FR2901794A1 - Composition, useful to dye human keratinous fibers, particularly hair, comprises a 2-imidazolium containing cationic diazo direct dye compound - Google Patents

Abstract

Composition for dyeing human keratinous fibers comprises a cationic diazo direct dye compound or its mesomer, additive salt of acid or solvate having 2-imidazolium group. Composition useful for dyeing keratinous fibers comprises a cationic diazo direct dye compound of formula (I) or (II) or its mesomer, additive salt of acid or solvate having 2-imidazolium group. R11-8C hydrocarbon (optionally substituted and interrupted by O, N, S, CO, SO and/or SO2, or a hydrocarbon chain having NO2, nitroso, peroxo or diazo and bonded to (non)quaternized N or imidazolium ring through C), phenyl or benzyl (both optionally substituted); R21-4C alkyl (optionally substituted by NH2 or OH), phenyl (optionally substituted) or halo; R3, R41-3C alkyl (optionally substituted by NH2 or OH), OH, 1-4C alkoxy, 1-4C (poly)hydroxyalkoxy, NH2 (optionally substituted by 1/2 1-4C alhyl or OH), R1aCONR2a, (R2a)2NCO-, (R2a)2NCONR2a, (R2a)2NSO2, R2aSO2-NR2a, CN or halo, preferably F or Cl; R1a : 1-4C alkyl; R2a : H or 1-4C alkyl; either R5, R6H, 1-8C hydrocarbon (optionally substituted and interrupted by O, N, S, CO, SO and/or SO2, or a hydrocarbon chain having NO2, nitroso, peroxo or diazo and bonded to (non)quaternized N or imidazolium ring through C), R1aSO2 or benzyl (optionally substituted by OH or NH2); or NR5R6 = 5-7 membered ring of formula (a) or (b); T : R5 or R6; o : 0-1; R : H or CH3; n : 0-2; n1 : 0-4, preferably 0-2; and n2 : 0-4, preferably 0-3. Provided that when n is less than 2, then the carbon atoms in (b) is non-substituted and carry hydrogen, similarly when n1 and n2 are less than 0-4. Independent claims are included for: (1) a process of coloring the keratinous fibers comprising applying the composition on dry or wet keratinous fibers; and (2) a device with compartments comprising a first compartment containing the composition and a second compartment containing an oxidant composition. [Image] [Image].

Description

1

  The subject of the present invention is a composition for dyeing keratinous fibers, and in particular human keratinous fibers such as the hair, comprising at least one dyestuff. direct cationic diazo 2-imidazolium. It is known to dye keratin fibers, and in particular human keratin fibers such as the hair, with dye compositions containing direct dyes. These compounds are colored molecules and dyes having an affinity for the fibers. It is known, for example, to use direct dyes of the nitrobenzene type, anthraquinone dyes, nitropyridines, dyes of the azo, xanthene, acridine, azine or triarylmethane type.

  Usually, these dyes are applied to the fibers, optionally in the presence of an oxidizing agent, if it is desired to obtain a simultaneous effect of lightening the fibers. Once the exposure time has elapsed, the fibers are rinsed, optionally washed and dried. The colorations that result from the use of direct dyes are temporary or semi-permanent dyes because the nature of the interactions that bind the direct dyes to the keratinous fiber, and their desorption of the surface and / or the core of the fiber are responsible their low dyeing power and their relative poor resistance to washes or perspiration. Some direct dyes may be unstable under conventional brightening conditions and / or have insufficient photostability properties. In particular, there are few direct dyes blue or purple that do not have these disadvantages. However, these dyes have the advantage of allowing the obtaining of fundamental and / or natural shades.

  The object of the present invention is to provide direct dyes not having the disadvantages of existing direct dyes. 2

  In particular, one of the aims of the present invention is to provide blue or violet direct dyes, stable in an oxidizing medium or in the light, which make it possible to obtain colorings resistant in time to external aggressions such as light, bad weather, washing, perspiration, friction. This object is achieved with the present invention which relates to a composition for the dyeing of keratinous fibers comprising, in a medium suitable for dyeing, at least one cationic direct diazo dye with a 2-imidazolium unit chosen from compounds of formula (I ) or (II) below, their mesomeric forms, as well as their addition salts with an acid and their solvates: (R An (I) (R 2) n NR 5 R 6 An (R 3) in which: • the R radicals represent, independently one of the other: a linear or branched, saturated, acyclic, optionally substituted C 1 -C 8 hydrocarbon-based chain, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, of preferably selected from oxygen, nitrogen or sulfur, CO, SO, SO2, or combinations thereof;

  hydrocarbon chain having no nitro, nitroso, peroxo or diazo function and being necessarily attached to the quaternized or non-quaternized nitrogen atom of the imidazolium ring via a carbon atom; an optionally substituted phenyl radical; an optionally substituted benzyl radical; The radicals R 2 represent, independently of one another: a linear C 1 -C 4 alkyl radical optionally substituted with an amino radical or a hydroxyl radical; an optionally substituted phenyl radical; a halogen atom; The radicals R3 represent, independently of each other: a linear C1-C4 alkyl radical, optionally substituted by an amino radical or a hydroxyl radical; a hydroxyl radical; a C1-C4 alkoxy radical; a mono- or polyhydroxyalkoxy radical C1-C4; an amino radical optionally substituted with one or two identical or different C1-C4 alkyl radicals optionally carrying at least one hydroxyl radical; a group RaCO-NRa'- in which the radical Ra represents a C1-C4 alkyl radical; the radical Ra 'represents a hydrogen atom or a C1-C4 alkyl radical; a (Rb) 2N-CO- group in which the radicals Rb represent, independently of one another, a hydrogen atom, a C1-C4 alkyl radical; - a group (R) 2N-CO-NRc- in which the radicals R, represent, independently of each other, a hydrogen atom, a C1-C4 alkyl radical; a group (Rd) 2N-SO 2 - in which the radicals Rd represent, independently of one another, a hydrogen atom or a C 1 -C 4 alkyl radical; 4

  a group ReSO2-NRe- in which the radicals Re represent, independently of one another, a hydrogen atom or a C1-C4 alkyl radical; a cyano radical; a halogen atom, preferably chlorine and fluorine; The radicals R4 represent, independently of each other: a linear C1-C4 alkyl radical; a hydroxyl radical; a C1-C4 alkoxy radical; a mono- or polyhydroxyalkoxy radical C1-C4; an amino radical optionally substituted with one or two identical or different C1-C4 alkyl radicals optionally carrying at least one hydroxyl radical; the two alkyl radicals which can form, together with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle optionally comprising another heteroatom which is identical to or different from nitrogen such as a pyrrolidine, morpholine or piperidine ring; optionally substituted with one or more methyl, hydroxyl, amino, mono or dimethylamino radicals; a group RaCO-NRa in which the radical Ra represents a C1-C4 alkyl radical; the radical Ra 'represents a hydrogen atom or a C1-C4 alkyl radical; a group (Rb) 2N-CO in which the Rb radicals represent, independently of one another, a hydrogen atom or a C1-C4 alkyl radical; - a group (R) 2N-CO-NRc- in which the radicals R, represent, independently of each other, a hydrogen atom, a C1-C4 alkyl radical; a group (Rd) 2N-SO 2 - in which the radicals Rd represent, independently of one another, a hydrogen atom or a C 1 -C 4 alkyl radical; a group ReSO2-NRe- in which the radicals Re represent, independently of one another, a hydrogen atom or a C1-C4 alkyl radical; a cyano radical; A halogen atom, preferably chlorine and fluorine; The radicals R5 and R6, which are identical or different, represent: a hydrogen atom; a linear or branched, saturated, acyclic, optionally substituted C1-C8 hydrocarbon chain, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, SO, SO2, or combinations thereof; the hydrocarbon chain having no nitro, nitroso, peroxo or diazo function and being necessarily attached to the nitrogen atom via a carbon atom; a radical (RfSO2-) in which the radical Rf represents a C1-C4 alkyl radical; a benzyl radical optionally substituted by one or more hydroxyl and / or amino radicals; the radicals R5 and R6 being able to form, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 7-membered heterocycle, optionally comprising another heteroatom which is identical or different from nitrogen; one of the radicals R5 and R6 being able to form, with the nitrogen atom to which it is attached, and with a radical R4 situated in ortho of the NR5R6 group, an optionally substituted 5- or 6-membered heterocycle of the following formula (III): 6

  in which: - o is an integer equal to 0 or 1; - Rx and Ry represent, independently of one another, a hydrogen atom or a methyl radical; the radicals R5 and R6 being able to form, with the nitrogen atom to which they are attached and each with a radical R4 located in ortho of the NR5R6 group, an optionally substituted 5- or 6-membered heterocycle of the following formula (IV): embedded image : o is an integer equal to 0 or 1; - Rx and Ry represent, independently of each other, a hydrogen atom or a methyl radical; • n is an integer between 0 and 2; when n is less than 2, the unsubstituted carbon atom (s) carry a hydrogen atom; • n 'is an integer between 0 and 4, preferably between 0 and 2; when n 'is less than 4, the unsubstituted carbon atom (s) carry a hydrogen atom; N is an integer from 0 to 4, preferably from 0 to 3, where n "is less than 4, the unsubstituted carbon atom (s) carry a hydrogen atom; the electroneutrality of the compounds of formula (I) or (II) being ensured by one or more cosmetically acceptable anions An, which are identical or different. The present invention also relates to a process for dyeing keratinous fibers using the composition according to the present invention. The present invention also relates to a multi-compartment device for implementing the method according to the invention. 7

  The present invention also relates to the use for dyeing keratinous fibers of the composition according to the invention. The present invention also relates to new cationic diazo direct dyes.

