopropyl) propionamide,
2-amino-N- (5-mercaptopentyl) propionamide,
2-amino-N- (2-mercaptoethoxy-2'-ethyl) propionamide,
3-amino-N- (3-mercaptopropyl) propionamide,
3-Amino-N- (5-mercapto-pentyl) propionamide,
3-amino-N- (2-mercaptoethoxy) -2'-ethylpropionamide,
4-amino-N- (2-mercaptoethyl) butanamide,
4-amino-N- (3-mercaptopropyl) butanamide,
6-amino-N- (5-mercapto-pentyl) butanamide,
4-amino-N - [(2-mercaptoethoxy) -2-ethyl] butanamide, and
6-amino-N- (2-mercaptoethyl) hexanamide,
as well as their hydrochlorides.

dans laquelle :
A, R1 et m ont les mêmes significations que celles données ci-dessus pour la formule générale (IV).The subject of the present invention is also the new disulphides of the following general formula (V)

in which :
A, R1 and m have the same meanings as those given above for the general formula (IV).

N, N '- [dithiobis (trimethylene)] bis [2-aminoacetamide],
N, N'-tdithiobis (pentamethylene) bis (2-aminoacetamide),
N, N'-dithiobis (2-ethyloxyethyl) 3-bis-2-aminoacetamide),
N, N'- [dithiodiethanediyl-2,1] bis-6-hexanamide),
N, N '- (dithiodiethanediyl-2,1) bis [4-aminobutanamide],
N, N'-pdithiobis (trimethylene) bis-4-aminobutanamide],
N, N'-dithiobis (pentamethylene) 9 bis [4-aminobutanamidea,
N, N'- [dithiobis (trimethylene)] bis-2-amino-propionamide,
N, N'-Cdithiobis (trimethylene) 9 bis-3-aminopropionamide,
N, N'-Edithiobis (pentamethylen bis Eamino-3 propionamide), and
N, N'-Cdithiobis (2-ethyloxyethyl)] bis-3-aminopropionamide.

dans laquelle
A, X, R1 et m ont les mêmes significations que celles données ci-dessus pour la formule générale (II), à l'exclusion des composés dans lesquels
(i) A représente -(CH2)2-, m est 0 ou 1, et Rlreprésente un atome d'hydrogène,
(ii) A représente -(CH2)2-, m est 0, R1 représente un radical méthyle, éthyle, isopropyle, isobutyle, méthylthioéthyle ou benzyle.The subject of the present invention is also, as new products, thioesters corresponding to the following general formula (VI)

in which
A, X, R1 and m have the same meanings as those given above for the general formula (II), with the exception of compounds in which
(i) A represents - (CH2) 2-, m is 0 or 1, and R1 represents a hydrogen atom,
(ii) A represents - (CH2) 2-, m is 0, R1 represents a methyl, ethyl, isopropyl, isobutyl, methylthioethyl or benzyl radical.

The compounds of general formula (VI) are obtained by reacting an aminothiol (I) with an amino acid acid halide (2) at a temperature between 40 and 1100C in the presence or absence of an inert solvent such as for example, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, acetonitrile, toluene, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,
N-methylpyrrolidone, dimethylacetamide or dimethylformamide, or a mixture of these solvents according to the following reaction

 The aminothiols and the acid halides used are prepared according to the conventional methods for synthesizing these compounds.

Among the thioesters of general formula (VI), mention may especially be made of
3-Amino-propyl thioglycinate dihydrochloride
5-amino pentyl thioglycinate dihydrochloride,
2-amino-2-ethoxy-2-ethyl thioglycinate dihydrochloride
2-amino-4-amino-4-thiobutyrate dihydrochloride,
3-aminopropylamino-4-thiobutyrate dihydrochloride,
5-aminopentyl amino-4-thiobutyrate dihydrochloride,
2-Amino-2-ethoxy-2-amino-4-thiobutyrate dihydrochloride
ethyl,
2-amino-6-amino-thiocaproate dihydrochloride,
3-aminopropylthioalaninate dihydrochloride,
5-amino-5-thioalaninate dihydrochloride, and
(2-amino-ethoxy) -2-ethyl thioalaninate dihydrochloride.

