FR2856059A1 - Para-phenylenediamine derivatives comprising a diazacycloheptane substituent substituted by a silyl radical, useful in compositions for dyeing of keratinic fibres - Google Patents

Abstract

Use of para-phenylenediamine derivatives comprising silyl-substituted diazacycloheptane substituents for the dyeing of keratinic fibres particularly human hair. Derivatives of paraphenylenediamine of formula (I) comprising a 1,4-diazacycloheptane substituent substituted by a silyl radical [Image] R1halogen, or a 1 - 6C hydrocarbon chain(aliphatic or alicyclic, saturated or unsaturated) in which one or more C atoms may be replaced by O, N, Si or S, SO or SO2 : it can not comprise peroxide, diazo, nitro or nitroso groups but may be substituted by one or more halogens, or one or more OH, NH2, mono- or di-alkyl(1 - 4C) amino or carboxy; n : 0 - 4(if n is greater than 1 radicals R1 may be identical or different); R2-SiR5R6R7 or 1 - 8C alkyl substituted by a radical -SiR5R6R7(one or more C atoms may be replaced by one or more O, N, Si, S, or ketone, and the alkyl may be substituted by OH, NH2, alkyl(1 - 6C)amino or dialkyl(1 - 6C)amino); R5, R6, R7phenyl or 1 - 6C alkyl possibly substituted by trialkyl(1 - 6C) silyl, OH, NH2, alkyl(1 - 6C)amino or dialkyl(1 - 6C)amino; R3H, alkyl(optionally unsaturated), OH, hydroxyalkyl, alkoxy, alkoxyalkyl, alkylcarbonyl, hydroxyalkoxyalkyl, NH2, monoalkylamino or dialkylamino, aminoalkyl(the amine being mono or disubstituted by alkyl, acetyl or hydroxyalkyl), hydroxyaminoalkyl, carboxyl, carboxyalkyl, carbamoyl, carbamoylalkyl, alkoxycarbonyl, or mono- or di-alkylaminocarbonyl; R4alkyl(optionally unsaturated), hydroxyalkyl, alkoxyalkyl, alkylcarbonyl, hydroxyalkoxyalkyl, aminoalkyl(the amine being mono- or di-substituted by alkyl, acetyl or hydroxyalkyl), hydroxyaminoalkyl, carboxyl, carboxyalkyl, carbamoyl, carbamoylalkyl, alkoxycarbonyl or mon- or di-alkyl-aminocarbonyl; m : 0 - 4(if m is greater than 1, radicals R4 may be identical or different). Independent claims are also included for their use in the oxidative dyeing of fibres, compositions containing the compounds and paranitroaniline precursors of the compounds (III). [Image].

Description

<Desc / Clms Page number 1>

PARA-PHENYLENEDIAMINE DERIVATIVES COMPRISING A CYCLE
DIAZACYCLOHEPTANE SUBSTITUTED BY A RADICAL SILYLE FOR
STAINING OF KERATIN FIBERS
The invention relates to para-phenylenediamine derivatives having a silyl radical substituted diazacycloheptane ring, as well as their use for dyeing keratinous fibers, and in particular human keratinous fibers such as the hair.

 It is known to dye keratinous fibers, and in particular human keratinous fibers such as the hair with dyeing compositions comprising oxidation dye precursors, in particular ortho- or para-phenylenediamines, ortho- or para-aminophenols heterocyclic compounds such as diaminopyrazole derivatives, pyrazolo [1,5-a] pyrimidine derivatives, pyrimidine derivatives, pyridine derivatives, 5,6-dihydroxyindole derivatives, 5,6-dihydroxyindoline derivatives, generally oxidation bases. The oxidation dye precursors, or oxidation bases, are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise, by a process of oxidative condensation, to colored or coloring compounds.

 It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from meta-phenylenediamines, meta-aminophenols, meta-hydroxyphenols and certain heterocyclic compounds such as, for example, pyrazolo [1,5-b] -1,2,4-triazole derivatives, pyrazolo [3,2-c] -1,2,4-triazole derivatives, derivatives thereof, pyrazolo [1,5-a] pyrimidine derivatives, pyridine derivatives, pyrazol-5-one derivatives, indoline derivatives and indole derivatives.

 The variety of molecules involved in the oxidation bases and couplers allows a rich palette of colors to be obtained.

<Desc / Clms Page number 2>

 The so-called "permanent" coloration obtained by virtue of these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity, to have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and friction.

 The dyes must also make it possible to cover the white hairs, and finally be the least selective possible, that is to say make it possible to obtain the lowest possible color differences throughout the same keratinous fiber, which can indeed be differently sensitized (ie damaged) between its tip and its root. They must also have good chemical stability in the formulations. They must have a good toxicological profile.

 In the field of hair dyeing, paraphenylenediamine and para-toluene diamine are widely used oxidation bases. They make it possible to obtain, with oxidation couplers, various shades.

 However, there is a need to discover new oxidation bases with a better toxicological profile than para-phenylenediamine and para-toluenediamine, while allowing to give the hair excellent color intensity properties, variety of shades, uniformity of color and toughness to external agents.

 It is already known to use 1,4-diazacycloheptane derivatives for the oxidation dyeing of keratinous fibers. For example, US Pat. No. 6,165,230 describes a dye composition comprising 1,4-diazacycloheptane derivatives substituted on the two nitrogen atoms of the ring by a 4'-aminobenzene group.

 It is clearly established that these compounds do not make it possible to confer a coloration of quality equivalent to that obtained with paraphenylenediamine or with para-toluenediamine because of a lack of intensity and uniformity of the color.

<Desc / Clms Page number 3>

 There is therefore a real need to discover new oxidation bases having both a good toxicological profile and properties such that the dye compositions comprising them make it possible to give the hair excellent properties of color intensity, variety of shades, uniformity of color and toughness vis-à-vis the various external aggressions that can undergo the hair.

 The object of the present invention is to develop new oxidation bases for dyeing keratinous fibers that do not have the drawbacks of the oxidation bases of the prior art by providing novel compounds for dyeing keratin fibers that do not degrade. keratinous fibers while being capable of generating intense colorations in various shades, not very selective, particularly resistant and having a good toxicological profile.

dans laquelle : ' Ri représente : - un atome d'halogène ; - une chaîne hydrocarbonée en C1-C6, aliphatique ou alicyclique, saturée ou insaturée, un ou plusieurs atomes de carbone de la chaîne hydrocarbonée pouvant être remplacés par un ou plusieurs atomes d'oxygène, d'azote, de silicium, de soufre, par un groupement
SO ou par un groupement S02, le radical Ri ne comportant pas de This object is achieved with the present invention which relates to the para-phenylenediamine derivatives of formula (I) having a 1,4-diazacycloheptane ring substituted with a silyl radical and their addition salts:

wherein: R1 represents: - a halogen atom; a saturated or unsaturated, aliphatic or alicyclic, C1-C6 hydrocarbon-based chain, one or more carbon atoms of the hydrocarbon-based chain being capable of being replaced by one or more oxygen, nitrogen, silicon or sulfur atoms, by a group
SO or by a group SO2, the radical Ri not having any

