FR3060345A1 - ACID COMPOSITION COMPRISING THIOLACTONES AND PROCESS FOR TREATING KERATINIC MATERIALS USING THE SAME - Google Patents

Abstract

The present invention relates to i) a process for treating keratin materials, in particular human keratinous fibers, comprising the application of an acidic aqueous composition comprising at least one particular thiolactone, in particular for shaping keratinous fibers and / or smoothing / straightening, ii) an acidic aqueous composition comprising the particular thiolactone (s), iii) and new thiolactones, iv) a process for the preparation of the new thiolactones, v) the use of said thiolactones for the treatment of keratinous fibers.

Description

® FRENCH REPUBLIC

NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number: 3,060,345 (to be used only for reproduction orders)

©) National registration number: 16 62992

COURBEVOIE © Int Cl ⁸ : A 61 K8 / 49 (2017.01), A 61 Q 5/04

A1 PATENT APPLICATION

©) Date of filing: 21.12.16. ©) Applicant (s): L'OREAL Société anonyme— FR. ©) Priority: @ Inventor (s): BLAISE CHRISTIAN. ©) Date of public availability of the request: 06.22.18 Bulletin 18/25. ©) List of documents cited in the preliminary search report: See the end of this booklet (© References to other related national documents: ©) Holder (s): L'OREAL Société anonyme. ©) Extension request (s): ©) Agent (s): L'OREAL Société anonyme.

FR 3 060 345 - A1 (54; ACID COMPOSITION COMPRISING THIOLACTONES AND PROCESS FOR TREATING KERATINIC MATERIALS USING THE SAME.

The present invention relates to i) a process for treating keratinous materials, in particular human keratinous fibers, comprising the application of an acidic aqueous composition comprising at least one particular thiolactone, in particular for shaping keratinous fibers and / or smoothing / straightening, ii) an acidic aqueous composition comprising the particular thiolactone (s), iii) and new thiolactones, iv) a process for preparing the new thiolactones, v) the use of said thiolactones for the treatment of keratin fibers.

ACID COMPOSITION COMPRISING THIOLACTONES AND PROCESS FOR TREATING KERATINIC MATERIALS USING THE SAME

The present invention relates to i) a process for treating keratinous materials, in particular human keratinous fibers, comprising the application of an acidic aqueous composition comprising at least one particular thiolactone, in particular for shaping keratinous fibers and / or smoothing / straightening, ii) an acidic aqueous composition comprising the particular thiolactone (s), iii) and new thiolactones, iv) a process for preparing the new thiolactones,

v) the use of said thiolactones for the treatment of keratin fibers.

In the hair sector, consumers wish to have compositions which make it possible to bring a temporary change to their hair, and this by aiming for good staying power of the effect achieved. In general, we want the change to persist in shampoos for at least 15 days, or more depending on the nature of the change.

Heat treatments are generally used to permanently modify the shape of the hair. These treatments allow a visual modification of the appearance of the hairstyle, combining a decrease in the degree of crimp, a reduction in the overall volume of the hair, a reduction in frizzotis, a gain in discipline, a smoother visual appearance, a substantial gain. shine, resistance to humidity and heat for maintaining the hairstyle all day.

In addition, this type of treatment has the advantage of facilitating the daily maintenance of the hair, with the use of less care products, in particular rinse-out treatments such as conditioners or masks, or leave-in treatments. such as serums, care creams or balms, disciplining foams. Hair drying is facilitated, with a significantly shortened brushing time and a reduction in the daily use of flat tweezers, both in time and in intensity. This thus limits the risk of damage to the hair by combined factors of mechanical and thermal stress.

Several technologies are associated with these heat treatments. A first technology is based on the use of compositions based on thiol reducers. These technologies require strict compliance with the application conditions recommended by suppliers, in particular in terms of quantity and break time. In addition, they may be contraindicated on overly sensitized hair and may not be compatible with the same day application of other treatments such as coloring or bleaching. They are also smelly.

Another technology is based on the use of compositions based on formalin (or formaldehyde) and its derivatives. The particularity of these treatments is that they are robust, perfectly compatible with all the other conventional hair treatments, such as the thiolated straightening mentioned above, the alkaline straightening, coloring or bleaching of all types, carried out before or after. They give the hair excellent discipline, very strong shine and ease of daily care. However, in case of repeated applications, new damage to the hair appears which can lead to hair breakage. In addition, for toxicological reasons, the use of some of these compounds is now prohibited and / or regulated. It is therefore increasingly sought to avoid the use of such substances, which can prove to be aggressive for the hair and other keratin materials.

Another technology is based on the use of acid-based compositions, and more particularly on the use of glyoxylic acid. It was thus proposed, by application WO 2011/104282, a new process for semi-permanent straightening of the hair, consisting in applying an alpha-ketoacid solution to the hair for 15 to 120 minutes, then drying and finally straightening with iron, at a temperature of about 200 ° C, the hair. The alphaketoacid used is preferably glyoxylic acid. However, it has been found that glyoxylic acid may not be well tolerated, especially when the scalp is sensitive and / or irritated. Its volatility, amplified by the use of heat from iron, can also be a problem. Furthermore, the compositions of the prior art can alter the hair and / or alter the color. Treatments have also been proposed using a composition comprising a base associated with a heat treatment for straightening the hair. Such treatments make it possible to obtain good relaxation of the curls but can lead to alterations of the hair fiber. Document EP 1 837 010 describes in particular a smoothing / straightening process using a composition comprising soda and a heat treatment. Document WO 2007/144707 describes a smoothing / straightening process using a composition comprising a non-hydroxylated base such as monoethanolamine, ethylene diamine, associated with a heat treatment. Document WO 2009/117344 also describes a smoothing / straightening process using a composition comprising a non-hydroxylated base and a protein denaturant associated with a heat treatment. To limit alterations in the hair fibers, it has also been proposed to use compositions comprising weak acids at alkaline pH associated with a heat treatment. The document WO 2010/049434 describes for example a smoothing / straightening process in which a composition comprising a dicarboxylic acid such as maleic acid and a heat treatment is applied.

There is still a need to develop a process for treating keratin materials, in particular keratin fibers such as the hair, more particularly a process for shaping or smoothing / straightening keratin fibers in an effective and lasting manner by limiting degradation. hair, in particular, remanent from successive shampoos.

