LU87378A1 - MERCAPTO-4 BUTYRAMIDES N-MONO OR N, N-DISUBSTITUTED BY A MONO OR POLYHYDROXYALKYL RADICAL, AND THEIR USE AS REDUCING AGENTS IN A PERMANENT HAIR DEFORMATION PROCESS - Google Patents

Abstract

4-Mercaptobutyramides N-mono or N,N-disubstituted by a mono- or polyhydroxyalkyl radical, characterised in that they correspond to the following general formula: <IMAGE> in which: R1 denotes a hydrogen atom, a lower alkyl radical or a monohydroxyalkyl or polyhydroxyalkyl radical containing from 1 to 6 carbon atoms which are optionally interrupted by an oxygen, nitrogen or sulphur atom, and R2 denotes a monohydroxylalkyl or polyhydroxylalkyl radical containing from 1 to 6 carbon atoms which are optionally interrupted by an oxygen, nitrogen or sulphur atom, or R1 and R2 taken together with the nitrogen atom form a piperazine ring substituted in the 4 position by a mono- or polyhydroxyalkyl radical containing from 1 to 6 carbon atoms, and their corresponding disulphides. Use of these compounds as reducing agents in a process for permanent deformation of hair.

Description

The present invention relates to new 4-mercapto-butyramides N-mono or Ν, Ν-disubstituted by a mono or polyhydroxyalkyl radical and their use, as reducing agents, in a process for 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 disulfide 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 decoupage.

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 and 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 for permanent use, and which leads to a reduction rate of approximately 50%.

However, these reducing agents have a major drawback insofar as they give off bad odors, which are 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 overcome this drawback, use is generally made of a perfume making it possible to mask odors.

Studies have also been conducted to develop new odorless reducing agents. Thus, in Japanese patent application (KOKAI) No. 260.058 / 86, the use of N-mercaptoalkylgluconamides which are water-soluble, low volatility and practically odorless compounds has been proposed.

These N-mercaptoalkylgluconamides are obtained by reaction of the glucono-lactone with an aminoalkanethiol.

These new reducing agents, although they make it possible to remedy the drawbacks of known reducing agents, do not however have excellent reducing properties compared with in particular thioglycolic acid.

Amides of thioglycolic acid and 3-mercapto-propionic acid are also known (see JW HAEFELE et al, Proceedings of Scientific Section, 1959, 32 p.52) and have been studied in skin sensitization (see J. Invest Dermatol. 32, 273-279, 1958). According to the test used for this study, N-hydroxyethyl thioglycolamide and N- (hydroxyethyl) mercapto-3 propionamide were found to be sensitizers.

It has now been found, quite surprisingly that by using a new class of mercaptoalkylamides, namely mercapto-4 butyramides N-mono or Ν, Ν-disubstituted by a mono or polyhydroxyalkyl radical, it was possible to overcome the drawbacks reducing agents mentioned above.

The mercapto-4 butyramides according to the invention are generally less toxic and are therefore very particularly suitable, because of their excellent reducing properties, as reducing agents in the processes of permanent deformation of the hair.

The reducing properties are indeed quite comparable to those of thioglycolic acid but the odor, which is less pronounced and moreover different from that of thioglycolic acid, is much easier to mask during use. .

The subject of the present invention is, as new industrial products, 4-mercapto-butyramides N-mono or N, N-disubstituted by a mono or polyhydroxyalkyl radical, soluble in water, corresponding to the following general formula:

(I) in which: r represents a hydrogen atom, a lower alkyl radical or a monohydroxyalkyl or polyhydroxyalkyl radical having from 1 to 6 carbon atoms, optionally interrupted by an oxygen, nitrogen or sulfur atom, and R2 represents a monohydroxyalkyl or polyhydroxyalkyl radical having from 1 to 6 carbon atoms optionally interrupted by an oxygen, nitrogen or sulfur atom, or Rj and R2, taken together with the nitrogen atom, form a piperazine ring substituted in 4 by a mono or polyhydroxyalkyl radical having from 1 to 6 carbon atoms.

By lower alkyl radical is meant a radical having from 1 to 6 carbon atoms and preferably the methyl, ethyl, propyl, isopropyl and butyl radical.

Among the monohydroxyalkyl and polyhydroxyalkyl radicals having from 1 to 6 carbon atoms, optionally interrupted by an oxygen, nitrogen or sulfur atom, there may be mentioned: the 2-hydroxyethyl radical, 2,3-dihydroxypropyl, dimethyl-1 1.1 hydroxy-2 ethyl, pentahydroxy-2,3,4,5,6 hexyl (rest of sorbitol) and hydroxy-2 ethyloxyethyl.