<Desc / Clms Page number 4>

un groupement hydroxyle, amino, alkyl(CI-C6)amino ou dialkyl(C-
C6)amino ; # R5, R6 et R7, identiques ou différents, représentent : - un radical phényle ; - un radical alkyle en Ci-Ce pouvant être substitué par un groupement

trialkyl(C1-Cs)silyle, hydroxyle, amino, alkyl(Cl-C6)amino ou dialkyl (C1-C6)amino ; # R3 représente : - un atome d'hydrogène ; - un radical alkyle pouvant être insaturé ; - un radical hydroxy ; - un radical hydroxyalkyle ; - un radical alcoxy ; - un radical alcoxyalkyle ; - un radical alkylcarbonyle ; - un radical hydroxyalcoxyalkyle ; - un radical amino ; - un radical monoalkylamino ou dialkylamino ; peroxide, or diazo radicals, nitro or nitroso, this chain may be substituted by one or more halogen atoms, one or more hydroxyl, amino, mono- or di-alkyl radicals (C1-
C4) amino, carboxy; # n is between 0 and 4, it being understood that when n is greater than 1, the radicals R 1 may be identical or different; # R2 represents: a radical -SiR5R6r7; a C1-C8 alkyl radical substituted with a radical-SiR5R6R7, the alkyl radical being unsaturated, linear or branched, one or more carbon atoms of the alkyl radical being able to be replaced by one or more oxygen or nitrogen atoms; of sulfur, by a ketone function and the alkyl radical may be substituted by

a hydroxyl, amino, (C 1 -C 6) alkyl amino or dialkyl group (C
C6) amino; # R5, R6 and R7, which may be identical or different, represent: a phenyl radical; a C1-C6 alkyl radical which may be substituted by a group

trialkyl (C1-Cs) silyl, hydroxyl, amino, (C1-C6) alkylamino or dialkyl (C1-C6) amino; # R3 represents: - a hydrogen atom; an alkyl radical which can be unsaturated; a hydroxyl radical; a hydroxyalkyl radical; an alkoxy radical; an alkoxyalkyl radical; an alkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an amino radical; a monoalkylamino or dialkylamino radical;

<Desc / Clms Page number 5>

an aminoalkyl radical, the amine possibly being mono or disubstituted by an alkyl, acetyl or hydroxyalkyl radical; a hydroxyaminoalkyl radical; a carboxyl radical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkyl radical; an alkoxycarbonyl radical; a mono- or dialkylaminocarbonyl radical; # R4 represents: an alkyl radical that can be unsaturated; a hydroxyalkyl radical; an alkoxyalkyl radical; an alkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an aminoalkyl radical, the amine possibly being mono or disubstituted by an alkyl, acetyl or hydroxyalkyl radical; a hydroxyaminoalkyl radical; a carboxyl radical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkyl radical; an alkoxycarbonyl radical; a mono- or dialkylaminocarbonyl radical; # m is between 0 and 4, it being understood that when m is greater than
1 then the radicals R4 may be identical or different.

 The present invention makes it possible in particular to obtain a chromatic keratin fiber coloring that is powerful, not very selective and tenacious.

 Another subject of the invention is the use of these paraphenylenediamine derivatives of formula (I) for dyeing keratinous fibers, and in particular human keratinous fibers such as the hair.

<Desc / Clms Page number 6>

 The subject of the invention is also a composition for dyeing keratinous fibers, and in particular human keratinous fibers such as the hair, comprising at least one para-phenylenediamine derivative of formula (1), as well as the process for dyeing keratin fibers using this composition.

 The derivatives of formula (I) are para-phenylenediamines whose amine is included in a 1,4-diazacycloheptane type ring, also known in the 1,4-diazepane literature.

 In the above definitions, the alkyl radicals are linear or branched and include, unless otherwise indicated, from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms. An alkoxy radical is an alkyl-O- radical, the alkyl radical being as defined previously.

 By unsaturated alkyl radical is meant an alkyl of 2 to 10 carbon atoms and comprising one or more double and / or triple bonds.

 A substituted alkyl radical is a mono or polysubstituted alkyl radical. For example, a hydroxyalkyl radical or an aminoalkyl radical is an alkyl radical which may be substituted by one or more hydroxy or amino groups.

 In the formula (1), the radical R 1 is for example chosen from a chlorine atom; a methyl radical; an ethyl radical; an isopropyl radical; a vinyl radical; an allyl radical; a methoxymethyl radical; a hydroxymethyl radical; a 1-carboxymethyl radical; a 1-aminomethyl radical; a 2-carboxyethyl radical; a 2-hydroxyethyl radical; a 3-hydroxypropyl radical; a 1,2-dihydroxyethyl radical; a 1-hydroxy-2-aminoethyl radical; a 1-amino-2-hydroxyethyl radical; a 1,2-diaminoethyl radical; a methoxy radical; an ethoxy radical; an allyloxy radical; a 2-hydroxyethyloxy radical.

 According to a particular embodiment of the invention, the radical R 1 is chosen from an alkyl radical; a hydroxyalkyl radical; an aminoalkyl radical; an alkoxy radical; a hydroxyalkoxy radical. By way of example, the radical R 1 can be a methyl radical; a hydroxymethyl radical; a 2-hydroxyethyl radical; a 1,2-dihydroxyethyl radical; a methoxy radical; a

<Desc / Clms Page number 7>

 2-hydroxyethoxy radical and more preferably a methyl radical; a hydroxymethyl radical; a 1,2-dihydroxyethyl radical.

 According to a preferred embodiment of the invention, the oxidation bases of formula (I) are such that n is equal to 0 or 1.

 According to a particular embodiment of the invention, the radical R2 is chosen from an alkyl radical substituted with one or two trialkylsilyl radicals; an alkylaminoalkyl radical substituted with a trialkylsilyl radical; an alkylcarbamoylaminoalkyl radical substituted with a trialkylsilyl radical; an alkylcarbonyl radical substituted with a trialkylsilyl radical, itself substituted with a trialkylsilyl radical; an alkylcarbonyl radical substituted with a trialkylsilyl radical; an alkoxyalkyl radical substituted with a trialkylsilyl radical; an alkylcarbonyl radical substituted with a dialkylphenylsilyl radical; an alkyl radical substituted with a trialkylsilyl radical, itself substituted with a trialkylsilyl radical. By way of example, the radical R 2 may be a 3- (trimethylsilyl) propyl radical; a radical (trimethylsilyl) methyl; a 2 - {[3- (trimethylsilyl) propyl] amino} ethyl radical; a 2- ({[(trimethylsilyl) methyl] carbamoyl} amino) ethyl radical; a {dimethyl [(trimethylsilyl) methyl] silyl} acetyl radical; a radical (trimethylsilyl) acetyl; a 2- [3- (trimethylsilyl) propoxy] ethyl radical; a 2- [(trimethylsilyl) methoxy] ethyl radical; a [(dimethyl) (phenyl) silyl] acetyl radical; a bis (trimethylsilyl) methyl radical; a {(dimethyl) [(trimethylsilyl) methyl] silyl} methyl radical.

 According to a particular embodiment of the invention, the radical R 3 is chosen from a hydrogen atom; a hydroxy radical; an alkyl radical; a hydroxyalkyl radical; an aminoalkyl radical; a carboxyl radical; an amino radical. By way of example, the radical R3 may be a hydrogen atom; a hydroxy radical; a carboxyl radical; an amino radical; a hydroxymethyl radical; an aminomethyl radical and more preferably a hydrogen atom.

 According to a particular embodiment of the invention, the radical R 4 is chosen from an alkyl radical; a hydroxyalkyl radical; an aminoalkyl radical; a carboxyl radical, a carbamoyl radical.

<Desc / Clms Page number 8>

 According to a preferred embodiment of the invention, the oxidation bases of formula (I) are such that m is equal to 0 or 1.