This (s) goal (s) is (are) achieved (s) by the use of an aqueous composition comprising at least one compound of formula (I) below:

(I)

As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates;

Formula (I) in which:

• Y represents an oxygen, sulfur atom or an NR group with R representing a hydrogen atom, a (Ci-C ₆ ) alkyl or hydroxy (CiC ₆ ) alkyl group, preferably Y represents an oxygen atom ;

• Ri, R ₂ , R ₃ , R ₄ , Rs and R ₆ , identical or different, represent:

i) a hydrogen atom;

ii) hydroxy;

iii) amino -NR'R ”, with R 'and R”, identical or different, represent a hydrogen atom, a (Ci-C ₆ ) alkyl or hydroxy (Ci-C ₆ ) alkyl group;

iv) cyano;

v) - (Y ') _P -C (Y ”) - (Y”') qR ₇ with R ₇ representing a hydrogen atom, a (Ci-C ₆ ) alkyl group, p and q, identical or different, valent 0 or 1, with preferably p + q = 0 or 1, Y ', Y ”and Y'”, identical or different, represent an oxygen, sulfur, NR atom with R as defined above, preferably Y '; Y ”and Y '” represent the oxygen atom;

vi) (Ci-C ₆₎ alkyl optionally substituted;

vii) (C ₂ -C ₆ ) optionally substituted alkenyl;

viii) (Ci-C ₆₎ alkoxy optionally substituted;

preferably said alkyl, alkenyl or alkoxy groups being optionally substituted by one or more groups chosen from hydroxy and - (O) _t -C (O) -R ₈ with t valant 0 or 1, R ₈ represents a) an atom of hydrogen, b) hydroxy, c) (Ci-C ₆ ) alkyl, d) (Ci-C ₆ ) alkoxy, e) (di) (Ci-C ₆ ) (alkyl) amino, f) (di) hydroxy (Ci-C ₆ ) alkylamino;

or :

ix) R-ι and R ₃ together form a covalent bond;

x) R-ι and R ₂ , and / or R ₃ and R ₄ , and / or R ₅ and R ₆ form together with the carbon atom which carry them a double bond oxo = 0 or = C (R ₉ ) -Ri ₀ with R _g and R ₁₀ represents a) a hydrogen atom, or a group chosen from b) hydroxy, c) (Ci-C ₆ ) alkyl optionally substituted by one or more hydroxy groups, and d) (C ₂ -C ₆ ) alkenyl, e) - (Y ') _p -C (Y ”) - (Y'”) _q -R ₇ with Y ', Y ”, Y'”, p, q, and R ₇ are as previously defined;

• n represents an integer inclusive between 0 and 6, particularly inclusive inclusive between 0 and 4, more particularly inclusive inclusive between 0 and 3, preferably n is 1;

Being heard that :

- when n is greater than or equal to 2, then the contiguous groups C (R ₅ ) -R ₆ may be identical or different; and

- Said composition is at acidic pH.

Another subject of the invention is a process for treating keratinous materials, in particular keratinous fibers, in particular human fibers such as the hair, for shaping keratinous fibers and / or smoothing / straightening said materials, using the or the compounds of formula (I) as defined above.

Another subject of the invention is the compounds of formula (I) as defined above.

Another object of the invention is a process for the preparation of the compounds of formula (I) as defined above.

Another object of the invention is the cosmetic use of the compounds of formula (I) as defined above for the treatment of keratin fibers, in particular human fibers such as the hair, preferably for the shaping of keratin fibers and / or smoothing / straightening said fibers

The compounds of formula (I) as defined above of the invention make it possible in particular to obtain good relaxation of curls, lasting in particular with respect to shampoos, while limiting the degradation of the hair.

Other characteristics and advantages of the invention will appear more clearly on reading the description and the examples which follow.

In what follows unless stated otherwise:

by “organic or mineral acid salt” is meant cosmetically acceptable organic or mineral acid salts, more particularly the salts chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H ₂ SO ₄ , iv) alkylsulfonic acids: Alk-S (O) ₂ OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) ₂ OH such as benzene sulfonic acid and toluene sulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-OS (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H ₃ PO ₄ ; xiii) acetic acid CH ₃ C (O) OH; xiv) triflic acid CF ₃ SO ₃ H and xv) tetrafluoroboric acid HBF ₄ ;

by “alkyl”, a linear or branched hydrocarbon radical containing from 1 to 8 carbon atoms, in particular from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, butyl, n-pentyl, n-hexyl, preferably methyl;

by “alkenyl”, a linear or branched hydrocarbon radical containing from 2 to 8 carbon atoms, in particular from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, and comprising at least one or more unsaturations, conjugates or not, such as ethylenyl, n-propylene, isopropylenyl, butylene, n-pentylene, n-hexylene;

by alkoxy is meant an alkyl oxy group with “alkyl” or “alkenyl”, as defined above;

by “optionally substituted” preceded by alkyl, alkenyl or alkoxy groups, it is meant that said groups can be substituted on the hydrocarbon radical by one or more, identical or different, groups chosen from i) hydroxy, ii) thiol, iii) halogen, iv) (Ci-C ₄ ) alkoxy, v) hydroxy (C ₂ C ₄ ) alkoxy; vi) (di) (hydroxy (Ci-C ₄ ) (alkyl) amino, vii) cyano, viii) nitro (so), ix) Ra-Z _a -C (Z _b ) -Z _c -, and x) R _a -Z _a -S (O) tZ _c - with Z _b , representing an oxygen or sulfur atom, or a group NR _a ', Z _a and Z _c , identical or different, representing a bond, an atom d oxygen, sulfur, or NR _a; R _a , representing a hydrogen atom, a (Ci-C ₄ ) alkyl group and R _a · representing a hydrogen atom or an alkyl group and t is 1 or 2;

moreover, the addition salts which can be used in the context of the invention are in particular chosen from addition salts with a cosmetically acceptable base such as the basifying agents as defined below as the alkali metal hydroxides such as sodium hydroxide , potash, ammonia, amines or alkanolamines;

The term “straightening” includes, according to the invention, the straightening, straightening or straightening of Caucasian or African hair. The term "straightening" includes, according to the invention, straightening, straightening or straightening Caucasian or African hair;

the expression "at least one" is equivalent to "one or more"; and the expression "inclusive" for a range of concentrations means that the bounds of the range are part of the defined range.

