FR2669332A1 - New thioesters, a process for their preparation and their use in the synthesis of aminomercaptoalkylamides - Google Patents

Abstract

New thioesters corresponding to the following general formula: 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 0, 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, and X is Cl or Br, with the exclusion of the 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 and R1 represents a methyl, ethyl, isopropyl, isobutyl, methylthioethyl or benzyl radical. These compounds constitute intermediates in the synthesis of aminomercaptoalkylamides.

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 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 the aid of a composition containing a reducing agent (reduction step), then after having preferably rinsed the hair5 to reconstitute in a second time said disulfide bonds by applying, on the hair under tension, an oxidizing composition4 (oxidation stage, 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 peeling. -
The compositions for carrying out 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 a reducing agent.

 Of 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 reference product permanently, leading 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 considerable research, it has now been found, quite unexpectedly and surprisingly, that by 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 being technical.

 The reducing agents of the compositions according to the invention not only have the advantage of being substantially odor-free but also allow to obtain a higher yield, nervousness and crimp beauty than those obtained according to the state of the art. 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 CH 3, n being an integer between 2 and 5, or the divalent radical - (CH 2) 2 -O- (CH 2) 2-,
m is O or an integer between I and 4,
(i) when m is 0, R1 is hydrogen, methyl, ethyl, isopropyl, isobutyl, methyl-2-butyl, benzyl, 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, R1 represents a hydrogen atom or a lower alkyl radical having 1 to 5 carbon atoms, provided that when m is 1 and A represents the divalent radical - ( CH2) 22-, 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 that 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,
3-amino-N- (5-mercapto-pentyl) propionamide,
3-amino-N- (2-mercaptoethoxy) -2'-ethylpropionamide, 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-pentanoic acid,
4-amino-5- (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,
first used and their ease of implementation.

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

in which
A, RI and m have the same meanings as above for the general formula (I) and,
X is Cl 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 into amino
mercaptoalkylamides of the general formula (i) by treatment with a base.

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

<tb> base
<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. FAT 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 pu 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 acyl derivatives C -C such as N-acetylcysteamine or N-propionyl cysteamine, cysteine, N-acetylcysteine, N-mercaptoalkylamides of sugars such as N- (mercapto-2-ethyl) gluconamide, F-mercaptopropionic acid and its derivatives, thiolactic acid, pantethine, thioglycerol, sulphites or bisulphites 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 also contain various ingredients such as, for example, cationic polymers such as those used in the compositions of French Pat. Nos. 79,320,78 and 80,26421, or cationic ionene polymers such as those used in the compositions of the French patent. No. 82.-173.64, softening agents and in particular lanolin-derived quaternary ammoniums, protein hydrolysates, waxes, opacifying agents, perfumes, colorants, 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 te; as methanol, 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 one 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 CI or Br.

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

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

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

The pH of the composition is then adjusted, if necessary, to
using an alkaline agent or an acidifying agent such as
previously mentioned.

Among these thioesters there may be mentioned the compounds
following
the dihydrochloride of the amino-ethyl thioglycinate,
the dihydrochloride of 2-aminoethyl thioalaninate,
2-Aminoethyl 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 2-aminoethyl thiomethioninate,
the dihydrochloride of 3-aminopropyl thioglycinate,
5-amino-thioglycinate dihydrochloride,
2- (2-aminoethoxy) -2-ethyl thioglycinate dihydrochloride,
3-Amino-3-aminopropylamino-3-thiopropionate dihydrochloride
5-Amino-5-pentylamino-3-thiopropionate dihydrochloride,
3-Amino-2-ethoxyethylamino-3-thiopropionate dihydrochloride,
2-amino-4-amino-4-thiobutyrate dihydrochloride
3-Amino-3-propylamino-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 le 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
so-called "self-neutralizing" or "self-regulating" form and in this case the
compound of general formula (I) is associated with at least one disulfide is
known for its use in a reducing composition for permanent
self-neutralizing agent derived from a compound of general formula (I) or
one of its salts and corresponding to the following general formula (II):

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 disulfides, there may be mentioned dithioglycolic acid, dithioglycerol, cystamine, N, N'-diacetyl-cystamine, cystine, pantethine, and disulfide 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