  The present invention makes it possible to obtain colorings that are resistant to the various aggressions that the hair can undergo, in particular to shampoos. The present invention also makes it possible to obtain blue or violet dyes, in particular low chromatic blue dyes, which lead to fundamental and / or natural shades. Furthermore, the direct dyes useful in the context of the invention are light-stable and under conventional lightening dyeing conditions, in particular in the presence of an oxidizing agent and / or ammonia. Unless otherwise indicated, the ranges of the ranges of values given below are included in these ranges. For the purposes of the present invention, and unless a different indication is given: an alkyl radical or the alkyl part of a radical is linear or branched; an alkyl radical or the alkyl part of a radical is said to be substituted when it comprises at least one substituent chosen from the groups: hydroxyl; C1-C4 alkoxy, mono- or polyhydroxyalkoxy C1-C4; Amino, optionally substituted with one or two identical or different C1-C4 alkyl radicals, optionally bearing at least one hydroxyl radical, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5-membered heterocyclic ring; or 6 members, optionally comprising at least one other heteroatom different or different from nitrogen; a hydrocarbon chain is said to be substituted when it comprises at least one substituent chosen from the groups: hydroxyl; C1-C4 alkoxy, mono- or polyhydroxyalkoxy C1-C4; 8

  Amino, optionally substituted with one or two identical or different C1-C4 alkyl radicals, optionally bearing at least one hydroxyl radical, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5-membered heterocyclic ring; or 6 members, optionally comprising at least one other heteroatom different or different from nitrogen; an aryl or heteroaryl radical or the aryl or heteroaryl part of a radical is said to be substituted when it comprises at least one substituent carried by a carbon atom chosen from: a C1-C16 alkyl radical, preferably a C1-C16 alkyl radical; C8, optionally substituted with one or more radicals chosen from hydroxyl, C1-C2 alkoxy, C1-C4 mono or polyhydroxyalkoxy, C1-C4 alkylcarbonylamino, amino substituted by two identical or different C1-C4 alkyl radicals, optionally carrying at least one hydroxyl radical, the two radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered, preferably 5 or 6-membered heterocyclic ring, optionally comprising another identical or different heteroatom; nitrogen; A halogen atom such as chlorine, fluorine or bromine; A hydroxyl radical; A C1-C2 alkoxy radical; a mono- or polyhydroxyalkoxy radical C1-C4; An amino radical optionally substituted with one or two identical or different C1-C4 alkyl radicals optionally carrying at least one hydroxyl or amino radical substituted by two optionally substituted C1-C2 alkyl radicals; An -NRa'-CORa radical in which the radical Ra represents a C1-C4 alkyl radical; the radical Ra represents a hydrogen atom or a C1-C4 alkyl radical; A radical (Rb) 2N-CO- in which the radicals Rb, which may be identical or different, represent a C1-C4 alkyl radical; A radical ReSO2-NRe-in which the radicals Re represent, independently of one another, a hydrogen atom, a C1-C4 alkyl radical or a phenyl radical; 9

  A radical (Rd) 2N-SO 2 - in which the radicals Rd, identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical; the cyclic or heterocyclic part of a non-aromatic radical or is said to be substituted when it comprises at least one substituent carried by a carbon atom chosen from the groups: hydroxyl; • C1-C4 alkoxy; mono or polyhydroxyalkoxy C1-C4. According to one particular embodiment of the invention, the radicals R 1 are chosen from a C 1 -C 4 alkyl radical, optionally terminated by a hydroxyl. By way of example, the radicals R1 represent a methyl radical; an ethyl radical or a 2-hydroxyethyl radical. According to another particular embodiment of the invention, n is 0 or the radicals R 2 are chosen from a C 1 -C 4 alkyl radical optionally substituted by an amino radical or a hydroxyl radical. By way of example, the radicals R2 are chosen from a methyl radical; an ethyl radical; a 2-hydroxyethyl radical; a 3-aminopropyl radical. According to another particular embodiment of the invention, the radicals R 3 are chosen from a C 1 -C 4 alkyl radical; a C1-C4 alkoxy radical; a halogen atom; an optionally substituted amino radical; a group RaCO-NRa- in which the radical Ra represents a C1-C4 alkyl radical; the radical Ra 'represents a hydrogen atom; a hydroxyl radical. By way of example, the radicals R 3 are chosen from a methyl radical; a methoxy radical; a chlorine atom; a hydroxyl radical; a methylcarbonylamino radical.

  According to another particular embodiment of the invention, the radicals R4 are chosen from an alkyl radical; a hydroxyl radical; an alkoxy radical; a mono- or di (alkyl) amino radical C1-C4; a C1-C4 di (hydroxyalkyl) amino radical; a halogen atom; a group RaCONRa'- in which the radical Ra represents a C1-C4 alkyl radical and the radical Ra 'represents a hydrogen atom. By way of example, the radicals R4 are chosen from a methyl radical; a hydroxyl radical; a radical 10

  ethylamino; a dimethylamino radical; a di (2-hydroxyethyl) amino radical; a chlorine atom; a methylcarbonylamino radical. According to another particular embodiment of the invention, the radicals R5 and R6, which are identical or different, represent: a C1-C4 alkyl radical, optionally substituted with at least one hydroxyl radical; a benzyl radical optionally substituted by one or more hydroxyl and / or amino radicals. According to another particular embodiment of the invention, the radicals R 5 and R 6 form, with the nitrogen atom to which they are attached, an optionally substituted 5- or 7-membered saturated or unsaturated heterocycle, optionally comprising another identical heteroatom. or different from nitrogen, such as, for example, a pyrrolidine, piperazine, homopiperazine or piperidine ring.

  According to another particular embodiment of the invention, one of the radicals R5 or R6 forms with the nitrogen atom to which it is attached and with a radical R4 located in ortho of the group NR5R6 a 5- or 6-membered heterocycle optionally substituted, of formula (III) below: wherein: o is an integer equal to 0 or 1; - Rx and Ry represent, independently of each other, a hydrogen atom or a methyl radical. By way of examples of rings of formula (III), mention may be made of the following rings: N 1 R 5 or R 6 R 5 or R 6 (OH) p (OH) p (OH) p with p = 0 or 1 According to another embodiment of In a particular embodiment of the invention, the radicals R 5 and R 6 form, with the nitrogen atom to which they are attached and each with a radical R 4 located in ortho of the NR 5 R 6 group, an optionally substituted 5 or 6-membered heterocycle of formula (IV) following: Ry in which: - o is an integer equal to 0 or 1; - Rx and Ry independently of each other represent a hydrogen or a methyl. By way of examples of rings of formula (IV), mention may be made of the following cycles: (OH) p with p = 0 or 1 In the compounds of formula (I) or (II), An represents an anion or a mixture of anions, organic or inorganic, which make it possible to balance the charge (s) of the compounds of formula (I) or (II), for example chosen from a 12

  halide such as chloride, bromide, fluoride, iodide ion; a hydroxide; sulphate; a hydrogen sulfate; an alkyl sulphate for which the linear or branched alkyl part is C1-C6, such as the methyl sulphate or ethyl sulphate ion; carbonates and hydrogen carbonates; salts of carboxylic acids such as formate, acetate, citrate, tartrate, oxalate; alkylsulphonates for which the linear or branched alkyl part is C1-C6, such as the methylsulphonate ion; arylsulphonates for which the aryl part, preferably phenyl, is optionally substituted by one or more C1-C4 alkyl radicals such as, for example, 4-tolylsulphonate; alkylsulfonyls such as mesylate. The acid addition salts of the compounds of formula (I) or (II) may be, for example, the addition salts with an organic or inorganic acid such as hydrochloric acid or hydrobromic acid, sulfuric acid or (alkyl- or phenyl) sulfonic acids such as p-toluenesulphonic acid or methylsulphonic acid. The solvates of the compounds of formula (I) or (II) represent the hydrates of such compounds and / or the combination of a compound of formula (I) or (II) with a linear or branched C 1 -C 4 alcohol such as methanol, ethanol, isopropanol, n-propanol.