Among the 4-mercapto-butyramides of formula (I) above, the following may in particular be cited: - N- (2-hydroxyethyl) 4-mercapto-butyramide, - N- (2-hydroxyethylethyloxyethyl) 4-mercapto-butyramide , - N- (2,3-dihydroxy propyl) mercapto-4 butyramide, - N, N-di (2-hydroxyethyl) mercapto-4 butyramide, - N- (mercapto-4 butyryl) N-methylglucamine, - N- (4-mercapto-butyryl-1) N '- (2-hydroxyethyl) piperazine, - N- (dimethyl-1,1,1-hydroxy-2 ethyl) mercapto-4 butyramide.

The present invention also relates to the method of

preparation of the 4-mercapto-butyramides according to the invention, this process consisting in reacting an amine (1) with -thiobutyrolactone (2) according to the following reaction scheme:

Among the amines (1) there may be mentioned in particular.

Ethanolamine, diethanolamine, diglycolamine, meglumine or N-methylglucamine, 2,3-dihydroxy propylamine, 2-amino-2-methyl propanol and 2-hydroxy-piperazine hydroxy.

The

-thiobutyrolactone (2) is a commercial product.

The opening reaction of the

-thiobutyrolactone is generally carried out under an inert atmosphere in an aromatic solvent such as toluene or an alcohol such as methanol, ethanol, isopropanol or butanol, and, depending on the boiling point of the solvent, at a temperature comprised between 50 and 110 ° C.

However, according to a preferred form of the invention, the reaction is carried out without solvent and in this case, amine (1) and -thiobutyrolactone (2) are mixed in stoichiometric proportions, then the mixture is brought to an inert atmosphere. a temperature between

50 and 110 ° C.

Depending on the basicity of the amine (1), the reaction time can be between 2 and 8 hours, the progress of the reaction being monitored by measuring the appearance of the thiol and the disappearance of the amine function.

If during the reaction a certain quantity of thiol is oxidized to the corresponding disulfide, the reaction mixture is then diluted by twice its volume of water and 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.

This treatment using a sulfonic resin also makes it possible to fix the traces of free amine (1) which has not reacted.

The 4-mercapto-butyramides can also be obtained by the amidation reaction of 4-mercapto-butyric acid or its esters. However, the preparation process described above from the

-thiobutyrolactone is faster and does not lead to the formation of side products which sometimes are very smelly and contaminate the final product.

The present invention also relates to a reducing composition, for the first time in a permanent hair deformation operation, containing in a suitable cosmetic vehicle, at least one 4-mercapto-butyramide of formula (I) as defined above , as a reducing agent.

Preferably, the reducing agent is present in the composition according to the invention at a concentration of between 2 and 20% by weight and preferably between 5 and 10% by weight relative to the total weight of the reducing composition.

The pH of the composition is generally between 6.5 and 10, and obtained using alkaline agents such as, for example, ammonia, monoethanolamine, diethanolamine, triethanolamine, a carbonate or an alkaline bicarbonate or ammonium.

The reducing composition can also contain various ingredients such as for example cationic polymers such as those used in the compositions of French patents No. 79.32078 and 80.26421 or also cationic polymers of the ionene type such as those used in the compositions of French patent No. 82.17364, softening agents and in particular quaternary ammoniums derived from lanolin, protein hydrolysates, waxes, opacifying agents, perfumes, dyes, surfactants or even treating agents.

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 emulsions, for example based on glyceryl stearate, glycol stearate, self-emulsifying waxes, fatty alcohols, etc. We can also 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 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 min, of a reducing composition as defined above then in a second step to reform said bonds by applying an oxidizing composition.

When it is a hair waving process, 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, on the coiled hair, an oxidizing composition is applied which makes it possible to reform the disulfide bonds I keratin for a time from 2 to 10min. 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 persei or a mixture of alkali bromate and a persei. The concentration of hydrogen peroxide can vary from 3 to 10 volumes, the concentration of alkaline bromate from 2 to 12% and that of persei from 0.1 to 15% by weight relative to the total weight of the oxidizing composition.

When it is a hair straightening or straightening process, a reducing composition according to the invention is applied to the hair and then the hair is subjected to mechanical deformation making 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 carefully and apply the oxidizing or fixing composition which is left to act for approximately 2 to 10 min and then rinsed abundantly hair.

