AU2003270217A1 - Hair dyes comprising m-phenylenediamine derivatives as coupling components - Google Patents

Description

H 05419 PCT/AU Modified Annex AU.IV VERIFICATION OF TRANSLATION I, ROGER CHARLES STANFORD TUNN of 4, Plymouth Park, Sevenoaks, Kent, United Kingdom declare as follows: 1. That I am well acquainted with both the English and German languages and 2. That the attached document is a true and correct translation made by me to the best of my knowledge and belief of the specification of International Bureau pamphlet numbered WO 2004/031164 of International patent application No. PCT/EP2003/10371. 17th February 2005.

WO 2004/031164 1 PCT/EP2003/010371 Hair Dyes Comprising m-Phenylenediamine Derivatives as Coupling Components This invention relates to preparations containing special m phenylenediamine derivatives, in which one of the two nitrogen atoms is part of a saturated heterocycle, for coloring keratinous fibers, to a process for coloring hair with these preparations and to some of these m 5 phenylenediamine derivatives themselves and intermediate products formed in the production of these compounds. By virtue of their intensive colors and good fastness properties, so called oxidation colorants play a prominent role in the coloring of keratin fibers, particularly human hair. Oxidation colorants contain oxidation dye 10 precursors, so-called primary intermediates and secondary intermediates. The primary intermediates form the actual dyes with one another or by coupling with one or more secondary intermediates in the presence of oxidizing agents or atmospheric oxygen. The primary intermediates normally used are primary aromatic 15 amines containing another free or substituted hydroxy or amino group in the para position or the ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6 tetraaminopyrimidine and derivatives thereof. Special representatives are, for example, p-phenylenediamine, p 20 toluylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N,N-bis-(2 hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenyl)-ethanol, 2-(2,5 diaminophenoxy)-ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6 triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4 25 hydroxypyrimidine and 1,3-N,N'-bis(2-hydroxyethyl)-N,N'-bis-(4-amino- WO 2004/031164 2 PCT/EP2003/010371 phenyl)-diamino-propan-2-ol. The secondary intermediates are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols. Suitable secondary intermediates are, in particular, 5 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2 methylphenol, m-aminophenol, resorcinol, resorcinol monomethylether, m phenylenediamine, 1 -phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3 aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2-chlororesorcinol, 4 chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5 10 methylresorcinol and 2-methyl-4-chloro-5-aminophenol. Good oxidation dye precursors are expected to satisfy above all the following requirements: they must form the required color tones with sufficient intensity and fastness during the oxidative coupling reaction. In addition, they must be readily absorbed onto the fibers with no significant 15 differences - particularly in the case of human hair - between damaged and freshly regrown hair (levelling behavior). They must be resistant to light, heat, perspiration, rubbing and the effect of chemical reducing agents, for example permanent wave lotions. Finally, if they are used to color hair, they should not overly stain the scalp and, above all, should be 20 toxicologically and dermatologically safe. In addition, the color obtained should be easily removable from the hair by blonding if it does not meet the individual wishes of the user and is to be taken out. In general, natural-looking hair colors cannot be obtained with a primary intermediate alone or with a special secondary 25 intermediate/primary intermediate combination. In practice, therefore, combinations of various primary intermediates and/or secondary intermediates are used. Accordingly, there is a constant need for new improved dye components which are also toxicologically and dermatologically safe. 30 Accordingly, the problem addressed by the present invention was to WO 2004/031164 3 PCT/EP2003/010371 provide new secondary intermediates which would satisfy the requirements oxidation dye precursors are expected to meet, particularly in regard to their toxicological and dermatological properties, and which would enable a broad range of colors with good fastness properties to be obtained. 5 It has now surprisingly been found that m-phenylenediamine derivatives, in which one of the two nitrogen atoms is part of a saturated heterocycle, satisfy the requirements secondary intermediates are expected to meet to a high degree. The secondary intermediates according to the invention enable intensive, brilliant shades with very good 10 fastness properties to be obtained, particularly in combination with p phenylenediamine derivatives, diaminopyrazole derivatives and oligoaminopyrimidine derivatives. Accordingly, in a first embodiment, the present invention relates to preparations for coloring keratinous fibers, more particularly human hair, 15 containing as secondary intermediate in a cosmetically acceptable carrier at least one m-phenylenediamine derivative corresponding to formula (1) or a physiologically safe salt thereof: N2R3 NRR R 6X 20 in which R1 is a hydrogen atom, a halogen atom, a C14 alkyl group, a C14 monohydroxyalkyl group, a C24 polyhydroxyalkyl group, a C 1 4 aminoalkyl group, a C 1 4 alkoxy-(C 1 4)-alkyl group or a C14 dialkylamino-(C 1 4)-alkyl group, 25 R 2 and R 3 independently of one another represent a hydrogen atom, a C14 WO 2004/031164 4 PCT/EP2003/010371 alkyl group, a C24 monohydroxyalkyl group, a C34 polyhydroxyalkyl group, a C 1 4 alkoxy-(C 14 )-alkyl group or a C14 aminoalkyl group and X is a saturated, 5-, 6- or 7-membered heterocycle containing at least one nitrogen atom and optionally another hetero atom selected from oxygen, 5 sulfur or nitrogen, the heterocycle being attached to the aromatic ring system by a nitrogen atom and optionally bearing two substituents different from hydrogen selected from a halogen atom, a C 1 4 alkyl group, a C14 monohydroxyalkyl group, a C24 polyhydroxyalkyl group, a C14 aminoalkyl group, a C14 alkoxy-(C14)-alkyl group or a C14 dialkylamino-(C 1 4)-alkyl 10 group. Keratinous fibers in the context of the invention are pelts, wool, feathers and, in particular, human hair. Although the oxidation colorants according to the invention are mainly suitable for coloring keratin fibers, there is nothing in principle to prevent their use in other fields of application, 15 more particularly in color photography. Since the m-phenylene derivatives according to the invention are amino compounds, the known acid addition salts can be prepared from them by standard methods. Accordingly, all the disclosures of the present specification and hence the claimed scope of protection relate both to the 20 compounds present in free form and to their water-soluble, physiologically compatible salts. Examples of such salts are the hydrochlorides, the hydrobromides, the sulfates, the phosphates, the acetates, the propionates, the citrates and the lactates. The hydrochlorides and the sulfates are particularly preferred. 25 Examples of the C14 alkyl groups mentioned as substituents in the compounds according to the invention are the methyl, ethyl, propyl, isopropyl and butyl groups. Preferred alkyl groups are ethyl and methyl. Preferred C14 alkoxy groups are the methoxy and ethoxy groups. In addition, preferred examples of a C14 monohydroxyalkyl group are a 30 hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl WO 2004/031164 5 PCT/EP2003/010371 group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C2- polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. According to the invention, examples of halogen atoms are F, Cl or Br atoms. Cl atoms are particularly preferred. The other terms used are 5 derived from the definitions given here. The m-phenylenediamine derivatives of formula (1) can be produced by conventional organic methods. Reference is made by way of example at this juncture to the tests described in the Examples section. In a preferred embodiment of the invention, the parent compound of the m 10 phenylenediamine derivatives of formula (1) may be synthesized, for example, by reaction of 3-fluoronitrobenzene with the corresponding saturated nitrogen-containing heterocycles. According to the invention, therefore, preferred m-phenylenediamine derivatives of formula (1) are those of which the parent compound can be prepared by reaction of 3 15 fluoronitrobenzene with one of the following compounds characterized here by their Chemical Abstract Number: CA No.: 100158-62-1, CA No.: 1003 28-7, CA No.: 102308-48-5, CA No.: 104-89-2, CA No.: 104678-13-9, CA No.: 109-05-7, CA No.: 109967-01-3, CA No.: 110-89-4, CA No.: 111-49-9, CA No.: 1121-44-4, CA No.: 114143-75-8, CA No.: 116574-75-5, CA No.: 20 118971-00-9, CA No.: 1193-12-0, CA No.: 121963-72-2, CA No.: 123-75-1, CA No.: 124602-03-5, CA No.: 133294-31-2, CA No.: 13748-14-6, CA No.: 138022-00-1, CA No.: 138617-51-3, CA No.: 14066-85-4, CA No.: 144230 52-4, CA No.: 14446-75-4, CA No.: 1484-80-6, CA No.: 1484-84-0, CA No.: 155106-17-5, CA No.: 15991-59-0, CA No.: 167704-69-0, CA No.: 1722 25 95-8, CA No.: 174073-64-4, CA No.: 1772-29-8, CA No.: 180258-82-6, CA No.: 1882-42-4, CA No.: 19168-71-9, CA No.: 198283-99-7, CA No.: 199475-41-7, CA No.: 205180-40-1, CA No.: 205443-01-2, CA No.: 205443-04-5, CA No.: 2088-78-0, CA No.: 21987-29-1, CA No.: 222314 27-4, CA No.: 222314-35-4, CA No.: 222314-40-1, CA No.: 22398-09-0, CA 30 No.: 22977-56-6, CA No.: 22990-77-8, CA No.: 23099-21-0, CA No.: WO 2004/031164 6 PCT/EP2003/010371 23356-96-9, CA No.: 24152-39-4, CA No.: 3197-42-0, CA No.: 3230-23-7, CA No.: 3238-60-6, CA No.: 32452-45-2, CA No.: 3378-71-0, CA No.: 3433-37-2, CA No.: 34375-89-8, CA No.: 344329-35-7, CA No.: 3446-98-8, CA No.: 35794-11-7, CA No.: 363179-66-2, CA No.: 372963-41-2, CA No.: 5 383127-24-0, CA No.: 383127-26-2, CA No.: 383128-18-5, CA No.: 383128-19-6, CA No.: 383129-05-3, CA No.: 383129-08-6, CA No.: 383129-13-3, CA No.: 383129-28-0, CA No.: 383129-30-4, CA No.: 4045 30-1, CA No.: 4209-65-8, CA No.: 452331-68-9, CA No.: 458-88-8, CA No.: 4606-65-9, CA No.: 504-03-0, CA No.: 5072-45-7, CA No.: 5119-88-0, CA 10 No.: 51503-10-7, CA No.: 5347-68-2, CA No.: 54288-70-9, CA No.: 555-92 0, CA No.: 57367-18-7, CA No.: 57395-89-8, CA No.: 57734-57-3, CA No.:60717-49-9, CA No.:60717-51-3, CA No.:6091-44-7, CA No.:622-26-4, CA No.:626-56-2, CA No.:626-58-4, CA No.:62617-70-3, CA No.:62848-20 8, CA No.:6287-19-0, CA No.:63126-47-6, CA No.:63639-02-1, CA 15 No.:637-49-0, CA No.:64168-10-1, CA No.:6457-49-4, CA No.:65337-42-0, CA No.:65944-50-5, CA No.:66928-78-7, CA No.:67318-88-1, CA No.:68832-13-3, CA No.:69500-64-7, CA No.:70144-18-2, CA No.:70724 66-2, CA No.:70754-93-7, CA No.:71172-94-6, CA No.:7144-05-0, CA No.:72939-22-1, CA No.:72939-23-2, CA No.:72939-24-3, CA No.:73579 20 06-3, CA No.:76025-62-2, CA No.:765-38-8, CA No.:766-17-6, CA No.:76946-27-5, CA No.:78197-27-0, CA No.:80053-54-9, CA No.:80053 55-0, CA No.:84025-81-0, CA No.:84039-87-2, CA No.:84367-22-6, CA No.:88057-03-8, CA No.:90203-05-7, CA No.:90290-05-4, CA No.:91187 81-4, CA No.:93621-94-4, CA No.: 10024-89-2, CA No.: 103003-01-6, CA 25 No.: 106-55-8, CA No.: 108-49-6, CA No.: 109-07-9, CA No.: 110-85-0, CA No.: 110-91-8, CA No.: 116143-27-2, CA No.: 122894-56-8, CA No.: 123 57-9, CA No.: 128454-20-6, CA No.: 130861-85-7, CA No.: 13961-37-0, CA No.: 141-91-3, CA No.: 142-63-2, CA No.: 142-64-3, CA No.: 171351-20-5, CA No.: 21655-48-1, CA No.: 25154-38-5, CA No.: 2815-34-1, CA No.: 30 28631-79-0, CA No.: 393781-72-1, CA No.: 4554-26-1, CA No.: 6091-62-9, WO 2004/031164 7 PCT/EP2003/010371 CA No.: 6284-84-0, CA No.: 6485-55-8, CA No.: 74879-18-8, CA No.: 75336-85-5, CA No.: 75336-86-6, CA No.: 75336-89-9 and CA No.: 84477 72-5. Some of the m-phenylenediamine derivatives of formula (1) are 5 already known from the prior art. However, there is nothing in the literature to suggest that these known derivatives could be used as secondary intermediates in hair colorants. Structurally distantly related m phenylenediamine derivatives are already known from DE-A1-26 22 451 which describes benzenes symmetrically bis-substituted by secondary 10 amines, including inter alia 1,3-bis-(piperidin-1-yl)-benzene. However, this prior art application does not in any way encourage the expert to use the m-phenylenediamine derivatives now being claimed as secondary intermediates. On the contrary, the synthesis strategy disclosed in that application does now allow production of the m-phenylenediamine 15 derivatives now being claimed and, hence, leads away from the subject of the present application. According to the invention, preferred m-phenylenediamine derivatives of formula (1) can be those where R 1 is a hydrogen atom, a halogen atom, a C1-4 alkyl group or a C 1 4 monohydroxyalkyl group. In a 20 particularly preferred embodiment, R 1 is a hydrogen atom, a chlorine atom, a methyl group or a 2-hydroxyethyl group. m-Phenylenediamine derivatives of formula (I) where R 1 is a hydrogen atom are most particularly preferred. According to the invention, other preferred m-phenylenediamine 25 derivatives of formula (1) can be those where R 2 and R 3 independently of one another represent a hydrogen atom, a C14 alkyl group or a C14 monohydroxyalkyl group. In a particularly preferred embodiment, the substituents R 2 and R 3 independently of one another represent a hydrogen atom, a methyl group or a 2-hydroxyethyl group. Most particularly 30 preferred are m-phenylenediamine derivatives corresponding to formula (1) WO 2004/031164 8 PCT/EP2003/010371 where - R 2 and R 3 each represent a methyl group, - one of the substituents R 2 or R 3 is a 2-hydroxyethyl group and the other is a hydrogen atom or 5 - each of the two substituents R 2 and R 3 represents a hydrogen atom. According to the invention, other preferred m-phenylenediamine derivatives of formula (1) can be those where X is a pyrrolidin-1-yl group, an imidazolidin-1-yl group, a piperidin-1-yl group, a piperazin-1-yi group, a morpholin-4-yl group, a hexahydroazepin-1-yl group or a hexahydro-1,4 10 oxazepin-4-yl group. Besides the compounds mentioned above, derivatives thereof substituted by an alkyl group, more particularly a methyl group, can also be preferred for the purposes of the invention. If the heterocycle has a second nitrogen atom, the substituted derivatives where the substituent is attached to the second nitrogen atom can be particularly 15 preferred. Particularly preferred m-phenylenediamine derivatives of formula (1) are those where X is a morpholin-4-yl group, a piperidin-1-yl group, a 4 methylpiperazin-1-yl group or a pyrrolidin-1-yl group. According to the invention, particularly preferred m 20 phenylenediamine derivatives of formula (1) are selected from the group consisting of 3-pyrrolidin-1-yi aniline, 3-piperidin-1-y aniline, 3-morpholin-4 yl aniline, 3-(4-methylpiperazin-1-yl)-aniline, N,N-dimethyl-3-(pyrrolidin-1 yl)-aniline, 2-[(3-morpholin-4-yl phenyl)-amino]-ethan-1-ol, 2-[(3-piperidin-1 yl phenyl)-amino]-ethan-1-ol and 2-[(3-pyrrolidin-1-yl phenyl)-amino]-ethan 25 1-ol. 3-Pyrrolidin-1-yl aniline, 2-[(3-morpholin-4-yl phenyl)-amino]-ethan-1 ol and 2-[(3-pyrrolidin-1-yl phenyl)-amino]-ethan-1-ol are most particularly preferred for the purposes of the present invention. Besides the m-phenylenediamine derivatives of formula (1), the 30 colorants according to the invention may additionally contain at least one WO 2004/031164 9 PCT/EP2003/010371 primary intermediate. This primary intermediate is normally selected from primary aromatic amines with another free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4 5 aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof. In a preferred embodiment of the invention, a p-phenylenediamine derivative or one of its physiologically compatible salts is used as the primary intermediate. Particular preference is attributed to p 10 phenylenediamine derivatives corresponding to formula (El): NGG G3 G4 (El)

NH

2 in which - G 1 stands for a hydrogen atom, a C14 alkyl radical, a C14 monohydroxyalkyl radical, a C24 polyhydroxyalkyl radical, a (C1.4) 15 alkoxy-(C 1

.