  In the context of the present invention, the direct dyes of formula (I) or (II) are preferably chosen from the direct dyes of formula (I ') or (II') below: NR'5R'6 in which: the radicals R 'represent, independently of one another, a C 1 -C 4 alkyl radical; a 2-hydroxyethyl radical; The R'3 radicals represent, independently of one another, a C1-C4 alkyl radical; a C1-C4 alkoxy radical; a halogen atom; a hydroxyl radical; a methylcarbonylamino radical; • m 'represents an integer equal to 0, 1 or 2; The R'4 radicals represent, independently of each other, a C1-C4 alkyl radical; a hydroxyl radical; an alkoxy radical; a mono or di (alkyl) amino radical; a di (hydroxyalkyl) amino radical; a halogen atom such as chlorine; a (C1-C4) alkylcarbonylamino radical; M "represents an integer equal to 0, 1, 2 or 3; the radicals R '5 and R' 6 represent, independently of one another, a C 1 -C 4 alkyl radical; a C 1 monohydroxyalkyl radical; -C4 or form with one or two radicals R'4 located in ortho of the group NR'5R'6 and the benzene ring to which they are attached a ring of formula (III) or (IV). As examples of direct dyes of formula (I) or (II), mention may be made of the compounds presented in the table below, An being as previously defined: Colorant 1 Year IN \ c / N`EN `NN \ Colorant 2 HN ~ N N + ~ NN HO An Colorant 3 N \ N ~ N \ Name. ~ N \\ NN CI \, O An Colorant 4 HO ~ + N \ N \ c / NN` NN \ An Colorant 5 CI ~ N ~ N \ <N + ~ NN An Colorant 6 IN \ ~ N`EN N \ NN \ An Colorant 7 I. ~ "~~ N \\ NN \\ NNN OH An Colorant 8 OH N N1 N ~ NN / N N / A Colorant 9 OH N N1 N ~ NN \ N / N / OH An Colorant 10 J OH N N N / N N O N / O An Colorant 11 I. N \ The direct dyes of formula (I) or (II) that are useful in the context of the invention may, for example, be prepared according to the synthesis method as described in US Pat. No. 3,173,907. and detailed below.

  NHAc 1. NaNO2 / HCI NN \\ NNc NHAc DMS / AcO-Na + H2N 1. NaNO2 / HCI 1 * (N 'NN \ An They can in particular be synthesized according to the following procedure Ni NHAc 1 NaNO2 / HCI (R2) n

  2. (R2) n1 N NHAc alkylating agent (R2) n NaOH / HCl 5-12N An H2N (R3) n 'N' N (R3) n '(R2) nNH2 R1 An 1. NaNO2 / HCI ( The direct dyes of formula (I) or (II) useful in the context of the invention may also be prepared according to the modes of synthesis as described below. (R 2) n -NH 2 NaNO 2 / HCl NH 2 2.H 2 N (R 3) n 'NH 2 (R 3) n' 1. NaNO 2 / HCl 2. (R 4) n "N, R 5 1 R 6 R 1 I (R 2) nN R 1 An H 1. NaNO 2 / HCl AcHN (R 3) n NaOH or HCl 5-12 N AcHN N, R 5 R 6 R 5 N, R 6 1. NaNO 2 / HCl 2. (R 2) n R 5 N ( R3) n '(Ra) n "R6 (R2) n (R2) n alkylating agent / base or (non) organic salt R5 N R6 R1 R1 (R3) n' (R4) n" An 1. NaNO2 / HCl 2. NaNO2 / HCl N-: n- (R5) R6 H2N (R3) n '(R4) n (R2) n R5 N, 1 R6 NH2 (R3) n' N 'N (R2) n alkylating agent / (In) organic salt or base (R 2) n An (R 3) n 'R 5 (R 3) n' (R 4) n N N R 6 Reduction / Na 2 S NH 2 1. NaNO 2 / HCl O 2 N O 2 N N, R 5 R 6 H 2 N (R 3) (R4) n R6 R5 (R2) n (R2) n1 alkylating agent / base or (in-) organic salt R5 N R6 R1 (R4) n- R1 An 19 (R2) n '1. NaNO2 / HCI Reduction / Na2S R5 N, R6 N, R5 R6 N, R5

  (R 3) n '(R 4) n R 6 3. alkylating agent / base or salt (in-) organic 2. (R 2) n (R 2) n R 1 R 1 R 1 An 1. NaNO 2 / HCI (R 3) n' 2. (R4) n "R5 N ~ (R3) n1 (R4) n" R6 N, R5 1 R6 NaOH / HCl 5-12 N 1. NaNO2 / HCl 2 (R2) n N 3. alkylating agent / salt ( ) organic or basic

R2) n R1, N, R1, R5, R6, R, 20

  The diazotisation reaction of an aromatic amine (or a 2-aminoimidazole or their derivatives) is carried out in the presence of a diazotization reagent such as sodium nitrite in an acid medium (a mineral acid such as hydrochloric acid). orthophosphoric acid or an organic acid such as acetic acid). The amine function is then converted into diazonium salt. Other reagents may be more suitable if the diazonium salt in question is not very stable in an aqueous medium; for example, alkyl nitrites, such as amyl nitrite, or nitrosylsulfuric acid. These reagents are formal equivalents of nitrous acid. The diazonium salt can be engaged in the next step directly (use of the reaction mixture), after being isolated (for example by precipitation and wringing), or after a modification of the characteristics of the mixture (change in pH, dilution, concentration, addition of a solvent other than the initial solvent). If necessary, the excesses of diazotization reagents used in the first step may be destroyed at the end of the operation by the addition in the reaction medium of sulfamic acid or urea. The step of reacting the previously obtained diazonium salt with an aromatic amine (or an imidazole or their derivatives) is possible either by pouring a solution of the latter into the diazonium salt solution as obtained according to the first step (or by resolubilization of the isolated diazonium salt), or, conversely, by pouring the diazonium salt solution into the solution of the aromatic amine (or imidazole or their derivatives). The pH of the reaction medium is adjusted by addition of a base because the so-called coupling reaction is normally carried out at a higher pH than that of the diazotization step. The base can be introduced into the reaction medium, before, but preferably at the same time or after bringing into contact with the aromatic amine and the diazonium salt. The sequence of these two reactions leads to the formation of an azo. The diazotization reaction is preferably carried out in an acidified polar (a-) protic solvent, such as water acidified with hydrochloric acid, acetic acid or sulfuric acid, in the presence where appropriate of a co-solvent such as ethyl alcohol, THF or dioxane, at a pH of less than 6. The temperature is less than 40 ° C., preferably less than 15 ° C. The reaction time is between one minute and twenty-five minutes. four hours. The coupling of the diazonium salt thus formed with the aromatic amine can be carried out in the same solvent, to which a co-solvent can be added, the pH being able to be raised by the addition to the reaction medium of an organic base. or mineral such as soda. The temperature is maintained below 40 C, preferably below 15 C. The reaction is carried out for a period of between 1 minute and twenty-four hours. The alkylation step is with an alkylating reagent such as alkyl sulfate, alkyl halide, alkyl alkyl sulfonate or alkyl aryl sulfonate. It is also possible to use an oxirane to carry out this alkylation. The alkylation reaction is carried out, for example, in a halogenated solvent, for example dichloromethane, 1,2-dichloroethane or an ester, for example ethyl acetate, at a temperature below 150 ° C., preferably under reflux. solvent in the presence of an inorganic base (MgO, K2CO3, Na2CO3, ...) or an organic salt (AcO-Na +, ...). The cationic dyes precipitate in apolar solvents which allows isolation and purification.

  The direct dye or dyes useful in the context of the invention generally represent from 0.01 to 5% by weight relative to the total weight of the composition, more particularly from 0.05 to 2% by weight relative to the total weight. of the composition. The composition according to the invention may further comprise an oxidation base. This oxidation base may be chosen from the oxidation bases conventionally used in oxidation dyeing, for example para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases. Among the para-phenylenediamines, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine and 2,6-diethyl-para-phenylenediamine may be mentioned by way of example; , 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N-bis- (33-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (33-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis (33-hydroxyethyl) amino-2-chloroaniline , 2-33-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (33-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, 33-hydroxyethyl) paraphenylenediamine, N- (3,3-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl-para-phenylenediamine, 2-33-hydroxyethyloxy-para-phenylenediamine, 2-33-acetylaminoethyloxy-para-phenylenediamine, N- (33-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylene diamine, 2-hydroxyethylamino-5-amino toluene and their addition salts with an acid. Among the para-phenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-33-hydroxyethyl paraphenylenediamine, 2-33-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (33-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-33-acetylaminoethyloxy-para-phenylenediamine, and acid-addition salts thereof are particularly preferred.

  Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( 13-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N ' -bis- (4'-amino, 23

  3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts with an acid. Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2 are exemplified. methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (3-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-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-amino phenol, and their addition salts with an acid. Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives and pyrazolo [1,2a] pyrazol-1-one 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, 2-03-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

  Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2 359 399; JP 88-169,571; JP 05 163 124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2 , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in the patent application FR-A-2,750,048 and among which mention may be made of pyrazolo- [ 1,5-a] -pyrimidine-3,7-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-amino-pyrazolo [1,5- 24

  a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy) ethyl) -amino] -ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo [1,5-a] pyrimidine 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo-3,7-diamine, 2,5-N-7-N-7-tetramethyl-pyrazolo [1,5-a] -pyrimidine-3,7-diamine [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 patents DE 3 843 892, DE 4 133 957 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-yl-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl -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-yl-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- me 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.

  Among the pyrazolo [1,2a] pyrazol-1-one derivatives, mention may be made of compounds such as 2,3-diamino-6,7-dihydro, 1H-5H-pyrazolo [1,2a] pyrazol-1 -one. The composition according to the invention may also 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 and heterocyclic couplers. 25

  By way of example, mention may be made of 2-methyl-5-aminophenol, 5-N- (R-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol and 3-amino phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (3-hydroxyethyloxy) benzene, 2- amino 4- (β-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene , sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (3-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (R-hydroxyethylamino) toluene and their addition salts with an acid. In the composition of the present invention, the oxidation base (s) are generally present in an amount of between 0.001 to 10% by weight relative to the total weight of the dye composition, and more preferably from 0.005 to 6% by weight. The coupler or couplers are generally present in an amount of between 0.001% and 10% by weight relative to the total weight of the dyeing composition and more preferably from 0.005% to 6% by weight. In general, the addition salts with an acid that can be used in the context of the dyeing compositions of the invention for the oxidation bases and the couplers are chosen in particular from hydrochlorides, hydrobromides, sulphates and citrates. succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. The composition according to the invention may optionally comprise at least one additional direct dye different from the compounds of formula (I) or (II). This can be chosen from cationic or nonionic species. By way of non-limiting examples, mention may be made of nitrobenzene dyes, azo, azomethine, methine, tetraazapenthamethine, anthraquinone, naphthoquinone, benzoquinone, phenotiazine indigo, xanthene, phenanthridine, phthalocyanine dyes, those derived from triarylmethane and natural dyes. alone or in mixtures. 26

  It may for example be chosen from the following red or orange nitro benzene dyes: 1-hydroxy-3-nitro-4-N- (γ-hydroxypropyl) amino benzene, N-O-hydroxyethyl-amino-3- Nitro-4-amino benzene, 1-amino-3-methyl-4-N-O-hydroxyethyl) amino-6-nitro benzene, 1-hydroxy-3-nitro-4-N-O-hydroxyethyl amino benzene, 1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-methylamino benzene, N-O-hydroxyethyl-2-nitro-para-phenylenediamine, 1-amino 2-nitro-4-yl-hydroxyethyl) amino-5-chloro-benzene, 2-nitro-4-amino-diphenylamine, 1-amino-3-nitro-6-hydroxybenzene, 1-03-aminoethyl ) amino-2-nitro-4-yl-hydroxyethyloxy) benzene, 1- (13-yl-dihydroxypropyl) oxy-3-nitro-4-yl-hydroxyethyl) amino benzene, 1-hydroxy-3- nitro-4-aminobenzene, 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-methoxy-3-nitro-4-yl-hydroxyethylamino benzene, 2-nitro-4'- hydroxydiphenylamine, - 1-amino-2-nitro-4-hydroxy-5-methylbenzene .

  The additional direct dye may also be chosen from yellow and yellow-green nitro-benzene direct dyes, for example compounds selected from: 1-33-hydroxyethyloxy-3-methylamino-4-nitrobenzene; methylamino-2-nitro-5-yl, y-dihydroxypropyl) oxybenzene, 1- (13-hydroxyethyl) amino-2-methoxy-4-nitrobenzene, 1- (13-aminoethyl) amino-2-nitro 5-methoxybenzene, 1,3-di (13-hydroxyethyl) amino-4-nitro-6-chlorobenzene, 1-amino-2-nitro-6-methylbenzene, 1- ( 13-hydroxyethyl) amino-2-hydroxy-4-nitrobenzene, N- (13-hydroxyethyl) -2-nitro-4-trifluoromethylaniline, 4- (13-hydroxyethyl) amino-3-nitro-benzenesulfonic acid 4-ethylamino-3-nitro-benzoic acid, 4-03-hydroxyethyl) amino-3-nitro-chlorobenzene, 4-03-hydroxyethylamino-3-nitro-methylbenzene, 4 -03, γ-dihydroxypropyl) amino-3-nitro-trifluoromethylbenzene, 1-03-ureidoethylamino-4-nitrobenzene, 1,3-diamino-4-nit robenzene, 1-hydroxy-2-amino-5-nitrobenzene, 1-amino-2- [tris (hydroxymethyl) methyl] amino-5-nitro-benzene, 1-03-hydroxyethyl) amino-2 nitrobenzene; 4-03-hydroxyethyl) amino-3-nitrobenzamide. Mention may also be made of blue or violet nitrobenzene direct dyes, for example: 1 - ([3-hydroxyethyl) amino-4-N, N-bis- (3-hydroxyethyl) amino-2-nitrobenzene; 1- (γ-Hydroxypropyl) amino 4-N, N-bis (13-hydroxyethyl) amino-2-nitrobenzene, 1-03-hydroxyethyl) amino 4- (N-methyl, N- [3-hydroxyethyl) amino 2-nitrobenzene, 1-03-hydroxyethyl) amino 4- (N-ethyl, N- [3-hydroxyethyl) amino-2-nitrobenzene, 1-03, 4-dihydroxypropyl) amino 4- (N-ethyl, N- [3-hydroxyethyl) amino-2-nitrobenzene, - 2-nitroparaphenylenediamines of the following formula: NHRA NO 2 in which: • RB represents a C 1 -C 4 alkyl radical, a [3-hydroxyethyl or 13-hydroxypropyl radical or hydroxypropyl; RA and Rc, which are identical or different, represent a [3-hydroxyethyl, [3-hydroxypropyl, γ-hydroxypropyl, or (3, γ-dihydroxypropyl) radical, at least one of the N RBRc 28

  radicals RB, Rc or RA representing a γ-hydroxypropyl radical and RB and Rc can not simultaneously designate a 13-hydroxyethyl radical when RB is a γ-hydroxypropyl radical, such as those described in French patent FR 2,692,572.

  Among the azo direct dyes that may be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772, EP 714954, FR 2 822 696, FR 2 825 702 and FR 2 825. 625, FR 2 822 698, FR 2 822 693, FR 2 822 694, FR 2 829 926, FR 2 807 650, WO 02/078660, WO 02/100834, WO 02/100369, FR 2 844 269. Among these compounds mention may be made in particular of the following dyes: 1,3-dimethyl-2 - [[4- (dimethylamino) phenyl] azo] -1H-imidazolium chloride, 1,3-dimethyl-2- [ (4-Aminophenyl) azo] -1H-imidazolium, 1-methyl-4 - [(methylphenylhydrazono) methyl] -pyridinium methylsulfate. Mention may also be made, among the azo direct dyes, of the following dyes, described in the COLOR INDEX INTERNATIONAL 3rd edition: -Disperse Red 17, -Acid Yellow 9, -Acid Black 1, -Basic Red 22, -Basic Red 76, -Basic Yellow 57, - Basic Brown 16, - Acid Yellow 36, - Acid Orange 7, - Acid Red 33, - Acid Red 35, - Basic Brown 17, - Acid Yellow 23, - Acid Orange 24, 29

  Disperse Black 9. Mention may also be made of 1- (4'-aminodiphenylazo) -2-methyl-4bis-3-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalene sulfonic acid. .

  Among the quinone direct dyes, mention may be made of the following dyes: - Disperse Red 15, - Solvent Violet 13, - Acid Violet 43, - Disperse Violet 1, - Disperse Violet 4, - Disperse Blue 1, - Disperse Violet 8, - Disperse Blue 3, - Disperse Red 11, - Acid Blue 62, - Disperse Blue 7, - Basic Blue 22, - Disperse Violet 15, - Basic Blue 99, as well as the following compounds: - 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone, 1-aminopropylamino-4-methylaminoanthraquinone, 1-aminopropylaminoanthraquinone, 5-33-hydroxyethyl-1,4-diaminoanthraquinone, 2-aminoethylaminoanthraquinone, 1,4-bis (3-yl) dihydroxypropylamino ) anthraquinone. Among the azine dyes, mention may be made of the following compounds: Basic Blue 17, Basic Red 2. Among the triarylmethane dyes that can be used according to the invention, mention may be made of the following compounds:

  - Basic Green 1, - Acid Blue 9, - Basic Violet 3, - Basic Purple 14, -Basic Blue 7, - Acid Violet 49, - Basic Blue 26, - Acid Blue 7. Among the indoamine dyes that can be used according to the invention, mention may be made of the following compounds: - 2- [3-hydroxyethlyamino-5- [bis- ([3-4'-hydroxyethyl) amino] anilino-1,4-benzoquinone, - 2- [3-hydroxyethylamino-5 (2'-methoxy-4'-amino) anilino-1,4-benzoquinone, 3-N (2'-chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1,4-benzoquinone imine, 3-N (3'-chloro-4'-methylamino) phenyl-ureido-6-methyl-1,4-benzoquinone imine, 3- [4'-N- (ethyl, carbamylmethyl) amino] phenyl -ureido-6-methyl-1,4-benzoquinone imine.