We will now give by way of illustration and without any limiting character, several examples of preparation of the 4-mercapto-butyramides as well as several examples of reducing compositions containing them.

EXAMPLE I

Preparation of N- (2-hydroxyethyl) mercapto-4 butyramide A 61.10 g of ethanolamine stirred under an inert atmosphere at 75 ° C. 102 g of

-thiobutyrolactone. The temperature rises to 90 ° C during the addition and at the end of this the mixture is further stirred for one hour at a temperature between 85 and 90 ° C, time after which the ethanolamine is completely transformed.

160 g of N- (2-hydroxyethyl) 4-mercapto-butyramide are obtained in liquid form at ordinary temperature, the dosage of thiol and the spectrum of R.M.N. conform to the expected structure.

The elemental analysis corresponds to a partially hydrated product: CgH NO S, 0.25 Hy.

C H N 0 S

Hold: 41.80 8.19 8.13 23.22 18.61

Tr: 42.09 7.89 8.15 23.20 18.70

EXAMPLE II

Preparation of N- (2-hydroxyethyloxyethyl) mercapto-4 butyramide

In half an hour, add 102g of

-thiobutyrolactone, drop by drop, to 105 g of diglycolamine stirred under an inert atmosphere at 70 ° C. The temperature rises to 95 ° C during the addition. This being completed, the mixture is further stirred for 2 hours at 85 ° C., at the end of which all the starting amine is transformed. 205 g of N- (2-hydroxyethyloxyethyl) mercapto-4 butyramide are obtained in the form of a slightly pink liquid. The thiol assay and the H spectrum R.M.N. correspond to the expected structure. The elementary analysis corresponds to a partially hydrated product: CgEyNOy, 0.25 Hy.

C H N o s

Calc: 45.36 8.32 6.61 24.55 15.14

Tr: 45.66 8.27 6.70 24d29 15.28

EXAMPLE III

Preparation of N- (2,3-dihydroxv-propyl) mercapto-4 butyramide A 91.1 g of 2,3-dihydroxy propylamine stirred under an inert atmosphere at a temperature of 80 ° C. 102 g of

-thiobutyrolactone. The reaction is exothermic. When the addition is complete, the mixture is further stirred for 2 hours at a temperature between 80 ° and 90 ° C. time after which all the amine is transformed. 190 g of N- (2,3-dihydroxy propyl) -mercapto-4-butyramide are obtained in the form of a white solid, the melting point of which is: 48 ° C. Thiol assay and spectrum ^ R.M.N. correspond to the expected structure.

Elemental analysis corresponds to a partially hydrated product: C7H15N03S ’0.25 H20.

C H N 0 S

Hold: 42.51 7.90 7.08 26.29 16.21

Tr: 42.76 7.89 7.10 26.09 16.40

EXAMPLE IV

Preparation of N- (4-mercapto-butyryl-1) N '~ (2-hydroxyethylQ piperazine A 130.2 g of N- (2-hydroxyethyl) piperazine agitated under an inert atmosphere at a temperature of 60 ° C. half an hour 102g of

-thiobutyrolactone. Then the mixture is maintained for 2 hours at a temperature of approximately 90-100 ° C. time after which all the

-thiobutyrolactone is transformed. 230 g of N- (4-mercapto-butyryl) 1 'N' - (2-hydroxyethyl) piperazine are obtained in the form of a viscous liquid, the thiol dosage and the R.M.N. correspond to the expected structure. The elemental analysis corresponds to a partially hydrated product: c ^ qH20N2 ° 2S ’0,5 H2 ° *

C · H N 0 S

Hold: 49.76 8.77 11.60 16.57 13.28

Tr: 49.37 8.72 11.39 17.13 13.47

EXAMPLE V

Preparation of N, N-di (2-hydroxyethyl) 4-mercapto-butyramide To 105.14 g of diethanolamine, stirred under an inert atmosphere at 70-80 ° C., 102 g of

-thiobutyrolactone.

No exothermicity is observed and the mixture is stirred for 6 hours at a temperature between 90 ° and 100 ° C.

206 g of N, N-di (2-hydroxyethyl) 4-mercapto-butyramide are obtained in the form of a viscous liquid at ordinary temperature. The assays of thiol, residual amine and the H spectrum R.M.N. correspond to the expected structure.