The thiolactone (s) of formula (I)

According to a particular embodiment of the invention, the compound or compounds of formula (I) are such that n is zero and preferably of formula (la):

O

S (the)

As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates;

Formula (la) in which:

• Ri, R ₂ , R ₃ , and R ₄ , are as defined above, in particular identical or different, represent:

i) a hydrogen atom, ii) - (O) _p -C (O) - (O) qR ₇ with R ₇ representing a hydrogen atom, a (Cr C ₆ ) alkyl group, p and q, identical or different, valent 0 or 1, with p + q = 0 or 1, iii) (Ci-C ₆ ) alkyl optionally substituted by one or more hydroxy groups, iv) (C ₂ -C ₆ ) alkenyl, or else:

v) R ₄ and R ₂ , and / or R ₃ and R ₄ , preferably R ₃ and R ₄ , form together with the carbon atom which carry them a double bond oxo = 0 or = C (R ₉ ) - Ri ₀ with R _g and R ₁₀ represents a hydrogen atom, or a (Ci-C ₆ ) alkyl group.

According to a particular embodiment of the invention, the compound or compounds of formula (I) are such that n is 1 or 2 and preferably of formula (lb):

As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates;

Formula (lb) in which:

• Ri, R ₂ , R ₃ , R ₄ , R ₅ and R ₆ , identical or different, represent:

i) a hydrogen atom, ii) hydroxy, iii) cyano, iv) amino -NR'R ”, with R 'and R”, identical or different, represent a hydrogen atom, a group (Ci-C ₆ ) alkyl or hydroxy (Ci-C ₆₎ alkyl;

v) - (Y ') _P -C (O) - (Y ”) _q -R ₇ with R ₇ representing a hydrogen atom, a (Ci-C ₆ ) alkyl group, p and q, identical or different, valent 0 or 1, with Y 'and Y ”, identical or different, representing an oxygen atom or NR with R as defined above, preferably with p + q = 0 or 1, vi) (Ci-C ₆ ) alkyl optionally substituted by one or more groups chosen from hydroxy and -C (O) -R ₈ with R ₈ represents a) a hydrogen atom, b) a hydroxy group, c) (Ci-C ₆ ) alkoxy, vii) (C ₂ -C ₆ ) alkenyl, viii) (Ci-C ₆ ) alkoxy, or else:

ix) R-ι and R ₂ , and / or R ₃ and R ₄ , and / or R ₅ and R ₆ form together with the carbon atom which carry them a double bond oxo = 0 or = C (R _g ) -Ri ₀ with R _g and R ₁₀ represents a) a hydrogen atom, or a group chosen from b) hydroxy, c) (Ci-C ₆ ) alkyl.

According to a particular embodiment of the invention, the compound or compounds of formula (I) are such that n is 1 and preferably of formula (I'b):

As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates; Formula (l'b) in which:

* Ri. R _2î Rît Rl · Rs and Re, identical or different, are as previously defined, in particular represent:

i) a hydrogen atom, ii) hydroxy, iii) cyano, iv) amino -NR'R ”, with R 'and R, identical or different, represent a hydrogen atom, a group (C _r C ₆ ) alkyl or hydroxy (C _r C ₆ ) alkyl;

v) ~ (Y ') p “C (O) - (O) _q -R ₇ with R ₇ representing a hydrogen atom, a group (ÇrGeJalkyle, and Y' representing an oxygen atom or NR with R tel as defined above, p and q, identical or different, are 0 or 1, with p + q = 0 or 1, vi) (C _r G ₆ ) optionally substituted alkyl, vii) (C2-C ₆ ) alkenyl, viii) (G-Ce) alkoxy.

said alkyl groups being optionally substituted by one or more groups chosen from hydroxy and - (O) tC (O) -R ₈ with t valant 0 or 1, R ₈ represents a) a hydrogen atom, b) a hydroxy group, c) (Ci-C ₆ ) alkyl, d) (Ci-CeJàlkoxy, e) (di) (C- | -C ₆ j (aIkyl) arriino, f) (diJhydroxyfC-i-Cejaïkylamino; or then:

ix) R-ι and R ₂ , and / or R ₃ and R ₄ , and / or R ₅ and Re form together with the carbon atom which carry them a double bond oxo = O or ^=: C (R ₉ ) -R ₁₀ with R _g and R ₁₀ represents i) a hydrogen atom, or a group chosen from ii) hydroxy, iii) (CrCeJalkyle optionally substituted by one or more hydroxy groups in particular R ₃ and R ₄ form together with l carbon atom an oxo group and / or in particular R | and R ₂ , together represent with the carbon atom = C (R ₉ ) -Ri ₀ .

According to another particular embodiment of the invention, the compound or compounds of formula (I) are such that n is 2 and preferably of formula (1 ”b):

(lb)

As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates;

Formula (l ”b) in which:

• Ri, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R's and R ' ₆ , identical or different, represent:

i) a hydrogen atom, ii) cyano, iii) -C (O) - (O) _q -R ₇ with R ₇ representing a hydrogen atom, a (Cr C ₆ ) alkyl group, p and q, identical or different, valent 0 or 1, iv) (Ci-C ₆ ) alkyl optionally substituted by one or more groups chosen from hydroxy and -C (O) -R ₈ , with R ₈ represents a) a hydrogen atom, b) a hydroxy group, c) (Ci-C ₆ ) alkoxy, or else:

v) R-ι and R ₂ , and / or R ₃ and R ₄ , and / or R ₅ and R ₆ and / or R ' ₅ and R' ₆ together form with the carbon atom which carry them a double bond oxo = 0 in particular R ₃ and R ₄ , or R ₅ and R ₆ or R ' ₅ and R' ₆ form together with the carbon atom which carry them a double bond oxo = 0.

According to a particular embodiment of the invention, the compound (s) of formula (I) are such that n is 1 or 2 and is of formula (le):

(the

As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates;

Formula (s) in which:

• R ₂ , R ₄ , Rs and R ₆ , identical or different, represent:

i) a hydrogen atom, ii) hydroxy, iii) cyano, iv) amino -NR'R ”, with R 'and R”, identical or different, represent a hydrogen atom, a group (Ci-C ₆ ) alkyl or hydroxy (Ci-C ₆₎ alkyl;

v) - (Y ') pC (O) - (O) _q -R ₇ with R ₇ representing a hydrogen atom, a (Ci-C ₆ ) alkyl group, p and q, identical or different, valent 0 or 1, with Y ′ representing an oxygen atom or NR with R as defined above, with p + q = 0 or 1, vi) (Ci-C ₆ ) alkyl optionally substituted by one or more groups chosen from hydroxy and - C (O) -R ₈ with R ₈ represents a) a hydrogen atom, b) a hydroxy group, c) (Ci-C ₆ ) alkoxy, vii) (C ₂ -C ₆ ) alkenyl, viii) (Ci -C ₆ ) alkoxy, or then:

ix) R ₅ and R ₆ form together with the carbon atom which carries them a double bond oxo = 0 or = C (R ₉ ) -Ri ₀ with R ₉ and R ₁₀ represents a hydrogen atom or a group ( Ci-C ₆ ) alkyl.