 The compounds of formula (I) may optionally be salified with strong mineral acids such as for example HCl, HBr, H 2 SO 4, or organic acids such as, for example, acetic, lactic, tartaric, citric or succinic acid.

molécule nomenclature si Y y 4-{4-[3-(triméthylsilyl)propyl]-1,4-diazépan-1 N yl}phénylamine NH2 / N N 4-{4-[(triméthylsilyl)méthyl]-1,4-diazépan-1yl}phénylamine NH2 H N#\ C) N -/S 4-[4-(2-{[3-(triméthylsilyl)propyl]amino}éthyl)-1,4diazépan-1-yl]aniline NH2 By way of examples of derivatives of formula (1), mention may be made of the compounds presented in the table below.

molecule nomenclature if 4- [4- [3- (trimethylsilyl) propyl] -1,4-diazepan-1 N yl} phenylamine NH 2 / NN 4- {4 - [(trimethylsilyl) methyl] -1,4-diazepan 1-methylphenylamine NH 2 HN (C) N - [4 - [4- (2 - {[3- (trimethylsilyl) propyl] amino} ethyl) -1,4-diazepan-1-yl] aniline NH 2

<Desc / Clms Page number 9>

z ( /#N /SI\ N-{2-[4-(4-aminophényl)-1,4-diazépan-1-yl]éthyl}-N'N [(triméthylsilyl)méthyl]urée NH2 /-< Aj A N 4-[4-( fdiméthyl[(triméthylsilyl)méthyl]silyl}acétyl)-1,4- ))J diazépan-1-yl]phénylamine NH2 0 \>--i C) 4-{4-((triméthylsilyl)acéty(]-1,4-diazépan-1N yllphénylamine NH2 N C) 4-(4-2-[3-(triméthylsilyl)propoxy]éthyl}-1,4-diazépan-1J yl)phénylamine NH, O 4-(4-{2-[(triméthylsilyl)méthoxy]éthyl}-1,4-diazëpan-1yl)phénylamine NH2

(/ # N / SI) N- {2- [4- (4-aminophenyl) -1,4-diazepan-1-yl] ethyl} -N'N [(trimethylsilyl) methyl] urea NH 2 / - AN 4- [4- (dimethyl [(trimethylsilyl) methyl] silyl} acetyl) -1,4-)) diazepan-1-yl] phenylamine NH 2 O- (C) -4- {4 - ((trimethylsilyl)} ) acetyl (1 - 1,4-diazepan-1N-ylphenylamine NH 2 NC) 4- (4-2- [3- (trimethylsilyl) propoxy] ethyl] -1,4-diazepan-1-yl) phenylamine NH 4 O ( 4- {2 - [(trimethylsilyl) methoxy] ethyl} -1,4-diazepan-1-yl) phenylamine NH 2

<Desc / Clms Page number 10>

SI / 1\ /"\ 2-méthyl-4-( 4-[3-(triméthylsilyl)propyl]-1 ,4-diazépan-1N yl)phénylamine NH2 SI 2-méthyl-4-{4-[(triméthylsilyl)méthyl]-1,4-diazépan-1N A yl}phénylamine NH2 C) Í -2-méthyl-4-[4-(2-{[3-(triméthylsilyl)propyl]amino}éthyl) A 1,4-diazépan-1-yl]aniline NH2 o ) -7S| N-{2-[4-(4-amino-3-méthylphényl)-1,4-diazépan-1- ï yl]éthyl}-N'-[(triméthylsilyl)méthyl]urée NH2 o nr-Si / C) / N T 1-[4-(4-amino-3-méthyl-phényl)-1,4-diazépan-1-yl]-2Ljl (diméthyl-triméthylsilanylméthyl-silanyl)-éthanone NH2

SI / 1-methyl-4- (4- [3- (trimethylsilyl) propyl] -1,4-diazepan-1N yl) phenylamine NH 2 Si 2 -methyl-4- {4 - [(trimethylsilyl) methyl] -1,4-diazepan-1N-yl} phenylamine NH 2 C) -2-methyl-4- [4- (2 - {[3- (trimethylsilyl) propyl] amino} ethyl) A 1,4-diazepan 1-yl] aniline NH 2 O) -7S N- {2- [4- (4-amino-3-methylphenyl) -1,4-diazepan-1-yl] ethyl} -N '- [(trimethylsilyl) ) methyl] urea NH 2 O nr-Si / C) / NT 1- [4- (4-amino-3-methyl-phenyl) -1,4-diazepan-1-yl] -2H] (dimethyltrimethylsilanylmethylsilanyl) -ethanone NH2

<Desc / Clms Page number 11>

Y 2-méthyl-4-{4-[(triméthylsilyl)acétyl]-1,4-diazépan-1N yl}phénylamine NH2 N C) 2-méthyl-4-(4-{2-[3-(triméthylsilyl)propoxy]éthyl}-1,4N 2-méthy!-4-(4-{2-[3-(triméthylsilyl)propoxy]éthyl}-1,4L diazépan-1-yl)phénylamine NH, iC) 2-méthyl-4-(4-2-[(triméthylsilyl)méthoxy]éthyl}-1,4- 2-méthy)-4-(4-{2-[(triméthy!si!y!)méthoxy]éthyt}-1,4N 2-méthyl-4-(4-{2-[(triméthylsilyl)méthoxy]éthyl}-1 diazépan-1-yl)phénylamine NH2 0 >-i Si \"Ph ( 4-(4-{[diméthyl(phényl)silyl]acétyl}-1,4-diazépan-1N yl)phénylamine NH2 \,,Ph C) 2-méthyl-4-(4-{[diméthyl(phényl)silyl]acétyl}-1,4N diazépan-1-yl)phénylamine NH2

Y 2-methyl-4- {4 - [(trimethylsilyl) acetyl] -1,4-diazepan-1N yl} phenylamine NH 2 NC) 2-methyl-4- (4- {2- [3- (trimethylsilyl) propoxy] ethyl) -1,4N 2-methyl-4- (4- {2- [3- (trimethylsilyl) propoxy] ethyl} -1,4L diazepan-1-yl) phenylamine NH, iC) 2-methyl-4- (4-2 - [(trimethylsilyl) methoxy] ethyl] -1,4-2-methyl) -4- (4- {2 - [(trimethylsilyl) methoxy] ethyl} -1.4N 2- methyl-4- (4- {2 - [(trimethylsilyl) methoxy] ethyl} -1-diazepan-1-yl) phenylamine NH 2 O -I-Si [Ph (4- (4 - {[dimethyl (phenyl) silyl] acetyl) -1,4-diazepan-1N yl) phenylamine NH 2 N, Ph C) 2-methyl-4- (4 - {[dimethyl (phenyl) silyl] acetyl} -1,4N diazepan-1-yl) phenylamine NH2

<Desc / Clms Page number 12>

\/ / 4-[4-{bis-(triméthylsilyl)méthyl}-1,4-diazépan-1li yl]phénylamine NH2 7 ,Si / 2-méthyl-4-[4-{bis-(triméthylsilyl)méthyl}-1,4-diazépanN 1-yl]phénylamine NH2 C) /Ss 4-{4-[((diméthyl)(triméthylsilylméthyl)silyl)méthyl]-1,4diazépan-1-yl}phénylamine NH2 N 2-méthyl-4-{4- -n- diméth I triméth Isil Iméth I sil I méth I -1 4diazépan-1-yl}phénylamine NH2
Parmi ces composés, les dérivés de para-phénylènediamine de formule (I) particulièrement préférés sont le 4-{4-[3-(triméthylsilyl)propyl]-1,4- diazépan-1-yl}phénylamine ; le 4-{4-[(triméthylsilyl)méthyl]-1,4-diazépan-1yl}phénylamine ; le 4-[4-(2-{[3-(triméthylsilyl)propyl]amino}éthyl)-1,4-diazépan-1- yl]aniline ; le N-{2-[4-(4-aminophényl)-1,4-diazépan-1-yl]éthyl}-N'- [(triméthylsilyl)méthyl]urée ; le 4-[4-({diméthyl[(triméthylsilyl)méthyl]silyl}acétyl)- 1,4-diazépan-1-yl]phénylamine ; le 4-{4-[(triméthylsilyl)acétyl]-1,4-diazépan-1yl}phénylamine ; le 4-(4-{2-[3-(triméthylsilyl)propoxy]éthyl}-1,4-diazépan-1-