4 )-alkyl radical, a 4'-aminophenyl radical or a C14 alkyl radical substituted by a nitrogen-containing group, a phenyl group or a 4'-aminophenyl group; - G 2 stands for a hydrogen atom, a C14 alkyl radical, a C1.4 monohydroxyalkyl radical, a C24 polyhydroxyalkyl radical, a (C1.4) 20 alkoxy-(C 1

.

4 )-alkyl radical or a C14 alkyl radical substituted by a nitrogen-containing group; - G 3 stands for a hydrogen atom, a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, a C14 alkyl radical, a C14 monohydroxyalkyl radical, a C24 polyhydroxyalkyl radical, a C14 25 hydroxyalkoxy radical, a C14 acetylaminoalkoxy radical, a C1.4 mesylaminoalkoxy radical or a C14 carbamoylaminoalkoxy radical; WO 2004/031164 10 PCT/EP2003/010371 - G 4 is a hydrogen atom, a halogen atom or a C 1 4 alkyl radical or - if G 3 and G 4 are in the ortho position to one another, they may together form a bridging a,o-alkylenedioxo group such as, for example, an ethylenedioxy group. 5 Examples of the C 1 4 alkyl groups mentioned as substituents in the compounds according to the invention are the methyl, ethyl, propyl, isopropyl and butyl groups. Ethyl and methyl groups are preferred alkyl groups. According to the invention, preferred C14 alkoxy groups are, for 10 example, methoxy or ethoxy groups. Other preferred examples of a C 14 hydroxyalkyl group are the hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl group. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C 24 polyhydroxyalkyl group is the 1,2 dihydroxyethyl group. According to the invention, examples of halogen 15 atoms are F, Cl or Br atoms. Cl atoms are most particularly preferred. According to the invention, the other terms used are derived from the definitions given here. Examples of nitrogen-containing groups corresponding to formula (El) are, in particular, the amino groups, C 14 monoalkylamino groups, C14 dialkylamino groups, C14 trialkylammonium 20 groups, C14 monohydroxyalkylamino groups, imidazolinium and ammonium. Particularly preferred p-phenylenediamines corresponding to formula (El) are selected from p-phenylenediamine, p-toluylenediamine, 2-chloro p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p 25 phenylenediamine, 2,6-diethyl-p-phenylenediamine, 2,5-dimethyl-p phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p phenylenediamine, N,N-dipropyl-p-phenylenediamine, 4-amino-3-methyl (N,N-diethyl)-aniline, N,N-bis-(p-hydroxyethyl)-p-phenylenediamine, 4-N,N bis-(p-hydroxyethyl)-amino-2-methylaniline, 4-N,N-bis-(P-hydroxyethyl) 30 amino-2-chloroaniline, 2-(p-hydroxyethyl)-p-phenylenediamine, 2-(a, P- WO 2004/031164 11 PCT/EP2003/010371 dihydroxyethyl)-p-phenylenediamine, 2-fluoro-p-phenylenediamine, 2 isopropyl-p-phenylenediamine, N-(p-hydroxypropyl)-p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N,N-dimethyl-3-methyl-p-phenylene diamine, N,N-(ethyl-p-hydroxyethyl)-p-phenylenediamine, N-(p,y-dihydroxy 5 propyl)-p-phenylenediamine, N-(4'-aminophenyl)-p-phenylenediamine, N phenyl-p-phenylenediamine, 2-(p-hydroxyethyloxy)-p-phenylenediamine, 2 (p-acetylaminoethyloxy)-p-phenylenediamine, N-(P-methoxyethyl)-p phenylenediamine and 5,8-diaminobenzo-1,4-dioxane and physiologically compatible salts thereof. 10 According to the invention, particularly preferred p phenylenediamine derivatives of formula (El) are p-phenylenediamine, p toluylenediamine, 2-(p-hydroxyethyl)-p-phenylenediamine, 2-(a,p dihydroxyethyl)-p-phenylenediamine and N, N-bis-(p-hyd roxyethyl)-p phenylenediamine. 15 In another preferred embodiment of the invention, compounds containing at least two aromatic nuclei substituted by amino and/or hydroxyl groups are used as primary intermediates. The binuclear primary intermediates which may be used in the coloring compositions according to the invention include in particular 20 compounds corresponding to formula (E2) and physiologically compatible salts thereof: ZI Z 2 G7 G 8 G5 Y G6 (E2) 910' 11 G12 NGG5 NGG 25 in which WO 2004/031164 12 PCT/EP2003/010371 - Z' and Z 2 independently of one another stand for a hydroxyl or NH 2 group which is optionally substituted by a C14 alkyl group, by a C 14 hydroxyalkyl group and/or by a bridging group Y or which is optionally part of a bridging ring system, 5 - the bridging group Y is a C1.14 alkylene group such as, for example, a linear or branched alkylene chain or an alkylene ring which may be interrupted or terminated by one or more nitrogen-containing groups and/or one or more hetero atoms, such as oxygen, sulfur or nitrogen atoms, and may optionally be substituted by one or more hydroxyl or 10 C 1 -s alkoxy groups or a direct bond, - G and G6 independently of one another stand for a hydrogen or halogen atom, a C 1 4 alkyl group, a C 1 4 monohydroxyalkyl group, a

C

24 polyhydroxyalkyl group, a C14 aminoalkyl group or a direct bond to the bridging group Y, 15 - G , Ga, G9, G10,G11 and G12 independently of one another stand for a hydrogen atom, a direct bond to the bridging group Y or a C14 alkyl group, with the provisos that - the compounds of formula (E2) contain only one bridging group Y 20 per molecule and - the compounds of formula (E2) contain at least one amino group bearing at least one hydrogen atom. According to the invention, the substituents used in formula (E2) are as defined in the foregoing. 25 Preferred binuclear primary intermediates corresponding to formula (E2) are, in particular, N,N'-bis-(p-hydroxyethyl)-N,N'-bis-(4'-aminophenyl) 1,3-diaminopropan-2-ol, N,N'-bis-(p-hydroxyethyl)-N,N'-bis-(4'-amino phenyl)-ethylenediamine, N,N'-bis-(4-aminophenyl)-tetramethylenediamine, N,N'-bis-(p-hydroxyethyl)-N,N'-bis-(4-aminophenyl)-tetramethylenediamine, 30 N,N'-bis-(4-methylaminophenyl)-tetramethylenediamine, N,N'-diethyl-N,N'- WO 2004/031164 13 PCT/EP2003/010371 bis-(4'-amino-3'-methylphenyl)-ethylenediamine, bis-(2-hydroxy-5-amino phenyl)-methane, 1,3-bis-(2,5-diaminophenoxy)-propan-2-ol, N,N'-bis-(4' aminophenyl)-1,4-diazacycloheptane, N,N'-bis-(2-hydroxy-5-aminobenzyl) piperazine, N-(4'-aminophenyl)-p-phenylenediamine and 1,10-bis-(2',5' 5 diaminophenyl)-1,4,7,10-tetraoxadecane and physiologically compatible salts thereof. Most particularly preferred binuclear primary intermediates of formula (E2) are N,N'-bis-(p-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1,3 diaminopropan-2-ol, bis-(2-hydroxy-5-aminophenyl)-methane, 1,3-bis-(2,5 10 diaminophenoxy)-propan-2-ol, N,N'-bis-(4'-aminophenyl)-1,4-diazacyclo heptane and 1,10-bis-(2',5'-diaminophenyl)-1,4,7,10-tetraoxadecane or a physiologically compatible salt thereof. In another preferred embodiment of the invention, a p-aminophenol derivative or a physiologically compatible salt thereof is used as the primary 15 intermediate. Particularly preferred p-aminophenol derivatives correspond to formula (E3): OH G 16 G13 (E3) G 14 NHG1 5 in which 20 - G 13 stands for a hydrogen atom, a halogen atom, a C14 alkyl group, a C1.4 monohydroxyalkyl group, a C2-4 polyhydroxyalkyl group, a (C1. 4)-alkoxy-(C 1 4)-alkyl group, a C 1 4 aminoalkyl group, a hydroxy-(C 1 . 4 )-alkylamino group, a C1.4 hydroxyalkoxy group, a C14 hydroxyalkyl

(C

1 4)-aminoalkyl group or a (di-C 1

.

4 -alkylamino)-(C 1 4)-alky group, 25 - G 14 stands for a hydrogen atom or a halogen atom, a C14 alkyl group, a C14 monohydroxyalkyl group, a C 2 4 polyhydroxyalkyl WO 2004/031164 14 PCT/EP2003/010371 group, a (C 1 4)-alkoxy-(C 1 4)-alkyl group, a C1- aminoalkyl group or a

C

1 4 cyanoalkyl group, - G 15 stands for hydrogen, a C14 alkyl group, a C14 monohydroxyalkyl group, a C 2 4 polyhydroxyalkyl group, a phenyl group or a benzyl 5 group and - G 16 stands for hydrogen or a halogen atom. According to the invention, the substituents used in formula (E3) are defined as in the foregoing. 10 Preferred p-aminophenols corresponding to formula (E3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3 methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethylamino-4 aminophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-(p hydroxyethoxy)-phenol, 4-amino-2-methylphenol, 4-amino-2 15 hyd roxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2 aminomethylphenol, 4-amino-2-(p-hydroxyethylaminomethyl)-phenol, 4 amino-2-(a,p-dihydroxyethyl)-phenol, 4-amino-2-fluorophenol, 4-amino-2 chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2-(diethylaminomethyl) phenol and physiologically compatible salts thereof. 20 Most particularly preferred compounds corresponding to formula (E3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2 aminomethylphenol, 4-amino-2-(a,p-dihydroxyethyl)-phenol and 4-amino-2 (diethylaminomethyl)-phenol. In addition, the primary intermediate may be selected from o 25 aminophenol and its derivatives such as, for example, 2-amino-4 methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol. The primary intermediate may also be selected from heterocyclic primary intermediates such as, for example, pyridine, pyrimidine, pyrazole, pyrazole-pyrimidine derivatives and physiologically compatible salts 30 thereof.

WO 2004/031164 15 PCT/EP2003/010371 Preferred pyridine derivatives are, in particular, the compounds described in GB 1,026,978 and GB 1,153,196, such as 2,5-diaminopridine, 2-(4'-methoxyphenyl)-amino-3-aminopyridine, 2,3-diamino-6-methoxy pyridine, 2-(p-methoxyethyl)-amino-3-amino-6-methoxypyridine and 3,4 5 diaminopyridine. Preferred pyrimidine derivatives are, in particular, the compounds described in DE 2359399, JP 02019576 A2 and WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2 hydroxy-4,5,6-triaminopyrimidine, 2-dimethylamino-4,5,6-triamino 10 pyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triaminopyridine. Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3843892 and DE 4133957 and in patent applications WO 94/08969, WO 94/08970, EP 740931 and DE 19543988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(p-hydroxyethyl) 15 pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4'-chlorobenzyl)-pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1 -methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5 hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methyl pyrazole, 4,5-diamino-3 tert. butyl-1 -methylpyrazole, 4,5-diamino-1-tert.butyl-3-methylpyrazole, 4,5 20 diamino-1 -(P-hyd roxyethyl)-3-methyl pyrazole, 4,5-diamino-1 -ethyl-3 methylpyrazole, 4,5-diamino-1-ethyl-3-(4'-methoxyphenyl)-pyrazole, 4,5 diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1 methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5 diamino-3-methyl-1 -isopropylpyrazole, 4-amino-5-(p-aminoethyl)-amino 25 1,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1 -methyl-3,4,5 triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5 diamino-4-(p-hydroxyethyl)-amino-1 -methylpyrazole. Preferred pyrazole-pyrimidine derivatives are, in particular, the derivatives of pyrazole-[1,5-a]-pyrimidine corresponding to formula (E4) 30 below and tautomeric forms thereof where a tautomeric equilibrium exists: WO 2004/031164 16 PCT/EP2003/010371 (X)-- N 3 -- [NG 7

G

18 ]p 62 (E4) (HO)n-- 7 - -[NG" 9

G

20 ]q 5 in which - G 17 , G", G 19 and G 20 independently of one another stand for a hydrogen atom, a C14 alkyl group, an aryl group, a C 1 .4 hydroxyalkyl group, a C 2 -4 polyhydroxyalkyl group, a (C 1 .4)-alkoxy-(C1.4)-alkyl group, a C 1 .4 aminoalkyl group which may optionally be protected by 10 an acetylureide or sulfonyl group, a (C 14 )-alkylamino-(C 1 4)-alkyl group, a di[(C 1 .4)-alkyl]-(C14)-aminoalky group, the dialkyl groups optionally forming a carbon cycle or a heterocycle with 5 or 6 links, a C1.4 hydroxyalkyl or a di-(C 14 )-[hydroxyalkyl]-(C 1

_

4 )-aminoalky group; 15 - the X's independently of one another stand for a hydrogen atom, a

C

1 4 alkyl group, an aryl group, a C14 hydroxyalkyl group, a C2-4 polyhydroxyalkyl group, a C14 aminoalkyl group, a (C 1 .4)-alkylamino

(C

1 .4)-alkyl group, a di[(C 14 )-alkyl]-(C 1 4)-aminoalky group, the dialkyl groups optionally forming a carbon cycle or a heterocycle with 20 5 or 6 links, a C 1 4 hydroxyalkyl or a di-(C 1 .4)-[hydroxyalkyl]-(C 1

_

4

)

aminoalkyl group, an amino group, a C1.4 alkyl or a di-(C 1

.