The elemental analysis corresponds to a partially hydrated product: CgH ^ NOgS; 0.25 H20

C H N 0 S

Hold: 45.36 8.32 6.61 24.55 15.13

Tr: 45.13 8.00 6.47 25.53 15.05

EXAMPLE VI

Preparation of N- (4-mercapto-butyryl) N-methylglucamine

A mixture of 102g of

-thiobutyrolactone and 195.2 g of N-methylglucamine is gradually brought under an inert atmosphere to a temperature between 90 and 100 ° C. This mixture is stirred at this temperature for 6 hours, at the end of which the reaction is complete.

296 g of N- (4-mercapto-butyryl) N-methylglucamine are obtained in the form of a glassy solid, the thiol dosage and the H R.M.N. spectrum.

correspond to the expected structure.

The elementary analysis corresponds to a partially hydrated product: ^^^ 23 ^ 6 ^ ’^ 0.

C H N 0 s

Hold: 42.49 7.94 4.50 34.73 10.31

Tr: 42.89 7.57 4.61 34.84 10.42

EXAMPLE VII

Preparation of N- (dimethvl-l, l hydroxy-2 ethyl) mercapto-4 butyramide In half an hour, 102 g of

-thiobutyrolactone, dropwise, at 89.14 g of 2-amino-1-methylpropanol stirred under an inert atmosphere at 65 ° C. The temperature rises to 70 ° C during the addition. This being completed, the mixture is further stirred for 8 hours at 100 ° C, time after which all the starting amine is transformed.

180 g of N- (dimethyl-1,1-hydroxy-2 ethyl) mercapto-4 butyramide are obtained in the form of a viscous liquid.

The R.M.N. corresponds to the expected structure and the elementary analysis for a partially hydrated product:

CgH17N02S, 0.25 H2O.

C H N 0 s

Hold: 49.07 8.94 7.15 18.39 16.37

Tr: 48.87 8.58 6.36 17.89 17.40

EXAMPLES OF COMPOSITIONS

EXAMPLE 1

According to the invention, a reducing composition for permanent hair deformation is prepared by mixing the following ingredients: - N- (4-mercapto-butyryl) N-methylglucamine ..... 18g - Monoethanolamine ...... ................... P® 8.5 - Fragrance ........................ ...............

- Preservative ................................. 0.5g - Demineralized water ......... ............... 100g

This composition is applied to wet hair previously wound on styling rollers. After having left the composition to act for about 15 minutes, rinse thoroughly with water and then apply the following oxidizing composition: - Hydrogen peroxide ....................... ......... 8 volumes - Stabilizer .................................. ^, 3g - Perfume ....................................... 0.1g - Lactic acid qs .. ....................... 3 - Demineralized water qs ...................... .. 100g

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

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

EXAMPLES 2 to 5

According to the same mode of application as described in Example 1 above, the permanent deformation of the hair was carried out using the following reducing and oxidizing compositions: EXAMPLE 2

Reducing composition - N- (2-hydroxyethyloxyethyl) mercapto-4 butyr amide .................................. . ^ g - Monoethanolamine qs ....................... P® 9 * - Perfume ............... ........................

- Conservative.................................

- Demineralized water qs ...................... 100g

Oxidizing composition - H202 qs ..................... 8 volumes - Stabilizers .................... .............

- Perfume .......................................

- Lactic acid qs ......................... PH 3 - Demineralized water ................ ........... 100g EXAMPLE 3

Reducing composition - N- (2,3-dihydroxy propyl) 4-mercapto-butyramide ................................. ..

- Monoethanolamine .......................... PH 8 »5 - Perfume ................ .......................

- Conservative.................................

- Demineralized water qs ........................ * - ° ®s

Oxidizing composition - H202 qs .................... 8 volumes - Stabilizers ..................... ............

- Perfume .......................................

- Lactic acid qs ......................... Pïï 8 - Demineralized water qs ............... ......... 100g EXAMPLE 4

Reducing composition - N- (2-hydroxyethyl) 4-mercapto-butyramide .... 7g - Ammonia qs ........................... ..PH ** »5 - Perfume .......................................

- Conservative.................................

- Demineralized water qs ........................

Oxidizing composition - H202 qs ..................... 8 volumes - Stabilizers .................... .............

- Perfume ................ · ......................

- Lactic acid qs ......................... PH 3 - Demineralized water qs ............... ......... 100g EXAMPLE 5

Reducing composition - N- (4-mercapto-butyryl-1) N '- (2-hydroxyethyl) 15g ........................... ................

