A METHOD OF COLORING HAIR USING CATIONIC DYES

Abstract: The cationic dyes of formula (1) specified in claim 1 are suitable especially for colouring keratin-containing fibres, more especially for colouring hair.

Description: A method of colouring hair using cationic dves The present invention relates to a method of colouring keratin-containing fibres using cationic imidazole dyes, to novel imidazole dyes and to a process for the preparation thereof. There is already known from EP-A-714 954 a cationic imidazolazo dye that is suitable for colouring hair and is obtained by diazotising 4-alkoxyaniline, coupling with imidazole, then alkylating and quaternising, and finally reacting with p-phenylenediamine. That dye does not however, meet all the demands made in practice of such direct hair dyes, its stability in aqueous solution, in particular, being unsatisfactory. It has now been found that that disadvantage can be overcome by acylating the free aromatic amino group of such dyes or replacing that group with an alkoxy group. As a result the stability is appreciably improved and the dyes have adequate storage stability also at relatively high pH values, for example at pH values of from 5 to 10, which is of decisive advantage especially for formulations for colouring hair. The present invention accordingly relates to a method of colouring keratin-containing fibres that comprises treating the fibres with a dye of formula wherein Y, and Y 2 are each independently of the other hydrogen, unsubstituted or substituted 0,-0 4 - alkyl, or halogen, R, and R 2 are each independently of the other hydrogen or unsubstituted or substituted C r C 4 alkyl, R 3 and R 4 are each independently of the other hydrogen, unsubstituted or substituted 0,-0 4 - alkyl, C 1 -C 4 alkoxy or halogen, R 5 is hydrogen, C,-C 4 alkyl, C 1 -C 4 alkoxy or halogen, X is CrC^alkoxy or a group of formula -N(R 6 )-CO-R 7 , wherein R 6 is hydrogen or C,-C 4 alkyl and R 7 is hydrogen, C,-C 4 alkyl or -NH 2 and A " is an anion. In accordance with the invention, alkyl radicals are to be understood generally as open-chain or branched alkyl radicals, for example methyl, ethyl, n- and iso-propyl and n-, sec- and tert- butyl. The alkyl radicals may be mono- or poly-substituted, for example by hydroxy, carboxy, halogen, cyano or C,-C 4 alkoxy. The alkoxy radicals may contain from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms. They are, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy , tert-butoxy, n-pentyloxy or n-hexyloxy. The alkoxy groups, too, may be substituted, for example by the radicals mentioned as possible substituents for the alkyl groups, especially by hydroxy or C,-C 4 alkoxy. There come into consideration as anion A " both inorganic and organic anions, for example halide, such as chloride, bromide or iodide, sulfate, hydrogen sulfate, methyl sulfate, boron tetrafluoride, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, nitrate, benzenesulfonate, formate, acetate, propionate, lactate, and complex anions, such as an anion of a zinc chloride double salt. The anion is generally governed by the preparation procedure. Preferably, chlorides, hydrogen sulfates, sulfates, methosulfates, phosphates, formates, lactates or acetates are present. Halogen is to be understood as fluorine, bromine or iodine or, especially, chlorine. Each of Y, and Y 2 is preferably methyl and especially hydrogen. Each of R, and R 2 is preferably ethyl, hydroxyethyl or methyl. R 3 and R 4 are preferably methoxy, methyl, hydrogen or chlorine. The preferred meaning of R 5 is hydrogen. X is preferably unsubstituted C,-C 4 alkoxy or a radical -NH-CO-R 7 , wherein R 7 is especially hydrogen, methyl, ethyl or -NH 2 . Special preference is given in accordance with the invention to the use of dyes of formula wherein R, and R 2 are each methyl or ethyl, X is unsubstituted C,-C 4 alkoxy or a radical -NH-CO-R 7 , wherein R 7 is hydrogen, methyl, ethyl or -NH 2 and A " is an anion. The dyes of formula (2) are novel and the invention relates also thereto. The dyes of formulae (1) and (2) are prepared, for example, by acylating the free amino group in a compound of formula wherein Y,, Y 2 , R,, R 2l R 3 , R 4 , R 5 and A " are as defined for formula (1), in a manner known per se. This is carried out, for example, by reaction with an appropriate acid, for example formic acid or acetic acid, an anhydride, for example acetic anhydride, or KOCN. Compounds of formulae (1) and (2) wherein X is an alkoxy group are obtained, for example, by reacting a compound of formula wherein Y,, Y 2 , R,, R 2 , R 3 and R 4 are as defined for formula (1) and R 8 is C,-C 4 alkyl, with a p- alkoxy-aniline under reaction conditions known per se. The compounds of formulae (3) and (4) are known or can be obtained in a manner known per se. The dyes of formulae (1) and (2) are suitable for colouring keratin-containing fibres. "Keratin- containing fibres" are to be understood as wool, furs, feathers and, especially, human hair. A prefered method of colouring keratin-containing fibres of the present invention comprises a1) treating the fibres with a composition, possessing a pH value of pH >7, and comprising a developing substance and at least one coupling substance and an oxidation agent, or a2)treating the fibres with a composition, possessing a pH value of pH <7, comprising a developing substance and at least one coupling substance and an oxidation agent, or a3) treating the fibres with a dye of formula (1), or with a dye of formula (4), or with a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH >7, and comprising a developing substance and at least one coupling substance and an oxidation agent, or a4) treating the fibres with a dye of formula (1 ) according to claim 1 , or with a dye of formula (4), or with a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH <7, and comprising a developing substance and at least one coupling substance and an oxidation agent, and b) then applying without intermediary rinsing for 5 to 30 minutes, and c1)then applying to the treated fibres a composition, possessing a pH value of pH < 7, and comprising a developing substance and at least one