4- [4- {bis (trimethylsilyl) methyl} -1,4-diazepan-1-yl] phenylamine NH 2 7, Si / 2-methyl-4- [4- {bis (trimethylsilyl) methyl} - 1,4-diazepan-1-yl] phenylamine NH 2 C) / Ss 4- {4 - [((dimethyl) (trimethylsilylmethyl) silyl) methyl] -1,4-diazepan-1-yl} phenylamine NH 2 N 2 -methyl-4- {4- (n-dimethyl) trimethylisil Imethylmethyl] -1-diazepan-1-yl} phenylamine NH2
Among these compounds, the particularly preferred para-phenylenediamine derivatives of formula (I) are 4- {4- [3- (trimethylsilyl) propyl] -1,4-diazepan-1-yl} phenylamine; 4- {4 - [(trimethylsilyl) methyl] -1,4-diazepan-1-yl} phenylamine; 4- [4- (2 - {[3- (trimethylsilyl) propyl] amino} ethyl) -1,4-diazepan-1-yl] aniline; N- {2- [4- (4-aminophenyl) -1,4-diazepan-1-yl] ethyl} -N '- [(trimethylsilyl) methyl] urea; 4- [4 - ((dimethyl [(trimethylsilyl) methyl] silyl} acetyl) -1,4-diazepan-1-yl] phenylamine; 4- {4 - [(trimethylsilyl) acetyl] -1,4-diazepan-1-yl} phenylamine; 4- (4- {2- [3- (trimethylsilyl) propoxy] ethyl} -1,4-diazepan-1-

<Desc / Clms Page number 13>

yl]phénylamine ; le 4-{4-[((diméthyl)(triméthylsilylméthyl)silyl)méthyl]-1,4diazépan-1 -yllphénylamine. yl) phenylamine; 4- (4- {2 - [(trimethylsilyl) methoxy] ethyl} -1,4-diazepan-1-yl) phenylamine; 4- (4 - {[dimethyl (phenyl) silyl] acetyl} -1,4-diazepan-1-yl) phenylamine; 4- [4- {bis (trimethylsilyl) methyl} -1,4-diazepan-1-

yl] phenylamine; 4- {4 - [((dimethyl) (trimethylsilylmethyl) silyl) methyl] -1,4diazepan-1 -yllphenylamine.

 The carbon substituted by R3 or by R4 may be of (R) and / or (S) configuration.

 The subject of the present invention is also the use, for the oxidation dyeing of keratinous fibers, and in particular human keratinous fibers such as the hair, of a paraphenylenediamine derivative of formula (I) as defined above.

 The subject of the present invention is also a composition for dyeing keratinous fibers, and in particular human keratin fibers such as the hair, comprising, in a medium suitable for dyeing, at least one para-phenylenediamine derivative of formula (1 ).

 The para-phenylenediamine derivative (s) of formula (I) are generally present in an amount of between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

 The dyeing composition of the invention may contain one or more couplers conventionally used for dyeing keratinous fibers.

Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.

 By way of example, mention may be made of 2-methyl-5-aminophenol; 5-N- (sshydroxyethyl) amino 2-methyl phenol; 6-chloro-2-methyl-5-aminophenol; 3-amino phenol; 1,3-dihydroxybenzene; 1,3-dihydroxy-2-methyl benzene; 4-chloro-1,3-dihydroxybenzene; 2,4-diamino 1- (ss-hydroxyethyloxy) benzene; 2-amino-4- (5-hydroxyethylamino) -1-methoxybenzene; 1,3-diamino benzene; 1,3-bis (2,4-diaminophenoxy) propane; 3-ureido aniline; 3-ureido 1-dimethylamino benzene; sesamol; 1- (hydroxyethylamino) -3,4-methylenedioxybenzene; α-naphthol; 2-methyl-1

<Desc / Clms Page number 14>

diamino-2,6-diméthoxypyridine ; le 1 -N-(R-hydroxyéthyl)amino-3,4méthylènedioxybenzène ; le 2,6-bis- I-hydroxyéthylamino) toluène et leurs sels d'addition avec un acide. naphthol; 6-hydroxyindole; 4-hydroxyindole; 4-hydroxy N-methyl indole; 2-amino-3-hydroxy pyridine; 6-hydroxy benzomorpholine; 3,5-

diamino-2,6-dimethoxypyridine; 1-N- (R-hydroxyethyl) amino-3,4-methylenedioxybenzene; 2,6-bis-1-hydroxyethylamino) toluene and their addition salts with an acid.

 In the composition of the present invention, the coupler or couplers are each generally present in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.

 The composition of the present invention may further comprise one or more additional oxidation bases conventionally used in oxidation dyeing other than those described above. By way of example, these additional oxidation bases are chosen from para-phenylenediamines other than the derivatives of formula (1), bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, ortho-aminophenols and ortho-aminophenols. phenylenediamines, heterocyclic bases and their addition salts.

4-amino N,N-diéthyl 3-méthyl aniline ; la N,N-bis-((3-hydroxyéthyl) paraphénylènediamine ; la 4-N,N-bis-(P-hydroxyéthyl)amino 2-méthyl aniline ; la 4-N,N-bis-(p-hydroxyéthyt)amino 2-chloro aniline ; la 2-(p-hydroxyéthyt) para- phénylènediamine ; la 2-fluoro para-phénylènediamine ; la 2-isopropyl paraphénylènediamine ; la N-(ss-hydroxypropyl) para-phénylènediamine ; la 2-hydroxyméthyl para-phénylènediamine ; la N,N-diméthyl 3-méthyl paraphénylènediamine ; la N,N-(éthyl, ss-hydroxyéthyl) para-phénylènediamine ; la N-(ss,[gamma]-dihydroxypropyl) para-phénylènediamine ; la N-(4'-aminophényl) paraphénylènediamine ; la N-phényl para-phénylènediamine ; la Among para-phenylenediamines, there may be mentioned, by way of example, para-phenylenediamine; para-tolylenediamine; 2-chloro-para-phenylenediamine; 2,3-dimethyl para-phenylenediamine; 2,6-dimethyl para-phenylenediamine; 2,6-diethyl para-phenylenediamine; 2,5-dimethyl para-phenylenediamine; N, N-dimethyl para-phenylenediamine; N, N-methyl para-phenylenediamine; N, N-dipropyl para-phenylenediamine; the

4-amino N, N-diethyl-3-methylaniline; N, N-bis - ((3-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (p-hydroxyethyl) amino 2-chloroaniline, 2- (p-hydroxyethyl) para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (ss-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine; N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, s-hydroxyethyl) para-phenylenediamine, N- (ss, [gamma] -dihydroxypropyl) para-phenylenediamine, N- (4 ') aminophenyl) paraphenylenediamine, N-phenyl para-phenylenediamine;

<Desc / Clms Page number 15>

2-(p-hydroxyéthyloxy) para-phénylènediamine ; la 2-(p-acétytaminoéthytoxy) para-phénylènediamine ; la N-(ss-méthoxyéthyl) para-phénylènediamine ; la 4aminophényl pyrrolidine ; la 2-thiényl para-phénylènediamine ; la 2-(sshydroxyéthylamino) 5-amino toluène ; la 3-hydroxy 1-(4'-aminophényl) pyrrolidine et leurs sels d'addition avec un acide.