<tb><SEP> N, N '- (dithiodiethanediyl-2, <SEP> 1) <SEP> bis <SEP> to min-2 <SEP> acetamide 2,
<tb><SEP>, N '- (dithiodiethanediyl-2.1) <SEP> bis <SEP> Camino-2 <SEP> propionamid
<tb><SEP> N, N'- <SEP> dithiobis <SEP> (trimethylene) <SEP> bis <SEP> Camino-2 <SEP> propionamide),
<tb><SEP> N <SEP>, N '<SEP> - (dithiodiethanediyl-2, <SEP> 1) bis <SEP> C <-amino <SEP> benzene
<tb> propionamide3 <SEP>,
<tb><SEP> N, N '- (dithiodiethanediyl-2.1) bis <SEP> Eamino-2 <SEP> methyl-4 <SEP> pentanamrdi <SEP>,
<tb><SEP>, N '- (dithiodiethanediyl-2.1) bis <SEP> to min-4 <SEP> butanamidell,
<tb><SEP> N, NT <SEP> [dithiobis <SEP> (trimethylene) bis <SEP> [amino-3 <SEP> propionamid3
<tb> acid <SEP> Udithiobis (ethanediylimino-2,1) g <SEP> -5,5 <SEP>'bis<SEP> pamino-4
<tb> oxo-5 <SEP> pentanolquea
<tb><SEP> N, N'-pdithiobis (trimethylene M <SEP> bisCamino-2 <SEP> acetamide3,
<Tb>

<tb><SEP> N, N '<SEP> -dithiobis <SEP>(pentamethylene>SEP> bis <SEP> O-amino-2 <SEP> acetamide
<tb> the <SEP> X, N'-0eithiobis (pentamethylene S <SEP> bis <SEP> Camino-4 <SEP> butanamidel
<sep> N, N'-ithiobis (ethyloxy-2 <SEP> ethyl) 3 <SEP> bis <SEP> Camino-2 <SEP> acetamide3 <SEP>, <SEP> and
<tb><SEP> N, N'-O (dithiodiethanediyl-2,1) O <SEP> bis <SEP> Camino-6 <SEP> hexanamid.
<Tb>

In self-neutralizing compositions the disulfide is
generally present in a molar ratio of 0.5 to 2.5 and preferably
1 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 in air or in
using known oxidants such as, for example, oxygenated slug in the presence
optionally metal salts such as for example ferrous salts.

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 (CE2)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 present invention also relates to products
new industrial amino-mercaptoalkylamides corresponding to the formula
General (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 (CE2) 2 and m is 0 or 1, and R1 represents a hydrogen atom, a linear or branched alkyl radical having 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 notably be made of:
2-amino-N- (3-mercaptopropyl) acetamide,
2-amino-N- (5-mercaptopentyl) acetamide,
2-amino-N - [(2-mercaptoethoxy) -2-ethyl] 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-mercapto-pentyl) propionamide,
3-amino-N - [(2-mercaptoethoxy) -2-ethyl] propionamide,
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).