coupling substance, or c2)then applying to the treated fibres a composition, possessing a pH value of pH > 7, and comprising a developing substance and at least one coupling substance, or c3)then applying to the treated fibres a dye of formula (1) according to claim 1, or a dye of formula (4) or a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH < 7, and comprising a developing substance and at least one coupling substance, or c4)then applying to the treated fibres a dye of formula (1), or a dye of formula (4), or a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH > 7, and comprising a developing substance and at least one coupling substance, or c5)then applying to the treated fibres a composition, possessing a pH value of pH > 7, and comprising a dye of formula (1), or a composition comprising a dye of formula (1),or c6)then applying to the treated fibres a composition, possessing a pH value of pH < 7, and comprising a dye of formula (1), or a composition comprising a dye of formula (1), with the proviso that least one dye of formula (1), or a composition comprising a dye of formula (1), applied to the hair. One preferred embodiment method of colouring keratin-containing fibres comprises a1) treating the fibres with a composition, possessing a pH value of pH >7, and comprising a developing substance and at least one coupling substance and an oxidation agent, or a2)treating the fibres with a composition, possessing a pH value of pH <7, comprising a developing substance and at least one coupling substance and an oxidation agent, and b) then applying without intermediary rinsing for 5 to 30 minutes, and c3)then applying to the treated fibres a dye of formula (1) according to claim 1, or a dye of formula (4) or a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH < 7, and comprising a developing substance and at least one coupling substance, or c4)then applying to the treated fibres a dye of formula (1), or a dye of formula (4), or a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH > 7, and comprising a developing substance and at least one coupling substance, or c5)then applying to the treated fibres a composition, possessing a pH value of pH > 7, and comprising a dye of formula (1), or a composition comprising a dye of formula (1),or c6)then applying to the treated fibres a composition, possessing a pH value of pH < 7, and comprising a dye of formula (1), or a composition comprising a dye of formula (1), or in a further embodiment of the invention c7)then applying to the treated fibres a dye of formula (1) according to claim 1 , or a dye of formula (4) or a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH < 7, and comprising a developing substance and at least one coupling substance and an oxidation agent, or c8)then applying to the treated fibres a dye of formula (1 ), or a dye of formula (4), or a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH > 7, and comprising a developing substance and at least one coupling substance and an oxidation agent, or c9)then applying to the treated fibres a composition, possessing a pH value of pH > 7, and comprising an oxidation agent and a dye of formula (1), or a composition comprising a dye of formula (1),or c10)then applying to the treated fibres a composition, possessing a pH value of pH < 7, and comprising an oxidation agent and a dye of formula (1), or a composition comprising a dye of formula (1), with the proviso that least one dye of formula (1), or a composition comprising a dye of formula (1), applied to the hair. One further preferred embodiment method of colouring keratin-containing fibres comprises a3) treating the fibres with a dye of formula (1), or with a dye of formula (4), or with a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH >7, and comprising a developing substance and at least one coupling substance and an oxidation agent, or a4) treating the fibres with a dye of formula (1) according to claim 1 , or with a dye of formula (4), or with a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH <7, and comprising a developing substance and at least one coupling substance and an oxidation agent, and b) then applying without intermediary rinsing for 5 to 30 minutes, and d)then applying to the treated fibres a composition, possessing a pH value of pH < 7, and comprising a developing substance and at least one coupling substance, or c2)then applying to the treated fibres a composition, possessing a pH value of pH > 7, and comprising a developing substance and at least one coupling substance, or c3)then applying to the treated fibres a dye of formula (1) according to claim 1 , or a dye of formula (4) or a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH < 7, and comprising a developing substance and at least one coupling substance, or c4)then applying to the treated fibres a dye of formula (1), or a dye of formula (4), or a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH > 7, and comprising a developing substance and at least one coupling substance, or c5)then applying to the treated fibres a composition, possessing a pH value of pH > 7, and comprising a dye of formula (1), or a composition comprising a dye of formula (1),or c6)then applying to the treated fibres a composition, possessing a pH value of pH < 7, and comprising a dye of formula (1), or a composition comprising a dye of formula (1), or in a further embodiment of the invention c7)then applying to the treated fibres a dye of formula (1) according to claim 1 , or a dye of formula (4) or a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH < 7, and comprising a developing substance and at least one coupling substance and an oxidation agent, or c8)then applying to the treated fibres a dye of formula (1), or a dye of formula (4), or a composition comprising a dye of formula (1), and a composition, possessing a pH value of pH > 7, and comprising a developing substance and at least one coupling substance and an oxidation agent, or c9)then applying to the treated fibres a composition, possessing a pH value of pH > 7, and comprising an oxidation agent and a dye of formula (1), or a composition comprising a dye of formula (1),or c10)then