2- (p-hydroxyethyloxy) para-phenylenediamine; 2- (p-acetylaminoethyloxy) para-phenylenediamine; N- (ss-methoxyethyl) para-phenylenediamine; 4-aminophenyl pyrrolidine; 2-thienyl para-phenylenediamine; 2- (5-hydroxyethylamino) -amino toluene; 3-hydroxy 1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid.

phénylènediamine ; la N,N-bis-(|3-hydroxyéthyl) para-phénylènediamine ; la 2-chloro para-phénylènediamine ; la 2-(p-acétytaminoéthytoxy) para- phénylènediamine et leurs sels d'addition avec un acide sont particulièrement préférées. Among the para-phenylenediamines mentioned above, para-phenylenediamine; para-toluenediamine; 2-isopropyl paraphenylenediamine; 2 - (- hydroxyethyl) para-phenylenediamine; 2- (5-hydroxyethyloxy) para-phenylenediamine; 2,6-dimethyl paraphenylenediamine; 2,6-diethyl para-phenylenediamine; 2,3-dimethyl para

phenylenediamine; N, N-bis- (3-hydroxyethyl) para-phenylenediamine; 2-chloro para-phenylenediamine; 2- (p-acetylaminoethyloxy) para-phenylenediamine and their acid addition salts are particularly preferred.

 Among the bisphenylalkylenediamines, N, N'-bis- (ss-hydroxyethyl) N, N'-bis- (4'-aminophenyl) -1,3-diamino propanol may be mentioned by way of example; N, N'-bis (ss-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine; N, N'-bis- (4-aminophenyl) tetramethylenediamine; N, N'-bis (ss-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine; N, N'-bis- (4-methylaminophenyl) tetramethylenediamine; N, N'-bis (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine; 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane and their addition salts with an acid.

 Among para-aminophenols, there may be mentioned, for example, para-aminophenol; 4-amino-3-methyl phenol; 4-amino-3-fluoro phenol; 4-amino-3-hydroxymethyl phenol; 4-amino-2-methyl phenol; 4-amino-2-hydroxymethyl phenol; 4-amino-2-methoxymethyl phenol; 4-amino-2-aminomethyl phenol; 4-amino-2- (ss-hydroxyethylaminomethyl) phenol; 4-amino-2-fluoro phenol and their addition salts with an acid.

 Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol; 2-amino-5-methyl phenol; 2-amino-6-methyl phenol; 2-amino phenolacetamido and their addition salts with an acid.

<Desc / Clms Page number 16>

 Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

 Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine; 2- (4-methoxyphenyl) amino-3-amino pyridine; 2,3-diamino-6-methoxy pyridine; 2- (ss-methoxyethyl) amino-3-amino-6-methoxy pyridine; 3,4-diamino pyridine and their addition salts with an acid.

pyrazolo[1,5-a]pyridine-5-ol ; la 3-amino-pyrazolo[1,5-a]pyridine-4-ol ; la 3- amino-pyrazolo[1,5-a]pyridine-6-ol ; la 3-amino-pyrazolo[1,5-a]pyridine-7-ol ; ainsi que leurs sels d'addition avec un acide ou avec une base. Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] pyridines oxidation bases or their addition salts described, for example, in the patent application FR 2 801. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-ylpyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-aminopyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-5-yl) ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-aminopyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino

pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; as well as their addition salts with an acid or with a base.

 Among the pyrimidine derivatives, mention may be made of the compounds described for example in the patents DE 23 59 399 and EP 0 770 375 or the patent application WO 96/15765 such as 2,4,5,6-tetraamino pyrimidine; 4-hydroxy 2,5,6-triamino pyrimidine; 2-hydroxy 4,5,6-triamino pyrimidine; 2,4-dihydroxy-5,6-diamino pyrimidine; 2,5,6-triamino pyrimidine and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2750048 and among which mention may be made of pyrazolo [1,5-a] -pyrimidine-3,7 -

<Desc / Clms Page number 17>

 diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) - ethanol, 2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-aminopyrazolo [1], 5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2 6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5, N 7, N 7 -tetramethylpyrazolo [1,5-a] -pyrimidine-3,7-diamine 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their acid addition salts and their tautomeric forms, when tautomeric equilibrium exists.

 Among the pyrazole derivatives, mention may be made of the compounds described in DE 38 43 892, DE 41 33 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as 4,5-diamino-1-methyl pyrazole; 4,5-diamino-1 - (- hydroxyethyl) pyrazole; 3,4-diamino pyrazole; 4,5-diamino 1- (4'-chlorobenzyl) pyrazole; 4,5diamino 1,3-dimethyl pyrazole; 4,5-diamino-3-methyl-1-phenyl pyrazole; 4,5-diamino-1-methyl-3-phenyl pyrazole; 4-amino-1,3-dimethyl-5-hydrazino pyrazole; 1-benzyl 4,5-diamino-3-methyl pyrazole; 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5-diamino-1- (ss-hydroxyethyl) -3-methyl-pyrazole; 4,5-diamino-1-ethyl-3-methyl pyrazole; 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole; 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole; 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole; 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole; 4,5-diamino-3-methyl-1-isopropyl pyrazole; 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole; 3,4,5-triamino pyrazole; 1-methyl 3,4,5-triamino pyrazole; 3,5-diamino-1-methyl-4-methylamino pyrazole; 3,5-diamino 4- (β-hydroxyethyl) amino-1-methyl pyrazole and their addition salts with an acid.

 The oxidation base (s) present in the composition of the invention are generally present each in an amount of between 0.001.

<Desc / Clms Page number 18>

 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

 In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

 The dye composition in accordance with the invention may also contain one or more direct dyes that may be chosen in particular from nitro dyes of the benzene series, azo direct dyes and methine direct dyes. These direct dyes may be nonionic, anionic or cationic in nature.

 The medium suitable for dyeing, also known as a dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent for solubilizing compounds that are not sufficiently soluble in water. water. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

 The solvents are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

 The dyeing composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, polymers

<Desc / Clms Page number 19>

 anionic, cationic, nonionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents , perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents.

 The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition.

 Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged.

 The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems.

 Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

 Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (II):

<Desc / Clms Page number 20>

dans laquelle W est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en C1-C4 ; Ra, Rb, Rc et Rd, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C1-C4 ou hydroxyalkyle en C1-C4.

wherein W is a propylene residue optionally substituted with a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

 The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and especially human hair.

 The process of the present invention is a process in which the composition according to the present invention as defined above is applied to the fibers, and the color is revealed using an oxidizing agent. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition on containing, applied simultaneously or sequentially to the composition of the invention.

 According to a particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration. The mixture obtained is then applied to the keratinous fibers. After a residence time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratinous fibers are rinsed, washed with shampoo, rinsed again and then dried.

 The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes. among which there may be mentioned peroxidases, 2-electron oxidoreductases

<Desc / Clms Page number 21>

 such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

 The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing hair and as defined above.

 The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dyeing composition, the pH of the resulting composition applied to the keratinous fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratinous fibers and as defined above.

 The ready-to-use composition which is finally applied to the keratin fibers may be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratinous fibers, and including human hair.

 The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains the dye composition of the present invention defined above and a second compartment contains an oxidizing composition. This device may be equipped with means for delivering the desired mixture to the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant.

 From this device, it is possible to dye the keratinous fibers from a process which comprises mixing a dye composition comprising at least one oxidation base of formula (I) with an oxidizing agent, and application of the mixture obtained on the keratin fibers for a time sufficient to develop the desired coloration.

 The para-phenylenediamine derivatives of formula (I) are obtained by reduction of the para-nitroaniline derivatives of formula (III) below:

<Desc / Clms Page number 22>

dans laquelle les radicaux R1, R2, R3 et R4 et les entiers n et m sont tels que définis précédemment. Ces composés peuvent être obtenus avec le mode général de synthèse ci-dessous s'inspirant de celui décrit la demande de brevet FR 2 828 488 au nom de la demanderesse :

wherein the radicals R1, R2, R3 and R4 and the integers n and m are as defined above. These compounds can be obtained with the general mode of synthesis below inspired by that described in the patent application FR 2 828 488 in the name of the Applicant:

The examples which follow serve to illustrate the invention without, however, being limiting in nature.