According to a more particular embodiment of the invention, the compound or compounds of formula (I) are of formula (le) and n is 1.

According to another particular embodiment of the invention, the compound or compounds of formula (I) are such that n is 2 and preferably of formula (e):

(the c)

As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates;

Formula (c) in which:

• R ₂ , R ₄ , R5, R6, R 5 and R 6, identical or different, represent:

i) a hydrogen atom, ii) hydroxy, iii) - (O) _p -C (O) - (O) qR ₇ with R ₇ representing a hydrogen atom, a (Ci-C ₆ ) alkyl group, p and q, identical or different, are 0 or 1 with p + q = 0 or 1, iv) (Ci-C ₆ ) alkyl,

v) (Ci-C ₆ ) alkoxy.

More preferably, the thiolactones of the invention are chosen from the following compounds:

18

OH

OH

OH

OH

OH

114

114 ’

115

115 ’

262

263

264

As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates;

Another subject of the invention is compounds of formula (I ”c):

As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates;

Formula (l ”c) in which:

Ru and R-12, identical or different, representing a hydrogen atom, or a (Ci-C ₆ ) alkyl group, such as methyl, or ethyl.

More particularly the compound or compounds of formula (I) are chosen from the following thiolactones

120

121

122

As well as basic, organic or mineral salts, optical isomers, and solvates such as hydrates.

More preferably, the compound has the formula 116.

Process for the preparation of the thiolactone (s)

Another object of the invention is a process for the preparation of the compound of formula (l ”c) as defined according to the following synthetic diagram:

OH

OH

ü)

Which consists in reacting in step i) 3-butene-1,2,3-tricarboxylic acid (A) with at least one molar equivalent of thiolacetic acid in particular in an aprotic organic solvent, preferably halogenated such as dichloromethane , or THF type ether, more particularly by heating the reaction medium until solvent reflux, preferably at a temperature between 40 ° C. and 80 ° C., to lead to compound (B), in step ii) the compound (B) reacts with a strong, organic or inorganic acid such as hydrochloric acid, in particular in a polar protic solvent such as water, more particularly by heating until reflux of the solvent, preferably at a temperature between 60 and 90 ° C, to yield the thiolactone (C) in steps iii) and v) the compound (C) is reacted with at least one equivalent of an alcohol R 'n-OH and R' ₁₂ - OH respectively, with R 'n and R' _12, identical or different, represent an (Ci-C ₆ ) alkyl group, in particular in a polar organic solvent such as ethyl acetate, preferably at low temperature such as 0 ° C, to lead to the monoesters (D) and (E) which can still in the presence of alcohol be esterified on the second carboxy group according to steps iv) and vi), to yield the diester (F), the compounds (D), (E) and (F) can be purified by chromatography for example on a silica column. Compounds (C), (D), (E) and (F) constituting the set of compounds of formula (1 ”c).

The composition of the invention:

The composition of the invention comprises one or more compound (s) of formula (I) as defined above.

According to a particular embodiment, the composition comprises one or more compound (s) of formula (I) as defined above in an amount inclusive between 0.01 and 50% by weight relative to the total weight of the composition, in particular between 0.1 and 30%, more particularly between 1 and 20%, preferably between 2 and 15%, more preferably between 5 and 10% by weight relative to the total weight of the composition.

According to a particular embodiment of the invention, the composition of the invention does not include a thiol reducing agent such as thiolactic acid, preferably the composition does not include a reducing agent.

According to one embodiment of the invention, the composition does not include an alkaline agent.

The pH of the composition used in the process of the invention is greater than or equal to 1 or less than or equal to 6.9. Preferably, the pH of the composition ranges from 2. to 6 and more preferably from 3 to 5.

/ es compositions

The composition (s) of the invention are cosmetic, ie contain a physiologically acceptable medium, that is to say compatible with the keratin materials of human beings such as the skin (body, face, eye area, scalp), hair, eyelashes, eyebrows, body hair, nails, lips.

The physiologically acceptable medium of the composition or compositions used in the process according to the invention is advantageously an aqueous medium. It can for example consist of water or a mixture of water and at least one cosmetically acceptable organic solvent. As organic solvent, mention may, for example, be made of lower C ₂ -C ₄ alcohols, such as ethanol and isopropanol; polyols, in particular those having from 2 to 6 carbon atoms such as glycerin, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol; polyol ethers such as 2-butoxyethanol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether; and their mixtures.

The cosmetic compositions of the invention are preferably aqueous and then comprise water at a concentration ranging from 10 to 99.5%, better from 30 to 95%, even better from 50 to 90% by weight relative to the weight total of the composition ..

The composition used according to the invention may also contain one or more cosmetic additives chosen from nonionic, anionic, cationic and amphoteric surfactants, vitamins and pro-vitamins including panthenol, sunscreens, fillers, coloring matters, pearlescent agents, opacifying agents, sequestering agents, film-forming polymers, cationic, anionic or neutral polymers, associative polymers, plasticizing agents, silicones, thickening agents, oils, anti-aging agents oxidizing agents, anti-foaming agents, moisturizing agents, emollient agents, penetration agents, perfumes and preservatives; preferably one or more nonionic, anionic, cationic and amphoteric surfactants, cationic, anionic, neutral polymers, or associative polymers.

Depending on their nature and the purpose of the composition, the usual cosmetic ingredients can be present in usual amounts, easily determinable by a person skilled in the art, and which can be understood, for each ingredient, between 0.01 to 80% by weight . A person skilled in the art will take care to choose the ingredients used in the composition, as well as their quantities, so that they do not harm the properties of the compositions of the present invention.

The compositions used in the process according to the invention can be in all the galenical forms conventionally used, and in particular in the form of an aqueous, alcoholic or hydroalcoholic, or oily solution or suspension; a solution or dispersion of the lotion or serum type; an emulsion, in particular of liquid or semi-liquid consistency, of the O / W, W / O or multiple type; a suspension or emulsion of soft consistency of the cream type (O / W) or (W / O); an aqueous or anhydrous gel, or any other cosmetic form.

These compositions can be packaged in pump dispensers or in aerosol containers, in order to ensure application of the composition in vaporized form (lacquer) or in the form of foam. Such forms of packaging are indicated, for example, when it is desired to obtain a spray or a foam, for the treatment of hair. In these cases, the composition preferably comprises at least one propellant.

pH of the composition (s):

According to a particular embodiment of the invention, the composition which comprises the thiolactone (s) of formula (I), as defined above is aqueous and its pH is between 2 and 6, preferably between 3 and 5.