applying to the treated fibres a composition, possessing a pH value of pH < 7, and comprising an oxidation agent and a dye of formula (1), or a composition comprising a dye of formula (1), or c11)then applying to the treated fibres a composition, possessing a pH value of pH < 7, and comprising a developing substance and at least one coupling substance, or c12)then applying to the treated fibres a composition, possessing a pH value of pH > 7, and comprising an oxidation agent and a developing substance and at least one coupling substance, or with the proviso that least one dye of formula (1), or a composition comprising a dye of formula (1), applied to the hair. In one preferred embodiment of the invention dyes of formula (1) or (4) or further cationic dyes are mixed with the other components of the compositions shortly before the applying to the hair. In addition, the methods of colouring of the present invention can be carried out on hair, with preference being given to locks of hair, locks of bleached hair, bleached hair, middle blonde hair. Further one preffered embodiment of methods of colouring of the present invention concerns the colouring by a comb. The present invention relates also to compositions comprising such dyes for colouring keratin-containing fibres. The compounds of formulae (1) and (2) are present in the compositions according to the invention preferably in an amount of from 0.001 % to 5 %, especially from 0.01 % to 1 %, based on the total dyeing composition. The multiplicity of shades and the colour fastness of the dyes of formulae (1) and (2) used in accordance with the invention can be increased by combination with other dyes used in the field of hair-dyeing compositions. They can be combined very readily both with oxidation dyes and with direct dyes, it being possible for the latter to be of cationic nature or also uncharged. Only in the case of anionic direct dyes is a certain degree of caution required, since precipitation may occur in the formulation under certain circumstances. In all dyeing compositions, the joint use of a plurality of different dyeing substances is also possible; similarly possible is the joint use of a plurality of different oxidation dye precursors from the group of the developer and coupler compounds, for example aromatic compounds having a primary or secondary amino group, nitrogen-containing heterocycles, aromatic hydroxy compounds or amino acids, as described, for example, in German Patent Application 19 717 224.5, especially page 3, line 31 to page 5, line 8. The dyes of formulae (1) and (2) according to the invention produce colour shades in the range from reddish-violet to violet, and the fastness properties are excellent. Attention is drawn to the property thereof that allows hair that is already dark in colour still to be distinctly altered in shade. For colouring hair there are preferably used dyes of formula (1) in admixture with one or more further cationic dyes, especially those described in particular on pages 11 to 27 of WO 95/01772. Especially suitable are dye mixtures comprising a dye of formula (1), and also the yellow dye according to Example 1 and/or the red dye according to Example 4 and/or the orange dye according to Example 46 of WO 95/1772. In a further embodiment, for the purpose of further modification of colour shades the dyeing compositions according to the invention comprise, in addition to the dyes of formula (1) according to the invention, customary direct dyes, for example from the group of the nitroanilines, nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenols, phenazines, phenothiazines, methines or the compounds known as Arianors, such as, for example, the compounds known by the international names or trade names HO Yellow 2, HC Yellow 4, HC Yellow 6, Basic Yellow 57, Basic Yellow 9, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, Basic Red 2, Basic Violet 14, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 12, Basic Blue 26, HC Blue 2, HC Blue 7, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1 , Disperse Violet 1 , Disperse Violet 4, Disperse Black 9, Basic Brown 16 und Basic Brown 17, and also picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 4-N- ethyl-1 ,4-bis(2'-hydroxyethylamino)-2-nitrobenzene hydrochloride and 1-methyl-3-nitro-4-(2'- hydroxyethyl)-aminobenzene. Also very suitable for combination with the dyes according to the invention are cationised nitroaniline and anthraquinone dyes, for example those described in the following patent specifications: US-5 298 029, especially in column 2, line 33 to column 5, line 38; US-5 360 930, especially in column 2, line 38 to column 5, line 49; US-5 169 403, especially in column 2, line 30 to column 5, line 38; US-5 256 823, especially in column 4, line 23 to column 5, line 15; US-5 135 543, especially in column 4, line 24 to column 5, line 16; EP-A-818 193, especially on page 2, line 40 to page 3, line 26; US-5486 629, especially in column 2, line 34 to column 5, line 29; and EP-A-758 547, especially on page 7, line 48 to page 8, line 19. Also cationic azo dyes, e.g. according to GB-A-2 319 776, as well as the oxazine dyes described in DE-A-29 912 327 and mixtures thereof with the other direct dyes mentioned therein, can likewise readily be combined. The compositions of the invention according to this embodiment contain the dyes preferably in an amount of from 0.01 to 5 % by weight, based on the total dyeing composition. In addition, the dyeing compositions according to the invention may also contain naturally occurring dyes, such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, Rhamnus frangula bark, sage, campeche wood, madder root, catechu, sedre and alkanet root. Such colouring methods are described, for example, in EP-A-404 868, especially page 3, line 55 to page 4, line 9. In respect of further customary dye components, reference is made expressly to the series "Dermatology", edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages 248-250 (direct dyes), and chapter 8, pages 264 - 267 (oxidation dyes), and to "Europaisches Inventar der Kosmetikrohstoffe", 1996, published by The European Commission, obtainable