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

 The subject of the present invention is also a method of waving the hair in which a reducing composition as defined above is applied to wet hair previously wound on rolls having a diameter of 4 to 20 mm, the composition possibly being applied as the hair is rolled up; the reducing composition is then left to act for a period of 5 to 60 minutes, preferably 5 to 30 minutes, and then rinsed thoroughly after application to the wound hair of an oxidizing composition for reforming the disulfide bonds of the keratin during a exposure time of 2 to 10 minutes. After removing the rollers, the hair is thoroughly rinsed.

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

 The present invention also relates to a hair straightening or decreping process in which is applied to the hair a reducing composition according to the invention and then the hair is subjected to a mechanical deformation allowar.t fix in their new shape, by a smoothing operation of the hair with a comb with wide teeth, with the back of a comb or by hand. After a laying time of 5 to 60 minutes, in particular of 5 to 30 minutes, a new smoothing is then carried out and then rinsed thoroughly and an oxidizing or fixing composition as defined above is applied, which is left behind. act for about 2 to 10 minutes then rinse the hair thoroughly.

 Several examples of the preparation of the compounds according to the invention as well as examples of reducing compositions according to the invention and their use in a permanent hair deformation process will now be given by way of illustration and without any limitation.

EXAMPLES OF PREPARATION
EXAMPLE 1 Preparation of 2-Amino N- (2-Mercapto) Hydrochloride
ethyl) propionamide
(a) Dihydrochloride of 2-aminoethyl thioalaninate
To a suspension of 11.4 g (0.1 mol) of cysteamine hydrochloride in 350 cm3 of anhydrous acetonitrile is added, under an inert atmosphere, 14.4 g of hydrochloride chloride acid DL-alanine then heated to 80 C with stirring. After two hours, the reaction is complete (end of the evolution of hydrochloric acid). It is cooled to room temperature, the thioester formed is filtered off and recrystallized in methanol. Thus, after drying in vacuo at 50 ° C., 13.8 g of 2-aminoethyl thioalaninate dihydrochloride are obtained in the form of a white solid of melting point: 226 ° C.

 The 80 MHz E spectrum is in accordance with the expected structure.

Elemental analysis: C5H12N2OS, 2HC1
C% H% N% O% S% Cl%
Calc. 27.16 6.38 12.67 7.23 14.50 32.06
Tr. 27.25 6.36 12.60 7.45 -14.40 32.02
(b) To a suspension of 22.1 g of 2-aminoethylthioalaninate dihydrochloride (0.1 mole), obtained above, in 50 cm3 of isopropanol, is added dropwise under an inert atmosphere, 20, 4 cm3 (0.15 mole) of 2.5% aqueous ammonia solution. The solution obtained is evaporated to dryness under reduced pressure. The residue is taken up in 100 cm3 of ethanol. The insoluble ammonium chloride is separated by filtration on sintered glass. The filtrate is evaporated to dryness and dried under vacuum at 500C. 17.5 g of 2-amino-N- (2-mercaptoethyl) propionamide are thus obtained in the form of a white solid with a melting point of 141 ° C.

 The FMH1H 80NXz spectrum is consistent with the expected structure.

Elemental analysis: C5H12N20S, HCl
C% H% N% O% S% Cl%
Calc. 32.52 7.09 15.17 8.66 17.36 19.2
Tr. 31.63 7.17 14.80 10.29 16.97 18.69
EXAMPLE 2 Preparation of 2-amino-N- (2-mercaptoethyl) acetamide hydrochloride
(a) 2-aminoethyl thioglycinate dihydrochloride
To a suspension of 11.4 g (0.1 mol) of cysteamine hydrochloride in 50 cm3 of anhydrous acetonitrile is added under an inert atmosphere and with stirring, 13 g (0.1 mole) of hydrochloride hydrochloride acid glycine then heated for three hours at 75 ° C. After cooling to room temperature, the crude thioester is filtered off, which is purified by two successive washes in 40 cm 3 of methanol. After drying under vacuum at 500 ° C., 15.1 g of dihydrochloride are obtained. 2-aminoethyl thioglycinate in the form of a white solid decomposing at 165 ° C.

 The spectrum REsE1H 80 MHz is in accordance with the expected structure.