The pHs can be adjusted by an organic or mineral acid, or by an alkaline agent chosen from mineral or organic or hybrid alkaline agents or their mixtures.

By “organic acid” is meant an acid, ie a compound capable of releasing a cation or proton H ⁺ , or H3O ⁺ in aqueous media, which comprises at least one hydrocarbon chain in Ci-C20, optionally unsaturated, linear or branched, a group (hetero) cycloalkyl, or (hetero) aryl and at least one acidic chemical function being in particular chosen from carboxy C (O) OH, sulfuric SO ₃ H, SO ₂ H, and phosphoric PO ₃ H ₂ , PO ₄ H ₂ .

More particularly, the acids used are chosen from hydrochloric acid HCl, hydrobromic acid HBr, sulfuric acid H ₂ SO ₄ , alkylsulfonic acids: (Cr C ₆ ) Alk-S (O) ₂ OH such as acid methylsulfonic and ethylsulfonic acid; arylsulfonic acids: Ar-S (O) ₂ OH such as benzene sulfonic acid and toluene sulfonic acid; (Ci-C6) alkoxysulfinic acids: Alk-OS (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; phosphoric acid H ₃ PO ₄ ; triflic acid CF ₃ SO ₃ H and tetrafluoroboric acid HBF ₄ and the carboxylic acid (s) of formula (K) below

Formula (K) or a salt thereof in which:

A represents a monovalent group when t is worth 0 or polyvalent when t is greater than or equal to 1, hydrocarbon comprising from 1 to 50 carbon atoms, saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic, optionally interrupted by one or more heteroatoms and / or optionally substituted in particular by one or more hydroxy groups; preferably A represents a monovalent (Ci-C ₆ ) alkyl or polyvalent (Ci-C ₆ ) alkylene group optionally substituted by one or more hydroxy groups.

Particularly the carboxylic acids (s) of formula (K) as defined above and preferably the acid or acids used is or are an alpha hydroxy acid such as lactic, glycolic, tartaric or citric acids.

The mineral alkaline agent (s) are preferably chosen from ammonia, alkali carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium or potassium hydroxides or their mixtures.

According to an advantageous embodiment of the invention, the alkaline agent (s) are organic amines, i.e. they contain at least one substituted or unsubstituted amino group.

The organic alkaline agent (s) are more preferably chosen from organic amines whose pK _b at 25 ° C is less than 12, and preferably less than 10, even more advantageously less than 6. It should be noted that it acts of pK _b corresponding to the highest basicity function.

Mention may be made, as hybrid compounds, of the salts of the amines mentioned above with acids such as carbonic acid, hydrochloric acid.

The organic alkaline agent (s) are for example chosen from alkanolamines, oxyethylenated and / or oxypropylenated ethylenediamines, amino acids and the compounds of formula (L) below:

^R \ z ^RZ

N-W-N

R ^{y / RR} (L)

Formula (L) in which:

• W is a divalent alkylene radical Ci-C _{6 alkyl} optionally substituted with a hydroxyl group or an alkyl radical Ci-C _6, and / or optionally interrupted by one or more heteroatoms such as oxygen or NR ^U;

• R ^x, R ^y, R ^z and R * R ^u, identical or different, represent a hydrogen atom, an alkyl radical Ci-C ₆ hydroxyalkyl or Ci-C ₆ aminoalkyl, Ci-C _6.

Preferably, the alkanolamine is ethanolamine (or monoethanolamine).

In a variant of the invention, the composition comprises, as alkaline agent, one or more alkanolamines (preferably ethanolamine) and ammonia. In this variant, the alkanolamine (s) are present in a majority amount relative to the ammonia.

More preferably the pH is adjusted so that the pH is inclusive between 2.5 and 9.5 or pH inclusive between 1 and 6, more particularly between 2 and 5, preferably between 3 and 4 using NH ₄ OH or citrate buffer.

Process for treating keratin fibers

Thus, an object of the present invention is a method for treating keratinous materials, in particular keratinous fibers, in particular human fibers such as the hair, comprising:

a) the application to said keratin materials of an acidic aqueous composition containing at least one thiolactone chosen from those of formula (I) as defined above as well as their acid or base, organic or mineral salt forms, their isomers optical, their solvates such as hydrates

According to a particular embodiment of the invention, the method is a method for treating keratin materials, in particular human keratin fibers such as the hair, comprising:

a) the application to said keratin materials of an acidic aqueous composition containing at least one thiolactone chosen from those of formula (I) as defined above as well as their acid or base, organic or mineral salt forms, their isomers optical, their solvates such as hydrates,

b) followed by a step of smoothing / straightening said keratin materials by means of a smoothing iron at a temperature of at least 100 ° C. or a step of shaping keratin fibers.

The smoothing iron is used at a temperature of at least 100 ° C, preferably at a temperature between, limits included, 100 ° C and 300 ° C, preferably between 120 ° C and 280 ° C, preferably still between 150 ° C and 250 ° C, and even better, between 200 and 250 ° C.

The composition of the invention can be applied to dry or wet keratin materials, preferably to dry or damp hair, preferably to dry hair.

The bath ratio of the applied composition can vary from 0.1 to 10, more particularly from 0.2 to 5, and preferably between 0.5 and 3. By bath ratio is meant the ratio between the total weight of the composition applied and the total weight of keratin materials to be treated.

The process of the invention may include other intermediate steps aimed at improving the smoothing of keratin fibers.

In particular, the step of applying the composition can be followed by an exposure time. The exposure time, namely the contact time of the composition on the hair, is preferably at least 5 minutes, preferably between 10 and 60 minutes, preferably between 15 and 45 minutes.

Rinsing of the hair may possibly be provided after the application of the composition and possibly after the application time.

The hair can then be towel-dried or not, preferably towel-dried.

A drying step with a hair dryer, whether or not combined with smoothing with a brush, can be provided before the smoothing step using a straightening iron.

According to a particular embodiment, the straightening with a straightening iron is carried out in several passages on the hair, in general 3 to 10 passages.

According to a particular embodiment, the method of the invention comprising the steps of applying the composition according to the invention to the hair, then of straightening with iron is carried out one or more times, spaced or not by one or more cosmetic treatments, preferably a shampoo, until the desired shape or intensity of shape is obtained.

According to a particular embodiment of the invention, the process for treating keratin materials of the invention does not use a thiolated reducing agent such as thiolactic acid, preferably the process does not use a reducing agent .