<Desc / Clms Page number 23>

Exemple de préparation : synthèse du 44-[3-(triméthylsi(yl)propylj-1,4- diazépan-1-yl}phénylamine

EXAMPLES

Preparation Example: Synthesis of 44- [3- (trimethylsilyl) propyl] -1,4-diazepan-1-yl} phenylamine

Synthèse du 1-(4-nitrophényl)-4-f3-(triméthylsilyl)propyll-1,4-diazépane (1) 4,42 g (0,02 mole) de 1-(4-nitrophényl)-1,4-diazépane et 5,52 g (0,04 mole) de carbonate de potassium sont chauffés dans 30 ml de DMF à 80 C. 6,02 g (0,04 mole) de chlorure de 3-(triméthylsilyl)propyle sont ajoutés goutte à goutte. Le mélange réactionnel est chauffé pendant 10 heures 30 minutes à 100 C, refroidi puis versé dans de la glace. Après extraction au dichlorométhane et séchage sur sulfate de sodium, le produit obtenu est isolé par chromatographie sur gel de silice. 1,77 g d'une poudre jaune sont obtenus, soit un rendement de 26 %.

Synthesis of 1- (4-nitrophenyl) -4- (3- (trimethylsilyl) propyll-1,4-diazepane (1) 4.42 g (0.02 mole) of 1- (4-nitrophenyl) -1,4- diazepane and 5.52 g (0.04 mol) of potassium carbonate are heated in 30 ml of DMF at 80 ° C. 6.02 g (0.04 mol) of 3- (trimethylsilyl) propyl chloride are added dropwise to drop. The reaction mixture is heated for 10 hours 30 minutes at 100 ° C., cooled and then poured into ice. After extraction with dichloromethane and drying over sodium sulphate, the product obtained is isolated by chromatography on silica gel. 1.77 g of a yellow powder are obtained, ie a yield of 26%.

The results of analysis obtained by 1 H NMR and by mass spectrometry are the following: 1 H NMR (400 MHz, DMSO) ppm 8.02 (d, J = 9.52 Hz, 2H); 6.82 (d, J = 9.52Hz, 2H); 3.61 (2 t, J = 4.12 Hz, J '= 6.2 Hz, 4H); 2.71 (m, 2H); 2.51 (m, 2H); (t, J = 7.12 Hz, 2H); 1.84 (m, 2H); 1.36 (m, 2H); 0.38 (m, 2H); -0.05 (s, 9H).

ESI +: m / z = 336 (MH +)

<Desc / Clms Page number 24>

Synthèse du 4-4-3-(triméthylsilyl)propyll-1,4-diazépan-1-yl}phénylaminei hydrochlorure (2) Dans un hydrogénateur de 1 litre, 1,7 g (5,06.10-3 mole) de 1-(4-nitrophényl)-4- [3-(triméthylsilyl)propyl]-1,4-diazépane (1) obtenu ci-dessus à l'étape précédente et 0,8 g de palladium sur charbon sont placés dans 350 ml d'éthanol.

Synthesis of 4-4-3- (trimethylsilyl) propyll-1,4-diazepan-1-yl} phenylamine hydrochloride (2) In a 1-liter hydrogenator, 1.7 g (5.06 × 10 -3 mol) of (4-nitrophenyl) -4- [3- (trimethylsilyl) propyl] -1,4-diazepane (1) obtained above in the previous step and 0.8 g of palladium on charcoal are placed in 350 ml of ethanol.

The reaction is carried out in 5 hours under a hydrogen pressure of about 11 bars and at a temperature of 50 C.

After filtration of the catalyst under nitrogen, the reaction medium is poured into aqueous hydrochloric acid. The filtrate is evaporated to dryness under reduced pressure.

After crystallization from isopropanol and drying at 40 ° C. under vacuum and over potassium hydroxide, 1.53 g of white crystals are obtained, ie a yield of 73%.

The results of analysis obtained by 1 H NMR and mass spectrometry are as follows:
1 H NMR (400MHz, D 2 O) δ 7.32 (d, J = 7.2 Hz, 2H); 6.95 (d, J = 7.2 Hz, 2H); 3.90 (m, 1H); 3.79 (m, 1H); 3.70 (m, 1H); 3.58 (m, 3H); 3.35 (m, 1H); 3.25 (m, 1H); 3.16 (m, 2H); 2.32 (m, 1H); 2.22 (m, 1H); 1.74 (m, 2H); 0.52 (m, 2H); 0.01 (m, 9H).

ESI +: m / z = 306 (M + 1), 328 (M + 1 + 22).

<Desc / Clms Page number 25>

EXAMPLES 1 TO 5 DYEING IN ALKALI MEDIUM The following dyeing compositions were prepared:

<Tb>
<tb> Examples <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 5 <SEP> 6
<tb> 4- {4- [3-
<tb> (trimethylsilyl) propyl] -1,4- <SEP> 10-3 <SEP> mol <SEP> 10-3 <SEP> mol <SEP> 10-3 <SEP> mol <SEP> 10-3 <SEP> mol <SEP> 10-3 <SEP> mol <SEP> 10-3 <SEP> mol <SEP>
<tb> diazepan-1-yl} phenylamine <SEP>;<September>
<tb> hydrochloride <SEP> (base)
<tb> 2- (2,4-diamino-phenoxy) -
<tb> ethanol, <SEP> dihydrochloride <SEP> 10-3 <SEP> mol <SEP>
<tb> (coupler)
<tb> 3-amino-2-chloro-6-methylphenol, <SEP> hydrochloride <SEP> - <SEP> 10-3 <SEP> mol <SEP> -
<tb> (coupler)
<tb> 3,6-dimethyl-1 <SEP> H- <SEP>
<tb> pyrazolo <SEP> [5,1-c] <SEP> [1,2,4] triazole <SEP> - <SEP> - <SEP> 10-3 <SEP> mol <SEP> -
<tb> (coupler)
<tb> 2-methyl-5-aminophenol
<tb> (coupler) <SEP> - <SEP> - <SEP> 10-3 <SEP> mol <SEP>
<tb> 2-Amino-3-hydroxypyridine
<tb> (coupler) <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 10-3 <SEP> mol <SEP> -
<tb> 6-Hydroxyindole <SEP> (coupler)
<tb> 10-3 <SEP> mol <SEP>
<tb> Support <SEP> of <SEP> tincture <SEP> (1) <SEP> (*) <SEP> (*) <SEP> (*) <SEP> (*) <SEP> (*) <SEP > (*)
<tb> Demineralized <SEP> Water <SEP> q. <SEP> sp <SEP> 100 <SEP> g <SEP> 100 <SEP> g <SEP> 100 <SEP> g <SEP> 100 <SEP> g <SEP> 100 <SEP> g <SEP> 100 <SEP > g
<Tb>

<Desc / Clms Page number 26>

(*) Dyeing medium (1) pH 9.5
96% ethyl alcohol 20.8 g
Sodium metabisulfite solution 0.23 g 35% aqueous MA
Pentasodium salt of the acid 0.48 g MA diethylene-triamine-pentaacetic in aqueous solution at 40%
C8-C10 alkyl polyglucoside in 3.6 g MA 60% aqueous solution
Benzyl alcohol 2.0 g
Polyethylene glycol with 8 oxide units 3.0 g ethylene NH4Cl 4.32 g
Ammonia at 20% NH3 2.94 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 9.5 is obtained.

Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

The following dyeing results were obtained.