  Among the tetraazapentamethine type dyes that may be used according to the invention, mention may be made of the following compounds: 2 - ((E) - {(E) - [(1,3-dimethyl-1,3-dihydro-2H) chloride imidazol-2-ylidene) hydrazono] methyl} diazenyl) -1,3-dimethyl-1H-imidazol-3-ium; 2 - {(E) - [(1Z) -N- (1,3-dimethyl-1,3-dihydro-2H-imidazol-2-ylidene) ethanehydrazonoyl] diazenyl} -1,3-dimethyl-chloride 1H-imidazol-3-ium; 4-methoxy-2 - ((E) - {(1 E) -1 - [(2E) - (4-methoxy-1-methylpyridin-2 (1H) -ylidene) hydrazono] ethyl} diazenyl chloride -1-methylpyridinium; 1-methyl-2 - ((E) - {(1 E) -1 - [(2E) - (1-methylpyridin-2 (1H) -ylidene) hydrazono] ethyl} diazenyl) pyridinium chloride; 1- (2-hydroxyethyl) -2 - [(E) - ((1E) -1 - {(2E) - [1- (2-hydroxyethyl) pyridin-2 (1H) -ylidene] chloride hydrazono} ethyl) diazenyl] pyridinium; 31

  1-methyl-2 - ((E) - {(E) - [(2Z) - (1-methylpyridin-2 (1H) -ylidene) hydrazono] methyl} diazenyl) pyridinium chloride; 1- (2-hydroxyethyl) -2 - [(E) - ((E) - {(2E) - [1- (2-hydroxyethyl) pyridin-2 (1H) -ylidene] hydrazono acetate} methyl) diazényl] pyridinium.

  Among the natural direct dyes that may be used according to the invention, lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna. If they are present, the content of additional direct dyes in the composition generally varies from 0.001 to 20% by weight relative to the weight of the composition, and preferably from 0.01 to 10% by weight relative to the weight of the composition. the composition.

  The appropriate medium for dyeing, also called dyeing medium, is generally constituted by water or a mixture of water and at least one organic solvent to solubilize compounds that are not sufficiently soluble in water . More particularly, the organic solvents are chosen from monoalcohols or diols, linear or branched, preferably saturated, comprising from 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2- methyl 2,4-pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol; aromatic alcohols such as benzyl alcohol, phenylethyl alcohol; glycols or glycol ethers such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol; and the alkyl ethers of diethylene glycol, especially C1-C4, for example diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture. 32

  The usual solvents described above, if they are present, usually represent from 1 to 40% by weight, more preferably from 5 to 30% by weight, relative to the total weight of the composition. 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, anionic, cationic, nonionic polymers. ionic, amphoteric, zwitterionic or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetration 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. These 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. Examples of acidifying agents that may be mentioned include, for example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid and 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: embedded image in which W is a propylene residue optionally substituted with a hydroxyl group or a C 1 -C 4 alkyl radical; RD, RE, RF and RG, 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 composition according to the invention may further comprise at least one oxidizing agent to allow simultaneous lightening. The oxidizing agent can be any oxidizing agent conventionally used in the field. Thus, it may be chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, as well as the enzymes among which may be mentioned peroxidases, oxides, 2-electron reductases such as uricases and 4-electron oxygenases such as laccases. The subject of the invention is also a dyeing method which comprises applying a dyeing composition according to the invention to dry or moist keratin fibers during a laying time which is sufficient to obtain the desired coloration. When the oxidizing agent is present, it may either be added to the composition comprising the compound (s) of formula (I) at the time of use, or it may be applied directly to the keratinous fiber. 34

  Whatever variant is chosen with or without an oxidizing agent, the exposure time is in general between a few seconds and 30 minutes, preferably between 3 and 15 minutes. The temperature at which the composition is allowed to act is generally between 15 and 220 ° C., more particularly between 15 and 80 ° C., preferably between 15 ° and 40 ° C. At the end of the exposure time, the composition is removed by rinsing with water, followed by washing with a shampoo, then possibly drying.

  Another object of the invention is a multi-compartment device or "kit" of dyeing in which a first compartment contains the dye composition of the invention and a second compartment contains the oxidizing composition. This device may be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR-2,586,913. The subject of the present invention is also the direct dyes of formula (I) or ( II) as defined above, with the exception of the compound of the following formula: NN as well as their mesomeric forms, their addition salts with an acid and their solvates. The examples which follow serve to illustrate the invention without, however, being limiting in nature.

  EXAMPLES Synthesis Examples Color 1 Synthesis Scheme 1. NaNO2 / HCl NH4N1NCl2 A mixture of monoazo dye (2.16 g), concentrated hydrochloric acid (2 mL) is cooled to 5 ° C. ), acetic acid (1 mL) and water (15 mL), then a solution of sodium nitrite (0.8 g) solubilized in water (2 mL) is added dropwise, maintaining After 30 minutes, urea (0.1 g) is added, and then the resulting diazonium salt solution is added dropwise to a solution of N, N-dimethylaniline ( 1.2 g), water (15 ml), ethanol (5 ml) and sodium hydrogencarbonate (1.08 g) while maintaining a temperature of less than 5 ° C. After stirring for 1 hour, the solution at pH 7 with an aqueous solution of NaHCO 3 and the temperature is allowed to rise to room temperature. The solution is evaporated under vacuum until the quarter. The remaining solution is poured into acetone (200 mL) and the precipitate obtained is filtered. It is dried under vacuum for 4 days at 40 ° C. This gives 2.6 g of brown crystals. The analyzes indicate that dye 1 was obtained (NMR, HPLC, MS). 25

  Colorant 2 HO CI - Synthesis Diagram I. NC) - N, • NH 2 NN CI- 1. NaNO 2 / HCl A mixture of monoazo dye (2.16 g), a mixture of concentrated hydrochloric acid (2 mL), acetic acid (1 mL) and water (15 mL) are added dropwise a solution of sodium nitrite (0.8 g) in water (2 ml), keeping the temperature below 5 ° C. After stirring for 30 minutes at 0 ° C., urea (0.1 g) is added and the resulting diazonium salt solution is then poured into a solution containing ethylaminocresol (1.51 g), water (25 mL), ethanol (30 mL) and sodium hydrogen carbonate (1.08 g) keeping the temperature below 5 C. After stirring for 1 hour, the pH is brought to 7 with an aqueous solution of NaHCO 3 and the temperature is allowed to rise to room temperature. The solution is evaporated under vacuum until the quarter. The solution is poured into 300 ml of acetone. A precipitate is obtained. This is filtered and dried under vacuum. 1.6 g of black crystals are thus obtained. The analyzes indicate that dye 2 was obtained (NMR, HPLC, MS).

  Dye 3 ci MeO Synthesis Diagram 1. NaNO2 / HCI MeO 1. NaNO2 / HCI Cl NN CI Cl HZN H2 2. MeO MeO DMS Cl MeOO Step 1 Cl N 1. NaNO2 / HCI H2N H2 A mixture consisting of: of 3-chloro-4- (dimethylamino) aniline (7 g), 5 N hydrochloric acid (22 ml) and water (54 ml) and then a solution consisting of sodium nitrite (2 g) is added dropwise. 83 g) solubilized in water (28 ml), maintaining a temperature of less than 5 ° C. After stirring for 1 hour, sulphamic acid (0.1 g) is added and then the solution is added. diazonium salt previously obtained dropwise to a solution of 5-methyl-2-methoxyaniline (5.92 g) solubilized in water (14 mL) and acetic acid (28 mL) while maintaining a temperature below C. After stirring for 2 hours at room temperature, the pH is brought to 8-9 by an aqueous solution of 4M K2CO3. After stirring for one hour at 0-5 ° C, water (600 ml) is added. . The aqueous phase is extracted with dichloromethane (4x200 mL) and the organic phases are combined. These are dried over Na2SO4, filtered and concentrated in vacuo. On 5 38

  14.2 g of brown powder is obtained. It is purified by chromatography on silica gel 60 using the heptane / ethyl acetate mixture as eluent. 9.33 g of pure product are thus obtained. The analyzes indicate that the expected product has been obtained (NMR, HPLC, MS).