According to a particular embodiment, the process for treating keratin materials does not use an anthionization step. Preferably, the process for treating keratin materials does not use an alkaline agent.

The following examples serve to illustrate the invention without, however, being limiting.

EXAMPLES

I) General synthesis process for the new compounds of the invention

The thiolacetic acid is added to the double bond of 3-butene 1,2,3 tricarboxylic acid in an apolar solvent such as dichloromethane, tetrahydrofuran at a temperature between 40 ° C and 80 ° C to lead to the triacid (B). This compound is then reacted in a strong acid as reagent and solvent such as 6N hydrochloric acid, at a temperature between 60 ° C and 90 ° C to yield thiolactone (116). This compound can then be reacted under the conditions of conventional peptide coupling (such as, for example, DCC, temperature 0 ° C., ethyl acetate) in the presence of the desired alcohol. Depending on the number of equivalent peptide coupling agent and alcohol reacted, compound (117) to (122) can be obtained after purification on a silica column.

esterification ₁₁₆ - 117 to 122

Compound (B):

1 ^st step: Synthesis of 4- (acétvlsulfanvl) butane-1,2,3-tricarboxylic acid (B)

Procedure:

18.8 ml were placed in a 500 ml three-necked flask equipped with a thermometer, a cooler, an argon inlet, a bubbler, an addition funnel and a magnetic stirrer. gr of 3-butene-1,2,3 tricarboxylic acid (0.1 mole) in 300 ml of tetrahydrofuran. The medium was cooled to 0-5 ° C with an ice bath. A solution containing 8.6 ml of thiolacetic acid (0.12 mol) in 100 ml of tetahydrofuran was then added dropwise, keeping the temperature below 5 ° C. The reaction medium, with stirring, was allowed to return at room temperature and then heated at reflux for 4 hours, following the progress of the reaction in thin layer chromatography. The reaction medium was left at room temperature for 8 hours and then concentrated under reduced pressure. The residue thus obtained was taken up with cold ethyl ether to crystallize the expected compound. The precipitate obtained was then filtered through a sintered glass, dried under vacuum in the presence of P ₂ O ₅ to a constant weight. There was thus obtained a white powder, conforming to NMR.

^2nd stage: Synthesis of 4- (Carboxymethyl) -5-oxotetrahydrothiophene-3carboxylique:

12 g of 4- (acetylsulfanyl) butane-1,2,3-tricarboxylic acid (0.045 mole) were placed in a 250 ml three-necked flask equipped with a condenser, a thermometer and a magnetic stirrer (compound (B)) in 200 ml of 6N hydrochloric acid (1.2 mole HCl). The reaction medium was stirred for 15 minutes at room temperature and then brought to 90 ° C for 4 hours. The progress of the reaction was followed by thin layer chromatography. The reaction medium was allowed to return to ambient temperature and then evaporated under reduced pressure. The powder thus obtained was then taken up with ethyl ether and then filtered through sintered glass, dried under vacuum in the presence of P ₂ O ₅ to a constant weight. We thus obtained a white powder, NMR compliant with the expected product

II) Examples of application (smoothing):

11) -1- Application protocol:

Before applying the active ingredients, the hair is washed according to the following protocol:

Step 1: Application of the cleaning shampoo (in order to obtain clean hair):

1- Weigh 0.4 ml of cleaning shampoo per gram of hair in a watch glass.

2- Moisten the wick under tap water by passing the wick for 5 seconds between your fingers.

3- Wring the lock of hair between two fingers.

4- Apply the cleaning shampoo along the lock of hair (from root to tip evenly).

5- Gently knead (in order to lather the shampoo) the wick between two fingers lengthwise for 15 seconds from top to bottom (without making knots).

6- Rinse under tap water for 10 seconds by passing the wick between your fingers

7- Wring the wick between two fingers.

8- Comb the wick.

9- Dry the wick with a hair dryer.

Protocol for applying the active ingredients of the invention:

Step 2: Application of the product to be tested of the invention:

1- Prepare the solution of the active ingredient at 10% w / w in water or a hydroalcoholic solution not containing more than 30% alcohol.

2- Place a 2.7 gram wick in a chute.

3- Apply the solution of the product to be tested along the lock of hair (from root to tip evenly).

4- Leave for 30 minutes

5- Wring the wick between two fingers.

6- Perform 20 brushing passes

7- Make 10 iron straightenings at 230 ° C in 30 seconds.

The locks are then shampooed according to the following protocol which can be repeated depending on the number of shampoos produced:

Step 3: Applying the Shampoo (Remanence):

1- Weigh 0.4 ml of DOP with chamomile per gram of hair in a watch glass.

2- Moisten the wick under tap water by passing the wick for 5 seconds between your fingers.

3- Wring the lock of hair between two fingers.

4- Apply the cleaning shampoo along the lock of hair (from root to tip evenly).

5- Gently knead (in order to lather the shampoo) the wick between two fingers lengthwise for 15 seconds from top to bottom (without making knots).

6- Rinse under tap water for 10 seconds by passing the wick between your fingers.

7- Wring the wick between two fingers.

8- Comb the wick.

9- Repeat steps 4 to 8 according to the number of shampoos to be produced (1 to 10 shampoos).

10- Dry the wick with a helmet.

Example (1) of application with gamma thiobutyrolactone at 10% by weight in water and 30% by weight of ethanol, spontaneous pH 5.4

S

Example (2) of application with thiophen-2 (5H) -one at 10% by weight in water and 30% by weight of ethanol, spontaneous pH 3.4

Example (3) of application with 4-hydroxythiophen-2 (5H) -one at 10% by weight in water and 30% by weight of ethanol, spontaneous pH 2.1

HO

From photos 1 to 4, it appears from the above results that the locks treated with the thiolactones of the invention make it possible to obtain a residual smoothing even after 10 shampoos. There is indeed a durability of the smoothing effect.