4 hydroxyalkyl)-amino group, a halogen atom, a carboxylic acid group or a sulfonic acid group, - i has the value 0, 1, 2 or 3, 25 - p has the value 0 or 1, - q has the value 0 or 1 and - n has the value 0 or 1, with the proviso that WO 2004/031164 17 PCT/EP2003/010371 - the sum of p + q is not 0, - where p + q = 2, n has the value 0 and the groups NG 17

G

18 and

NG

1 9

G

2 0 occupy the (2,3); (5,6); (6,7); (3,5) or (3,7) positions; - where p + q = 1, n has the value 1 and the groups NG 17 G" (or 5 NG 1 9

G

2 0 ) and the group OH occupy the (2,3); (5,6); (6,7); (3,5) or (3,7) positions. According to the invention, the substituents used in formula (E4) are as defined in the foregoing. 10 If the pyrazole-[1,5-a]-pyrimidine corresponding to formula (E4) above contains a hydroxy group in one of the positions 2, 5 or 7 of the ring system, a tautomeric equilibrium exists as illustrated, for example, in the following scheme: 15 NG17 G18 H NG17 G18 NG G NGG8 N N N. NN N-~N OH 0 Among the pyrazole-[1,5-a]-pyrimidines corresponding to formula 20 (E4) above, the following may be particularly mentioned: - pyrazole-[1,5-a]-pyrimidine-3,7-diamine; - 2,5-dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine; - pyrazole-[1,5-a]-pyrimidine-3,5-diamine; - 2,7-dimethylpyrazole-[1,5-a]-pyrimidine-3,5-diamine; 25 - 3-aminopyrazole-[1,5-a]-pyrimidin-7-ol; - 3-aminopyrazole-[1,5-a]-pyrimidin-5-ol; - 2-(3-aminopyrazole-[1,5-a]-pyrimidin-7-ylamino)-ethanol; WO 2004/031164 18 PCT/EP2003/010371 - 2-(7-aminopyrazole-[1,5-a]-pyrimidin-3-ylamino)-ethanol; - 2-[(3-aminopyrazole-[1,5-a]-pyrimidin-7-yl)-(2-hydroxyethyl)-amino] ethanol; - 2-[(7-aminopyrazole-[1,5-a]-pyrimidin-3-yl)-(2-hydroxyethyl)-amino] 5 ethanol; - 5,6-dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine; - 2,6-dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine; - 3-amino-7-dimethylamino-2,5-dimethylpyrazole-[1,5-a]-pyrimidine; and physiologically compatible salts thereof and tautomeric forms thereof 10 where a tautomeric equilibrium exists. The pyrazole-[1,5-a]-pyrimidines corresponding to formula (E4) above may be prepared by cyclization from an aminopyrazole or from hydrazine, as described in the literature. In another preferred embodiment, the colorants according to the 15 invention contain at least one other secondary intermediate. m Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives are generally used as secondary intermediates. Particularly suitable secondary intermediates are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2 20 methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m phenylenediamine, 1 -phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3 aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2-chlororesorcinol, 4 chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-amino-3 hydroxypyridine, 2-methyl resorcinol, 5-methyl resorcinol and 2-methyl-4 25 chloro-5-aminophenol. According to the invention, preferred secondary intermediates are - m-aminophenol and derivatives thereof, such as for example 5-amino-2 methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6 30 methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3- WO 2004/031164 19 PCT/EP2003/010371 aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino 4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methyl phenol, 5-(2' hyd roxyethyl)-amino-2-methylphenol, 3-(diethylamino)-phenol, N cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)-benzene, 3 5 ethylamino-4-methylphenol und 2,4-dichloro-3-aminophenol, - o-aminophenol and derivatives thereof, - m-diaminobenzene and derivatives thereof, such as for example 2,4 diaminophenoxyethanol, 1,3-bis-(2',4'-diaminophenoxy)-propane, 1 methoxy-2-amino-4-(2'-hydroxyethylamino)benzene, 1,3-bis-(2',4' 10 diaminophenyl)-propane, 2,6-bis-(2'-hydroxyethylamino)-1 -methyl benzene and 1-amino-3-bis-(2'-hydroxyethyl)-aminobenzene, - o-diaminobenzene and derivatives thereof. such as for example 3,4 diaminobenzoic acid and 2,3-diamino-1-methylbenzene, - di- or trihydroxybenzene derivatives, such as for example resorcinol, 15 resorcinol monomethylether, .2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, - pyridine derivatives, such as for example 2,6-dihydroxypyridine, 2 amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino 20 2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6 methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine, - naphthalene derivatives, such as for example 1-naphthol, 2-methyl-1 naphthol, 2-hydroxymethyl-1 -naphthol, 2-hydroxyethyl-1 -naphthol, 1,5 25 dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxy naphthalene, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene, - morpholine derivatives, such as for example 6-hydroxybenzomorpholine and 6-aminobenzomorpholine, 30 - quinoxaline derivatives, such as for example 6-methyl-1,2,3,4- WO2004/031164 20 PCT/EP2003/010371 tetrahydroquinoxaline, - pyrazole derivatives, such as 1-phenyl-3-methylpyrazol-5-one for example, - indole derivatives, such as for example 4-hydroxyindole, 6 5 hydroxyindole and 7-hydroxyindole, - pyrimidine derivatives, such as for example 4,6-diaminopyrimidine, 4 amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6 trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy-6 methylpyrimidine and 4,6-dihydroxy-2-methylpyrimidine, or 10 - methylenedioxybenzene derivatives, such as for example 1-hydroxy 3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1-(2'-hydroxyethyl)-amino-3,4-methylenedioxybenzene. According to the invention, particularly preferred secondary 15 intermediates are 1-naphthol, 1,5-, 2,7- und 1,7-dihydroxynaphthalene, 3 aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy 3,4-dimethylpyridin. 20 According to the invention, the following secondary inter mediate/primary intermediate combinations have proved to be particularly suitable: - 3-pyrrolidin-1-yl aniline / p-toluylenediamine, 25 - 3-pyrrolidin-1-yl aniline / 2,4,5,6-tetraaminopyrimidine, - 2-[(3-pyrrolidin-1-yl phenyl)-amino]-ethan-1-ol / p-toluylenediamine, - 2-[(3-pyrrolidin-1-yl phenyl)-amino]-ethan-1-ol / 1-(2-hydroxyethyl) 4,5-diaminopyrazole, - 2-[(3-morpholin-4-yl phenyl)-amino]-ethan-1-ol I p-toluylenediamine, 30 - 2-[(3-morpholin-4-yl phenyl)-amino]-ethan-1-ol / 1-(2-hydroxyethyl)- WO 2004/031164 21 PCT/EP2003/010371 2,5-diaminobenzene, - 2-[(3-morpholin-4-yl phenyl)-amino]-ethan-1-ol / 4-hydroxy-2,5,6 triaminopyrimidine, - 2-[(3-morpholin-4-yl phenyl)-amino]-ethan-1-ol / 1-(2-hydroxyethyl) 5 4,5-diaminopyrazole and - 2-[(3-morpholin-4-yl phenyl)-amino]-ethan-1-ol / 2,4,5,6-tetraamino pyrimidine. In another embodiment of the present invention, the colorants may 10 contain at least one precursor of a "nature-analogous" dye. Preferred precursors of "nature-analogous" dyes are indoles and indolines which contain at least one hydroxy or amino group, preferably as a substituent on the six ring. These groups may carry further substituents, for example in the form of an etherification or esterification of the hydroxy group or an 15 alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and/or indoline derivative. Particularly suitable precursors of "nature-analogous" hair dyes are derivatives of 5,6-dihydroxyindoline corresponding to formula (Ila): 20 4 3 R2 R-O N R (Ila) 25 Ri in which - independently of one another - R 1 is hydrogen, a C1.4 alkyl group, a C 1

-

4 hydroxyalkyl group or a C 2 -4 polyhydroxyalkyl group, 30 - R 2 is hydrogen or a -COOH group, the -COOH group optionally being present as a salt with a physiologically compatible cation, - R 3 is hydrogen or a C1.4 alkyl group, WO 2004/031164 22 PCT/EP2003/010371 - R 4 is hydrogen, a C 1 4 alkyl group or a group -CO-R , where R 6 is a C14 alkyl group, and - R 5 is one of the groups mentioned for R 4 , and physiologically compatible salts of these compounds with an organic or 5 inorganic acid. Particularly preferred derivatives of indoline are 5,6-dihydroxy indoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxy indoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4 10 aminoindoline. Within this group, particular emphasis is placed on N-methyl-5,6 dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxy indoline, N-butyl-5,6-dihydroxyindoline and, in particular, 5,6-dihydroxy indoline. 15 Other particularly suitable precursors of "nature-analogous" hair dyes are derivatives of 5,6-dihydroxyindole corresponding to formula (llb): R4-3 20 s O R R-O N R2 (Ib) in which - independently of one another 25 R' is hydrogen, a C14 alkyl group or a C 14 hydroxyalkyl group,

R

2 is hydrogen or a -COOH group, the -COOH group optionally being present as a salt with a physiologically compatible cation,

R

3 is hydrogen or a C 1

.

4 alkyl group,

R

4 is hydrogen, a C14 alkyl group or a group -CO-R , where R 6 is a C 14 30 alkyl group, and

R

5 is one of the groups mentioned for R 4

,

WO 2004/031164 23 PCT/EP2003/010371 and physiologically compatible salts of these compounds with an organic or inorganic acid. Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6 5 dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2 carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Within this group, particular emphasis is placed on N-methyl-5,6 dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole and, in particular, 5,6-dihydroxyindole. 10 The indoline and indole derivatives may be used both as free bases and in the form of their physiologically compatible salts with inorganic or organic acids, for example hydrochlorides, sulfates and hydrobromides, in the colorants used in the process according to the invention. The indole or indoline derivatives are present in these colorants in quantities of normally 15 0.05 to 10% by weight and preferably 0.2 to 5% by weight. In another preferred embodiment of the invention, the indoline or indole derivative may be used in combination with at least one amino acid or an oligopeptide in hair colorants. The amino acid is advantageously an a-amino acid. Most particularly preferred a-amino acids are arginine, 20 ornithine, lysine, serine and histidine, especially arginine. In another preferred embodiment of the present invention, the colorants according to the invention contain one or more substantive dyes besides the m-phenylenediamine derivatives (1) according to the invention for the purpose of shading. Substantive dyes are typically nitro 25 phenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are the compounds known under the International names or commercial names of HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, Acid 30 Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid WO 2004/031164 24 PCT/EP2003/010371 Red 33, Acid Red 52, HC Red BN, Pigment Red 57:1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1 and Acid Black 52 and also 1,4-diamino-2-nitrobenzene, 2-amino-4 5 nitrophenol, 1,4-bis-(p-hydroxyethyl)-amino-2-nitrobenzene, 3-nitro-4-(p hydroxyethyl)-aminophenol, 2-(2'-hydroxyethyl)-amino-4,6-dinitrophenol, 1 (2'-hydroxyethyl)-amino-4-methyl-2-nitrobenzene, 1 -amino-4-(2' hydroxyethyl)-amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1-(2' ureidoethyl)-amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2' 10 carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4 naphthoquinone, picramic acid and salts thereof, 2-amino-6-chloro-4 nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1 hydroxy-4-nitrobenzene. In addition, the preparations according to the invention may contain 15 a cationic substantive dye. Particularly preferred are (a) cationic triphenylmethane dyes such as, for example, Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14, (b) aromatic systems substituted by a quaternary nitrogen group such as, for example, Basic Yellow 57, Basic Red 76, Basic Blue 99, 20 Basic Brown 16 and Basic Brown 17 and (c) substantive dyes containing a heterocycle with at least one quaternary nitrogen atom as disclosed, for example, in EP-A2 998 908, to which reference is specifically made at this juncture, in claims 6 to 11. 25 Preferred cationic substantive dyes of group (c) are, in particular, the following compounds: WO 2004/031164 25 PCT/EP2003/010371 H

CH

3 -~ N H N(DZ1)

CH

3 SO4 H

CH

3 N +N (DZ2)

H

3 C'

OCH

3 .cf

CH

3 H I/ N N N N N H (DZ3)

CH

3

CH

3 H N N N N

CH

3 (DZ4)

CH

3 Cf

CH

3

CH

3 [N N

CH

3 (DZ5)

CH

3 Cf WO 2004/031164 26 PCT/EP2003/010371

CH

3 H N-- (DZ6)

CH

3 Cf

NH

2

H

3 CN ' (DZ7) N 0N2'

CH

3 Cf

H

3 C N CH3 H3CsN a ONH2 + (DZ8)

CH

3 Cf

H

3 C Cf NCH 3

H

3 C\ , (DZ9) N The compounds corresponding to formula (DZ1), (DZ3) and (DZ5), which are also known by the names of Basic Yellow 87, Basic Orange 31 and Basic Red 51, are most particularly preferred cationic substantive dyes of group (c). According to the invention, the cationic substantive dyes marketed under the name of Arianor@ are also particularly preferred cationic substantive dyes.

WO 2004/031164 27 PCT/EP2003/010371 The preparations according to the invention of this embodiment contain the substantive dyes in a quantity of preferably 0.01 to 20% by weight, based on the colorant as a whole. The preparations according to the invention may also contain 5 naturally occurring dyes such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, black alder bark, sage, logwood, madder root, catechu, sedre and alkanet. The oxidation dye precursors or the substantive dyes do not have to be single compounds. On the contrary, other components may be present 10 in small quantities in the hair colorants according to the invention due to the processes used to produce the individual dyes providing these other components do not adversely affect the coloring result or have to be ruled out for other reasons, for example toxicological reasons. Another way of coloring keratin-containing fibers is to use colorants 15 which, besides the m-phenylenediamine derivatives of formula (1) according to the invention, contain reactive carbonyl compounds, i.e. compounds containing at least one reactive carbonyl group, and/or CH-acid compounds. In general, the compounds mentioned are not themselves dyes and, accordingly, are not suitable on their own for coloring keratin 20 containing fibers. In combination, they form dyes in a non-oxidative process. This process - also known as oxo coloring - is described for example in WO-A1-99/18916, WO-A1-00/38638, WO-A1-01/34106 and WO-A1 -01/47483. Reactive carbonyl compounds according to the invention contain at 25 least one carbonyl group as reactive group which reacts to form a covalent bond. According to the invention, other suitable reactive carbonyl compounds are compounds in which the reactive carbonyl group is derivatized in such a way that the carbon atom of the derivatized carbonyl group always retains its reactivity to the secondary intermediates according 30 to the invention and/or the CH-acid compounds. These derivatives are WO 2004/031164 28 PCT/EP2003/010371 preferably addition compounds of a) amines and derivatives thereof to form imines or oximes as addition compounds, 5 b) alcohols to form acetals or ketals as addition compounds onto the carbon atom of the carbonyl group of the reactive carbonyl compound and c) water to form hydrates. 10 The reactive carbonyl compound is preferably selected from compounds corresponding to formula (01): R3 R-- AR-Z-Y-R (01) 15 in which " AR stands for benzene, naphthalene, pyridine, pyrimidine, pyrazine, pyridazine, carbazole, pyrrole, pyrazole, furan, thiophene, 1,2,3-triazine, 1,3,5-triazine, quinoline, isoquinoline, indole, indoline, indolizine, indane, imidazole, 1,2,4-triazole, 1,2,3-triazole, tetrazole, 20 benzimidazole, 1,3-thiazole, benzothiazole, indazole, benzoxazole, quinoxaline, quinazoline, quinolizine, cinnoline, acridine, julolidine, acenaphthene, fluorene, biphenyl, diphenylmethane, benzophenone, diphenylether, azobenzene, chromone, coumarin, diphenylamine, stilbene; the N-heteroaromatic compounds may also be quaternized, 25 * R 1 is a hydrogen atom, a C-C 6 alkyl group, C 2

-C

6 acyl group, C 2

-C

4 alkenyl group, C-C 4 perfluoroalkyl group, an optionally substituted aryl or heteroaryl group, e R 2 , R 3 and R 4 independently of one another represent a hydrogen WO 2004/031164 29 PCT/EP2003/010371 atom, a halogen atom, a C1-C6 alkyl group, C1-C6 alkoxy group, C1-C6 aminoalkyl group, C1-C6 hydroxyalkyl group, a C 1

-C

6 -alkoxy-C 1

-C

6 alkyloxy group, a C2-C6 acyl group, an acetyl, carboxyl, carboxylato, carbamoyl, sulfo, sulfato, sulfonamide, sulfonamido, C2-C6 alkenyl 5 group, an aryl group, an aryl-C 1

-C

6 -alkyl group, a hydroxy group, a nitro group, a pyrrolidino group, a morpholino group, a piperidino group, an amino group or ammonio group or a 1-imidazol(in)io group; the last three groups may be substituted by one or more C1-C6 alkyl, C1-C6 carboxyalkyl, C1-C6 hydroxyalkyl, C2-C6 alkenyl, C1-C 6 -alkoxy-C 1 -C6 10 alkyl groups, by optionally substituted benzyl groups, by sulfo-(C 1

-C

4

)

alkyl or heterocycle-(C 1

-C

4 )-alkyl groups; two of the substituents R 2 , R 3 , R 4 and Z-Y-R 1 , together with the rest of the molecule, may form a fused, optionally substituted 5-, 6- or 7 membered ring, which may also carry a fused aromatic ring, in which 15 case the system AR - depending on the size of the ring - may carry other substituents which, independently of one another, may stand for the same groups as R 2 , R 3 and R 4 , * Z is a direct bond, a carbonyl group, a carboxy-(C1-C 4 )-alkylene group, an optionally substituted C2-C6 alkenylene group, a C4-C6 20 alkadienylene group, a furylene group, a thienylene group, an arylene group, a vinylenearylene group, a vinylenefurylene group, a vinylenethienylene group; Z together with the -Y-R 1 group may also form an optionally substituted 5-, 6- or 7-membered ring, " Y is a group selected from carbonyl, a group corresponding to formula 25 (02) or a group corresponding to formula (03): -R6 C=N-R5 OsR7 (02) R (VI) where * R 5 is a hydrogen atom, a hydroxy group, a C1.4 alkoxy group, a C1.6 WO 2004/031164 30 PCT/EP2003/010371 alkyl group, a C 1

.