  Step 2 1. NaNO 2 / HCl 2. 0 H 2 Cl 2 MeO CI To the product obtained above (0.509 g), previously solubilized in 5 N hydrochloric acid (3 mL) and acetonitrile (8 mL), are added to the product. dropwise a solution of sodium nitrite (0.108 g) solubilized in water (1 mL) while maintaining a temperature below 5 C. After 30 minutes, is added sulfamic acid (0.1 g) and a solution containing imidazole (0.108 g) solubilized in water (1 mL) is added. After stirring for 2 hours at room temperature, the pH was brought to 8-9 with an aqueous solution of 4M K2CO3. After stirring for 1 hour, water was added. The aqueous phase is extracted with dichloromethane (3x75 mL). The organic phases are combined and then dried over Na 2 SO 4. After filtration, the organic phase is concentrated in vacuo. 616 mg of brown / yellow powder is obtained. This is then purified by chromatography on silica gel 60 using the dichloromethane / methanol mixture as eluent. In this way 332 mg of pure product is obtained. The analyzes indicate that the expected product has been obtained (NMR, HPLC, MS).

  Step 3 N 2 Me 2 SO 4 AcO-Na * 65 C, 3 h Cl MeO Cl 39

  To the product obtained above (100 mg) solubilized in THF (2 mL) and in the presence of sodium acetate (22.7 mg), dimethylsulphate (66.6 mg) is added, and the reaction mixture is then kept stirring. at 65 C for 3 hours. Subsequently, the reaction medium is concentrated by vacuum distillation of the solvents, and the resulting oil (186 mg) is purified by chromatography on silica gel 60 using the dichloromethane / methanol binary system as eluent. In this way 82 mg of pure product is obtained. The analyzes indicate that the expected product was obtained (NMR, HPLC). 1H NMR (300 MHz, MeOD, b ppm): 2.70 (3H, s); 3.01 (6H, $); 3.70 (3H, $); 4.10 (3H, $); 4.18 (6H, $); 7, 28 (1H, $); 7.48 (1H, $); 7.79 (2H, $); 7.89 (1H, $); 7.97 (1H, d); 8.00 (1 H, $). MS (ESI +): M + = 426.13.

  Dye 4 McSO4-Synthesis Scheme MeO 1. NaNO 2 / HCl OMe-NN-N 2 NH 2 MeO NH 2 2. 1. NaNO 2 / HCl MeO DMS MeO Step 1 1. NaNO 2 / HCl MeO OMe NH 2 NH 2 And with stirring a mixture containing 2-aminoimidazole sulfate (9.63 g), sulfuric acid (29 mL) and water (38 mL), then a solution of nitrite is added dropwise. of sodium (5.53 g) solubilized in water (15 mL) keeping a temperature below 5 C. After stirring for one hour, sulphamic acid (0.1 g) is added and then added the solution of diazonium salt obtained dropwise to a solution consisting of 5-methoxy-2-methylaniline (10 g) and glacial acetic acid (50 ml) while maintaining the reaction medium at a temperature below 5 C. After stirring for 4 hours at room temperature, the pH is brought to 7-8 with the aid of an aqueous Na 2 CO 3 solution, a paste is formed and, after decantation, the juices are removed. is solubilized in ethanol then dried over Na2SO4, filtered and finally concentrated under vacuum. 17.2 g of red powder are obtained. The product is reworked in acetone. The insoluble material is filtered and then dried under vacuum. 15.9 g of red powder are thus obtained. The analyzes indicate that the expected product was obtained (NMR, HPLC).

  Step 2 1. NaNO2 / HCl NH2 \ N / MeO 2. To the product obtained in the previous step (2 g), sulfuric acid (12 mL) and water (20 mL) are added. The reaction medium is cooled to 0-5 ° C. and then a solution of sodium nitrite (0.656 g) solubilized in water (2 ml) is added to the reaction medium dropwise while maintaining a temperature of 40.degree.

  After one hour of reaction, sulfamic acid (0.1 g) is added and then a solution of N, N-dimethylaminophenol (1.19 g) solubilized in water is added dropwise. glacial acetic acid (6 mL) while maintaining a temperature below 5 C. After stirring for 2 hours at 0-5 ° C., the reaction mixture is poured onto ice and the pH is brought to 8 with the aid of an aqueous solution of Na2CO3. A precipitate is formed. This is filtered, rinsed with water and then with diethyl ether and finally dried under vacuum in the presence of P2O5. 1.82 g of violet-blue powder are obtained. This powder is purified by chromatography on silica gel 60 using the dichloromethane / methanol binary mixture as eluent. 546 mg of violet powder are thus obtained. HPLC purity is greater than 99%.

  Step 3 Me 2 SO 4 / AcO-Na * N 65 C, 3 h. MeO McSO4- The product obtained in the previous step (385 mg) is solubilized in THF (23 mL) in the presence of sodium acetate (91.6 mg). Dimethylsulfate (269 mg) is added, and the reaction mixture is stirred at 65 ° C. for 3 hours. Subsequently, the reaction medium is cooled to room temperature. The precipitate obtained is filtered, rinsed with ethyl acetate and then dried under vacuum. The solid obtained is recrystallized with a mixture of methanol / tert-butyl methyl ether. After filtration and then drying under vacuum, 155 mg of a violet powder are obtained. This new powder is again taken up in pentane, filtered and dried under vacuum. 137 mg of violet powder are thus obtained. HPLC purity is greater than 99%.

  Dye 5 Ci 42 Synthesis Scheme 1. NaNO2 / HCl 2. Cl Cl NH2 NN 02N 02N Sulfite S1 H2N 1. NaNO2 / Cl Cl Cl Step 1 NH2 1. NaNO2 / HCl 2. Cl 02N CI 02N Cool to 5C a mixture consisting of 4-nitro-2-chloroaniline hydrochloride (3.5 g), a solution of 1 N hydrochloric acid (90 ml) and acetonitrile (50 ml) and then added dropwise a solution of sodium nitrite (1.41 g) solubilized in water (15 mL), maintaining a temperature below 5 C. After 30 minutes of reaction, sulfamic acid (0.1 g) is added and then the mixture is poured into a solution consisting of N, N-dimethylaniline (2.68 ml), 1 N hydrochloric acid (80 ml) and acetonitrile (80 ml), keeping the reaction medium at a temperature below C. After stirring for 1.5 hours at 0 ° C., the pH is adjusted to 12 with an aqueous solution of 4M K 2 CO 3. After stirring for 1 hour at 0.degree. add water (600 mL). The aqueous phase is extracted with dichloromethane (3x400 mL). The organic phases obtained are combined, dried over Na 2 SO 4, filtered and then evaporated. We get 5 g of 43

  black powder. This is purified by chromatography on silica gel (40-60 pm) using as eluent the binary mixture heptane / ethyl acetate. 1.89 g of pure product are thus obtained. The analyzes indicate that the expected product was obtained (NMR, HPLC). Step 2 The product obtained in the previous step (0.5 g) is solubilized in ethanol (50 mL). Sodium sulphite monohydrate (0.79 g) is added, and the reaction mixture is then stirred under reflux for 1 hour. Subsequently, the reaction medium is concentrated by distillation under vacuum, and the residue thus obtained is dissolved in water. The aqueous phase is extracted with dichloromethane, then dried over Na2SO4, filtered and evaporated. 0.4 g of pure product are thus obtained. The analyzes indicate that the expected product has been obtained (NMR, MS).

  Step 3 CI CI 02N 1. NaNO2 / HCI ~ N 2.// N CI H2N 20 To the product obtained in the previous step (0.45 g) solubilized in 5N hydrochloric acid (36.5 mL) and acetonitrile (11.5 mL) was added dropwise a solution of sodium nitrite (0.113 g) solubilized in water (13 mL) keeping the reaction medium at a temperature below 5 C. After 30 minutes of reaction, sulfamic acid (0.1 g) is added and then a solution consisting of imidazole (0.112 g) solubilized in water (1.2 ml) is added. After stirring for 4 hours at 0 ° C., the pH is adjusted to 10 with an aqueous solution of 4M K 2 CO 3. After stirring for 1 hour at 0 ° C., water is added. . The aqueous phase is extracted with dichloromethane (3x400 mL). The organic phases obtained are combined, dried over Na 2 SO 4, filtered and then concentrated under vacuum. 667 mg of crude product is obtained. This is purified by chromatography on silica gel 60 using the dichloromethane / methanol binary mixture as eluent. 233 mg of pure product are thus obtained. The analyzes indicate that the expected product was obtained (NMR, HPLC). Step 4 Ci Me2SO4 65 C, 2h The product obtained in step 3 (233 mg) is solubilized in THF (50 mL) in the presence of sodium acetate (60 mg). Dimethylsulfate (174 mg) is added, and the reaction mixture is stirred at 65 ° C for 2 hours. The reaction medium is then concentrated by vacuum distillation of the solvents, and the residue thus obtained is purified by chromatography on silica gel 60 using the dichloromethane / methanol binary mixture as eluent. 215 mg of product are thus obtained. A second purification step consists of re-batching the product in heptane for 45 minutes. After filtration and then drying under vacuum, 150 mg of pure product are obtained. The analyzes indicate that the expected product was obtained (NMR, HPLC). 1H NMR (300 MHz, MeOD, b ppm): 3.18 (6H, s); 3.65 (4H, $); 4.15 (6H, $); 6.84 (2H, d); 7.73-8.18 (7H, m). MS (ESI +): M + = 382.16. Colorant 6 McSOq10 Cl- Synthesis Diagram I. NC) N, NH 2 N I. 1. NaNO 2 / HCl (N, N-N-C) A mixture of monoazo dye (2, 5 g), concentrated hydrochloric acid (2.5 ml), acetic acid (2 ml) and water (38 ml) are then added dropwise a solution of sodium nitrite (0.8 g solubilized in water (2 mL), keeping the reaction medium at a temperature below 5 C. After 30 minutes of reaction, urea (0.1 g) is added. previously obtained is poured dropwise into a solution consisting of julolidine (1.73 g) solubilized in water (25 mL) and ethanol (10 mL) in the presence of sodium hydrogen carbonate (2 g) , taking care to maintain the reaction medium at a temperature below 5 C. After stirring for one hour, the pH is brought to 7 with an aqueous NaHCO 3 solution and the temperature is allowed to return to room temperature. ambian The solution is evaporated in vacuo and the residue obtained is purified by chromatography on silica gel 60 using the dichloromethane / methanol binary mixture as eluent. After evaporation under vacuum, 450 mg of blue powder are thus obtained. The analyzes indicate that the expected product has been obtained (NMR, HPLC, MS).