dans laquelle
A, X, R1 et m ont les mêmes significations que celles données ci-dessus pour la formule générale (Il), 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.<tb> the <SEP> N, N'-<SEP> Cdithiobis (trimethylene) g <SEP> bis <SEP> tamino-2 <SEP> acetamidje,
<tb><SEP> N, N'-<SEP> Sdithiobis (pentamethylene) J <SEP> bis <SEP> Camino-2 <SEP> acetamidej,
<tb><SEP> N, N'-<SEP> rdithiobis (ethyloxy-2 <SEP> ethyl) <SEP> bis <SEP> Camino-2 <SEP> acetamide9,
<tb><SEP> N <SEP> dithiodiethanediyl-2,13 <SEP> bis <SEP> Camino-6 <SEP> hexanamidea,
<tb><SEP> N, N'-<SEP> pdithiodiethanedyl-2, <SEP> u <SEP> bis <SEP> (amino-4 <SEP> butanamidil,
<tb> the <SEP> N, <SEP> dithiobis (trimethylene) <SEP> bis <SEP> Camino-4 <SEP> butanamide,
<tb><SEP> N, N'-<SEP> tdithiobis (pentamethylene) 9 <SEP> bis <SEP> Eamino-4 <SEP> butanamidea,
<tb> the <SEP> N, N'-<SEP> Cdithiobis (trimethyleneg <SEP> bis <SEP> Camino-2 <SEP> propionamide),
<tb><SEP> N, N'-<SEP> Cdithiobis (trimethylene) 9 <SEP> bis <SEP> Camino-3 <SEP> propionamide,
<tb> the <SEP> N, N'- <SEP> Edithiobis (pentamethylene S <SEP> bis <SEP> Eamino-3 <SEP> propionamide), and
<tb><SEP> N, N '<SEP> - <SEP> Cdithiobis (ethyloxy-2 <SEP> ethyl <SEP> bis <SEP> Camino-3 <SEP> propionamide.
<Tb>
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 (1) 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 of synthesis. of 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-ethoxy-2-ethyl thioglycinate dihydrochloride,
2-amino-4-amino-4-thiobutyrate dihydrochloride,
3-Amino-3-aminopropylamino-4-thiobutyrate dihydrochloride
5-aminopentyl amino-4-thiobutyrate dihydrochloride,
(2-amino-ethoxy) -2-amino-4-thiobutyrate dihydrochloride
ethyl,
2-amino-6-amino-thiocaproate dihydrochloride,
3-Amino-propyl thioalaninate 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, in 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 possibly allowing oxygen to act 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 allowed to act for a period of time
from 5 to 60 minutes, preferably from 5 to 30 minutes, then rinsed thoroughly
after which, on the coiled hair, an oxidizing composition is applied
to reform the disulfide bonds of keratin during a
exposure time of 2 to 10 minutes. After removing the rollers, rinse
abundantly the hair.

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

The present invention also relates to a method of
straightening or straightening hair in which one applies on
hair a reducing composition according to the invention and then subject
hair to a mechanical deformation allow to fix them in their
new shape, by a smoothing operation of the hair with a comb to
wide teeth, with the back of a comb or by hand. After a set time
from 5 to 60 minutes, in particular from 5 to 30 minutes, then
new smoothing then rinse thoroughly and apply a composition
oxidizing or fixing agent as defined above, which is allowed to act
for about 2 to 10 minutes then rinses the hair thoroughly.

We will now give as an illustration and without any
limiting nature, several examples of 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 deformation process
hair.

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 in 350 cm3 of anhydrous acetonitrile is added, under an inert atmosphere, 14.4 g of chloride hydrochloride DL-alanine acid and then heated to 800C 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 1 H NMR 80 HHz spectrum is consistent with the expected structure.

Elemental analysis: C5H12N20S, 2HCl
C% H% N% OZS% CI%
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-aminoethyl thioalaninate dihydrochloride (0.1 mol), obtained above, in 50 cm 3 of isopropanol, is added dropwise, under an inert atmosphere, 20.4 cm3 (0.15 mole) of aqueous ammonia solution at 2.5 Z. The solution obtained is evaporated to dryness under reduced pressure. The residue is taken up in 100 cm3 of methanol. The insoluble ammonium chloride is separated by filtration on sintered glass. The filtrate is evaporated to dryness and dried under vacuum at 500 ° C. 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 PMN1H 80MHz spectrum is in accordance with the expected structure.

Elemental analysis: C5H12N20S, ECI
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 the glycine is 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 50 ° C., 15.1 g of dihydrochloride of 2-aminoethyl thioglycinate in the form of a white solid decomposing at 1650 C.

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

Elemental analysis: C4H10N20S, 2HCl
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. 100 cm3 of isopropanol 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 centrifugation and drying under vacuum, 16.4 g of 2-aminohydrochloride are obtained.
N- (2-mercaptoethyl) acetamide in the form of a white solid of melting point: 122 C.

 The 250 MHz and 13C NMR spectra are in accordance with the expected structure.

Elemental analysis: C4H10N20S, HCI r-
C% H% N% O% S% Cl%
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 Amino-4-Aminoethyl 4-thiobutyrate dihydrochloride ethyl
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 800C. After cooling to room temperature, the white solid is drained on sintered glass and then recrystallized from a 50/50 ethanol / methanol mixture. After drying under vacuum at 50 ° C., 17.6 g of 4-amino-thiobutyrate dihydrochloride are obtained. 2-aminoethyl in the form of a white solid of melting point: 186 C.

 The REN1H spectrum 80MHz is consistent with the expected structure.