6 hydroxyalkyl group, a C2-6 polyhydroxyalkyl group, a

C

1

.

6 -alkoxy-C 1

.

6 -alkyl group, * R 6 and R 7 independently of one another represent a C 1

.

6 alkyl group, an aryl group or, together with the structural element 0-C-0 of formula 5 (01), form a 5- or 6-membered ring. In a particularly preferred embodiment, the reactive carbonyl compound is selected from the group consisting of acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hy 10 droxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3-hydroxy utyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5 dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxy acetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-trihydroxyaceto 15 phenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethylketal, 4-hHydroxy-3-methoxy acetophenone, 3,5-dimethoxy-4-hydroxyacetophenone, 4 aminoacetophenone, 4-dimethylaminoacetophenone, 4 morpholinoacetophenone, 4-piperidinoacetophenone, 4 20 imidazolinoacetophenone, 2-hydroxy-5-bromoacetophenone, 4-hydroxy-3 nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4 carboxylic acid, benzophenone, 4-hydroxybenzophenone, 2 aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxy benzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzo 25 phenone, 2-hydroxy-1 -acetonaphthone, 1 -hydroxy-2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3-hydroxyflavone, 3,5,7 trihydroxyflavone, 4',5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1,8 dihydroxyanthrone, vanillin, coniferylaldehyde, 2-methoxybenzaldehyde, 3 30 methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, WO 2004/031164 31 PCT/EP2003/010371 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxy benzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde, 4-hydroxy-2,6 dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3 methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2,5 5 dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy 3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5 diethoxy-4-hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3 hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2 ethoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 4 10 ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3 dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde, 2,5 dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4 dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4 trimethoxybenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3,6 15 trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5 trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2 hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5 dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4 20 dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4 trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3,6 trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5 trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydroxy-2 methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4 25 diethylaminobenzaldehyde, 4-dimethylamino-2-hydroxybenzaldehyde, 4 diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, 4 morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenz aldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2 hydroxy-1 -naphthaldehyde, 2,4-dihydroxy-1-napthaldehyde, 4-hydroxy-3 30 methoxy-1-naphthaldehyde, 2-hydroxy-4-methoxy-1-naphthaldehyde, 3- WO 2004/031164 32 PCT/EP2003/010371 hydroxy-4-methoxy-1 -naphthaldehyde, 2,4-dimethoxy-1 -naphthaldehyde, 3,4-dimethoxy-1 -naphthaldehyde, 4-hydroxy-1 -naphthaldehyde, 4 dimethylamino-1-naphthaldehyde, 4-dimethylaminocinnamaldehyde, 2 dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4 5 dimethylamino-2-methylbenzaldehyde, 4-diethylaminocinnamaldehyde, 4 dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4 dimethylamino-2-methoxybenzaldehyde, 4-(1 -imidazolyl)-benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8-hydroxy-1 H,5H-benzo[ij]quinolizine-9-carboxaldehyde, 10 N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribase aldehyde), 2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3 aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2-(1',3',3'-trimethyl-2-in dolinylidene)-acetaldehyde, 1 -methylpyrrole-2-aldehyde, 1 -methyl-2 15 acetylpyrrole, 4-pyridinealdehyde, 2-pyridinealdehyde, 3-pyridinealdehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3 aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofur fural, 2-thienoyltrifluoroacetonr, chromone-3-aldehyde, 3-(5'-nitro-2'-furyl) acrolein, 3-(2'-furyl)-acrolein and imidazol-2-aldehyde, 1,3-diacetylbenzene, 20 1,4-diacetylbenzene, 1,3,5-triacetylbenzene, 2-benzoylacetophenone, 2 (4'-methoxybenzoyl)-acetophenone, 2-(2'-furoyl)-acetophenone, 2-(2' pyridoyl)-acetophenone and 2-(3'-pyridoyl)-acetophenone, benzyli deneacetone, 4-hydroxybenzylideneacetone, 2 hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3 25 methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4 methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4 piperid!inobenzylideneacetone, 4-morpholinobenzylideneacetone, 4 diethylaminobenzylideneacetone, 3-benzylidene-2,4-pentanedione, 3-(4' hyd roxybenzylidene)-2,4-pentanedione, 3-(4'-dimethylaminobenzylidene) 30 2,4-pentanedione, 2-benzylidenecyclohexanone, 2-(4'-hydroxy- WO 2004/031164 33 PCT/EP2003/010371 benzylidene)-cyclohexanone, 2-(4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1,3-cyclohexanedione, 2-(4' hydroxybenzylidene)-1,3-cyclohexanedione, 3-(4'-di methylaminobenzylidene)-1,3-cyclohexanedione, 2-benzylidene-5,5 5 dimethyl-1,3-cyclohexanedione, 2-(4'-hydroxybenzylidene)-5,5-d imethyl 1,3-cyclohexanedione, 2-(4'-hydroxy-3-methoxybenzylidene)-5,5-dimethyl 1,3-cyclohexanedione, 2-(4'-dimethylaminobenzylidene)-5,5-dimethyl-1,3 cyclohexanedione, 2-benzylidenecyclopentanone, 2'-(4-hy droxybenzylidene)-cyclopentanone, 2-(4'-dimethylaminobenzylidene) 10 cyclopentanone, 5-(4-dimethylaminophenyl)penta-2,4-dienal, 5-(4 diethylaminophenyl)-penta-2,4-dienal, 5-(4-methoxyphenyl)-penta-2,4 dienal, 5-(3,4-dimethoxyphenyl)-penta-2,4-dienal, 5-(2,4-dimethoxyphenyl) penta-2,4-dienal, 5-(4-piperidinophenyl)-penta-2,4-dienal, 5-(4 morpholinophenyl)-penta-2,4-dienal, 5-(4-pyrrolidinophenyl)-penta-2,4 15 dienal, 6-(4-d imethylaminophenyl)-hexa-3,5-dien-2-one, 6-(4 diethylaminophenyl)-hexa-3,5-dien-2-one, 6-(4-methoxyphenyl)-hexa-3,5 dien-2-one, 6-(3,4-dimethoxyphenyl)-hexa-3,5-dien-2-one, 6-(2,4-dimeth oxyphenyl)-hexa-3,5-dien-2-one, 6-(4-piperidinophenyl)-hexa-3,5-dien-2 one, 6-(4-morpholinophenyl)-hexa-3,5-dien-2-one, 6-(4-pyrrolidinophenyl) 20 hexa-3,5-dien-2-one, 5-(4-dimethylamino-1-naphthyl)-penta-3,5-dienal, 2 nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3 nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3 nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5 nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3 25 nitrobenzaldehyde, 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3 nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2 nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5 dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5 30 nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde, 3- WO2004/031164 34 PCT/EP2003/010371 nitro-4-formylbenzenesulfonic acid, 4-nitro-1 -naphthaldehyde, 2 nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9 methyl-3-carbazolealdehyde, 9-ethyl-3-carbazolealdehyde, 3-acetyl carbazole, 3,6-diacetyl-9-ethylcarbazole, 3-acetyl-9-methylcarbazole, 1,4 5 dimethyl-3-carbazolealdehyde, 1,4,9-trimethyl-3-carbazolealdehyde, 4 formyl-1 -methylpyridinium-, 2-formyl-1 -methylpyridinium-, 4-formyl-1 ethylpyridinium-, 2-formyl-1 -ethylpyridiniu m-, 4-formyl-1-benzylpyridinium-, 2-formyl-1-benzylpyridinium-, 4-formyl-1,2-dimethylpyridinium-, 4-formyl 1,3-dimethylpyridinium-, 4-formyl-1 -methylquinolinium-, 2-formyl-1 10 methylquinolinium-, 4-acetyl-1 -methylpyridinium-, 2-acetyl-1-methyl pyridinium-, 4-acetyl-1-methylquinolinium-, 5-formyl-1-methylquinolinium-, 6-formyl-1-methylquinolinium-, 7-formyl-1-methylquinolinium-, 8-formyl-1 methylquinolinium, 5-formyl-1 -ethylquinolinium-, 6-formyl-1 ethylquinolinium-, 7-formyl-1-ethylquinolinium-, 8-formyl-1-ethylquinolinium, 15 5-formyl-1-benzylquinolinium-, 6-formyl-1-benzylquinolinium-, 7-formyl-1 benzylquinolinium-, 8-formyl-1-benzylquinolinium, 5-formyl-1-allylquino linium-, 6-formyl-1-allylquinolinium-, 7-formyl-1-allylquinolinium- and 8 formyl-1 -allylquinolinium-, 5-acetyl-1 -methylquinolinium-, 6-acetyl-1 methylquinolinium-, 7-acetyl-1 -methylquinolinium-, 8-acetyl-1 20 methylquinolinium, 5-acetyl-1 -ethylquinolinium-, 6-acetyl-1 ethylquinolinium-, 7-acetyl-1-ethylquinolinium-, 8-acetyl-1-ethylquinolinium, 5-acetyl-1-benzylquinolinium-, 6-acetyl-1-benzylquinolinium-, 7-acetyl-1 benzylquinolinium-, 8-acetyl-1-benzylquinolinium, 5-acetyl-1 allylquinolinium-, 6-acetyl-1-allylquinolinium-, 7-acetyl-1-allylquinolinium 25 and 8-acetyl-1-allylquinolinium, 9-formyl-10-methylacridinium-, 4-(2'-formyl vinyl)-1 -methylpyridinium-, 1,3-dimethyl-2-(4'-formylphenyl)-benzimidazo lium-, 1,3-dimethyl-2-(4'-formylphenyl)-imidazolium-, 2-(4'-formylphenyl)-3 methylbenzothiazolium-, 2-(4'-acetylphenyl)-3-methylbenzothiazolium-, 2 (4'-formyl phenyl)-3-methyl benzoxazol iu m-, 2-(5'-formyl-2'-furyl)-3-methyl 30 benzothiazolium-, 2-(5'-formyl-2'-furyl)-3-methylbenzothiazolium-, 2-(5'- WO 2004/031164 35 PCT/EP2003/010371 formyl-2'-thienyl)-3-methylbenzothiazoliu m-, 2-(3'-formylphenyl)-3-methyl benzothiazolium-, 2-(4'-formyl-1-naphthyl)-3-methylbenzothiazolium-, 5 chloro-2-(4'-formylphenyl)-3-methylbenzothiazolium-, 2-(4'-formylphenyl) 3,5-dimethylbenzothiazolium-benzenesulfonate, -p-toluenesulfonate, -me 5 thanesulfonate, -perchlorate, -sulfate, -chloride, -bromide, -iodide, -tetra chlorozincate, -methylsulfate-, trifluormethanesulfonate, -tetrafluoroborate, isatin, 1-methylisatin, 1-allylisatin, 1-hydroxymethylisatin, 5-chloroisatin, 5 methoxyisatin, 5-nitroisatin, 6-nitroisatin, 5-sulfoisatin, 5-carboxyisatin, quinisatin, 1-methylquinisatin and mixtures of the above compounds. 10 The CH-acid compounds are preferably selected from the group consisting of 1,2,3,3-tetramethyl-3H-indolium iodide, 1,2,3,3-tetramethyl 3H-indolium-p-toluenesulfonate, 1,2,3,3-tetramethyl-3H-indolium methane sulfonate, 1,3,3-trimethyl-2-methylene indoline (Fischer's base), 2,3-dime thylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium-p-toluenesulfon 15 ate, 2,3-dimethylnaphtho[1,2-d]thiazolium-p-toluenesulfonate, 3-ethyl-2 methylnaphtho[1,2-d]thiazolium-p-toluenesulfonate, rhodanine, rhodanine 3-acetic acid, 1,4-dimethylquinolinium iodide, 1,2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1,3-dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-ind 20 oxylacetate, 2-coumaranone, 5-hydroxy-2-coumaranone, 6-hydroxy-2 coumaranone, 3-methyl-1 -phenylpyrazolin-5-one, indane-1,2-dione, indane-1,3-dione, indane-1-one, benzoylacetonitrile, 3-dicyano methyleneindane-1 -one, 2-amino-4-imino-1,3-thiazoline hydrochloride, 5,5 dimethylcyclohexan-1,3-dione, 2H-1,4-benzoxazine-4H-3-one, 3-ethyl-2 25 methylbenzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1 ethyl-4-methylquinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,2,3 trimethylquinoxalinium iodide, 3-ethyl-2-methylbenzoxazolium-p-toluene sulfonate, 3-ethyl-2-methylbenzothiazolium-p-toluenesulfonate, 1-ethyl-4 methylquinolinium-p-toluenesulfonate, 1 -ethyl-2-methylquinolinium-p 30 toluenesulfonate, 1,2,3-trimethylquinoxalinium-p-toluenesulfonate, 1,2- WO 2004/031164 36 PCT/EP2003/010371 dihydro-1,3,4,6-tetramethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3 diethyl-4,6-dimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-dipropyl 4,6-dimethyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2 oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-diethyl-4,6-dimethyl-2 5 oxopyrimidiniurm hydrogen sulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl-2 oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3,4-trimethyl-2-oxo pyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-oxopyrimidinium hydro gen sulfate, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4-methyl-2-oxopyrimidinium hydrogen sulfate, 1,2 10 dihydro-1,3-dipropyl-4-methyl-2-oxopyrimidinium chloride, 1,2-dihydro-1,3 dipropyl-4-methyl-2-oxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3,4,6 tetramethyl-2-thioxopyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4,6 dimethyl-2-thioxopyrimidinium chloride, 1,2-dihydro-1,3-dipropyl-4,6 dimethyl-2-thioxopyrimidinium chloride, 1,2-dihydro-1,3,4,6-tetramethyl-2 15 thioxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3-dipropyl-4,6-dimethyl 2-thioxopyrimidinium hydrogen sulfate, 1,2-dihydro-1,3,4-trimethyl-2-thioxo pyrimidinium chloride, 1,2-dihydro-1,3,4-trimethyl-2-thioxopyrimidinium hydrogen sulfate, 1,2-d ihydro-1,3-d iethyl-4-methyl-2-thioxopyrimidinium chloride, 1,2-dihydro-1,3-diethyl-4-methyl-2-thioxopyrimidinium hydrogen 20 sulfate, 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxopyrimidinium chloride and 1,2-dihydro-1,3-dipropyl-4-methyl-2-thioxopyrimidinium hydrogen sulfate. So far as the dyes suitable for use in the hair colorants and tinting preparations according to the invention are concerned, reference is also 25 expressly made to the work by Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive dyes) and Chapter 8, pages 264-267; oxidation dye precursors), published as Volume 7 of the Series "Dermatology" (Ed.: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York/Basle, 1986, and to the "Europaische Inventar der Kosmetik 30 Rohstoffe" published by the Europsische Gemeinschaft and available in WO 2004/031164 37 PCT/EP2003/010371 disk form from the Bundesverband Deutscher Industrie- und Handelsunternehmen fOr Arzneimittel, Reformwaren und Kbrperpflegemittel d.V., Mannheim. The colorants according to the invention may also contain any of the 5 known active substances, additives and auxiliaries typical of such preparations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. In many cases, however, it has proved to be of advantage to select the surfactants from anionic, zwitterionic or nonionic 10 surfactants. Suitable anionic surfactants for the preparations according to the invention are any anionic surface-active substances suitable for use on the human body. Such substances are characterized by a water-solubilizing anionic group such as, for example, a carboxylate, sulfate, sulfonate or 15 phosphate group and a lipophilic alkyl group containing around 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide and hydroxyl groups may also be present in the molecule. The following are examples of suitable anionic surfactants - in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanol 20 ammonium salts containing 2 or 3 carbon atoms in the alkanol group: - linear fatty acids containing 10 to 22 carbon atoms (soaps), - ether carboxylic acids corresponding to the formula R-O-(CH 2