<Tb>
<Tb>

Examples <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 5 <SEP> 6
<tb> Grade <SEP> Purple- <SEP> Purple- <SEP> Purple- <SEP> Purple <SEP> Purple- <SEP> Red Observed <SEP> Blue <SEP> Blue <SEP> Red <SEP> Red <SEP > Violet
<tb> chromatic
<Tb>

<Desc / Clms Page number 27>

EXAMPLES 6 TO 10 OF ACID DYEING The following dyeing compositions were prepared:

<Tb>
<tb> Examples <SEP> 7 <SEP> 8 <SEP> 9 <SEP> 10 <SEP> 11 <SEP> 12
<Tb>

4-{4-[3-(triméthylsilyl)propyl]- 1,4-diazépan-1- 10-3 mol 10-3 mol 10-3 MOI 10.3 mol 10-3 mol 10-3 MOI

4- {4- [3- (trimethylsilyl) propyl] -1,4-diazepan-1- 10-3 mol 10-3 mol 10-3 MOI 10.3 mol 10-3 mol 10-3 ME

<Tb>
<tb> yl} phenylamine <SEP>;
<tb> hydrochloride <SEP> (base)
<tb> 2- <SEP> (2,4-Diamino-phenoxy) -
<tb> ethanol, <SEP> dihydrochloride <SEP> 10-3 <SEP> mol <SEP> -
<tb> (coupler) <SEP> ~~~~ <SEP> ~~~~ <SEP> ~~~~
<tb> 3-Amino-2-chloro-6-methyl
<tb> - <SEP> 10-3 <SEP> mol <SEP> - <SEP> phenol, <SEP> hydrochloride
<tb> (coupler)
<tb> 2-methyl-5-aminophenol <SEP> 10-3 <SEP> mol
<tb> (coupler)
<tb> Dihydroxy-1,3-benzene
<tb> (coupler) <SEP> - <SEP> - <SEP> - <SEP> 10-3 <SEP> mol <SEP> -
<tb> 2-Amino-3-hydroxypyridine
<tb> (coupler) <SEP> - <SEP> - <SEP> - <SEP> 10-3 <SEP> mol <SEP> -
<tb> 6-Hydroxyindole <SEP> (coupler)
<tb> 10-3 <SEP> mol
<tb> Support <SEP> of <SEP> tincture <SEP> (2) <SEP> (*) <SEP> (*) <SEP> (*) <SEP> (*) <SEP> (*) <SEP > (*)
<tb> Demineralized <SEP> water <SEP> qsp <SEP> 100 <SEP> g <SEP> 100 <SEP> g <SEP> 100 <SEP> g <SEP> 100 <SEP> g <SEP> 100g <SEP > 100g
<Tb>

<Desc / Clms Page number 28>

(*) Dye support (2) pH 7
96% ethyl alcohol 20.8 g
Sodium metabisulfite in 35% aqueous solution 0.23 g MA
Pentasodium salt of diethylenetriaminepentaacetic acid 40% aqueous solution 0.48 g MA
C8-C10 alkyl polyglucoside in 60% aqueous solution 3.6 g MA
Benzyl alcohol 2.0 g
Polyethylene glycol with 8 units of ethylene oxide 3.0 g
Na2HPO4 0.28 g KH2PO4 0.46 g At the time of use, each composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight). A final pH of 7 is obtained.

Each mixture obtained is applied to locks of gray hair at 90% white. After 30 minutes of exposure, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

The following dyeing results were obtained.

<Tb>
<Tb>

Example <SEP> 7 <SEP> 8 <SEP> 9 <SEP> 10 <SEP> 11 <SEP> 12
<tb> s
<tb> Nuance <SEP> Purple- <SEP> Purple- <SEP> Purple <SEP> Red- <SEP> Purple <SEP> Purple Observed <SEP> Blue <SEP> Blue <SEP> Purple <SEP> Red
<Tb>

Claims (23)

1. Para-phenylenediamine derivatives of formula (I) having a 1,4-diazacycloheptane ring substituted with a silyl radical and their addition salts:

 in which: # R1 represents: - a halogen atom; a saturated or unsaturated C 1 -C 6 hydrocarbon chain, aliphatic or alicyclic, one or more carbon atoms of the hydrocarbon chain may be replaced by one or more oxygen, nitrogen, silicon or sulfur atoms, by a group SO or with a group SO 2, the radical R 1 having no peroxide bond, or diazo, nitro or nitroso radicals, this chain possibly being substituted by one or more halogen atoms, one or more hydroxyl, amino, mono-, or di-alkyl (C1- C4) amino, carboxy; # n is between 0 and 4, it being understood that when n is greater than 1 then the radicals R1 may be identical or different; # R2 represents: a radical -SiR5R6R7; a C1-C8 alkyl radical substituted with a radical-SiR5R6R7, the alkyl radical being unsaturated, linear or branched, one or more carbon atoms of the alkyl radical being able to be replaced by one or more oxygen or nitrogen atoms; , sulfur, <Desc / Clms Page number 30>  trialkyl (C1-C6) silyl, hydroxyl, amino, (C1-C6) alkylamino or dialkyl (C1-C6) amino; # R3 represents: - a hydrogen atom; an alkyl radical which can be unsaturated; a hydroxyl radical; a hydroxyalkyl radical; an alkoxy radical; an alkoxyalkyl radical; an alkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an amino radical; a monoalkylamino or dialkylamino radical; an aminoalkyl radical, the amine possibly being mono or disubstituted by an alkyl, acetyl or hydroxyalkyl radical; a hydroxyaminoalkyl radical; a carboxyl radical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkyl radical; an alkoxycarbonyl radical; a mono- or dialkylaminocarbonyl radical; # R4 represents: an alkyl radical that can be unsaturated; a hydroxyalkyl radical; an alkoxyalkyl radical;