in diskette form from the Bundesverband der deutschen Industrie- und Handelsunternehmen fur Arzneimittel, Reformwaren und Korperpflegemittel e.V., Mannheim. It is not necessary for the oxidation dye precursors optionally present or for the dyes each to be single compounds, but rather there may be present in the dyeing compositions according to the invention in addition, in lesser amounts, further components associated with the preparation procedures for the individual dyes, provided such components do not have an adverse effect on the dyeing result or do not need to be excluded for other, for example toxicological, reasons. The dyes of formula (1) according to the invention may also readily be used in combination with other dyes and/or adjuvants used in the colouring of hair, for example with • oxidising agents to achieve lightened colouration, as described in WO 97/20545, especially page 9, lines 5 to 9, • oxidising agents in the form of permanent-wave fixing solution, as described in DE-A-19 713 698 , especially page 4, lines 52 to 55, or EP-A-1 062 940, especially page 6, lines 41 to 47, (and in the equivalent WO 99/40895), • oxidation dyeing compositions, as described in EP-A-850 636, especially page 5, line 41 to page 7, line 52, EP-A-850 637, especially page 6, line 50 to page 8, line 44, EP-A-850 638, especially page 7, line 20 to page 9, line 26, and EP-A-852 135, especially page 4, line 54 to page 6, line 53, • oxidation dyeing compositions with cationic couplers, as described in WO 99/48856, especially page 9, line 16 to page 13, line 8, and WO 99/48875, especially page 11 , line 20 to page 12, line 13, • oxidation dyes in the presence of oxidoreductase enzyme, as described in WO 99/17730, especially page 4, line 11 to page 13, line 28, and WO 99/36034, especially pages 3 to 15, • autooxidisable oxidation dyes, as described in WO 99/20234, especially page 26, line 16 to page 28, line 15, or • nitrobenzene derivatives, as described in WO 99/20235, especially page 26, line 7 to page 30, line 15, • polyols or polyethers, as described in EP-A-962 219, especially page 27, lines 14 to 38, • thickening polymers, as described in EP-A-970 684, especially page 48, line 16 to page 51 , line 4, • sugar-containing polymers, as described in EP-A-970 687, especially page 28, line 17 to page 29, line 23, • quaternary ammonium salts, as described in WO 00/10517, especially page 44, line 16 to page 46, line 23, • anionic surfactants, as described in WO 00/10518, especially page 45, line 11 to page 48, line 3, • non-ionic surfactants, as described in WO 00/10519, especially page 45, line 11 to page 50, line 12, or • silicones, as described in WO 00/12057, especially page 45, line 9 to page 55, line 2. The dyeing compositions according to the invention result in intense colourations even at physiologically tolerable temperatures of less than 45°C. They are accordingly suitable especially for colouring human hair. For use on human hair, the dyeing compositions can usually be incorporated into an aqueous cosmetic carrier. Suitable aqueous cosmetic carriers include, for example, creams, emulsions, gels and also surfactant-containing foaming solutions, e.g. shampoos or other preparations, that are suitable for use on keratin-containing fibres. Such forms of use are described in detail in Research Disclosure 42448 (August 1999). If necessary, it is also possible to incorporate the dyeing compositions into anhydrous carriers, as described, for example, in US-3 369 970, especially column 1 , line 70 to column 3, line 55. The dyeing compositions according to the invention are also excellently suitable for the colouring method described in DE-A-3 829 870 using a colouring comb or a colouring brush. The dyeing compositions according to the invention may furthermore comprise any active ingredient, additive or adjuvant known for such preparations. The dyeing compositions in many cases comprise at least one surfactant, there being suitable in principle anionic and also zwitterionic, ampholytic, non-ionic and cationic surfactants. In many cases, however, it has proved advantageous to select the surfactants from anionic, zwitterionic and non-ionic surfactants. Anionic surfactants suitable for use in the preparations according to the invention include all anionic surface-active substances that are suitable for use on the human body. Such substances are characterised by an anionic group that imparts water solubility, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having approximately from 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and also hydroxy groups may be present in the molecule. The following are examples of suitable anionic surfactants, each in the form of sodium, potassium or ammonium salts or mono-, di- or tri-alkanolammonium salts having 2 or 3 carbon atoms in the alkanol group: - linear fatty acids having from 10 to 22 carbon atoms (soaps), - ether carboxylic acids of formula R-O-(CH 2 -CH 2 -O) x -CH 2 -COOH, in which R is a linear alkyl group having from 10 to 22 carbon atoms and x = 0 or from 1 to 16, - acyl sarcosides having from 10 to 18 carbon atoms in the acyl group, - acyl taurides having from 10 to 18 carbon atoms in the acyl group, - acyl isothionates having from 10 to 18 carbon atoms in the acyl group, - sulfosuccinic mono- and di-alkyl esters having from 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having from 8 to 18 carbon atoms in the alkyl group and from 1 to 6 oxyethyl groups, - linear alkane sulfonates having from 12 to 18 carbon atoms, - linear α-olefin sulfonates having from 12 to 18 carbon atoms, - -sulfo fatty acid methyl esters of fatty acids having from 12 to 18 carbon atoms, - alkyl sulfates and alkyl polyglycol ether sulfates of formula R'-O(CH 2 -CH 2 -O) x -SO 3 H, in which R' is a preferably linear alkyl group having from 10 to 18 carbon atoms and x' = 0 or from 1 to 12, - mixtures of surface-active hydroxysulfonates according to DE-A-3 725 030, especially page 3, lines 40 to 55, - sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropylene glycol ethers according to DE-A-3 723 354, especially page 4, lines 42 to 62, - sulfonates of unsaturated fatty acids having from 12 to 24 carbon atoms and from 1 to 6 double bonds according to DE-A-3 926 344, especially page 2, lines 36 to 54, - esters of tartaric acid and citric acid with alcohols which are addition products of approximately from 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols having from 8 to 22 carbon atoms. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having from 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and also especially salts of saturated and especially unsaturated C 8 -C 22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid. Surface-active compounds that carry at least one quaternary ammonium group and at least one -COO H or -SO 3 H group in the molecule are termed zwitterionic surfactants. Zwitterionic surfactants that are especially suitable are the so-called betaines, such as the N-alkyl- N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyl- dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name cocamidopropyl betaine. Ampholytic surfactants are to be understood as meaning surface-active compounds that, in addition to a C 8 -C 18 -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants include N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl- glycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each having approximately from 8 to 18 carbon atoms in the alkyl group. Ampholytic surfactants to which special preference is given are N-cocoalkyl- aminopropionate, cocoacylaminoethylaminopropionate and C 12 -C 18 acylsarcosine. Non-ionic surfactants contain as the hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example: - addition products of from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol of propylene oxide with linear fatty alcohols having from 8 to 22 carbon atoms, with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group, - C 12 -C 22 fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with glycerol, - C 3 -C 22 alkyl-mono- and -oligo-glycosides and ethoxylated analogues thereof, - addition products of from 5 to 60 mol of ethylene oxide with castor oil and hydrogenated castor oil, - addition products of ethylene oxide with sorbitan fatty acid esters, - addition products of ethylene oxide with fatty acid alkanolamides. Examples of cationic surfactants that can be used in the hair-treatment compositions according to the invention are especially quaternary ammonium compounds. Preference is given to ammonium halides, such as alkyltrimethylammonium chlorides, dialkyldimethyl- ammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethyl- ammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylamrnonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants that can be used in accordance with the invention are quatemised protein hydrolysates. Also suitable in accordance with the invention are cationic silicone oils, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilised trimethylsilylamodimethicone), Dow Corning 929 emulsion (comprising a hydroxylamino- modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and also Abil ® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80). Alkylamidoamines, especially fatty acid amidoamines, such as the stearylamidopropyl- dimethylamine obtainable under the name Tego Amid ® 18, are distinguished not only by a good conditioning action but also especially by their good biodegradability Quaternary ester compounds, so-called "esterquats", such as the methyl hydroxyalkyl- dialkoyloxyalkylammonium methosulfates marketed under the trade mark Stepantex ® , are also very readily biodegradable. An example of a quaternary sugar derivative that can be used as cationic surfactant is the commercial product Glucquat ® 100, according to CTFA nomenclature a "lauryl methyl gluceth-10 hydroxypropyl dimonium chloride". The alkyl-group-containing compounds used as surfactants may be single substances, but the use of natural raw materials of vegetable or animal origin is generally preferred in the preparation of such substances, with the result that the substance mixtures obtained have different alkyl chain lengths according to the particular starting material used. The surfactants that are addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of such addition products may either be products having a "normal" homologue distribution or products having a restricted homologue distribution. "Normal" homologue distribution is to be understood as meaning mixtures of homologues obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Restricted homologue distributions, on the other hand, are obtained when, for example, hydrotalcites, alkali metal salts of ether carboxylic acids, alkali metal oxides, hydroxides or alcoholates are used as catalysts. The use of products having restricted homologue distribution may be preferred. Examples of further active ingredients, adjuvants and additives are as follows: - non-ionic polymers, for example vinylpyrrolidone/vinyl acrylate copopylmers, polyvinyl- pyrrolidone and vinylpyrrolidone/vinyl acetate copolymers and polysiloxanes, - cationic polymers, such as quatemised cellulose ethers, polysiloxanes having quaternary groups, dimethyldiallylammonium chloride polymers, copolymers of dimethyldiallylammonium chloride and acrylic acid, as available commercially under the name Merquat R 280 and the use of which in hair colouring is described, for example, in DE-A-4 421 031 , especially page 2, lines 20 to 49, or EP-A-953 334, especially page 27, line 17 to page 30, line 11 , acrylamide/dimethyldiallylammonium chloride copolymers, diethyl-sulfate-quatemised dimethylaminoethyl methacrylate/vinylpyrrolidone copolymers, vinylpyrrolidone/imidazolinium methochloride copolymers, - quatemised polyvinyl alcohol, - zwitterionic and amphoteric polymers, such as, for example, acrylamidopropyl-trimethylammonium chloride/acrylate copolymers and octylacrylamide/- methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, - anionic polymers, such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobomyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers, - thickeners, such as agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean flour, linseed