  Examples of dyeing The following dyeing compositions are prepared: Composition 1 2 Color 1 10-3 mole 10-3 mole Dyeing medium (1) (2) Dyeing medium (1), pH = 7: Ethyl alcohol 96 20.8 g Pentasodium salt of diethylenetriamine pentaacetic acid in 40% aqueous solution 0.48 g MA C3-Clo alkyl polyglucoside in 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol 8 g ethylene oxide units 3.0 g 0.28 g 0.46 g

  Dye carrier (2), pH = 9.5: Ethyl alcohol 96 20.8 g Pentasodium salt of diethylenetriaminepentaacetic acid 40% aqueous solution 0.48 g MA C3-Clo alkyl polyglucoside 60% aqueous solution 3.6 g MA benzyl alcohol 2.0 g Polyethylene glycol with 8 ethylene oxide units 3.0 g NH4Cl 4.32 g Ammonia 20% NH3 2.94 g For the colorations carried out in non-lightening conditions (without oxidant), these compositions are applied directly to the hair. For colorings carried out under lightening conditions, an oxidizing medium is used. In this case, 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 equal to 7 and 9.5 is obtained. Na2HPO4 KH2PO45 47

  Each composition with or without an oxidizing agent is applied to locks of gray hair at 90% white, at the rate of 6 g of composition per 1 g of hair. 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. pH7 pH9.5 pH7 pH9.5 (without oxidizer) (without oxidizer) (with oxidizer) (with oxidizer) Colorant 1 Blue slightly Blue slightly Blue slightly Blue little chromatic Chromatic chromatic Chromatic Colorant 2 Blue slightly Blue little Blue little Blue little chromatic chromatic chromatic chromatic Colorant 3 Violet little Violet little Violet little Violet little chromatic chromatic chromatic chromatic Coloring 4 Blue little Blue little Blue little Blue little chromatic chromatic chromatic chromatic Coloring 5 Violet little Violet little Violet little Violet chromatic chromatic chromatic Coloring 6 Blue Blue Blue Blue The locks thus colored are subjected to a washing resistance test, which consists of carrying out 12 shampoos (with a standard shampoo) and evaluating the color after these 12 shampoos. After 12 shampoos, the locks are always colored.

Claims (34)