Elemental analysis: C4H1oN2OS, 2HC1
C% H% N% O% S% Cl%
Calc. 23.20 5.84 13.53 7.72 15.48 34.23
Tr. 23.37 5.93 13.32 7.96 15.42 33.99
(b) To a suspension of 30 g (0.145 mol) of 2-aminoethyl thioglycinate dihydrochloride, obtained above, is added dropwise in 15 minutes, at room temperature under an inert atmosphere and with stirring, 152 cm3 aqueous ammonia solution at 5%. The solution obtained is evaporated to dryness under reduced pressure. Isopropanol (100 cc) is added to the residue: and evaporated again to dryness and then 200 cm3 of ethanol are added, the mixture is stirred at ambient temperature to disperse finely and the ammonium chloride is filtered off with sintered glass. The filtrate is evaporated to dryness. The white solid obtained (23.3 g) is recrystallized from isopropanol. After drying and drying under vacuum, 16.4 g of 2-amino-hydrochloride are obtained.
N- (2-mercaptoethyl) acetamide as a white solid, m.p .: 122 ° C.

 The spectra EMN1H 250 NHz and 13C are in accordance with the expected structure.

Elemental analysis: C4H10N2O2, HC1 CZHZN2OZSZ Cl Z
Calc. 28.15 6.50 16.41 9.37 18.79 20.77
Tr. 27.74 6.57 16.26 10.33 18.41 20.46
EXAMPLE 3 Preparation of 2-aminoethyl 4-amino-2-thiobutyrate dihydrochloride
To a suspension of 11.4 g (0.1 mole) of cysteamine hydrochloride in 40 cm3 of anhydrous acetonitrile is added, under an inert atmosphere and with stirring, 15.8 g (0.1 mole) of chloride hydrochloride. of 4-aminobutyric acid and heated for 5 hours at 80 ° C. After cooling to room temperature, the white solid is drained on sintered glass and then recrystallized from a 50/50 ethanol / methanol mixture. 50 ° C, 17.6 g of 2-amino-4-amino-4-thiobutyrate dihydrochloride are obtained in the form of a white solid with a melting point of 186 ° C.

 The 1 H NMR spectrum is consistent with the expected structure.

 Elemental analysis: C6H14N20S, 2HCl.

C% H% N% O% S% Cl%
Calc. 30.64 6.86 11.91 6.80 13.63 30.15
Tr. 29.88 6.92 11.59 7.46 13.40 29.33
EXAMPLE 4 Preparation of 2-aminoethyl 6-amino-thiocaproate dihydrochloride
This compound is prepared according to the same procedure as in Example 3 but starting from 18.6 g (0.1 mol) of hydrochloride of the acid chloride of 6-amino-caproic acid. After heating for 4 hours at 800 ° C., the mixture is cooled, filtered and recrystallized from a 70/30 ethanol / methanol mixture.

After drying under vacuum at 50 ° C., 15.8 g of 2-amino-2-amino-6-thiocaproate dihydrochloride are obtained in the form of a white solid with a melting point of 181 ° C.

 The KMN1H 80MHz spectrum is consistent with the expected structure.

 Elemental analysis: C8H18N2O2, 2HCl.

C% H% N% O% S% Cl%
Calc. 36.50 7.66 10.64 6.08 12.18 26.94
Tr. 36.48 7.22 11.38 6.44 12.70 26.72%
EXAMPLE 5 Preparation of N, N '- (dithiodiethanediyl-2,1) bis [2-aminoacetamide
To a solution of 50.5 g (0.29 mol) of 2-aminohydrochloride
N- (2-mercaptoethyl) acetamide, obtained in Example 2, in 500 cm3 of absolute ethanol is added dropwise 15.2 cm3 (0.15 mole) of hydrogen peroxide to 110 volumes while maintaining the temperature below 250C. After stirring for 24 hours, the crystallization of the disulphide is complete. We spin on ..

sintered glass, washed with 100 cm3 of absolute ethanol and dried under vacuum at 60 ° C.

43.1 g of white crystals of N, N '- (dithiodiethanediyl-2, 1) bis are obtained.
Camino-2 acetamidei melting point: 168-170C.

 The 80 MHz NMR spectrum is consistent with the expected structure.