gums, dextrans, cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such amylose, amylopectin and dextrins, clays, e.g. bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol, - structuring agents, such as glucose and maleic acid, - hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin, and cephalins, silicone oils, and also conditioning compounds, for example such as those described in DE-A-19 729 080, especially page 2, lines 20 to 49, EP-A-834 303, especially page 2, line 18 to page 3, line 2, or EP-A-312 343, especially page 2, line 59 to page 3, line 11. - protein hydrolysates, especially elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolysates, condensation products thereof with fatty acids and also quatemised protein hydrolysates, - perfume oils, dimethyl isosorbitol and cyclodextrins, - solubilisers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, - anti-dandruff active ingredients, such as piroctones, olamines and zinc Omadine, - further substances for adjusting the pH value, - active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extracts and vitamins, - cholesterol, - light stabilisers and UV absorbers, as described, for example, in EP-A-819 422, especially page 4, lines 34 to 37, - consistency regulators, such as sugar esters, polyol esters or polyol alkyl ethers, - fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters, - fatty alkanolamides, - polyethylene glycols and polypropylene glycols having a molecular weight of from 150 to 50 000, for example such as those described in EP-A-801 942, especially page 3, lines 44 to 55, - complexing agents, such as EDTA, NTA and phosphonic acids, - swelling and penetration substances, such as polyols and polyol ethers, as listed extensively, for example, in EP-A-962 219, especially page 27, lines 18 to 38, for example glycerol, propylene glycol, propylene glycol monoethyl ether, butyl glycol, benzyl alcohol, carbonates, hydrogen carbonates, guanidines, ureas and also primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole, - opacifiers, such as latex, - pearlising agents, such as ethylene glycol mono- and di-stearate, - propellants, such as propane-butane mixtures, N 2 O, dimethyl ether, CO 2 and air, and also - antioxidants. The constituents of the aqueous carrier are used in the preparation of the dyeing compositions according to the invention in the amounts customary for that purpose; for example emulsifiers are used in concentrations of from 0.5 to 30 % by weight and thickeners in concentrations of from 0.1 to 25 % by weight of the total dyeing composition. The pH value of the ready-to-use dyeing preparations are usually from 2 to 11 , preferably from 5 to 10. To colour keratin-containing fibres, especially to colour human hair, the dyeing compositions are usually applied to the hair in an amount of from 50 to 100 g in the form of the aqueous cosmetic carrier, left there for approximately 30 minutes and then rinsed off or washed off with a commercially available hair shampoo. The dyes used according to the invention and the optionally used oxidation dye precursors may be applied to the keratin-containing fibres either simultaneously or in succession, the order in which they are applied being unimportant. The dyes used according to the invention and the optionally used oxidation dye precursors of the compositions according to the invention may be stored separately or together, either in a liquid to paste-like preparation (aqueous or non-aqueous) or in the form of a dry powder. When the components are stored together in a liquid preparation, the preparation should be substantially anhydrous in order to reduce reaction of the components. When they are stored separately, the reactive components are intimately mixed with one another only immediately before use. In the case of dry storage, before use a defined amount of hot (from 50 to 80°C) water is usually added and a homogeneous mixure prepared. The following Examples serve to illustrate the invention without limiting the invention thereto. Unless specified otherwise, parts and percentages relate to weight. Example 1: 16 g of the compound of formula are introduced into 65 g of acetic anhydride and stirring is carried out for 2 hours at a bath temperature of approximately 75°C, after which time all starting material has disappeared. After cooling, filtration is carried out and then washing with acetic anhydride. In order to remove the acetic anhydride, the filter cake is suspended in 200 ml of isopropanol, and the suspension is stirred for 2 hours and filtered again and washed with isopropanol. 17.8 g of the compound of formula is obtained in very pure form. In aqueous solution, the compound dyes bleached yak hair a brilliant red-tinged violet. The acetylation can also be carried out in solvents, for example in water: 110 g of the above-described starting compound are suspended in 300 ml of water and, at a temperature of approximately 70°C, a total of 61.4 g of acetic anhydride (=100 % excess) are added over a period of one hour. The reaction mixture is cooled with stirring, then filtered and washed with water. After drying, 122.5 g of the acetylated compound are obtained in which only traces of the starting material are still present. Example 2: With stirring, 15 g of the compound of formula are slowly added to 30 g of formic acid (98 %) and heating is carried out for 3 hours at 65°C. 100 ml of isopropanol are added dropwise to the hot solution, which is then stirred until cold. Filtration followed by thorough washing with isopropanol are carried out. The moist filter cake is first stirred into 65 ml of methanol barely at reflux, and then filtration at 45°C followed by washing with methanol are carried out. The filter cake is then dissolved hot in 1.5 litres of methanol, the solution is clarified and the mother liquor is concentrated to approximately 85 g using a rotary evaporator, in the course of which there is already partial precipitation of the dye. After cooling suction filtration is carried out, followed by washing with a small amount of methanol and drying. Approximately 9 g of the dye of formula are obtained. In aqueous solution, the dye colours bleached yak hair a brilliant red-tinged violet. Example 3: 10.3 g of the compound of formula are dissolved in 33 ml of 1 N hydrochloric acid in an ice-cooled apparatus. 