-CH

2 0)

CH

2 -COOH, in which R is a linear alkyl group containing 10 to 22 carbon atoms and x = 0 or 1 to 16, 25 - acyl sarcosides containing 10 to 18 carbon atoms in the acyl group, - acyl taurides containing 10 to 18 carbon atoms in the acyl group, - acyl isethionates containing 10 to 18 carbon atoms in the acyl group, - sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl 30 esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 WO 2004/031164 38 PCT/EP2003/010371 oxyethyl groups, - linear alkane sulfonates containing 12 to 18 carbon atoms, - linear a-olefin sulfonates containing 12 to 18 carbon atoms, - a-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon 5 atoms, - alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the formula R-O(CH 2

-CH

2 0)-SO 3 H, in which R is a preferably linear alkyl group containing 10 to 18 carbon atoms and x = 0 or I to 12, - mixtures of surface-active hydroxysulfonates according to DE-A-37 25 10 030, - sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354, - sulfonates of unsaturated fatty acids containing 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344, 15 - esters of tartaric acid and citric acid with alcohols in the form of addition products of around 2 to 15 mol ethylene oxide and/or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the 20 alkyl group and up to 12 glycol ether groups in the molecule and, in particular, salts of saturated and, more particularly, unsaturated C 8

-

22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. Nonionic surfactants contain, for example, a polyol group, a poly 25 alkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are - products of the addition of 2 to 30 mol ethylene oxide and/or 0 to 5 mol propylene oxide onto linear fatty alcohols containing 8 to 22 carbon atoms, onto fatty acids containing 12 to 22 carbon atoms and onto 30 alkylphenols containing 8 to 15 carbon atoms in the alkyl group, WO 2004/031164 39 PCT/EP2003/010371 - C 12

-

22 fatty acid monoesters and diesters of products of the addition of 1 to 30 mol ethylene oxide onto glycerol, - C 8

-

22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof and 5 - products of the addition of 5 to 60 mol ethylene oxide onto castor oil and hydrogenated castor oil. Preferred nonionic surfactants are alkyl polyglycosides corresponding to the general formula R 1 O-(Z)x. These compounds are characterized by the following parameters. 10 The alkyl group R 1 contains 6 to 22 carbon atoms and may be both linear and branched. Primary linear and 2-methyl-branched aliphatic groups are preferred. Such alkyl groups are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl and 1 myristyl are particularly preferred. Where so-called "oxo alcohols" are used 15 as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate. The alkyl polyglyosides suitable for use in accordance with the invention may, for example, contain only one particular alkyl group R 1 . However, such compounds are normally prepared from natural fats and oils 20 or mineral oils. In this case, mixtures corresponding to the starting compounds or corresponding to the particular working up of these compounds are present as the alkyl groups R 1 . Particularly preferred alkyl polyglycosides are those in which R 1 consists 25 - essentially of C8 and C10 alkyl groups, - essentially of C12 and C 14 alkyl groups, - essentially of C8 to C16 alkyl groups or - essentially of C12 to C16 alkyl groups. Any mono- or oligosaccharides may be used as the sugar unit Z. 30 Sugars containing 5 or 6 carbon atoms and the corresponding WO 2004/031164 40 PCT/EP2003/010371 oligosaccharides are normally used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar units are glucose, fructose, galactose, arabinose and sucrose; glucose is particularly 5 preferred. The alkyl polyglycosides suitable for use in accordance with the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides with x values of 1.1 to 1.6 are preferred. Alkyl oligoglycosides where x is 1.1 to 1.4 are most particularly preferred. 10 Besides acting as surfactants, the alkyl polyglycosides or alkyl oligoglycosides may also be used to improve the fixing of perfume components to the hair. Accordingly, in cases where the effect of the perfume oil on the hair is intended to last longer than the duration of the hair treatment, alkyl poly- or oligoglycosides will preferably be used as 15 another ingredient of the preparations according to the invention. Alkoxylated homologs of the alkyl polyglycosides mentioned may also be used in accordance with the invention. These homologs may contain on average up to 10 ethylene oxide and/or propylene oxide units per alkyl glycoside unit. 20 Zwitterionic surfactants may also be used, particularly as co surfactants. In the context of the invention, zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one -COO( or -SO 3 group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, 25 such as N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, cocoacylaminopropyl dimethyl ammonium glycinate and 2-alkyl 3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl 30 carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid WO 2004/031164 41 PCT/EP2003/010371 amide derivative known by the INCI name of Cocamidopropyl Betaine. Also suitable, particularly as co-surfactants, are ampholytic surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C 8

.

1 8 alkyl or acyl group, contain at least one free amino 5 group and at least one -COOH or -SO 3 H group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N-alkyl iminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl 10 aminopropionic acids and alkyl aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl aminopropionate, cocoacyl aminoethyl aminopropionate and C 12

.

1 8 acyl sarcosine. According to the invention, the cationic surfactants used are 15 particularly those of the quaternary ammonium compound, esterquat and amidoamine type. Preferred quaternary ammonium compounds are ammonium halides, more particularly chlorides and bromides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl 20 methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride and the imidazolium compounds known under the INCI names of Quaternium-27 25 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably contain 10 to 18 carbon atoms. Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as structural element. Preferred esterquats are quaternized ester salts of fatty acids 30 with triethanolamine, quaternized ester salts of fatty acids with diethanol WO 2004/031164 42 PCT/EP2003/010371 alkylamines and quaternized ester salts of fatty acids with 1,2 dihydroxypropyl dialkylamines. Such products are marketed, for example, under the names of Stepantex@, Dehyquart@ and Armocare@. The products Armocare@ VGH-70, an N, N-bis-(2-palmitoyloxyethyl)-d imethyl 5 ammonium chloride, and Dehyquart@ F-75 and Dehyquart@ AU-35 are examples of such esterquats. The alkyl amidoamines are normally prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkyl aminoamines. A compound from this group particularly suitable for the purposes of the 10 invention is the stearamidopropyl dimethylamine obtainable under the name of Tegoamid@ S 18. Other cationic surfactants suitable for use in accordance with the invention are the quaternized protein hydrolyzates. Also suitable for the purposes of the invention are cationic silicone 15 oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethicone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil@-Quat 3270 and 20 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl siloxanes, Quaternium-80). One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat@100 (INCI name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride). 25 The compounds containing alkyl groups used as surfactants may be single compounds. In general, however, these compounds are produced from native vegetable or animal raw materials so that mixtures with different alkyl chain lengths dependent upon the particular raw material are obtained. 30 The surfactants representing addition products of ethylene and/or WO 2004/031164 43 PCT/EP2003/010371 propylene oxide with fatty alcohols or derivatives of these addition products may be both products with a "normal" homolog distribution and products with a narrow homolog distribution. Products with a "normal" homolog distribution are mixtures of homologs which are obtained in the reaction of 5 fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with 10 a narrow homolog distribution can be of advantage. The colorants according to the invention may also contain other active substances, auxiliaries and additives such as, for example, - nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate 15 copolymers and polysiloxanes, - cationic polymers, such as quaternized cellulose ethers, polysiloxanes containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyldiallyl ammonium chloride copolymers, dimethylaminoethyl methacrylate/vinyl pyrrolidone copolymers 20 quaternized with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, - zwitterionic and amphoteric polymers such as, for example, acrylamido propyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2 25 hydroxypropyl methacrylate copolymers, - anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/buty maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic 30 anhydride copolymers and acrylic acid/ethyl acrylate/N-tert.butyl WO 2004/031164 44 PCT/EP2003/010371 acrylamide terpolymers, - thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, hydroxyalkyl cellulose and 5 carboxymethyl cellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as, for example, bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol, - structurants, such as maleic acid and lactic acid, 10 - hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and kephalins, - protein hydrolyzates, more particularly elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolyzates, condensation products thereof with fatty acids and quaternized protein hydrolyzates, 15 - perfume oils, dimethyl isosorbide and cyclodextrins, - solvents and solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, - fiber-structure-improving agents, more particularly mono-, di- and oligosaccharides such as, for example, glucose, galactose, fructose and 20 lactose, - quaternized amines, such as methyl-1 -alkylamidoethyl-2 alkylimidazoliniurm methosulfate, - defoamers, such as silicones, - dyes for coloring the preparation, 25 - antidandruff agents, such as piroctone olamine, zinc omadine and climbazol, - UV filters, more particularly derivatized benzophenones, cinnamic acid derivatives and triazines, - substances for adjusting the pH value, for example typical acids, more 30 particularly food-grade acids and bases, WO 2004/031164 45 PCT/EP2003/010371 - active substances, such as allantoin, pyrrolidone carboxylic acids and salts thereof and bisabolol, - vitamins, provitamins and vitamin precursors, more particularly those of groups A, B 3 , B 5

,B

6 , C, E, F and H, 5 - plant extracts, such as the extracts of green tea, oak bark, stinging nettle, hamamelis, hops, camomile, burdock root, horse willow, hawthorn, lime blossom, almond, aloe vera, pine needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lemon, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, lady's 10 smock, creeping thyme, yarrow, thyme, balm, restharrow, coltsfoot, hibiscus, meristem, ginseng and ginger root, - cholesterol, - consistency factors, such as sugar esters, polyol esters or polyol alkyl ethers, 15 - fats and waxes, such as spermaceti, beeswax, montan wax and paraffins, - fatty acid alkanolamides, - complexing agents, such as EDTA, NTA, p-alanine diacetic acid and phosphonic acids, 20 - swelling and penetration agents, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, - opacifiers, such as latex, styrene/PVP and styrene/acrylamide copolymers, 25 - pearlizers, such as ethylene glycol mono- and distearate and PEG-3 distearate, - pigments, - stabilizers for hydrogen peroxide and other oxidizing agents, - propellents, such as propane/butane mixtures, N 2 0, dimethyl ether, 30 CO 2 and air, WO2004/031164 46 PCT/EP2003/010371 - antioxidants. Information on other optional components and the quantities in which they are used can be found in the reference books known to the expert, for example Kh. Schrader, Grundlagen und Rezepturen der 5 Kosmetika, 2nd Edition, Huthig Buch Verlag, Heidelberg, 1989. The preparations according to the invention contain the dye precursors preferably in a suitable aqueous, alcoholic or aqueous/alcoholic carrier. For coloring hair, such carriers are, for example, creams, emulsions, gels or even surfactant-containing foaming solutions such as, 10 for example, shampoos, foam aerosols or other preparations suitable for application to the hair. However, the dye precursors may even be integrated into a powder-form or tablet-form formulation. Aqueous/alcoholic solutions in the context of the invention are aqueous solutions containing 3 to 70% by weight of a C 1

.

4 alcohol, more 15 particularly ethanol or isopropanol. The preparations according to the invention may additionally contain other organic solvents such as, for example, methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Water-soluble organic solvents are preferred. In principle, the actual oxidative coloring of the fibers may be carried 20 out with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, particularly when human hair is to be not only colored, but also lightened. Particularly suitable oxidizing agents are persulfates, chlorites and, in particular, hydrogen peroxide or addition products thereof with urea, melamine or sodium borate. According to the invention, 25 however, the oxidation colorant may also be applied to the hair together with a catalyst which activates the oxidation of the dye precursors, for example by atmospheric oxygen. Such catalysts are, for example, metal ions, iodides, quinones or certain enzymes. Suitable metal ions are, for example, Zn2+, Cu 2 +, Fe2+, Fe3+, Mn 2+ 30 Mn 4 *, Li*, Mg2+, Ca2+ and A13+. Zn2+, Cu 2 + and Mn2+ are particularly WO 2004/031164 47 PCT/EP2003/010371 suitable. Basically, the metal ions may be used in the form of a physiologically compatible salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. Development of the hair color can be accelerated and the color tone can be 5 influenced as required through the use of these metal salts. Suitable enzymes are, for example, peroxidases which are capable of significantly enhancing the effect of small quantities of hydrogen peroxide. According to the invention, other suitable enzymes are those which directly oxidize the oxidation dye precursors with the aid of 10 atmospheric oxygen, such as the laccases for example, or which produce small quantities of hydrogen peroxide in situ and thus biocatalytically activate the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of the dye precursors are the so-called 2-electron oxidoreductases in combination with the substrates specific to them, for 15 example - pyranose oxidase and, for example, D-glucose or galactose, - glucose oxidase and D-glucose, - glycerol oxidase and glycerol, 20 - pyruvate oxidase and pyruvic acid or salts thereof, - alcohol oxidase and alcohol (MeOH, EtOH), - lactate oxidase and lactic acid and salts thereof, - tyrosinase oxidase and tyrosine, - uricase and uric acid or salts thereof, 25 - choline oxidase and choline, - amino acid oxidase and amino acids. The actual hair colorant is preferably prepared immediately before application by mixing the preparation of the oxidizing agent with the 30 preparation containing the oxidation dye precursors. The ready-to-use hair WO 2004/031164 48 PCT/EP2003/010371 coloring preparation formed should preferably have a pH value in the range from 6 to 12. In a particularly preferred embodiment, the hair colorant is used in a mildly alkaline medium. The application temperatures may be in the range from 15 to 400C. After a contact time of about 5 to 45 minutes, 5 the hair colorant is removed from the hair to be colored by rinsing. There is no need for the hair to be washed with a shampoo where a carrier of high surfactant content, for example a coloring shampoo, has been used. In the particular case of hair which is difficult to color, the preparation containing the oxidation dye precursors may be applied to the hair without 10 preliminary mixing with the oxidation component. The oxidation component is applied after a contact time of 20 to 30 minutes, optionally after rinsing. After another contact time of 10 to 20 minutes, the hair is rinsed and, if desired, shampooed. In a first variant of this embodiment where the preliminary application of the dye precursors is intended to improve 15 penetration into the hair, the corresponding formulation is adjusted to a pH value of about 4 to 7. In a second variant, oxidation with air is initially carried out, the formulation applied preferably having a pH value of 7 to 10. In the subsequent accelerated post-oxidation phase, it can be of advantage to use acidified peroxydisulfate solutions as the oxidizing agent. 20 In a second embodiment, the present invention relates to the use of the m-phenylenediamine derivatives according to the invention for coloring keratinous fibers. In a third embodiment, the present invention relates to a process for coloring keratinous fibers, in which a hair colorant according to the 25 invention is applied to the fibers and, after a contact time, is rinsed off again. In a fourth embodiment, the present invention relates to m phenylenediamine derivatives selected from the group consisting of N,N dimethyl-3-(pyrrolidin-1 -yl)-aniline, 2-[(3-morpholin-4-yl phenyl)-amino] 30 ethan-1-ol, 2-[(3-piperidin-1-yl phenyl)-amino]-ethan-1-ol and 2-[(3- WO 2004/031164 49 PCT/EP2003/010371 pyrrolidin-1-yl phenyl)-amino]-ethan-1-ol. In a fifth embodiment, the present invention relates to the first intermediate stages of the synthesis of the m-phenylenediamine derivatives according to the invention selected from the group consisting of (2 5 chloroethoxy)-N-(3-morpholin-4-y phenyl)-carboxamide, (2-chloroethoxy) N-(3-piperidin-1-yl phenyl)-carboxamide and (2-chloroethoxy)-N-(3 pyrrolidin-1-yl phenyl)-carboxamide. In a sixth embodiment, the present invention relates to the second intermediate stages of the synthesis of the m-phenylenediamine derivatives 10 according to the invention selected from the group consisting of 3-(3 morpholin-4-yl phenyl)-1,3-oxazolidin-2-one, 3-(3-piperidin-1-yi phenyl)-1,3 oxazolidin-2-one and 3-(3-pyrrolidin-1-yl phenyl)-1,3-oxazolidin-2-one. Examples 15 1 Syntheses 1.1 3-Pyrrolidin-1-yl aniline