  1. Composition for dyeing keratinous fibers comprising, in a medium suitable for dyeing, at least one cationic direct diazo dye with a pattern   2-imidazolium chosen from the compounds of formula (I) or (II) below, their mesomeric forms, as well as their addition salts with an acid and their solvates: (R An (I) (R 2) n NN RI An NR 5 R 6 in which: the R radicals represent, independently of one another: a linear or branched, saturated, acyclic, optionally substituted C1-C8 hydrocarbon chain, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen or sulfur, CO, SO, SO 2, or combinations thereof, the hydrocarbon chain having no nitro, nitroso, peroxo or diazo function; and being necessarily attached to the quaternized or non-quaternized nitrogen atom of the imidazolium ring via a carbon atom; - an optionally substituted phenyl radical; - an optionally substituted benzyl radical; entent, independently of one another: a linear C 1 -C 4 alkyl radical, optionally substituted with an amino radical or a hydroxyl radical; an optionally substituted phenyl radical; a halogen atom; The radicals R3 represent, independently of each other: a linear C1-C4 alkyl radical, optionally substituted by an amino radical or a hydroxyl radical; a hydroxyl radical; a C1-C4 alkoxy radical; a mono- or polyhydroxyalkoxy radical C1-C4; an amino radical optionally substituted with one or two identical or different C1-C4 alkyl radicals optionally carrying at least one hydroxyl radical; a group RaCO-NRa'- in which the radical Ra represents a C1-C4 alkyl radical; the radical Ra 'represents a hydrogen atom or a C1-C4 alkyl radical; a (Rb) 2N-CO- group in which the radicals Rb represent, independently of one another, a hydrogen atom, a C1-C4 alkyl radical; - a group (R) 2N-CO-NRc- in which the R radicals represent, independently of each other, a hydrogen atom, a C 1 -C 4 alkyl radical, - a group (Rd) 2N-SO 2 in which the radicals Rd represent, independently of one another, a hydrogen atom, a C 1 -C 4 alkyl radical; a group ReSO2-NRe- in which the radicals Re represent, independently of one another, a hydrogen atom or a C1-C4 alkyl radical; a cyano radical; a halogen atom, preferably chlorine and fluorine; The radicals R4 represent, independently of one another: a linear C1-C4 alkyl radical; a hydroxyl radical; a C1-C4 alkoxy radical; a mono- or polyhydroxyalkoxy radical C1-C4; an amino radical optionally substituted with one or two identical or different C1-C4 alkyl radicals optionally carrying at least one hydroxyl radical; the two alkyl radicals which can form, together with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle optionally comprising another heteroatom which is identical to or different from nitrogen such as a pyrrolidine, morpholine or piperidine ring; optionally substituted with one or more methyl, hydroxyl, amino, mono or dimethylamino radicals; a group RaCO-NRa in which the radical Ra represents a C1-C4 alkyl radical; the radical Ra 'represents a hydrogen atom or a C1-C4 alkyl radical; - a group (Rb) 2N-CO- in which the Rb radicals represent, independently of one another, a hydrogen atom, a C1-C4 alkyl radical; - a group (R) 2N-CO-NRc- in which the radicals R, represent, independently of each other, a hydrogen atom, a C1-C4 alkyl radical; a group (Rd) 2N-SO 2 - in which the radicals Rd represent, independently of one another, a hydrogen atom or a C 1 -C 4 alkyl radical; a group ReSO2-NRe- in which the radicals Re represent, independently of one another, a hydrogen atom or a C1-C4 alkyl radical; a cyano radical; a halogen atom, preferably chlorine and fluorine; The radicals R5 and R6, which are identical or different, represent: a hydrogen atom; A linear or branched, saturated, acyclic, optionally substituted C1-C8 hydrocarbon chain, optionally interrupted by one or more heteroatoms and / or by one or more groups comprising at least one heteroatom, preferably chosen from oxygen, nitrogen, sulfur, CO, SO, SO2, or combinations thereof; the hydrocarbon chain having no nitro, nitroso, peroxo or diazo function and being necessarily attached to the nitrogen atom via a carbon atom; a radical (RfSO2-) in which the radical Rf represents a C1-C4 alkyl radical; a benzyl radical optionally substituted by one or more hydroxyl and / or amino radicals; the radicals R5 and R6 being able to form, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- or 7-membered heterocycle, optionally comprising another heteroatom which is identical or different from nitrogen; one of the radicals R5 and R6 being able to form, with the nitrogen atom to which it is attached, and with a radical R4 situated in ortho of the NR5R6 group, an optionally substituted 5- or 6-membered heterocycle of the following formula (III): in which: - o is an integer equal to 0 or 1; - Rx and Ry represent, independently of one another, a hydrogen atom or a methyl radical; the radicals R5 and R6 being able to form, with the nitrogen atom to which they are attached and each with a radical R4 located in ortho of the group NR5R6, an optionally substituted 5- or 6-membered heterocycle of the following formula (IV): in which: o is an integer equal to 0 or 1; - Rx and Ry represent, independently of each other, a hydrogen atom or a methyl radical; • n is an integer between 0 and 2; when n is less than 2, the unsubstituted carbon atom (s) carry a hydrogen atom; • n 'is an integer between 0 and 4, preferably between 0 and 2; when n 'is less than 4, the unsubstituted carbon atom (s) carry a hydrogen atom; • n "is an integer between 0 and 4, preferably between 0 and 3. When n" is less than 4, the unsubstituted carbon atom (s) carry a hydrogen atom; the electroneutrality of the compounds of formula (I) or (II) being ensured by one or more cosmetically acceptable anions An, which are identical or different. 2. Composition according to claim 1, wherein the radicals RI are chosen from a C1-C4 alkyl radical, optionally terminated by a hydroxyl.   3. Composition according to claim 2, wherein the radicals RI represent a methyl radical; an ethyl radical or a 2-hydroxyethyl radical.   4. Composition according to any one of the preceding claims, in which n is 0 or the radicals R 2 are chosen from a C 1 -C 4 alkyl radical optionally substituted with an amino radical or a hydroxyl radical. 53   5. Composition according to claim 4, in which the radicals R2 are chosen from a methyl radical; an ethyl radical; a 2-hydroxyethyl radical; a 3-aminopropyl radical.   6. Composition according to any one of the preceding claims, in which the radicals R3 are chosen from a C1-C4 alkyl radical; a C1-C4 alkoxy radical; a halogen atom; an optionally substituted amino radical; a group RaCO-NRa- in which the radical Ra represents a C1-C4 alkyl radical; the radical Ra 'represents a hydrogen atom; a hydroxyl radical.   7. Composition according to claim 6, in which the radicals R3 are chosen from a methyl radical; a methoxy radical; a chlorine atom; a hydroxyl radical; a methylcarbonylamino radical.   8. Composition according to any one of the preceding claims, in which the radicals R4 are chosen from an alkyl radical; a hydroxyl radical; an alkoxy radical; a mono- or di (alkyl) amino radical C1-C4; a C1-C4 di (hydroxyalkyl) amino radical; a halogen atom; a group RaCO-NRa'- in which the radical Ra represents a C1-C4 alkyl radical and the radical Ra 'represents a hydrogen atom.   9. Composition according to claim 8, in which the radicals R4 are chosen from a methyl radical; a hydroxyl radical; an ethylamino radical; a dimethylamino radical; a di (2-hydroxyethyl) amino radical; a chlorine atom; a methylcarbonylamino radical.   10. Composition according to any one of the preceding claims, in which the radicals R5 and R6, which are identical or different, represent: a C1-C4 alkyl radical, optionally substituted with at least one hydroxyl radical; a benzyl radical optionally substituted by one or more hydroxyl and / or amino radicals.   11. Composition according to any one of claims 1 to 9, wherein the radicals R5 and R6 form, with the nitrogen atom to which they are attached, a 5- or 7-membered, saturated or unsaturated, optionally substituted 5- or 7-membered heterocycle, optionally another heteroatom identical to or different from the nitrogen.   12. Composition according to any one of claims 1 to 9, wherein one of the radicals R5 or R6 forms with the nitrogen atom to which it is attached and with a radical R4 located in ortho of the NR5R6 group a heterocycle to 5 or 6-membered, optionally substituted, of the following formula (III): in which: o is an integer equal to 0 or 1; - Rx and Ry independently of each other, represent a hydrogen or a methyl.   13. Composition according to claim 12, in which one of the radicals R5 or R6 forms, with the nitrogen atom to which it is attached, and with an R4 radical located in ortho of the NR5R6 group, one of the saturated or unsaturated heterocycles at Substituted or unsubstituted 5 or 6 members of the following formulas: N R5 or R6 R5 or R6 (OH) p (OH) p (OH) p with p = 0 or 1   14. Composition according to any one of Claims 1 to 9, in which the radicals R5 and R6 form, with the nitrogen atom to which they are attached and each with an R4 radical located in ortho of the NR5R6 group, a 5-membered heterocycle or 6-membered, optionally substituted, of the following formula (IV): wherein: o is an integer of 0 or 1; -Rx and Ry independently of each other represent a hydrogen or a methyl.   15. Composition according to claim 14, in which the radicals R5 and R6 form, with the nitrogen atom to which they are attached and each with a radical R4 located in ortho of the NR5R6 group, one of the saturated or unsaturated heterocycles at 5 or 6-membered substituted or unsubstituted chains of the following formulas: 10 (OH) p with p = 0 or 1   16. Composition according to any one of the preceding claims, in which n 'is an integer between 0 and 2.   17. A composition according to any one of the preceding claims, wherein n "is an integer from 0 to 3.   18. Composition according to any one of the preceding claims, in which An represents an anion or a mixture of organic or inorganic anions chosen from a halide; a hydroxide; sulphate; a hydrogen sulfate; an alkyl sulphate wherein the linear or branched alkyl moiety is C1-C6; carbonates and hydrogen carbonates; carboxylic acid salts; alkylsulphonates for which the linear or branched alkyl part is C1-C6; arylsulfonates for which the aryl moiety is optionally substituted with one or more C1-C4 alkyl radicals; alkylsulfonyls.   19. Composition according to any one of the preceding claims, in which the direct dye (s) of formula (I) or (II) are chosen from the direct dyes of formula (I ') or (II') below: NR ' In which: • the R 'radicals represent, independently of one another, a C 1 -C 4 alkyl radical; a 2-hydroxyethyl radical; The R'3 radicals represent, independently of one another, a C1-C4 alkyl radical; a C1-C4 alkoxy radical; a halogen atom; a hydroxyl radical; a methylcarbonylamino radical; • m 'represents an integer equal to 0, 1 or 2; The R'4 radicals represent, independently of each other, a C1-C4 alkyl radical; a hydroxyl radical; an alkoxy radical; a mono or di (alkyl) amino radical; a di (hydroxyalkyl) amino radical; a halogen atom such as chlorine; a (C1-C4) alkylcarbonylamino radical; • m "represents an integer equal to 0, 1, 2 or 3; An (R'3) m '57 • the radicals R'5 and R'6 represent, independently of one another, an alkyl radical C1-C4, a C1-C4 monohydroxyalkyl radical or form with one or two radicals R'4 located in ortho of the group NR'5R'6 and the benzene ring to which they are attached a ring of formula (III) or (IV).   20. Composition according to any one of the preceding claims, in which the direct dye (s) of formula (I) are chosen from the compounds presented in the table below, An being as defined in claim 1 or 16: Colorant 1 Year N \ N ~ 1 \ 1 N Colorant 2 H \ N`.NNN HO An Colorant 3 ~ + N \ N \ NN` \\ N Cl An Colorant 4 HO N + N. ~ N \ NN An Colorant 5 1+ Cl ~ NN ~ <N ~ N \\ NN An Colorant 6 INC \ ~ N`NN`NNN \ Anolorant 7 1. OH (NrN \\ NN \\ NNN OH An Colorant 8 OH N1 OH ç N / N \ N \ N \ N \ An Anant 9 N / N ~ \ NN``N N1 OH \ OH N An Colorant 10 J N1 OH N / N`EN N \\ N \ OH l \ N / O Year Dye 11 I. N \ N ~ _N`EN N`EN N \ N   21. Composition according to any one of the preceding claims, in which the direct dye (s) represent (s) from 0.01 to 5 by weight relative to the total weight of the composition.   22. Composition according to any one of the preceding claims comprising at least one oxidation base chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases. 59   23. Composition according to Claim 22, in which the oxidation base (s) represent (s) from 0.001 to 10% by weight relative to the total weight of the composition.   24. A composition according to claim 22 or 23 comprising at least one coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers and heterocyclic couplers.   25. Composition according to claim 24, wherein the coupler or couplers represent from 0.001 to 10% by weight relative to the total weight of the composition.   26. Composition according to any one of the preceding claims, in which the composition comprises at least one additional direct dye.   27. Composition according to claim 26, in which the additional direct dye or dyes are chosen from nitrobenzene dyes, azo, azomethine, methine, tetraazapentamethine, anthraquinone, naphthoquinone, benzoquinone, phenotiazine, indigoid, xanthenic, phenanthridine, phthalocyanine dyes. those derived from triarylmethane and natural dyes, alone or in mixtures.   28. Composition according to claim 26 or 27, in which the additional direct dye (s) represent from 0.001 to 20% by weight approximately of the total weight of the composition.   29. Composition according to any one of the preceding claims, in which the composition comprises at least one additive chosen from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic or amphoteric polymers. , zwitterionic or mixtures thereof, inorganic or organic thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents, film-forming agents, ceramides, preserving agents stabilizing agents, opacifying agents.   30. Composition according to any one of the preceding claims comprising at least one oxidizing agent.   31. The composition of claim 30, wherein the oxidizing agent (s) is (are) selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, and enzymes.   32. A method of dyeing keratinous fibers comprising contacting a composition as defined in any one of claims 1 to 31 with said fibers, dry or wet, for a time sufficient to obtain the desired effect.   33. A multi-compartment device in which a first compartment contains the composition according to any one of claims 1 to 29 and a second compartment containing an oxidizing composition.   34. Cationic diazo direct dyes of formula (I) or (II) as defined in any one of claims 1 to 20, with the exception of the compound of the following formula: NN ~ N \ NNN and their mesomeric forms, their addition salts with an acid and their solvates.