 Elemental analysis: C8H18N4O2S2, 2HCl.

C% H% N% O% S% Cl%
Calc. 28.32 5.94 16.51 9.43 18.90 20.90
Tr. 28.04 6.09 16.23 10.45 18.69 20.64
EXAMPLE 6 Preparation of 4-amino-thiobutyrate dihydrochloride
3-amino propyl
A suspension of 12.8 g (0.1 mol) of mercapto-3 hydrochloride
propylene oxide and 11.58 g (0.1 mole) of hydrochloride
4-aminobutyric acid in 75 cm3 of anhydrous acetonitrile is stirred under an inert atmosphere and is heated for 4 hours under reflux.

After cooling to room temperature, the crude thioester
is drained, washed with ice-cold methanol and then recrystallized from a mixture
Ethanol / Ethanol (75/25). :
After drying under vacuum at 50 ° C., 17.5 g of
3-amino-4-aminopropylamino-4-thiobutyrate dihydrochloride in the form of a
white solid of melting point 205 C.

 The EMNlH 80 NEz spectrum is consistent with the expected structure.

EXAMPLE 7 Preparation of dichlorhydrate of thioglycinate dt (amino-2
ethoxy) -2 ethyl
A suspension of 15.7 g (0.1 mol) of hercapto-2 hydrochloride
ethoxy) -2'-ethylamine and 13 g (0.1 mole) of chloride hydrochloride
of glycine acid in 120 cm3 of anhydrous acetonitrile, is heated under
inert atmosphere and with stirring at 30 C for 30 minutes, then at reflux
during 1 h 30.

After cooling to room temperature, the crude thioester
is drained and then recrystallized in approximately 250 cm3 of ethanol.

After drying under vacuum at 400 ° C., 10 g of dihydrochloride are obtained.
(2-amino-ethoxy) -2-ethyl thioglycinate in the form of a white solid
melting point 145 C (decomposition).

 The NMR1H80 NEz spectrum is consistent with the expected structure.

EXAMPLE 8 Preparation of the Dihydrochloride of the Amino-5 Thioglycinate
pentyl
A suspension of 15.55 g (0.1 mol) of mercapto-5 hydrochloride
pentylamine and 13 g (0.1 mole) of the acid chloride hydrochloride of the
glycine in 60 cm3 of anhydrous acetonitrile, is heated under
inert, and with stirring for 3 hours at reflux.

After cooling to room temperature, the crude thioester
is drained, washed with isopropanol and then recrystallized from a mixture
of ethanol-methanol.

After drying under vacuum at 30 ° C., 18.6 g of
5-Amino-5-pentyl thioglycinate dihydrochloride in the form of a solid
melting point white 230oC (decomposition).

The 1H NMR spectrum is in accordance with the expected structure
EXAMPLES OF COMPOSITION
EXAMPLE A
According to the invention, a reducing composition of
permanent deformation of the hair by mixing the ingredients
following
A. REDUCTIVE COMPOSITION
2-amino-N-hydrochloride (2-mercaptoethyl) acetamide 17 17 g
Honethanolamine qs pH 8.5
Oleocetyl dimethyl hydroxyethyl amine chloride 0.3 g
Preservative ............................................. 0.2 g Perfume; 0.8 g
Demineralized water ............... qsp .............. 100 g
This composition is applied on wet hair
previously rolled up on rollers.
composition 15 minutes, rinse thoroughly with water and apply
next oxidizing composition
B. OXIDIZING COMPOSITION
Hydrogen peroxide ............................................... 1.5 g
Sodium lauryl ether sulphate oxyethylenated with 2 moles of ethylene oxide ................................... 3.75 g
Citric acid ........................................... 0,5 g
Sodium hydrogen phosphate ............................. 0.5 g
Perfume 0.3 g
Demineralised water qs 100 g
The oxidizing composition is allowed to act for about 5 minutes, after which the rollers are removed, and the hair is thoroughly rinsed with water. After drying under helmet, the hair has beautiful curls.