 Elemental analysis: C6H14N2OS, 2HC1.

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 80 ° 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 dihydrochloride are obtained.
2-amino-amino-6-thiocaproate in the form of a white solid of melting point: 1810C.

 The spectrum tNN1H 80MHz is consistent with the expected structure.

 Elemental analysis: C8H18N2OS, 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, 15.2 cm3 (0.15 mole) of hydrogen peroxide at 110 volumes are added dropwise while maintaining temperature below 25 C. After 24 hours of stirring, crystallization of the disulfide is complete. It is filtered 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 '- (dithiodiéthanediyl-2,1) bis [amino-2-acetamide] with a melting point of 168-170 ° C. are obtained.

 The 80 MHz REN1H spectrum is in accordance 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
of 3-aminopropyl A suspension of 12.8 g (0.1 mole) 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
inert atmosphere and is heated for 4 hours at reflux.

After cooling to room temperature, the crude thioester
is drained, washed with ice-cold methanol and then recrystallized from a mixture
Ethanol / Methanol (75/25).

After drying: under vacuum at 50 ° C., 17.5 g of
3-aminopropylamino-4-thiobutyrate dihydrochloride in the form of a
white solid of melting point 205 C.

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

EXAMPLE 7 Preparation of the dihydrochloride of thioglycinate of (amino-2
ethoxy) -2 ethyl
A suspension of 15.7 g (0.1 mol) of tmercapto-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 300C 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 1H 80 MHz NMR 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
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
white melting point 230 C (decomposition).

 The 1 H NMR spectrum is consistent 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. REDUCING COMPOSITION:
2-amino-N-hydrochloride (2-mercaptoethyl) acetamide ..... 17 g
Monoethanolamine qs pH 8.5
Oleocetyl dimethyl hydroxyethyl amine chloride 0.3 g
Preservative 0.2 g Perfume; 0.8 g
Demineralised water qs 100 g
This composition is applied on wet hair
previously rolled up on rollers. After letting act
composition 15 minutes, rinse thoroughly with water and apply
next oxidizing composition
B. OXIDIZING CONTENT
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 ....... qsp .......................... 100 g
The oxidizing composition is allowed to act for about 5 minutes: then the rollers are removed, and the hair is thoroughly rinsed off.
the water. After drying under helmet, the hair has beautiful curls.

According to the same embodiment as in example A, we have
proceeded to a permanent deformation of the hair using the compositions
reducing and oxidizing examples B to J
EXAMPLE B
A. REDUCTIVE COMPOSITION
2-amino-N-hydrochloride (2-mercaptoethyl) acetamide ..... 21 g
Ethylene diamine tetracetic acid ..................... 0.2 g
Trienolamine qsp ..... pH 6.8 Lauramine oxide sold under the name of
"Aromox DMMCD / W" by AKZO ................... 2.15 g
Perfume 0.6 g
Demineralized water qs ............................... 100 q
B. OXIDIZING COMPOSITION
Hydrogen peroxide ............................................. 2.0 g
Droleocetyl dimethyl hydroxyethyl ammonium chloride 0.3 g
Phosphoric acid ....................................... 0,5 g
p-ethoxyacetanilide (phenacetine) ........................ 0.1 g
Hidrolisat of proteins .................................. 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
Cocoamidopropyl betaine sold under the name of
"Tegobetaine 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 the company MERCK ............... 1.25 g
Citric acid ........................................ 0.6 g
Perfume 0.5 g
Demineralized water ... qsp ........................... 100 g EXAMPLE D
A. REDUCTIVE COMPOSITION
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 MERCK Company .................. 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-methyl-3-pentenylcyclohexene-3
methanol (Bisabolol) sold under the trade name of
"Dragosantol 2/012681" by the company DRAGOCO ................. 0.3 g
Lauryl dimethyl amine oxide ................................ 0.7 g
Fragrance 0.4 g Lactic acid qsp fold 3.0
Demineralized water qs ..................................... 100 g
EXAMPLE E
A. REDUCTIVE COMPETITION
Dihydrochloride of 2-aminoethyl thioglycianate .............. 5 g
2-Aminoethyl 4-amino-thiobutyrate dihydrochloride 6.5 g
Ammonia solution at 20% .................................... 4.4 g
Monoethanolamine qs ................ 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 pentaacetic acid ................................. 0.5 g
Perfume 0.3 g
Demineralized water qs .......................................