C6) amino; # R5, R6 and R7, which may be identical or different, represent: a phenyl radical; a C1-C6 alkyl radical which may be substituted by a group  by a ketone function and the alkyl radical may be substituted by a hydroxyl, amino, (C 1 -C 6) alkylamino or dialkyl (C 1 -C 6) group. <Desc / Clms Page number 31> 1 then the radicals R4 may be identical or different.  an alkylcarbonyl radical; a hydroxyalkoxyalkyl radical; an aminoalkyl radical, the amine possibly being mono or disubstituted by an alkyl, acetyl or hydroxyalkyl radical; a hydroxyaminoalkyl radical; a carboxyl radical; a carboxyalkyl radical; a carbamoyl radical; a carbamoylalkyl radical; an alkoxycarbonyl radical; a mono- or dialkylaminocarbonyl radical; m is between 0 and 4, with the proviso that when m is greater than  2. Derivatives according to claim 1 of formula (I) wherein R1 is selected from an alkyl radical; a hydroxyalkyl radical; an aminoalkyl radical; an alkoxy radical; a hydroxyalkoxy radical.  3. Derivatives according to claim 2 of formula (I) wherein R1 is selected from a methyl radical; a hydroxymethyl radical; a 2-hydroxyethyl radical; a 1,2-dihydroxyethyl radical; a methoxy radical; a 2-hydroxyoxyoxy radical.  4. Derivatives according to any preceding claim of formula (I) wherein n is 0 or 1.  5. Derivatives according to any one of the preceding claims of formula (I) wherein R2 is selected from an alkyl radical substituted with one or two trialkylsilyl radicals; an alkylaminoalkyl radical substituted with a trialkylsilyl radical; an alkylcarbamoylaminoalkyl radical substituted with a trialkylsilyl radical; an alkylcarbonyl radical substituted with a trialkylsilyl radical, itself substituted with a trialkylsilyl radical; an alkylcarbonyl radical substituted by a trialkylsilyl radical; an alkoxyalkyl radical substituted by a trialkylsilyl radical; an alkylcarbonyl radical substituted with a dialkylphenylsilyl radical; an alkyl radical substituted with a trialkylsilyl radical, itself substituted with a trialkylsilyl radical. <Desc / Clms Page number 32>  6. Derivatives according to claim 5 of formula (I) wherein R2 is selected from a 3- (trimethylsilyl) propyl radical; a radical (trimethylsilyl) methyl; a 2 - {[3- (trimethylsilyl) propyl] amino} ethyl radical; a 2 - ({[(trimethylsilyl) methyl] carbamoyl} amino) ethyl radical; a {dimethyl [(trimethylsilyl) methyl] silyl} acetyl radical; a radical (trimethylsilyl) acetyl; a 2- [3- (trimethylsilyl) propoxy] ethyl radical; a 2- [(trimethylsilyl) methoxy] ethyl radical; a [(dimethyl) (phenyl) silyl] acetyl radical; a bis (trimethylsilyl) methyl radical; a {(dimethyl) [(trimethylsilyl) methyl] silyl} methyl radical.  7. Derivatives according to any one of the preceding claims of formula (I) wherein R3 is selected from a hydrogen atom; a hydroxy radical; unradical alkyl; a hydroxyalkyl radical; an aminoalkyl radical; a carboxyl radical; an amino radical.  8. Derivatives according to claim 7 of formula (I) wherein R3 is selected from a hydrogen atom; a hydroxy radical; a carboxyl radical; an amino radical; a hydroxymethyl radical; an aminomethyl radical.  9. Derivatives according to any one of the preceding claims of formula (I) wherein R4 is selected from an alkyl radical; a hydroxyalkyl radical; an aminoalkyl radical; a carboxyl radical; a carbamoyl radical.  10. Derivatives according to any one of the preceding claims of formula (I) wherein m is equal to 0 or 1.  11. Derivatives according to any one of the preceding claims of formula (I) chosen from 4- {4- [3- (trimethylsilyl) propyl] -1,4-diazepan-1-yl} phenylamine; 4- {4 - [(trimethylsilyl) methyl] -1,4-diazepan-1-yl} phenylamine; 4- [4- (2 - {[3- (trimethylsilyl) propyl] amino} ethyl) -1,4-diazepan-1-yl] aniline; N- {2- [4- (4-aminophenyl) -1,4-diazepan-1-yl] ethyl} -N '- [(trimethylsilyl) methyl] urea; 4- [4 - ((dimethyl [(trimethylsilyl) methyl] silyl} acetyl) -1,4-diazepan-1-yl] phenylamine; 4- {4 - [(trimethylsilyl) acetyl] -1,4-diazepan-1-yl} phenylamine; 4- (4- {2- [3- (trimethylsilyl) propoxy] ethyl} -1,4-diazepan-1-yl) phenylamine; 4- (4- {2 - [(trimethylsilyl) methoxy] ethyl} -1,4-diazepan-1-yl) phenylamine; 2-methyl-4- (4- [3- (trimethylsilyl) propyl] -1,4-diazepan-1-yl) phenylamine; 2-methyl-4- {4- <Desc / Clms Page number 33>  (trimethylsilyl) methyl] -1,4-diazepan-1-yl] phenylamine; 2-methyl-4- [4- {bis (trimethylsilyl) methyl} -1,4-diazepan-1-yl] phenylamine; 4- {4 - [((dimethyl) (trimethylsilylmethyl) silyl) methyl] -1,4-diazepan-1-yl} phenylamine; 2-methyl-4- {4 - [((dimethyl) (trimethylsilylmethyl) silyl) methyl] -1,4-diazepan-1-yl} phenylamine.

 amino-3-methylphenyl) -1,4-diazepan-1-yl] ethyl} -N '- [(trimethylsilyl) methyl] urea; 1- [4- (4-amino-3-methyl-phenyl) -1,4-diazepan-1-yl] -2- (dimethyltrimethylsilanylmethylsilanyl) -ethanone; 2-methyl-4- {4 - [(trimethylsilyl) acetyl] -1,4-diazepan-1-yl} phenylamine; 2-methyl-4- (4- {2- [3- (trimethylsilyl) propoxy] ethyl} -1,4-diazepan-1-yl) phenylamine; 2-methyl-4- (4- {2 - [(trimethylsilyl) methoxy] ethyl} -1,4-diazepan-1-yl) phenylamine; 4- (4 - {[dimethyl (phenyl) silyl] acetyl} -1,4-diazepan-1-yl) phenylamine; 2-methyl-4- (4 - {[dimethyl (phenyl) silyl] acetyl} -1,4-diazepan-1-yl) phenylamine; the 4- [4- {bis-

 [(trimethylsilyl) methyl] -1,4-diazepan-1-yl} phenylamine; 2-methyl-4- [4- (2 - {[3- (trimethylsilyl) propyl] amino} ethyl) -1,4-diazepan-1-yl] aniline; the N- {2- [4- (4-  12. Derivatives according to claim 11 of formula (I) chosen from 4- {4- [3- (trimethylsilyl) propyl] -1,4-diazepan-1-yl} phenylamine; 4- {4- [(trimethylsilyl) methyl] -1,4-diazepan-1-yl} phenylamine; 4- [4- (2 - {[3- (trimethylsilyl) propyl] amino} ethyl) -1,4-diazepan-1-yl] aniline; N- {2- [4- (4-aminophenyl) -1,4-diazepan-1-yl] ethyl} -N '- [(trimethylsilyl) methyl] urea; 4- [4- (dimethyl [(trimethylsilyl) methyl] silyl} acetyl) -1,4-diazepan-1-yl] phenylamine; 4- {4 - [(trimethylsilyl) acetyl] -1,4-diazepan-1-yl} phenylamine; 4- (4- {2- [3- (trimethylsilyl) propoxy] ethyl} -1,4-diazepan-1-yl) phenylamine; 4- (4- {2 - [(trimethylsilyl) methoxy] ethyl} -1,4-diazepan-1-yl) phenylamine; 4- (4 - {[dimethyl (phenyl) silyl] acetyl} -1,4-diazepan-1-yl) phenylamine; 4- [4- {bis (trimethylsilyl) methyl} -1,4-diazepan-1-yl] phenylamine; 4- {4 - [((dimethyl) (trimethylsilylmethyl) silyl) methyl] -1,4-diazepan-1-yl} phenylamine.  13. Use for the oxidation dyeing of keratinous fibers of a para-phenylenediamine derivative of formula (I) as defined in any one of claims 1 to 12.  14. Composition for dyeing keratinous fibers comprising, in a medium suitable for dyeing, at least one paraffin derivative <Desc / Clms Page number 34>  phenylenediamine of formula (I) as defined in any one of claims 1 to 12.  15. The composition of claim 14 wherein the amount of para-phenylenediamine derivatives of formula (I) is between 0.001 and 10% by weight of the total weight of the dye composition.  16. The composition of claim 14 or 15 further comprising a coupler selected from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.  17. The composition of claim 16 wherein the amount of each of the couplers is between 0.001 and 10% by weight of the total weight of the dye composition.  18. Composition according to any one of claims 14 to 17 comprising an additional base selected from para-phenylenediamines other than the para-phenylenediamine derivatives of formula (I) as described in any one of claims 1 to 12, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, ortho-phenylenediamines, heterocyclic bases and their addition salts.  19. Composition according to any one of claims 14 to 18 wherein the amount of each of the oxidation bases is between 0.001 and 10% by weight of the total weight of the dye composition.  20. A process for dyeing keratinous fibers, characterized in that a composition as defined in any one of claims 14 to 19 is applied to the keratinous fibers in the presence of an oxidizing agent for a time sufficient to develop the coloration. desired.  21. The method of claim 20 wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.  22. A multi-compartment device in which a first compartment contains a dye composition as defined in one of the following: <Desc / Clms Page number 35>  any of claims 14 to 19 and a second compartment contains an oxidizing agent.  23. Derivatives of para-nitroaniline of formula (III) below:

 wherein the radicals R1, R2, R3 and R4 and the integers n and m are as defined in claims 1 to 12.