According to the same embodiment as in Example A, the hair was permanently deformed using the reducing and oxidizing compositions of Examples B to J below.
EXAMPLE B
A. REDUCTIVE COMPOSITION
2-amino-N-hydrochloride (2-mercaptoethyl) acetamide ....... 21 g
Ethylene diamine tetracetic acid ....................... 0,2 g
Triethanolamine qs pH 6.8
Lauramine oxide sold under the name "Armox DCD / w" by the company AKZO - 2.15 g
Perfume 0.6 g
Demineralized water qs ................................. 100 g
B. OXIDIZING CONTENT
Hydrogen peroxide ............................................. 2,0 g
Oleocetyl dimethyl hydroxyethyl ammonium chloride 0.3 g
Phosphoric acid 0.5 g p-ethoxyacetanilide (phenacetin) 0.1 g;
Protein hydrolyzate .................................. 0,5 g
Perfume 0.5 g Demineralized water ... .qsp 100 g
EXAMPLE C
A. REDUCTIVE COMPOSITION
2-Aminoethyl thioglycinate dihydrochloride 10 g
Ammonia solution at 20% NH3 .......................... 4.1 g
Monoethanolamine qsp pH 8.0
Ammonium hydrogen carbonate 2.0 g
Cocoamidopropylbetaine sold under the name "Tagabetaine HS" by the company GOLDSCHMIDT ............... 0.9 g
Demineralized water ... qsp ............................... 100 g
B. OXIDIZING CONTENT
Hydrogen peroxide ............................................... 2 , 5 g
Sodium stannate ......................................... 0.03 g
N, N dimethyl N-2 propenyl-2 propene-1 chloride
ammonium (polyquaternium-6) sold under the name
of "Merquat 100" by Mlerck Company - 1.25 g
Citric acid ................................................ 0.6 g
Perfume 0.5 g
Demineralized water ... qsp ................................. 100 g
EXAMPLE D
A. REDUCTIVE COMPETITION
2-aminoethyl thioglycinate dihydrochloride ............... 15 g
N, N '- (dithiodiethanediyl-2,1) bis [2-aminoacetamide] ...... 4.5 g
Pentasodium salt of diethylene triamine pentaacetic acid ... 0.2 g
Monoethanolamine..qsp ........ pH 8.9
Hydrogenated castor oil oxyethylenated with
60 moles of ethylene oxide sold under the name of
"NIKKOL HCO 60" by the company NIKKO CHEMICAL ............... 4 g
N, N dimethyl N-2 propenyl-2 propene-1 ammonium chloride
(polyquaternium 7) sold under the name of
"Merquat 550" by the company MERCK .......................... 3.8 g
Perfume 0.3 g
Demineralized water qs .................................... 100 g
B. OXIDIZING COMPOSITION
Hydrogen peroxide (200 volumes) ................................. 4.8 g
Stabilizer 0,1 g
D.Panthenol ............................................... 1.0 g
4-dimethyl-4 '- (4-methyl-3-pentenyl) cyclohexene-3
methanol (Bisabolol) sold under the trade name of
1, Dragosantol 2/012681 "by the company DRAGOCO 0.3 g
Lauryl dimethyl amine oxide ............................. 0.7 g
Perfume 0.4 g
Lactic acid qsp pH 3.0
Demineralized water qs ................................... 100 g
EXAMPLE E
A. REDUCTIVE COMPETITION
Dihydrochloride of 2-aminoethyl thioglycinate 5 g
2-Aminoethyl 4-amino-thiobutyrate dihydrochloride 6.5 g
Ammonia solution at 20% .................................. 4.4 g
Monoethanolamine qsp .... pH 7.5
Oleyl ether oxyethylenated with 20 moles of ethylene oxide 6.0 g
Lauryl ether oxyethylenated with 23 moles of ethylene oxide 1.0 g
Pentasodium salt of diethylene triamine pentacetic acid 0.5 g
Perfume 0.3 g
Demineralized water qs ................................... 100 g
B. OXIDIZING COMPOSITION
Hydrogen peroxide 1.5 g
Sodium lauryl ether sulphate oxyethylenated with 2 moles
ethylene oxide 3.75 g
Citric acid.; 0.5 g
Sodium hydrogen phosphate ............................... 0.5 g
Perfume 0.3 g
Demineralized water qs ................................... 100 g
EXAMPLE F
A. REDUCTIVE COMPOSITION
2-aminoethyl thioglycinate dihydrochloride 4 g
Dihydrochloride of 2-aminoethyl thioalaninate 3 g
2-Amino N- (2-mercaptoethyl) propionamide hydrochloride 2.5 g
Monoethanolamine qs pH 8.7
Cetrimonium chloride sold under the name "Dehyquart A" by Henkel, 1 g
Perfume 0.7 g
Demineralized water qs ................................... 100 g
B. OXIDIZING CONTENT