30 g of ice are added to the reaction solution and then, over a period of half an hour, 2.4 g of potassium cyanate are added in portions. Towards the end a honey-like residue forms, which may sometimes block the stirrer. After standing for from 1 to 2 hours in an ice bath, the residue has turned into a brittle mass that can readily be crushed using a glass rod. The suspension, readily stirrable again, still contains significant amounts of starting material and therefore a further 9 ml of HCI (1 N) and 1.2 g of KOCN are added. The ice bath is then removed and filtration at room temperature is carried out. The residue is suspended in water again and stirred at 75°C for 2 hours. After cooling, filtration and washing with water are carried out. For purification, the residue is dissolved hot in 12 litres of methanol and the solution is clarified by way of a preheated pressurised suction filter. The filtrate is concentrated to approximately 2 litres using a rotary evaporator, the dye precipitating in pure form. Following cooling, filtration and washing with methanol, 24 g of the dye of formula are obtained. In aqueous solution, the dye colours bleached yak hair a brilliant violet, the shade of which is slightly less red-tinged than that of the formyl-substituted dye of Example 2. Example 4: 13 g of p-anisidine are dissolved at approximately 50°C in 45 g of dimethylformamide in a suitable stirring apparatus. Then, with stirring, 26.7 g of the compound of formula are added in portions and the mixture is stirred for 80 hours at a bath temperature of 90°C under nitrogen. While still hot, the reaction mixture is diluted with a further 50 g of dimethylformamide, allowed to cool slightly and filtered at approximately 40°C. The crystalline filter cake is washed with a further 50 g of DMF in portions, and finally thoroughly suction-filtered dry. In order to remove small amounts of starting material that are still present, the filter cake is suspended in 80 g of water and stirred for 2 hours at a temperature of from 70 to 75°C. After cooling with stirring, filtration is carried out, followed by washing with a total of 50 g of water, in portions, and drying. 22 g of the dye of formula are obtained. In aqueous solution, the dye colours bleached yak hair a brilliant red-tinged violet. Example 5: A 10 % solution of a non-ionic surfactant (Plantaren® 2000 [Henkel]) is adjusted to pH 9.5 using citric acid. 0.06 % of the dye from Example 1 are dissolved therein. A 1 g strand of undamaged human hair ("Italian white virgin", Imhair Ltd) is treated for 20 minutes at room temperature with 2 g of the dye solution and then rinsed and shampooed. A very attractive violet colouration is obtained, which even after washing eight times can still be seen clearly. The fastness to light of the colouration is excellent. Example 6: A 10 % solution of a non-ionic surfactant (Plantaren® 2000 [Henkel]) is adjusted to pH 5.5 using citric acid. The following dyes are dissolved in 100 g of that solution: 0.20 g of the yellow dye according to Example 1 in WO 95/01772 0.05 g of the dye according to the invention from Example 4 of the present Application. A 1 g strand of undamaged human hair ("Italian white virgin", Imhair Ltd) is treated for 20 minutes at room temperature with 2 g of the above dye solution and then rinsed and shampooed. A very attractive copper colouration having excellent fastness to washing, rubbing and light is obtained. Example 7: A 10 % solution of a non-ionic surfactant (Plantaren® 2000 [Henkel]) is adjusted to pH 5.5 using citric acid. The following dyes are dissolved in 100 g of that solution: 0.25 g of the yellow dye according to Example 1 in WO 95/01772 0.08 g of the orange dye according to Example 46 in WO 95/01772 0.06 g of the dye according to the invention from Example 2 of the present Application. 0.11 g of the blue dye according to Example 6 in WO 95/01772. A strand of bleached human hair is treated for 20 minutes at room temperature with double the amount thereof of the above dyeing solution, and is then rinsed and shampooed once. A black colouration having good fastness to washing and rubbing is obtained. Example 8: The following cationic emulsion base is prepared: 3.8 g of behenic trimonium chloride (Genamin KDM-P [Hoechst]) 4.0 g of cetyl alcohol (Lanette 16 [Henkel]) 0.5 g of phenoxyethanoϊ (Uniphen P23 [Induchem]) 0.1 g of perfume (PO Cinque 226482 [drom]) water ad 100 0.06 g of the dye according to Example 4 of the present Application is dissolved in the above base and the pH is adjusted to 6.5 using monoethanolamine. A 1 g strand of undamaged medium-brown human hair (virgin medium-brown hair, Imhair Ltd.) is treated for 20 minutes at room temperature with 2 g of the above dyeing emulsion, and is then rinsed and shampooed once. The hair acquires a very attractive intense aubergine shade having excellent fastness properties. Example 9: A 10 % solution of a non-ionic surfactant (Plantaren R 2000 [Henkel]) is adjusted to pH 5.5 using citric acid. The following dyes are dissolved in 100 g of that solution: 0.06 g of the yellow dye according to Example 1 in WO 95/01772 0.09 g of the orange dye according to Example 46 in WO 95/01772 0.03 g of the dye according to the invention from Example 4 of the present Application 0.07 g of the blue dye according to Example 6 in WO 95/01772. A strand of bleached human hair and a strand of undamaged white human hair are each treated for 20 minutes at room temperature with double the amount thereof of the above dyeing solution, and are then rinsed and shampooed once. In both cases the result is a dark- brown colouration with a distinct, very attractive violet tinge. Example 10: The following dyes are dissolved in 100 g of a solution of a non-ionic surfactant as described in Example 5 (pH 9.5): 0.14 g of Basic Red 76 (Arianor R Madder Red), 0.14 g of the dye according to the invention from Example 4, 0.28 g of Basic Blue 99 (Arianor R Steel Blue), 0.28 g of HC Yellow 2 and 0.14 g of the yellow dye according