NH

2 N 20 1.1.1 3-Pyrrolidin-1-yl nitrobenzene 23.5 g of 3-fluoronitrobenzene and 66.8 g of pyrrolidine were dissolved in 250 ml of dimethyl sulfoxide and stirred for 60 h at 100*C. After cooling, the solution was poured into 2 liters of water. The product precipitated was filtered off under suction and dried in vacuo. 25 Yield: 31 g (95%) WO 2004/031164 50 PCT/EP2003/010371 Melting point: 85-87 0 C 1.1.2 3-Pyrrolidin-1-yl aniline 30.8 g of 3-pyrrolidin-1-yl nitrobenzene were dissolved in 450 ml of 5 ethanol and 50 ml of water and 0.3 g of Pd/C (5%) was added to the resulting solution. The whole was then hydrogenated in an autoclave for 12 h at 50*C/50 bar. After cooling and filtration, the product was concentrated in a rotary evaporator. The brown oil obtained was distilled in a bulb tube (boiling point: 132-155*C at 0.08 to 0.1 mbar). A clear brown 10 liquid was obtained. Yield: 16.8 g (65%) 1.2 3-Piperidin-1-yl aniline

NH

2 N 15 1.2.1 3-Piperidin-1-yl nitrobenzene 14.1 g of 3-fluoronitrobenzene and 46.8 g of piperidine were dissolved in 150 ml of dimethyl sulfoxide and stirred for 60 h at 100*C. After cooling, the solution was poured into I liter of water. The mixture was repeatedly extracted with tert.butyl methyl ether and the combined organic 20 phases were dried with sodium sulfate. The solvent was then distilled off in a rotary evaporator. The required product was obtained as a light brown liquid. Yield: 20.9 g (100%) 25 1.2.2 3-Piperidin-1-yl aniline 20.Og of 3-piperidin-1-yl nitrobenzene were dissolved in 270 ml of WO 2004/031164 51 PCT/EP2003/010371 ethanol and 30 ml of water and 0.2 g Pd/C (5%) was added to the resulting solution. The whole was then hydrogenated in an autoclave for 12 h at 80*C/100 bar. After cooling and filtration, the product was concentrated in a rotary evaporator. 5 Yield: 11.4 g (68%) 1.3 3-Mornholin-1-yl aniline

NH

2 N 0 10 1.3.1 3-Morpholin-4-yl nitrobenzene 14.1 g of 3-fluoronitrobenzene and 48.0 g of morpholine were dissolved in 150 ml of dimethyl sulfoxide and stirred for 60 h at 1000C. After cooling, the solution was poured into 1 liter of water. The product precipitated was filtered off under suction and dried in vacuo. 15 Yield: 18.8 g (90%) Melting point: 109-110OC 1.3.2 3-Morpholin-4-yl aniline (6) 18.5 g of 3-morpholin-1-yl nitrobenzene were dissolved in 270 ml of 20 ethanol and 30 ml of water and 0.2 g of Pd/C (5%) was added to the resulting solution. The whole was then hydrogenated in an autoclave for 12 h at 50*C/30 bar. After cooling and filtration, the product was concentrated in a rotary evaporator. The light brown crystals obtained were dried in vacuo. 25 Yield: 12.6 g (80%) Melting point: 117-118"C.

WO 2004/031164 52 PCT/EP2003/010371 1.4 3-(4-Methylpiperazin-1 -yl)-aniline

NH

2 N '_CH3 1.4.1 3-(4-Methylpiperazin-1 -yl)-nitrobenzene 5 14.1 g of 3-fluoronitrobenzene and 48.0 g of N-methylpiperazine were dissolved in 150 ml of dimethyl sulfoxide and stirred for 60 h at 100 0 C. After cooling, the solution was poured into 1 liter of water and repeatedly extracted with tert.butyl methyl ether. The product was then concentrated to dryness in a rotary evaporator. The wax-like product 10 precipitated was dried in vacuo. Yield: 19.5 g (88%) Melting point: 40-48 0 C. 1.4.2 3-(4-Methylpiperazin-1-yl)-aniline 15 19.2 g of 3-(4-methylpiperazin-1-yl)-nitrobenzene were dissolved in 270 ml of ethanol and 30 ml of water and 0.2 g of Pd/C (5%) was added to the resulting solution. The whole was then hydrogenated in an autoclave for 12 h at 50*C/30 bar. After cooling and filtration, the product was concentrated in a rotary evaporator. The product was obtained as a highly 20 viscous oil. Yield: 12.6 g (83%) 1.5 N,N-Dimethyl-3-(pyrrolidin-1 -vl)-aniline WO 2004/031164 53 PCT/EP2003/010371 CH3 N CH 3 6N 6.5 ml of sulfuric acid (25%) and 7.5 ml of aqueous formaldehyde solution (37%) were dissolved in 50 ml of tetrahydrofuran at room temperature and introduced into a reaction vessel. A suspension of 5.5 g 5 of sodium borohydride and 4.1 g of 3-pyrrolidin-1-yl aniline (see 1.1) in tetrahydrofuran was then added in portions. The temperature of the reaction mixture was controlled so that the temperature did not exceed 35"C. After half the suspension had been added, another 6.5 ml of sulfuric acid (25%) were introduced. After the addition, the whole was stirred for 1 10 h at room temperature, diluted with 200 ml of water and adjusted to pH 10 11 with 50% KOH. The organic phase formed was removed and the aqueous phase was extracted twice with tert.butyl methyl ether. The combined organic phases were washed twice with a saturated aqueous NaCl solution and dried over sodium sulfate. After concentration in vacuo, 15 the black viscous liquid obtained was distilled in a bulb tube (123-143*C at 0.06 - 0.08 mbar). Yield: 1.5 g (32%) 1.6 2-[(3-Morpholin-4-yl phenyl)-aminol-ethan-1-ol HO0 NH N 20 1.6.1 (2-Chloroethoxy)-N-(3-morpholin-4-y phenyl)-carboxamide 50 g of 3-morpholin-1-yl aniline (for preparation, see 1.3) and 50.6 g WO 2004/031164 54 PCT/EP2003/010371 of calcium carbonate were introduced into 800 ml of dioxane and heated to 90 0 C. 44.5 g of 2-chloroethyl chloroformate were then added dropwise over a period of 15 minutes and the whole was stirred for another 4 h and monitored by thin-layer chromatography (TLC). After cooling, the salts 5 were filtered off and the filtrate was introduced into 1 liter of ice water. The mixture of filtrate and ice water was repeatedly extracted with ethyl acetate, the combined organic phases were dried over sodium sulfate and concentrated to dryness in a rotary evaporator. The residue was dried in vacuo overnight. 10 Yield: 45 g (56%) Melting point: 116-1190C 1.6.2 3-(3-Morpholin-4-yi phenyl)-1,3-oxazolidin-2-one 200 ml of 20% NaOH were introduced into a three-necked flask and 15 heated to 450C. 44.0 g of (2-chloroethoxy)-N-(3-morpholin-4-yl phenyl) carboxamide were then introduced in portions. A heterogeneous system was formed in a mildly exothermic reaction. After addition of 400 ml of dioxane, a clear solution was obtained and was stirred overnight at room temperature, poured onto ice water and neutralized with semiconcentrated 20 HCI. The product precipitated was thoroughly washed and dried in vacuo overnight. Yield: 33.4 g (90%) Melting point: 166-1680C. 25 1.6.3 2-[(3-Morpholin-4-yl phenyl)-amino]-ethan-1-ol 33 g of 3-(3-morpholin-4-yl phenyl)-1,3-oxazolidin-2-one were heated under reflux for 3 hours in 500 ml of 20% ethanolic KOH. The mixture was then added to 1.5 liters of water, neutralized with semiconcentrated HCI and repeatedly extracted with ethyl acetate. The 30 combined organic phases were dried over sodium sulfate and WO 2004/031164 55 PCT/EP2003/010371 concentrated. The residue was distilled in a bulb tube (0.08 mbar, 200 2300C). Yield: 17.9 g (62%) 5 1.7 2-[(3-Piperidin-1-yl phenyl)-aminol-ethan-1-ol HO NH N 1.7.1 (2-Chloroethoxy)-N-(3-piperidin-1-yl)-carboxamide 65 g of 3-piperidin-1-yl aniline (for preparation, see 1.2) and 66.5 g of calcium carbonate were introduced into 1 liter of dioxane and heated to 10 90*C. 59.3 g of 2-chloroethyl chloroformate were then added dropwise over a period of 15 minutes and the whole was stirred for another 4 h and monitored by thin-layer chromatography (TLC). After cooling, the salts were filtered off and the filtrate was introduced into 1 liter of ice water. The mixture of filtrate and ice water was repeatedly extracted with ethyl acetate, 15 the organic phase was dried over sodium sulfate and concentrated to dryness in a rotary evaporator. The residue was dried in vacuo overnight, a black oil being obtained Yield: 16.5 g (16%) 20 1.7.2 3-(3-Piperidin-1-yl phenyl)-1,3-oxazolidin-2-one 80 ml of 20% NaOH were introduced into a three-necked flask and heated to 450C. 16.0 g of (2-chloroethoxy)-N-(3-piperidin-1-y phenyl) carboxamide were then introduced in portions. A heterogeneous system was formed in a mildly exothermic reaction. After addition of 400 ml of 25 dioxane, a clear solution was obtained and was stirred overnight at room temperature, poured onto ice water and neutralized with semiconcentrated WO 20041031164 56 PCT/EP2003/010371 HCI. The aqueous phase was repeatedly extracted with ethyl acetate. The combined organic phases were concentrated in vacuo to dryness, a dark oil being obtained. Yield: 6.0 g (43%) 5 1.7.3 2-[(3-Piperidin-1-yl phenyl)-amino]-ethan-1-ol 6 g of 3-(3-piperidin-1-yl phenyl)-1,3-oxazolidin-2-one were heated under reflux for 3 hours in 200 ml of 20% ethanolic KOH. The mixture was then added to 1.0 liter of water, neutralized with semiconcentrated HCI and 10 repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated. The residue was distilled in a bulb tube (0.08 mbar, 160-204*C). Yield: 2.0 g (37%) 15 1.8 2-[(3-Pyrrolidin-1-vi phenyl)-aminol-ethan-1-ol HO"- NH N 1.8.1 (2-Chloroethoxy)-N-(3-pyrrolidin-1-yI phenyl)-carboxamide 60 g of 3-pyrrolidin-1-yl aniline (for preparation, see 1.1) and 66.5 g of calcium carbonate were introduced into 1 liter of dioxane and heated to 20 90 0 C. 59.3 g of 2-chloroethyl chloroformate were then added dropwise over a period of 15 minutes and the whole was stirred for another 4 h and monitored by thin-layer chromatography (TLC). After cooling, the salts were filtered off and the filtrate was introduced into 1 liter of ice water. The mixture of filtrate and ice water was repeatedly washed with ethyl acetate, 25 the combined organic phases were dried over sodium sulfate and concentrated to dryness in a rotary evaporator. The residue was dried in WO 2004/031164 57 PCT/EP2003/010371 vacuo overnight. Yield: 71 g (72%) Melting point: 87-90*C. 5 1.8.2 3-(3-Pyrrolidin-1-yl phenyl)-1,3-oxazolidin-2-one 340 ml of 20% NaOH were introduced into a three-necked flask and heated to 45 0 C. 70 g of (2-chloroethoxy)-N-(3-pyrrolidin-1-yl phenyl) carboxamide were then introduced in portions. A heterogeneous system was formed in a mildly exothermic reaction. After addition of 400 ml of 10 dioxane, a clear solution was obtained and was stirred overnight at room temperature, poured onto ice water and neutralized with semiconcentrated HCL. The product precipitated was thoroughly washed and dried in vacuo overnight. Yield: 58.8 g (97%) 15 Melting point: 138-142 0 C 1.8.3 2-[(3-Pyrrolidin-1-yl phenyl)-amino]-ethan-1-ol 58 g of 3-(3-pyrrolidin-1-yl phenyl)-1,3-oxazolidin-2-one were heated under reflux for 3 hours in 500 ml of 20% ethanolic KOH. The mixture was 20 then added to 1.5 liters of water, neutralized with semiconcentrated HCI and repeatedly extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated. The residue was distilled in a bulb tube (0.08 mbar, 205-225*C). Yield: 38.3 g (62%) 25 Melting point: 36-380C (74%) 2. Coloring 2.1 Procedure 30 To prepare the coloring cream, 50 g of a cream base were weighed WO 2004/031164 58 PCT/EP2003/010371 into a 250 ml glass beaker and melted at 80*C. The cream base used had the following composition: Hydrenol* D' 17.0 % by weight 5 Lorol* tech.