Sodium bromine ............................................ 8.0 Triethanolamine qsp; pH 8.0
Monosodium phosphate hydrate (12 H2O) ..................... 0.3 g
Trisodium phosphate hydrate (2 H 2 O) 0.5 g Cocoamidopropylbetaine sold under the trade name "Tegobetaine HS" by GOLDSCHMIDT ............. 1.0 g
Perfume 0.4 g
Demineralized water qs ................................... 100 g
EXAMPLE G
A. REDUCTIVE COMPETITION
2-Aminoethyl thioglycinate dihydrochloride 3.0 g
L-cysteine ............................................... .. 5.0 g
Monoethanolamine qs pH 9.3
Polyethylenated stearic ester with 8 moles of ethylene oxide sold under the name "yrj 45" by the company ICI ........................ ................. 1 g
Preservative 0.4 g
Perfume................................................. 0.3 g,
Demineralized water qs ................................... 100 g
B. OXIDIZING CONTENT
Oxygenated water................................................ 2.5 g
Sodium stannate .......................................... 0.02 g
Lauryl ammonium sulphate 1.5 g
Protein hydrolyzate ..................................... 0.6 g
Citric acid .............................................. 0, 5 g
Perfume 0.4 g
Demineralized water qs ................................... 100 g EXAMPLE H
A. REDUCTIVE COMPETITION
2-aminoethyl thioglycinate dihydrochloride 2.0 g
N-acetylcysteamine .......................................... 6.0 g
Ammonia solution qs .............. pH 8.0
Hydrogen ammonium carbonate ............................... 2.0 g
N, N dimethyl N-2 propenyl-2 propene-1 chloride
ammonium (polyquaternium-6) sold under the name of
"Merquat 100" by MERCK .......................... 2.5 g
Collagen hydrolyzate ..................................... 0.5 g
Oleocetyl dimethyl hydroxyethyl ammonium chloride. 1.0 g
Perfume 0.8 g
Demineralized water qs ................................... 100 g
B. OXIDIZING CONTENT
Hydrogen peroxide (200 vol.) ................................. 4.8 g
Stabilizer 0,1 g
D. Panthenol 1.0 g 4-dimethyl-4'- (4-methyl-3-pentenyl) cyclohexene-3
methanol (Bisabolol) sold under the name of
"Dragosantol 2/012681" for the DRAGOCO Company ............... 0.3 g
Lauryl dimethyl amine oxide .............................. 0,7 g
Fragrance 0.4 g Lactic acid qsp ~ pH 3.0
Demineralized water qs ................................... 100 g
EXAMPLE I
A. REDUCTIVE COMPETITION
Dihydrochloride of 2-aminoethyl thioglycinate 5.5 g
2-Aminoethyl 6-amino-thiocaproate dihydrochloride 7.3 g
Ammonia (20%) ............................................... 5 1 g Honoethanolamine qsp pH 8.3
Cocoamidopropylbetaine sold under the name "Tagobetaine HS" by GOLDSCHMIDT ............. 0.9 g
Vinyl pyrrolidone / methacrylamidopropyltrimethylammonium chloride 20% copolymer in water sold under the name "Gafquat HS 100" by GAF .................... 1.0 g
Preservative 0.2 g
Perfume 0.7 g
Demineralized water qs ................................... 100 g
B. OXIDIZING COMPOSITION
Oxygenated water................................................ 2.0 g
Oleocetyl dimethyl hydroxyethyl ammonium chloride 0.3 g
Phosphoric acid * 0.5 g p-ethoxyacetanilide (Phenyacetin) .......................... 0,1 g
Protein hydrolyzate ...................................... 0.8 g
Perfume................................................. 0.5 g
Demineralized water qs ................................... 100 g
EXAMPLE J
A. REDUCTIVE COMPOSITION
2-aminoethyl thioglycinate dihydrochloride ............ 1.5 g
Cysteamine, HCl .............................................. 5 , 2 g
Monoethanolamine qs pH 9.5
Cetyl trimethyl ammonium chloride ........................ 1.0 g
Perfume 0.6 g
Preservative 0.15 g
Demineralized water qs ................................... 100 g
B. OXIDIZING COMPOSITION
Sodium bromate .......................................... 8 g
Triethanolamine qsp pH 8.0
Monosodium phosphate hydrate (12H2O) 0.3 g
Trisodium phosphate hydrate (2 H 2 O) 0.5 g Cocoamidopropyl betaine sold under the name "Tagobetaine HS" by GOLDSCHMIDT ................ 1.0 g
Perfume 0.4 g
Demineralized water qs ................................... 100 g