Claims (18)

1. Aqueous composition comprising one or more compounds of formula (I) below: (I) As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates; Formula (I) in which: • Y represents an oxygen, sulfur atom or an NR group with R representing a hydrogen atom, a (Ci-C ₆ ) alkyl or hydroxy (CiC ₆ ) alkyl group, preferably Y represents an oxygen atom ; • Ri, R ₂ , R ₃ , R ₄ , R5 and R ₆ , identical or different, represent: i) a hydrogen atom, ii) hydroxy, iv) cyano, v) - (Y ') _P -C (Y ”) - (Y”') qR ₇ with R ₇ representing a hydrogen atom, a (Ci-C ₆ ) alkyl group, p and q, identical or different, valent 0 or 1, Y ', Y ”and Y” ”, identical or different, represent an oxygen or sulfur atom, NR with R as defined above, preferably Y', Y” and Y '”represent l oxygen atom, vi) (Ci-C ₆ ) optionally substituted alkyl, vii) (C ₂ -C ₆ ) optionally substituted alkenyl, viii) (Ci-C ₆ ) optionally substituted alkoxy, preferably said alkyl, alkenyl groups or alkoxy being optionally substituted by one or more groups chosen from hydroxy and - (O) _t -C (O) -R ₈ with t being 0 or 1, R ₈ represents a) a hydrogen atom, b) a hydroxy group , c) (Ci-C ₆ ) alkyl, d) (Ci-C ₆ ) alkoxy, e) (di) (Ci-C ₆ ) (alkyl) amino, f) (di) hydroxy (Ci-C ₆ ) alkylamino ; or : x) R ₄ and R ₃ together form a covalent bond; xi) R-ι and R ₂ , and / or R ₃ and R ₄ , and / or R ₅ and R ₆ form together with the carbon atom which carry them a double bond oxo = 0 or = C (R ₉ ) -Ri ₀ with R ₉ and R ₁₀ represents a) a hydrogen atom, or a group chosen from b) hydroxy, c) (Ci-C ₆ ) alkyl optionally substituted by one or more hydroxy groups, andd) (C ₂ -C ₆ ) alkenyl, e) - (Y ') _p -C (Y ”) - (Y'”) _q -R ₇ with Y ', Y ”, Y'”, p, q, and R ₇ are such as previously defined; • n represents an integer inclusive between 0 and 6, particularly inclusive inclusive between 0 and 4, more particularly inclusive inclusive between 0 and 3, preferably n is 0, 1 or 2; Being heard that : - when n is greater than or equal to 2, then the contiguous groups C (R ₅ ) -R ₆ may be identical or different; and - Said composition is at acidic pH. 2. Composition according to the preceding claim in which the compound or compounds of formula (I) are such that n is zero and preferably of formula (la): O S (the) As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates; Formula (la) in which: • Ri, R ₂ , R ₃ , and R ₄ , are as defined above, in particular identical or different, represent: i) a hydrogen atom, ii) - (O) _p -C (O) - (O) qR ₇ with R ₇ representing a hydrogen atom, a (Cr C ₆ ) alkyl group, p and q, identical or different, valent 0 or 1, with p + q = 0 or 1, iii) (Ci-C ₆ ) alkyl optionally substituted by one or more hydroxy groups, iv) (C ₂ -C ₆ ) alkenyl, or else: v) R-ι and R ₂ , and / or R ₃ and R ₄ , preferably R ₃ and R ₄ , form together with the carbon atom which carry them a double bond oxo = 0 or = C (R ₉ ) -Ri ₀ with R ₉ and R ₁₀ represents a hydrogen atom, or a (Ci-C ₆ ) alkyl group. 3. Composition according to claim 1 in which the compound (s) of formula (I) are such that n is 1 or 2 and preferably of formula (lb): As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates; Formula (lb) in which: • Ri, R ₂ , R ₃ , R ₄ , Rs and R ₆ , identical or different, represent: i) a hydrogen atom, ii) hydroxy, iii) cyano, iv) - (Y ') pC (O) - (Y ”) _q -R ₇ with R ₇ representing a hydrogen atom, a group (Ci -C ₆ ) alkyl, p and q, identical or different, valent 0 or 1, with Y 'and Y ”, identical or different, representing an oxygen atom or NR with R as defined above, preferably with p + q = 0 or 1, v) (Ci-C ₆ ) alkyl optionally substituted by one or more groups chosen from hydroxy and -C (O) -R ₈ with R ₈ represents a) a hydrogen atom, b) a hydroxy group, c) (Ci -C ₆ ) alkoxy, vi) (C ₂ -C ₆ ) alkenyl, vii) (Ci-C ₆ ) alkoxy, or else: viii) R-ι and R ₂ , and / or R ₃ and R ₄ , and / or R ₅ and R ₆ form together with the carbon atom which carry them a double bond oxo = 0 or = C (R ₉ ) -Ri ₀ with R ₉ and R ₁₀ represents a) a hydrogen atom, or a group chosen from b) hydroxy, c) (Ci-C ₆ ) alkyl. 4. Composition according to any one of claims 1 or 3 in which the compound or compounds of formula (I) are such that n is 1 and of formula (I'b): As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates; Formula (l'b) in which: • R _t , R ₂ , Ra, R4, R5 and R _s , identical or different, are as defined in claim 1, in particular represent: i) a hydrogen atom, ii) hydroxy, iii) cyano, iv) - (O) pC (O) - (O) _q -R ₇ with R ₇ representing a hydrogen atom, a group (CrCsjalkyle, p and q, identical or different, are 0 or 1, with p + q = 0 or 1, v) (Ci-Ç ₆ ) optionally substituted alkyl, vi) (C ₂ -C ₆ ) alkenyl, vii) (Ci-C _B ) alkoxy, said alkyl groups being optionally substituted by one or more groups chosen from hydroxy and - ( O) _r C (O) -R ₈ with t valant 0 or 1, R ₈ represents a) a hydrogen atom, b) a hydroxy group, c) (Ci-C ₆ ) alkyie, d) (Cf-C ₆ ) alkoxy, e) (di) (C-rC ₆ ) (alkyl) amino, f) (di) hydroxy (Ci-C _B ) alkylamino; or : viii) Ri and R ₂ , and / or R ₃ and R4, and / or R _s and Re form together with the carbon atom which carry them a double bond oxo = O or = C (R9) -R ₁₀ with R ₉ and R ₁₀ represents i) a hydrogen atom, or a group chosen from ii) hydroxy, iii) (Gi-Cs) alkyl optionally substituted by one or more hydroxy groups in particular R ₃ and R ₄ form together with the carbon atom an oxo group and / or in particular R _t and R ₂ , together represent with the carbon atom = C (R ₉ ) -Ri ₀ . 5. Composition according to any one of claims 1, 3 or 4 in which the Or the compounds of formula (I) are such that n is 1 and of formula (Γc); As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates; Formula (l ”c) in which: Ru and R-12, identical or different, representing a hydrogen atom, or a (Ci-C ₆ ) alkyl group, such as methyl, or ethyl, preferably a hydrogen atom. 6. Composition according to any one of claims 1 or 3 in which the compound or compounds of formula (I) are such that n is 2 and of formula (1 ”b): (lb) As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates; Formula (l ”b) in which: • Ri, R ₂ , R ₃ , R ₄ , R5, Re, R'5 and R ' ₆ , identical or different, represent: i) a hydrogen atom, ii) cyano, iii) -C (O) - (O) _q -R ₇ with R ₇ representing a hydrogen atom, an (C1C ₆ ) alkyl group, p and q, identical or different, valent 0 or 1, iv) (Ci-C ₆ ) alkyl optionally substituted by one or more groups chosen from hydroxy and -C (O) -R ₈ , with R ₈ represents a) a hydrogen atom, b ) a hydroxy group, c) (Ci-C ₆ ) alkoxy, or else: v) R-ι and R ₂ , and / or R ₃ and R ₄ , and / or R ₅ and R ₆ and / or R ' ₅ and R' ₆ together form with the carbon atom which carry them a double bond oxo = 0 in particular R ₃ and R ₄ , or R ₅ and R ₆ or R ' ₅ and R' ₆ form together with the carbon atom which carry them a double bond oxo = 0. 