- Ammonia qs ............................. P® ® - Perfume ............. .....................* ' * * * - Conservative...................... ...........

- Demineralized water qs ........................ 100g

Oxidizing composition - H202 qs ..................... 8 volumes - Stabilizers .................... .............

- Perfume .......................................

- Lactic acid qs ......................... pH 3 - Demineralized water qs ............... ......... 100g

Claims (13)

1. Mercapto — 4 butyramides N — mono or Ν, Ν-disbustxtues by a mono or polyhydroxyalkyl radical, characterized in that they correspond to the following general formula:

(I), in which: R ^ represents a hydrogen atom, a lower alkyl radical or a monohydroxyalkyl or polyhydroxyalkyl radical having from 1 to 6 carbon atoms, optionally interrupted by an oxygen, nitrogen or sulfur atom , and R ^ represents a monohydroxyalkyl or polyhydroxyalkyl radical having from 1 to 6 carbon atoms optionally interrupted by an oxygen, nitrogen or sulfur atom, or R ^ and R ^, taken together with the nitrogen atom , form a piperazine ring substituted in 4 by a mono or polyhydroxyalkyl radical having from 1 to 6 carbon atoms. 2. Compounds according to claim 1, characterized in that the lower alkyl radical is the methyl, ethyl, propyl, isopropyl or butyl radical. 3. Compounds according to claim 1, characterized in that the monohydroxyalkyl or polyhydroxyalkyl radical having from 1 to 6 carbon atoms, optionally interrupted by an oxygen, nitrogen or sulfur atom is the hydroxy-2 ethyl radical, .dihydroxy-2,3 propyl, dimethyl-1,1,2-hydroxy-ethyl, pentahydroxy-2,3,4,5,6. hexyl and 2-hydroxyethyloxyethyl. 4. Compounds according to any one of claims 1 to 3, characterized in that they are: - N- (2-hydroxyethyl) mercapto-4 butyramide, - N- (2-hydroxyethylethyloxyethyl) mercapto- 4 butyramide, - N- (2,3-dihydroxy propyl) mercapto-4 butyramide, - N, N-di (2-hydroxyethyl) mercapto-4 butyramide, - N- (4-mercapto butyryl) N- methylglucamine, - N- (4-mercapto-butyryl-1) N '- (2-hydroxyethyl) piperazine, - N- (dimethyl-1.1,1-2-hydroxyethyl) mercapto-4 butyramide. 5. Process for the preparation of 4-mercapto-butyramides according to claims 1 to 4, characterized in that it consists in reacting an amine of formula

R ^ and having the same meanings as in claim 1, on -thiobutyrolactone, the reaction being carried out, with or without solvent, at a temperature between 50 and 110 ° C. 6. Method according to claim 5, characterized in that the reaction is carried out in the presence of toluene or an alcohol taken from the group consisting of methanol, ethanol, isopropanol or butanol. 7. Method according to any one of claims 5 and 6, characterized in that the amine is ethanolamine, diethanolamine, diglycolamine, meglumine, 2,3-dihydroxy propylamine, 1 amino-2 methyl- 2 hydroxy-2 propanol ethyl piperazine. 8. Cosmetic reducing composition for the first stage of a permanent hair deformation operation, characterized in that it contains, in a suitable cosmetic vehicle, as reducing agent, at least one 4-mercapto-butyramide of formula (I) according to any one of claims 1 to 4, - or obtained according to any one of claims 5 to 7. 9. Composition according to Claim 8, characterized in that the reducing agent is present at a concentration of between 2 and 20% by weight and preferably between 5 and 10% by weight relative to the total weight of the composition. 10. Composition according to any one of claims 8 and 9, characterized in that its pH is between 6.5 and 10. 11. Composition according to any one of claims 8 to 10, characterized in that it also contains at least one cationic polymer, a softening agent, a protein hydrolyzate, a wax, an opacifying agent, a perfume, a dye, a nonionic or cationic surfactant or a treating agent. 12. A method of permanent deformation of the hair consisting in a first step in reducing the disulfide bonds of keratin by application of a reducing composition and then in a second step in reforming said bonds by application of an oxidizing composition, characterized in that the reduction step is carried out using a reducing cosmetic composition as claimed in any one of claims 8 to 11. 13. The method of claim 12, characterized in that the reducing composition is allowed to act for a time between 5 and 60 min. %