2 4.0 % by weight Texapon* NSO 3 40.0 % by weight Dehyton* K4 25.0 % by weight Eumulgin* B2 5 1.5 % by weight Water 12.5 % by weight 10

C

1 6 -1 8 -fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis) 2 C 1 2 -1 8 -fatty alcohol (INCI name: Coconut Alcohol) (Cognis) 3 Laurylether sulfate, sodium salt (ca. 27.5% active substance; INCI name: Sodium Laureth Sulfate) (Cognis) 15 4 N,N-Dimethyl-N-(C 8 -1-cocoamidopropyl)-ammonium acetobetaine (ca. 30% active substance; INCI name: Aqua (Water), Cocamidopropyl Betaine) (Cognis) 5 Cetylstearyl alcohol containing ca. 20 EO units (INCI name: Ceteareth-20) (Cognis) 20 Quantities of 1/400 mol of the primary intermediate or secondary intermediate were separately suspended or dissolved with heating in distilled water. Ammonia (< 1 ml; 25% ammonia solution) was then added to pH 9 - 10. 25 The dissolved dye precursors were successively incorporated in the hot cream. The cream was then made up to 97 g with distilled water and adjusted to pH 9.5 with ammonia. After making up to 100 g with distilled water, the mixture was cold-stirred (<300C), resulting in the formation of a homogeneous cream. 30 For coloring, quantities of 25 g of coloring cream (unless otherwise indicated) were mixed with 25 g of the following oxidizing agent preparation: WO 2004/031164 59 PCT/EP2003/010371 Dipicolinic acid 0.1 % by weight Sodium pyrophosphate 0.03 % by weight Turpinal* SL 6 1.50 % by weight Texapon* N28 7 2.00 % by weight 5 Acrysol* 228 0.60 % by weight Hydrogen peroxide. 50 12.0 % by weight or 2 % by weight Sodium hydroxide, 45% 0.80 % by weight Water ad 100 10 6 1-Hydroxyethane-1,1-diphosphonic acid (ca. 58 - 61% active substance content; INCI name: Etidronic Acid, Aqua (Water)) (Solutia) 7 Laurylether sulfate sodium salt (at least 26.5 % active substance content; INCI name: Sodium Laureth Sulfate) (Cognis) 8 Acrylate polymer (ca. 29.5 - 30.5% solids in water; INCI name: 15 Acrylates/Steareth-20 Methacrylate Copolymer) A hair tress (80% gray; weight 330 mg to 370 mg) was placed in each of the mixtures thus obtained. The mixtures and the hair tresses were then placed on a watch glass and the hair tresses were thoroughly 20 embedded in the coloring creams. After a contact time of 30 minutes (± 1 minute) at room temperature, the hair tresses were removed and washed with an aqueous Texapon@ EVR solution 9 until the excess color had been removed. The hair tresses were dried in air and their color was determined under a daylight lamp (HE240A color tester) and scored (Taschenlexikon 25 der Farben, A. Kornerup u. J.H. Wanscher, 3. unverAnderte Auflage 1981, MUSTER-SCHMIDT Verlag; Zurich, G6ttingen). 9 Lauryl ether sulfate sodium salt with special additives (ca. 34 to 37% active substance content; INCI name: Sodium Lauryl Sulfate, 30 Sodium Laureth Sulfate, Lauramide MIPA, Cocamide MEA, Glycol Stearate, Laureth-10) (Cognis) The results obtained in the coloring tests are set out in the following Tables.

WO 2004/031164 60 PCT/EP2003/010371 2.2 Coloring with 3-pyrrolidin-1-yl aniline (color developed with 6% by weight hydrogen peroxide solution) Primary intermediate Color p-Toluylenediamine sulfate black-blue 2,4,5,6-Tetraaminopyrimidine sulfate yellow-brown p-Aminophenol dark purple 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate deep magenta 5 2.3 Coloring with 3-piperidine-1-vl aniline (color developed with 1 % by weight hydrogen peroxide solution) Primary intermediate Color p-Toluylenediamine sulfate black-blue 2,4,5,6-Tetraaminopyrimidine sulfate olive p-Aminophenol gray-ruby 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate deep magenta 2.4 Coloring with 3-morpholin-4-vl aniline (color developed with 6% by weight hydrogen peroxide solution) Primary intermediate Color p-Toluylenediamine sulfate dark blue 2,4,5,6-Tetraaminopyrimidine sulfate yolk yellow p-Aminophenol mouse gray 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate deep violet 10 2.5 Coloring with 3-(4-methylpiperazin-1-yl)-aniline (color developed with 6% by weight hydrogen peroxide solution) Primary intermediate Color p-Toluylenediamine sulfate dark blue 2,4,5,6-Tetraaminopyrimidine sulfate chamois yellow WO 2004/031164 61 PCT/EP2003/010371 p-Aminophenol brown-orange 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate deep violet 2.6 Coloring with NN-dimethyl-3-(pyrrolidin-1-yl)-aniline (color developed with 6% by weight hydrogen peroxide solution) Primary intermediate Color p-Toluylenediamine sulfate dark blue 2,4,5,6-Tetraaminopyrimidine sulfate madeira brown p-Aminophenol gray-brown 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate deep magenta 2.7 Coloring with 2-[(3-morpholin-4-yl phenyl)-aminol-ethan-1-ol 5 (color developed with 6% by weight hydrogen peroxide solution) Primary intermediate Color p-Toluylenediamine sulfate dark violet 2,4,5,6-Tetraaminopyrimidine sulfate dark red p-Aminophenol gray-red 3-Methyl-p-aminophenol gray-brown 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate deep violet 2.8 Coloring with 2-[(3-piperidin-1-yl phenyl)-aminol-ethan-1-ol (color developed with 6% by weight hydrogen peroxide solution) Primary intermediate Color p-Toluylenediamine sulfate black-blue 2,4,5,6-Tetraaminopyrimidine sulfate dark violet p-Aminophenol gray-ruby Bis-(5-amino-2-hydroxyphenyl)-methane plum-colored dihydrochloride 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate deep violet 10 2.9 Coloring with 2-f(3-pyrrolidin-1-yl phenyl)-aminol-ethan-1-ol WO 2004/031164 62 PCT/EP2003/010371 (color developed witht 6% by weight hydrogen peroxide solution) Primary intermediate Color p-Toluylenediamine sulfate black-blue 2,4,5,6-Tetraaminopyrimidine sulfate dark magenta p-Aminophenol gray-ruby 2-(2-Hydroxyethyl)-p-phenylenediamine sulfate deep magenta 3-Methyl-p-aminophenol gray-magenta 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate dark purple 3. Application formulations 3.1 Formulation 1 Raw material % by weight Fatty alcohol mixture C10 - C22 6.0 Eumulgin* B1 10 0.3 Eumulgin* B2 0.3 Texapon* NSO 10.0 Dehyton* K 5.0 Polymer JR* 40011 0.3 Gafquat* 75512 0.3 Celquat* L 20013 0.1 Ascorbic acid 0.3 Ammonium sulfate 0.4 p-Phenylenediamine dihydrochloride 0.18 p-Toluylenediamine sulfate 0.22 N,N-Bis-(2-hydroxyethyl)-p-phenylene diamine 0.25 sulfate 2-(2-Hydroxyethyl)-p-phenylenediamine sulfate 0.25 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate 0.72 2-(3-Morpholin-4-yl phenylamino)-ethanol 1.77 dihydrochloride I _I WO 2004/031164 63 PCT/EP2003/010371 5-Amino-2-methylphenol 0.12 3-Amino-2-chloro-6-methylphenol 0.16 2,4-Diaminophenoxyethanol sulfate 0.005 2-Amino-4-(2-hydroxyethyl)-aminoanisole 0.005 2-Methylamino-3-amino-6-methoxypyridine 0.002 1 -Naphthol 0.002 1,5-Dihydroxynaphthalene 0.001 1 -Phenyl-3-methylpyrazol-5-one 0.003 2,6-Bis-(2-hydroxyethylamino)-toluene 0.001 Water to 100 Aqueous ammonia solution (25%) to pH 9.5-10.2 Color Dark blue-violet 3.2 Formulation 2 Raw material % by weight Fatty alcohol mixture C 1 0

-C

22 6.0 Eumulgin* B1 0.3 Eumulgin* B2 0.3 Texapon* NSO 10.0 Dehyton* K 5.0 Polymer JR 400 0.3 Gafquat* 755 0.3 Celquat* L 200 0.1 Ascorbic acid 0.3 Ammonium sulfate 0.4 p-Toluylene diamine sulfate 0.02 4-Aminophenol 0.02 4-Amino-3-methylphenol 0.011 Bis-(5-amino-2-hydroxyphenyl)-methane 1.82 dihydrochlorid 2,4,5,6-Tetraminopyrimidine sulfate 0.36 4-Hydroxy-2,5,6-triaminopyrimidine sulfate 0.08 WO 2004/031164 64 PCT/EP2003/010371 2-(3-Morpholin-4-yl phenylamino)-ethanol 2.27 dihydrochloride Resorcinol 0.015 2-Methylresorcinol 0.040 4-Chlororesorcinol 0.015 3-Aminophenol 0.003 3-Amino-2,4-dichlorophenol 0.012 1,3-Bis-(2,4-diaminophenoxy)-propane 0.001 tetrahydrochloride 2-Amino-3-hydroxypyridine 0.006 Aqueous ammonia solution (25%) to pH 9.5-10.2 Water to 100 Color Dark red-violet 3.3 Formulation 3 Raw material % by weight Fatty alcohol mixture C 10

-C

22 6.0 Eumulgin* B1 0.3 Eumulgin* B2 0.3 Texapon* NSO 10.0 Dehyton* K 5.0 Polymer JR 400 0.3 Gafquat* 755 0.3 Celquat* L 200 0.1 Ascorbic acid 0.3 Ammonium sulfate 0.4 p-toluylenediamine sulfate 0.005 N,N-Bis-(2-hydroxyethyl)-p-phenylenediamine sulfate 0.005 4-Aminophenol 0.02 4-Amino-3-methylphenol 0.01 4-Amino-2-(diethylamino)-methylphenol 0.02 dihydrochloride 2,4,5,6-Tetraminopyrimidine sulfate 1.70 WO 2004/031164 65 PCT/EP2003/010371 4-Hydroxy-2,5,6-triaminopyrimidine sulfate 0.09 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate 0.01 3-(Pyrrolidin-1-yl)-aniline dihydrochloride 1.77 2-Methylresorcinol 0.02 4-Chlororesorcinol 0.02 1,3-Bis-(2,4-diaminophenoxy)-propane 0.01 tetrahydrochloride 2-Methylamino-3-amino-6-methoxypyridine 0.01 5,6-Dihydroxyindoline hydrobromide 0.05 4-Amino-2-nitrodiphenylamine-2-carboxylic acid 0.02 HC Red B54 14 0.01 Acid Red 5215 0.01 Aqueous ammonia solution (25%) to pH 9.5-10.2 Water to 100 Color Dark red-brown 3.4 Formulation 4 Raw material % by weight Fatty alcohol mixture C1 0 - C 22 10.0 Texapon* K14 S70C 16 2.5 Plantaren* 1200 UP 17 2.0 Akypo Soft* 45 NV 18 12.0 Eutanol* G 19 1.0 Eumulgin* B1 0.5 Polymer W 3719420 0.5 Cosmedia Guar* C26 121 2.0 Mirapol* Al 522 0.5 Ascorbic acid 0.4 Sodium metabisulfite 0.2 Ammonium sulfate 0.5 p-Toluylenediamine sulfate 0.009 2-(2-Hydroxyethyl)-p-phenylenediamine sulfate 0.011 4-Aminophenol 0.007 WO 2004/031164 66 PCT/EP2003/010371 Bis-(5-amino-2-hydroxyphenol)-methane 0.020 dihydrochloride 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate 0.002 3-(Pyrrolidin-1-yl)-aniline dihydrochloride 0.03 2-Methylresorcinol 0.01 3-Aminophenol 0.01 2-Methylamino-3-amino-6-methoxypyridine 0.003 1 -Naphthol 0.015 2-Methyl-1 -naphthol 0.022 1,5-Dihydroxynaphthalene 0.005 Aqueous ammonia solution (25%) to pH 9.5-10.2 Water to 100 Perfume q.s. Color Violet-tinged light gray 3.5 Formulation 5 Raw material % by weight

C

10 - C 22 fatty alcohol mixture 10.0 Texapon®O K14 S70C 2.5 Plantaren0 1200 UP 2.0 Akypo Softo 45 NV 12.0 Eutanol® G 1.0 Eumulgine B1 0.5 Eumulgine B2 0.5 Polymer W 37194 2.0 Cosmedia Guar® C261 0.2 Mirapole Al 50.5 Ascorbic acid 0.4 Sodium metabisulfite 0.2 Ammonium sulfate 0.5 4-Amino-2-(diethylamino)-methyl)-pheno 0.18 dihydrochloride________ WO 2004/031164 67 PCT/EP2003/010371 Bis-(5-amino-2-hydroxyphenol)-methane 2.40 dihydrochloride 2,4,5,6-Tetraaminopyrimidine sulfate 0.48 3-(Pyrrolidin-1-yl)-aniline dihydrochloride 0.23 2-(3-Morpholin-4-yl phenylamino)-ethanol 0.30 2-Methylamino-3-amino-6-methoxypyridine 2.04 2,6-Dihydroxy-3,4-dimethylpyridine 0.01 3,5-Diamino-2,6-dimethoxypyridine 0.02 1,2,3,4-Tetrahydro-6-nitroquinoxoline 0.01 HC Red BN 23 0.2 2-Ethylamino-4-nitro-6-chlorophenol 0.07 4-Amino-3-nitrophenol 0.02 Aqueous ammonia solution (25%) to pH 9.5-10.2 Water to 100 Color Dark henna red 3.6 Formulation 6 Raw material % by weight Fatty alcohol mixture C10 - C22 10.0 Texapon* K14 S70C 2.5 Plantaren* 1200 UP 2.0 Akypo Soft* 45 NV 12.0 Eutanol* G 1.0 Eumulgin* B1 0.5 Eumulgin® B2 0.5 Polymer W 37194 2.0 Cosmedia Guar* C261 0.2 Mirapol* Al 5 0.5 Ascorbic acid 0.4 Sodium metabisulfite 0.2 Ammonium sulfate 0.5 p-Phenylenediamine dihydrochloride 0.02 WO 2004/031164 68 PCT/EP2003/010371 p-Toluylenediamine sulfate 0.02 N,N-Bis-(2-hydroxyethyl)-p-phenylendiamine sulfate 0.03 2-(2-Hydroxyethyl)-p-phenylenediamine sulfate 0.03 Bis-(5-amino-2-hydroxyphenol)-methane 1.70 dihydrochloride 3-(Pyrrolidin-1-yi)-aniline dihydrochloride 1.74 2-(3-Morpholin-4-yl phenylamino)- 0.08 ethanol dihydrochloride 5-Amino-2-methylphenol 0.02 5-(2-Hyd roxyethyl)amino-2-methylphenol 0.01 5-Amino-4-chloro-2-methylphenol 0.02 3-Amino-2-chloro-6-methylphenol 0.02 3-Amino-2,4-dichlorophenol 0.01 2,4-Diaminophenoxyethanol sulfate 0.01 Aqueous ammonia solution (25%) to pH 9.5-10.2 Water to 100 Color Dark Bordeaux red 3.7 Formulation 7 Raw material % by weight Fatty alcohol mixture C10 - C22 8.0 Texapon* NSO 2.0 Dehytone K 1.0 Potassium oleate 2.0 Potassium isostearate 2.0 Myristic acid 1.0 Eumulgin* B2 0.5 Westvaco Diacid* H240, K salt 24 2.0 Merquat* 55025 0.2 Luviquat* FC 37026 0.1 Merquat* 28027 0.1 Gafquat* HS-1 0028 0.1 Ascorbic acid 0.4 WO 2004/031164 69 PCT/EP2003/010371 Ammonium sulfate 0.5 p-Phenylendiamine dihydrochloride 0.05 4-Amino-2-aminomethylphenol 0.02 dihydrochloride 2,4,5,6-Tetraaminopyrimidine sulfate 1.30 2-(3-Morpholin-4-yl phenylamino)- 0.29 ethanol dihydrochloride 2-Methylresorcinol 0.59 2,6-Bis-(2-hydroxyethylamino)-toluene 0.08 HC Red BN 0.05 HC Red B54 0.05 1,4-Diamino-2-nitrobenzene 0.2 Acid Red 52 0.05 Acid Red 3329 0.02 Aqueous ammonia solution (25%) to pH 9.5-10.2 Water to 100 Perfume q.s. Color Dark strawberry red 3.8 Formulation 8 Raw material % by weight C1o - C 22 fatty alcohol mixture 8.0 Texapon* NSO 2.0 Dehyton* K 1.0 Potassium oleate 2.0 Poptassium isostearate 2.0 Myristic acid 1.0 Eumulgin* B2 0.5 Westvaco Diacid* H240, K salt 2.0 Merquat* 550 0.2 Luviquat* FC 370 0.1 Merquat* 280 0.1 Gafquat* HS-100 0.1 Ascorbic acid 0.4 Ammonium sulfate 0.5 p-Phenylenediamine dihydrochloride 0.01 WO 2004/031164 70 PCT/EP2003/010371 p-Toluylenediamine sulfate 0.80 N,N-Bis-(2-hydroxyethyl)-p-phenylenediamine sulfate 0.04 2-(2-Hydroxyethyl)-p-phenylenediamine sulfate 0.05 4-Amino-2-aminomethylphenol dihydrochloride 0.01 4-Amino-2-(diethylamino)-methyl)-phenol 0.01 dihydrochloride 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate 0.36 3-(Pyrrolidin-1-yl)-aniline dihydrochloride 0.07 2-(3-Morpholin-4-yl phenylamino)- 0.44 ethanol dihydrochloride 2-Methylresorcinol 0.02 3-Aminophenol 0.02 5-Amino-2-methylphenol 0.15 5-(2-Hydroxyethyl)-amino-2-methylphenol 0.02 5-Amino-4-chloro-2-methylphenol 0.09 3-Amino-2-ch loro-6-methylphenol 0.07 3-Amino-2,4-dichlorophenol 0.01 2-Methylamino-3-amino-6-methoxypyridine 0.005 1,5-Dihydroxynaphthalene 0.05 2,7-Dihydroxynaphthalene 0.08 1 -Phenyl-3-methylpyrazol-5-one 0.02 2,6-Bis-(2-hydroxyethylamino)-toluene 0.02 4-Amino-2-nitro-diphenylamin-2-carboxylic acid 0.10 Aqueous ammonia solution (25%) to pH 9.5-10.2 Water to 100 Color Dark strawberry red 3.9 Formulation 9 Raw material % by weight Edenor* PK 180530 7.0 Texapon* NSO 4.0