Claims (3)

 1. New compounds, characterized by the fact that they correspond to the following general formula (IV)

 their corresponding disulfides.  hydrogen atom, and the salts of said compounds of formula (IV) as well as  (ii) A represents - (CH2) 3- and m is I, and R1 represents a  carbon atoms, a benzyl radical or a 2-carboxy-ethyl radical,  a hydrogen atom, a linear or branched alkyl radical having from 1 to 5  (i) A represents -iCH2i-2 and m is O or 1, and R1 represents  excluding compounds in which:  carbon,  hydrogen atom or a lower alkyl radical having 1 to 5 carbon atoms  (ii) when m is an integer from 1 to 4, R1 represents a  ethyl, a carboxymethyl radical or a 2-carboxyethyl radical,  4-amino-butyl, a 3-guanidinopropyl radical, a 2-methylthio radical  isobutyl, a methyl-2-butyl radical, a benzoyl radical, a radical  methyl radical, an ethyl radical, an isopropyl radical, a radical  (i) when m is 0, R1 represents a hydrogen atom, a  m is O or an integer from 1 to 4,  integer between 2 and 5, or the divalent radical - (CH2) 2 -O- (CH2) 2-,  in which - A represents the divalent radical - (CH2) n-, n being a number  2. Compounds according to claim 1, characterized in that  the compounds of formula (IV) are chosen from  2-amino-N- (3-mercaptopropyl) acetamide,  2-amino-N- (5-mercapto-pentyl) acetamide,  2-amino-N - [(2-mercaptoethoxy) -2'-ethylg acetamide,  2-amino-N- (3-mercaptopropyl) propionamide,  2-amino-N- (5-mercapto-pentyl) propionamide,  2-amino-N- (2-mercapto-ethoxy-2'-ethyl) propionamide,  3-amino-N- (3-mercaptopropyl) propionamide,  3-amino-N- (5-mercaptopentyl) propionamide,  3-amino-N-(2-mercaptoethoxy) -2'-ethylpropionamide,  4-amino-N- (2-mercaptoethyl) butanamide,  4-amino-N- (3-mercaptopropyl) butanamide,  4-amino-N- (5-mercapto-pentyl) butanamide,  4-amino-N - [(2-mercaptoethoxy) -2-ethylbutanamide, and  6-amino-N- (2-mercaptoethyl) hexanamide,  as well as their hydrochlorides.  3. Compounds according to claim 1, characterized in that  the disulfides are selected from  N, N- [dithiobis (trimethylene)] bis [2-aminoacetamide],  N, N- [dithiobis (pentamethylene)] bis [2-aminoacetamide],  N, N- [dithiobis (2-ethyloxyethyl)] bis [2-aminoacetamide], N, N'- [dithiodiethanediyl-2,1] bis-6-aminohexanamide,  N, N- [2-dithiethanediyl] bis [2-aminobutanamide],  N, N- [dithiobis (trimethylene)] bis [2-aminoacetamide],  N, N'- [dithiobis (pentamethylene)] bis-4-butanamide),  N, N- [dithiobis (trimethylene)] bis [2-amino-propionamide],  N, N- [dithiobis (trimethylene)] bis [3-aminopropionamide],  N, N- [dithiobis (pentamethylene)] bis [3-aminopropionamide], and  N, N- [dithiobis (2-ethyloxyethyl)] bis [3-aminopropionamide].