B. OXIDIZING COMPOSITION
Oxygenated water................................................ ... 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 gX
Demineralized water qs ....................................... 100 g
EXAMPLE F
A. REDUCTIVE COMPETITION
2-aminoethyl thioglycinate dihydrochloride 4 g
Dihydrochloride of 2-aminoethyl thioalaninate 3 g
2-Amino N- (2-mercaptoethyl) propionamide hydrochloride 2.5 g
Monoethanolamine qsp fold 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 bromate ............................................. 8, 0 g Triethanolamine qsp ply 8.0
Monosodium phosphate hydrate (12 H2O) ......................... 0.3 g
Trisodium phosphate hydrate (2 H2O) ........................... 0.5 g
Cocoamidopropylbetaine sold under the trade name
of "Tagobetaine HS" by the company 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 qsp fold 9.3
Polyethylenated stearic ester with 8 moles of oxide
ethylene sold under the name "Myrj 45"
by the Company HERE ............................................. 1 g
Preservative 0.4 g
Perfume 0.3 gs,
Demineralized water qs ...................................... 100 g
B. OXIDIZING CONTENT
Oxygenated water................................................ .... 2.5 g
Sodium stannate .............................................. 0 , 02 g
Lauryl ammonium sulphate ....................................... 1.5 g
Hydrolysing Protein * 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 qsp; .pw 8.0
Ammonium hydrogen carbonate .................................. 2,0 g
N, N dimethyl N-2 propenyl-2 propene-1 chloride
ammonium (polyquaternium-6) sold under the name of
"Marquat 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 COMPOSITION
Hydrogen peroxide (200 volumes) ...................................... 4.8 g
Stabilizing................................................. 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" by the company DRAGOCO ................... 0.3 g
Lauryl dimethyl amine oxide ................................. 0,7 g
Perfume 0.4 g
Lactic acid qsp pE 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
Monoethanolamine qsp pH 8.3 Cocoamidopropylbetaine sold under the name "Tegobetaine HS" by GOLDSCHMIDT ................ 0.9 g
Vinyl pyrrolidone / methacrylamidopropyl chloride copolymer
trimethylammonium 20% in water sold under the name "Gafquat HS 100" by the company GAF ........................ 1.0 g
Preservative 0.2 g
Perfume 0.7 g
Demineralized water qs ...................................... 100 g
B. OXIDIZING CONTENT
Oxygenated water................................................ ..2.0 g
Oleocetyl dimethyl hydroxyethyl ammonium chloride 0.3 g Phosphoric acid, 0.5 g
p-ethoxyacetilanilide (Phenacetin) ........................... 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
Monoethanoamine qs pH 9.5
Cetyl Trimethylammonium 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 (12 H2O) .......................... 0.3 g
Trisodium phosphate hydrate (2H2O) 0.5 g
Cocoamidopropylbetaine sold under the name
"Tegobetaine HS" by the company GOLDSCHMIDT .................... 1.0 g
Perfume................................................. ........ 0.4 g
Demineralized water qs ....................................... 100 g

Claims (3)

 1. New compounds characterized by the fact that they satisfy the following general formula (VI)

 methyl, ethyl, isopropyl, isobutyl, methylthioethyl or benzoyl.  (ii) A represents - (CH2) 2-, m is 0, R1 represents a radical  hydrogen atom,  (i) A represents -4CH2 + 2, m is 0 or 1 and R1 represents a  excluding compounds in which  carbon, and X is CI or  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 benzyl radical, a radical  methyl radical, an ethyl radical, an isppropyl radical, a radical  (i) when m is O, 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, A represents the divalent radical - (CH2) n-.n being a number  in which  2. Compounds according to claim 1, characterized by the fact  that they are chosen from  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-Amino-5-pentyl 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.  3. Process for the preparation of compounds according to claims 1 and 2, characterized in that it consists in reacting an aminothiol of formula: LiX, H2N-A-SH with an amino acid acid halide of formula

 inert.  approximately 40 and 110 ° C. in the presence or absence of at least one organic solvent  A, X, R1 and m have the same meanings as those given in claim 1, the reaction being conducted at a temperature between  in which