C

12

-C

18 fatty alcohol mixture 7.5 Dehydol* CS2 31 8.0 Isopropanol 14.5 Sodium metabisulfite 0.1 Ascorbic acid 0.1 L-Arginine 1.0 Monoethanolamine 8.0 WO 2004/031164 71 PCT/EP2003/010371 p-Toluylenediamine sulfate 0.033 2-(2-Hydroxyethyl)-p-phenylenediamine sulfate 0.002 4-Amino-2-aminomethylphenol dihydrochloride 0.01 Bis-(5-amino-2-hydroxyphenol)-methane 0.03 dihydrochloride 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfate 0.002 3-(Pyrrolidin-1-yl)-aniline dihydrochloride 0.003 2-(3-Morpholin-4-yl phenylamino)- 0.004 ethanol dihydrochloride Resorcinol 0.006 2,4-Diaminophenoxyethanol sulfate 0.001 2-Amino-4-(2-hydroxyethyl)-aminoanisole 0.001 1,3-Bis-(2,4-diaminophenoxy)-propane 0.001 tetrahydroch loride 1 -Naphthol 0.02 Aqueous ammonia solution (25%) to pH 9.5-10.2 Water to 100 Perume q.s. Color Blue-tinged light gray 3.10 Formulation 10 Raw material % by weight Fatty alcohol mixture Ca-C 2 2 10.0 Eumulgin* B1 1.0 Eumulgin* B2 1.0 Texapon* NSO 3.0 Dehyton K 1.0 Akypo RLM* 45N 32 3.0 Aminoxid* WS 3533 0.5 Merquat* 10034 0.05 Merquat* 280 0.05 Polymer JR* 400 0.05 Mirapol* A 15 0.05 Silkall 10035 0.5 Nutrilan Keratin* W 3 6 2.0 WO 2004/031164 72 PCT/EP2003/010371 Soda waterglass 40/4237 0.5 Ascorbic acid 0.2 Ammonium sulfate 0.4 p-Phenylenediamine dihydrochloride 0.07 p-Toluylenediamine sulfate 0.70 N,N-Bis-(2-hydroxyethyl)-p-phenylenediamine 0.05 sulfate 2-(2-Hydroxyethyl)-p-phenylenediamine sulfate 0.05 4-Aminophenol 0.04 4-Amino-3-methylphenol 0.40 4,5-Diamino-1-(2-hydroxyethyl)-pyrazole sulfat 0.20 3-(Pyrrolidin-1-yi)-anilin dihydrochloride 0.14 2-(3-Morpholin-4-yl phenylamino)- 0.27 ethanol dihydrochloride Resorcinol 0.02 2-Methylresorcinol 0.04 4-Chlororesorcinol 0.02 Resorcinol monomethylether 0.02 5-(2-Hydroxyethyl)-amino-2-methylphenol 0.04 3-Amino-2-chloro-6-methylphenol 0.72 3-Amino-2,4-dichlorophenol 0.01 2-Amino-3-hydroxypyridine 0.19 1,5-Dihydroxynaphthalene 0.01 1 -Phenyl-3-methylpyrazol-5-one 0.02 5,6-Dihydroxyindole 0.02 Aqueous ammonia solution (25%) to pH 9.5-10.2 Water to 100 Color Dark blue-violet 1.1 Oxidizing agent preparation Raw material % by weight Texapon* N28 2.0 Dipicolinic acid 0.1 Sodium pyrophosphate 0.03 Turpinal* SL 1.5 Dow Corninge DB 110 A3 0.07 Aculyn* 3339 12.0 Hydrogen peroxide (50%) 12.0 WO 2004/031164 73 PCT/EP2003/010371 Ammonia, 25% I to pH 4 Water to 100 The following raw materials were used in the application formulations: 10 Cetylstearyl alcohol containing ca. 12 EO units (INCI name: Ceteareth-12) 5 (Cognis) 11 quaternized hydroxyethylcellulose (INC[ name: Polyquaternium-10) (Amerchol) 12 Dimethylaminoethyl methacrylate/vinylpyrrolidone copolymer, quaternized with diethylsulfate (ca. 19% solids in water; INCI name: Polyquaternium 10 11) (ISP) 13 quaternized cellulose derivative (INCI name: Polyquaternium-4) (National Starch) 14 4-[(2-Hydroxyethyl)-amino]-3-nitrophenol (INCI name: 3-Nitro-p-Hydroxy ethylaminophenol) 15 15 (INCI name: Cl 45100) 16 Laurylmyristyl ether sulfate sodium salt (ca. 68% to 73% active substance content; INCI name: Sodium Myreth Sulfate) (Cognis) 17 C 12

-C

16 -fatty alcohol-1.4-glucoside, no preservative, boron-free ca. 50-53% active substance) (Cognis Corporation (Emery)) 20 1 Lauryl alcohol-4.5-EO-acetic acid sodium salt (at least 21% active substance content; INCI name: Sodium Laureth-6 Carboxylate) (Chem-Y) 19 2-Octyldodecyl alcohol (INCI name: Octyldodecanol) (Cognis) 20 ca. 20% by wt. active substance content in water; INCI name: Acrylamidopropyltrimonium Chloride/Acrylates Copolymer (Stockhausen) 25 21 Guar hydroxypropyl trimethylammonium chloride (at least 93% solids; INCI name: Guar Hydroxypropyltrimonium Chloride) (Cognis Corporation Cosmedia) 22 Poly[N-(3-(dimethylammonium)propyl]-N'-[3-ethyleneoxyethylenedimethyl ammonium)-propyl]-urea dichloride (ca. 64% solids in water; INCI name: 30 Polyquaternium-2) (Rhodia) 23 4[(3-Hydroxypropyl)-amino]-3-nitropheno 24 4-Hexyl-5(6)-carboxy-2-cyclohexene-1-octanoic acid potassium salt (ca. 41% active substance in water) (Westvaco Chemicals) 25 Dimethyldiallyl ammonium chloride/acrylamide copolymer (ca. 8.1-9.1% 35 active substance in water; INCI name: Polyquaternium-7) (Ondeo-Nalco) 26 Vinylimidazolium methochloride/vinylpyrrolidone copolymer (30:70) (38 42% solids in water; INCI name: Polyquaternium-16) (BASF) 27 Dimethyldiallyl ammonium chloride/acrylic acid copolymer (ca. 35% active substance in water; INCI name: Polyquaternium-22) (Ondeo-Nalco) 40 28 Vinylpyrrolidon/methacrylamidopropy trimethylammonium chloride copolymer (19-21% active substance in water; INCI name: WO 2004/031164 74 PCT/EP2003/010371 Polyquaternium-28) (ISP) 29 2,7-naphthalenedisulfonic acid, 5-amino-4-hydroxy-3-(phenylazo)-disodium salt 30 Oleic acid (INCI name: Oleic Acid) (Cognis Deutschland GmbH (Caldic)) 5 31 C 1214 -fatty alcohol containing ca. 2 EO units (INCI name: Laureth-2) (Cognis Deutschland GmbH) 32 Laurylalcohol containing ca. 4.5 EO units - acetic acid sodium salt (ca. 80 84% active substance in water; INCI name: Sodium Laureth-5 Carboxylate) (Kao) 10 33 N,N-dimethyl-N-(C 8 -1-cocoacylamidopropyl)-amin-N-oxide (ca. 35% active substance in water; INCI name: Cocamidopropylamine Oxide) (Goldschmidt) 34 Poly(dimethyldiallylammoniumchloride) (ca. 40% solids; INCI name: Polyquaternium-6) (Ondeo-Nalco) 15 35 Silk protein (ca. 99% protein; INC[ name: Silk, Serica (Linne)) (Ikeda Bussan Kaisha) 36 Hydrolyzate of pure Merino wool, enzymatically obtained (21-23% solids; INCI name: Aqua (Water), Hydrolyzed Keratin, Phenoxyethanol, Methylparaben, Butylparaben, Ethylparaben, Propylparaben) (Cognis 20 Deutschland GmbH (Grunau)) 37 ca. 40% active substance (INC[ name: Sodium Silicate) (HENKEL) 38 nonionic silicone emulsion (INCI name: Dimethicone, ca. 10% active substance) (Dow Corning) 39 acid-containing, crosslinked acrylate copolymer (INCI name: Acrylates 25 Copolymer, ca. 28% active substance) (Rohm&Haas) 3.12 Coloring Dye precursor preparations 1 to 10 were mixed with a 6% hydrogen 30 peroxide preparation (see 3.11) in a ratio of 1:1 immediately before use. The resulting preparation was applied to natural white tresses (Kerling) and left there for 30 mins. at 32 0 C. The tresses were then thoroughly rinsed with water and washed with a commercially available shampoo.

Claims (16)

1. Preparation for coloring keratinous fibers, more particularly human hair, containing as secondary intermediate in a cosmetically acceptable carrier at least one m-phenylenediamine derivative corresponding to 5 formula (I) or a physiologically safe salt thereof: N2R3 NRR R 1 6 X in which R 1 is a hydrogen atom, a halogen atom, a C14 alkyl group, a C1.4 10 monohydroxyalkyl group, a C24 polyhydroxyalkyl group, a C14 aminoalkyl group, a C 1 4 alkoxy-(C 1 4 )-alkyl group or a C14 dialkylamino-(C 1 4)-alkyl group, R 2 and R 3 independently of one another represent a hydrogen atom, a C14 alkyl group, a C24 monohydroxyalkyl group, a C34 polyhydroxyalkyl group, 15 a C14 alkoxy-(C 14 )-alkyl group or a C 14 aminoalkyl group and X is a saturated, 5-, 6- or 7-membered heterocycle containing at least one nitrogen atom and optionally another hetero atom selected from oxygen, sulfur or nitrogen, the heterocycle being attached to the aromatic ring system by a nitrogen atom and optionally bearing two substituents different 20 from hydrogen selected from a halogen atom, a C14 alkyl group, a C14 monohydroxyalkyl group, a C24 polyhydroxyalkyl group, a C14 aminoalkyl group, a C14 alkoxy-(C 1 4 )-alkyl group or a C14 dialkylamino-(C 1 4 )-alkyl group.

2. Preparation as claimed in claim 1, characterized in that it contains 25 an m-phenylenediamine derivative of formula (1), in which R 1 is a hydrogen WO 2004/031164 76 PCT/EP2003/010371 atom, a chlorine atom, a methyl group or a 2-hydroxyethyl group.

3. Preparation as claimed in claim I or 2, characterized in that it contains an m-phenylenediamine derivative of formula (I), in which R 2 and R 3 independently of one another represent a hydrogen atom, a methyl 5 group or a 2-hydroxyethyl group.

4. Preparation as claimed in claim 3, characterized in that it contains an m-phenylenediamine derivative of formula (I), in which R 2 and R 3 each represent a methyl group.

5. Preparation as claimed in claim 3, characterized in that it contains 10 an m-phenylenediamine derivative of formula (I), in which one of the substituents R 2 or R 3 is a 2-hydroxyethyl group and the other is a hydrogen atom.

6. Preparation as claimed in claim 3, characterized in that it contains an m-phenylenediamine derivative of formula (1), in which R 2 and R 3 each 15 represent a hydrogen atom.

7. Preparation as claimed in any of claims 1 to 6, characterized in that it contains an m-phenylenediamine derivative of formula (I), in which X is a morpholin-4-yl group, a piperidin-1-yl group, a 4-methylpiperazin-1-yl group or a pyrrolidin-1-yl group. 20

8. Preparation as claimed in claim 1, characterized in that the m phenylenediamine derivative of formula (I) is selected from 3-pyrrolidin-1-yl aniline, 3-piperidin-1-yl aniline, 3-morpholin-4-yl aniline, 3-(4 methylpiperazin-1-yl)-aniline, N,N-dimethyl-3-(pyrrolidin-1-yl)-aniline, 2-[(3 morpholin-4-yl phenyl)-amino]-ethan-1-ol, 2-[(3-piperidin-1-yl phenyl) 25 amino]-ethan-1-ol and 2-[(3-pyrrolidin-1-yl phenyl)-amino]-ethan-1-ol.

9. Preparation as claimed in any of claims 1 to 8, characterized in that it contains at least one primary intermediate.

10. Preparation as claimed in any of claims 1 to 9, characterized in that it contains at least one other secondary intermediate. 30

11. Preparation as claimed in any of claims 1 to 10, characterized in that WO 2004/031164 77 PCT/EP2003/010371 it additionally contains at least one substantive dye.

12. Preparation as claimed in claim 11, characterized in that the substantive dye is cationic.

13. Process for coloring keratinous fibers, in which the preparation 5 claimed in any of claims 1 to 12 is applied to the fibers and, after a contact time, is rinsed off again.

14. m-Phenylenediamine derivatives selected from the group consisting of N,N-dimethyl-3-(pyrrolidin-1-yl)-aniline, 2-[(3-morpholin-4-yl phenyl) amino]-ethan-1-ol, 2-[(3-piperidin-1-yl phenyl)-amino]-ethan-1-ol and 2-[(3 10 pyrrolidin-1-yl phenyl)-amino]-ethan-1-ol.

15 Synthesis intermediates selected from the group consisting of (2 chloroethoxy)-N-(3-morpholin-4-yl phenyl)-carboxamide, (2-chloroethoxy) N-(3-piperidin-1-yl phenyl)-carboxamide and (2-chloroethoxy)-N-(3 pyrrolidin-1-yl phenyl)-carboxamide. 15

16. Synthesis intermediates selected from the group consisting of 3-(3 morpholin-4-yl phenyl)-1,3-oxazolidin-2-one, 3-(3-piperidin-1-yl phenyl)-1,3 oxazolidin-2-one and 3-(3-pyrrolidin-1-yl phenyl)-1,3-oxazolidin-2-one.