7. Composition according to claim 1 in which the compound (s) of formula (I) are such that n is 1 or 2 and of formula (le): (the) As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates; Formula (s) in which: • R ₂ , R ₄ , Rs and R ₆ , identical or different, represent: i) a hydrogen atom, ii) hydroxy, iv) cyano, v) - (O) _p -C (O) - (O) qR ₇ with R ₇ representing a hydrogen atom, a (Ci-C ₆ ) alkyl group, p and q, identical or different, valent 0 or 1 with p + q = 0 or 1, vi) (Ci-C ₆ ) alkyl optionally substituted by one or more groups chosen from hydroxy and -C (O) -R ₈ with R ₈ represents a) a hydrogen atom, b ) a hydroxy group, c) (Ci-C ₆ ) alkoxy, vii) (C ₂ -C ₆ ) alkenyl, viii) (Ci-C ₆ ) alkoxy, or else: x) R ₅ and R ₆ together form with the carbon atom which carries them a double bond oxo = 0 or = C (R ₉ ) -Ri ₀ with R ₉ and R ₁₀ represents a hydrogen atom or a group ( Ci-C ₆ ) alkyl. 8. Composition according to the preceding claim in which the compound or compounds of formula (I) are of formula (Ie) and n is 1. 9. Composition according to any one of claims 1 or 7 in which the compound or compounds of formula (I) are such that n is 2 and of formula (e): (the c) As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates; 5 Formula (c) in which: • R ₂ , R ₄ , R5, R6, R'5 and R ' ₆ , identical or different, represent: i) a hydrogen atom, ii) hydroxy, iii) - (O) _p -C (O) - (O) _q -R ₇ with R ₇ representing a hydrogen atom, a group 10 (Ci-C ₆ ) alkyl, p and q, identical or different, are 0 or 1 with p + q = 0 or 1, iv) (Ci-C ₆ ) alkyl, or v) (Ci-C ₆ ) alkoxy. 10. Composition according to any one of the preceding claims, in which the compound or compounds of formula (I) are chosen from the following compounds: OH Ο Ό ο ο 129 130 153 154 155 182 OH 180 OH 186 183 187 249 250 251 252 257 258 266,267 265 As well as their acid or base salts, organic or mineral, their optical isomers, their geometric isomers, their tautomers and their solvates such as hydrates. 11. Composition according to any one of the preceding claims, in which the compound or compounds of formula (I) are present in an amount inclusive between 0.01 and 50% by weight relative to the total weight of the composition, in particular between 0, 1 and 30%, more particularly between 1 and 20%, preferably between 2 and 15%, more preferably between 5 and 10% by weight relative to the total weight of the composition. 12. Composition according to any one of the claims which does not comprise thiol reducing agents such as thiolactic acid, preferably does not comprise 15 of reducing agent. 13. Compound chosen from those of formulas (1 ”c) as defined in claim 5; preferably the compounds are chosen from those of formula 116, 117, 118, 119, 120, 121 and 122: 120 121 122 As well as their acid or base salts, organic or mineral, their optical isomers, and their solvates such as hydrates. 14. Process for the preparation of the compounds of formula (I ”c) as defined in the preceding claim according to the following synthetic scheme: which consists in reacting in step i) 3-butene-1,2,3-tricarboxylic acid (A) with at least one molar equivalent of thiolacetic acid in particular in an aprotic organic solvent, preferably halogenated such as dichloromethane , or THF type ether, more particularly by heating the reaction medium until solvent reflux, preferably at a temperature between 40 ° C. and 80 ° C., to lead to compound (B), in step ii) compound (B) reacts with a strong, organic or inorganic acid such as hydrochloric acid, in particular in a polar protic solvent such as water, more particularly by heating until the solvent refluxes, preferably at a temperature between 60 and 90 ° C, to yield the thiolactone (C) in steps iii) and v) the compound (C) is reacted with at least one equivalent of an alcohol R 'n-OH and R' ₁₂ - OH respectively, with R 'n and R' _12, identical or different, represent an (Ci-C ₆ ) alkyl group, in particular in a polar organic solvent such as ethyl acetate, preferably at low temperature such as 0 ° C, to lead to the monoesters (D) and (E) which can still in the presence of alcohol, to be esterified on the second carboxy group according to steps iv) and vi), to yield the diester (F), the compounds (D), (E) and (F) being able to be purified by chromatography for example on silica column; compounds (C), (D), (E) and (F) constituting the set of compounds of formula (1 ”c). 15. Cosmetic use of one or more compounds of formula (I), as defined in any one of claims 1 to 10, for the treatment of keratin fibers, especially human fibers such as the hair, preferably for the shaping of keratin fibers and / or smoothing / straightening of said fibers. 16. Process for treating keratin materials, in particular human keratin fibers such as hair, comprising: a) the application to said keratin materials of a composition as defined in any one of claims 1 to 11. 17. Method according to the preceding claim comprising after step a) followed by a step b) of smoothing / straightening said keratin materials by means of a smoothing iron at a temperature of at least 100 ° C or a step of shaping of said keratin materials; preferably at a temperature comprised 5 between, limits included, 100 ° C and 300 ° C, preferably between 120 ° C and 280 ° C, more preferably between 150 ° C and 250 ° C, and even better, between 200 and 250 ° C. 18. Method according to any one of claims 16 or 17 which does not use a thiolated reducing agent such as thiolactic acid, preferably does not 10 work of reducing agent Photos 1 to 4: Untreated wick Wick treated with example 1 after 10 shampoos successive Wick treated with example 2 after 10 shampoos successive Wick treated with example 3 after 10 shampoos successive Natural type IV caucasian dsE | * AT I