to Example 1 in WO 95/01772. A strand of white, undamaged hair is treated for 20 minutes at room temperature with the above solution. The result is a light-brown colouration with an attractive copper tinge. Example 11 : The procedure is as in Example 10, except that the dyes specified are replaced by 0.4 g of the red dye according to Example 3 in WO 95/01772 and 0.1 g of the dye according to the invention from Example 4. The result on the white hair is a very attractive, intensely ruby-red colouration having excellent fastness properties. Example 12 Compositions (A) below, in accordance with the invention, are prepared (contents in grams): Composition 1(A) 2(A) 3(A) 4(A) 5(A) 6(A) 7(A) 8(A) Para-toluylenediamine 0.25 0.70 2,4-Diamino-1-(-(β- 0.35 hydroxyethyloxy)benzene Para-phenylenediamine - 0.20 - 0.30 1.00 0.70 0.70 Para-aminophenol 0.30 0.50 0.15 5-N-(β-Hydroxyethyl) 0.50 0.80 0.17 amino-2-methylphenol 1 ,3-Dihydroxybenzene 0.50 0.50 5-Amino-methylphenol 0.30 Cationic dye of example 4 0.15 0.20 0.05 0.10 0.25 0.10 0.50 0.40 Common dye support (*) (*) (*) O (*) ( * ) O ( * ) O Water qs 100 100 100 100 100 100 100 100 (*) Common dve support: Oleyl alcohol polyglycerolated with 4.0 9 2 mol of glycerol Oleyl alcohol polyglycerolated with 5.69 g A.M. 4 mol of glycerol, containing 78% active material (A.M.) Oleic acid 3.0 g Oleylamine containing 2 mol of ethylene oxide, sold under the trade name Ethomeen 012 by the company Akzo Diethylaminopropyllaurylaminosuccinamate, 3.0 g A.M. sodium salt, containing 55% A.M. Oleyl alcohol 5.0 g Oleic acid diethanolaminde 12.0 g Propylene glycol 3.5 g Ethyl alcohol 7.0 g Dipropylene glycol 0.5 g Propylene glycol monomethyl ether 9.0 g Sodium metabisulphite as an aqueous solution 0.455 g A.M. containing 35% A.M. Ammonium acetate 0.8 g Antioxidant, sequestering agent qs Fragrance, preserving agent qs Aqueous ammonia containing 20% NH 3 10.0 g Compositions 9(A) ' to 32 (A) ' are identical to composition 2(A), and compositions 9(A) " to 32 (A) " are identical to composition 4 (A), and compositions 9 (A) "' to 32 (A) '" are identical to composition 5(A), and compositions 9 (A) ι to 32 (A) ιv are identical to composition 6 (A), and compositions 9 (A) v to 32 (A) v are identical to composition 7 (A), with the proviso that para- phenylenediamine is replaced by a compound C as given below in table 1. Compositions 34(A)' to 57 (A)' are identical to composition 8(A), with the proviso that 2,4- diamino-1-(-(β-hydroxyethyloxy)benzene is replaced by a compound C as given below in table t Compositions 59(A)' to 81(A)' are identical to composition 1(A), and compositions 59(A) 1' ' to 81 (A) π identical to composition 8 (A), with the proviso that para-toluylenediamine is replaced by a compound C as given below in table 1. Table 1 Compositions Compound C 9(A)' " , 34(A)', 59(A)'- 2-chloro-para-phenylendiamine 10(A)' "V , 35(A) , 60(A)'-" 2,3-dimethyl-para-phenylenediamine 11 (A)'- V , 36(A) , 61 (A)'-" 2,6-dimethyl-para-phenylenediamine 12(A)' "V , 37(A) , 62(A)'-" 2,6-diethyl-para-phenylenediamine 13(A)'- V , 38(A) 1 , 63(A)'-" 2,5-dimethyl-para-phenylenediamine 14(A)'- V , 39(A) , 64(A)'-" N,N-dimethyl-para-phenylenediamine 15(A)'- V , 40(A) 1 , 65(A)'-" N.N-diethyl-para-phenylenediamine 16(A)'- V , 41(A) , 66(A)'-" N,N-dipropyl-para-phenylenediamine 17(A)' "V , 42(A) , 66(A)'-" 4-amino-N,N-diethyl-3-methylaniline 18(A)'- V , 43(A) , 66(A)'-" N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine 19(A)'- , 44(A) , 67(A)'-" 4-amino-N,N-bis(.beta.-hydroxyethyl)-3-rnethylaniline 20(A)'- V , 45(A) , 68(A)'-" 4-amino-3-chloro-N,N-bis(.beta.-hydroxyethyl)aniline 21 (A)'- 46(A) , 69(A)'-" 2-.beta.-hydroxyethyl-para-phenylenediamine 22(A)'- V , 47(A) , 70(A)'-" 2-fluoro-para-phenylenediamine 23(A) I , 48(A) , 71 (A)'-" 2-isopropyl-para-phenylenediamine 24(A)' "V , 49(A) , 72(A)'-" N-(.beta.-hydroxypropyl)-para-phenylenediamine 25(A)'- V , 50(A)', 74(A)'-" 2-hydroxymethyl-para-phenylenediamine 26(A)'- V , 51 (A)', 75(A)'-" N,N-dimethyl-3-methyl-para-phenylenediamine 27(A)'- V , 52(A)', 76(A)'-" N,N-(ethyl-.beta.-hydroxyethyl)-para-phenylenediamine 28(A)'- V , 53(A)', 77(A)'-" N-(.beta.,.gamma.-dihydroxypropyl)-para-phenylenediamine 29(A)'- V , 54(A)', 78(A)'-" N-(4'-aminophenyl)-para-phenylenediamine 30(A)'- V , 55(A)', 79(A)'-" N-phenyl-para-phenylenediamine 31 (A)'- |V , 80(A)'-" 2-.beta.-hydroxyethyloxy-para-pheπylenediamine 32(A) μv , 57(A)', 81(A)'-" 2-.beta.-acetylaminoethyloxy-para-phenyleπediamine Compositions 100 (A)' to 107(A)' are identical to composition 1(A), and compositions 100(A) " to 107(A)" are identical to composition 8(A), with the proviso that para-toluylenediamine is replaced by a compound C as given below in table 2. Compositions 108(A) 1 to 114(A) ' are identical to composition 1 (A), and compositions 108(A) " to 114 (A)" are identical to composition 8 (A), with the proviso that para-phenylenediamine is replaced by a compound C as given below in table 2. Table 2 Compositions Compound C 100(A)'-", 108(A)'-" N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3- diaminopropanol 101(A)'-", 109(A)'-" N,N'-bis(.beta.-hydroxyethyl)-N,N'-bis(4'- aminophenyl)ethylenediamine 103(A)'-", 110(A)'-" N,N'-bis(4-aminophenyl)tetramethylenediamine 104(A)"-", 111(A)'-" N,N'-bis(.beta.-hydroxyethyl)-N 105(A)'-", 112(A)'-" N'-bis(4-aminophenyl)tetramethylenediamine 106(A)'-", 113(A)'-" N,N'-bis(4-methylaminophenyl)tetramethylenediamine 107(A) 1 -", 114(A)'-" N.N'-bisfethyO-N.N'-bis^'-amino-S - methyiphenyl)ethylenediamine Compositions 200(A) ' to 210(A) ' are identical to composition 1 (A), and compositions 200(A) " to 210(A)" are identical to composition 2 (A), and compositions 200(A) " 1 to 210(A) 1 " are identical to composition 3 (A), with the proviso that para-aminophenol is replaced by a compound C as given below in table 3. Table 3 Compositions Compound C 200(A)'-"' 4-amιno-3-methylphenol 203(A)'-"' 4-amιno-3-fluorophenol 204(A) 1 - 1 " 4-amιno-3-hydroxymethylphenol 205(A)'-" 1 4-amιno-2-methylphenol 206(A)'-" 1 4-amιno-2-hydroxymethylphenol 207(A)'-" 1 4-amιπo-2-methoxymethyl-pheπol 208(A)'-'" 4-ammo-2-amιnomethylphenol 209(A)'-'" 4-amιno-2-( beta -hydroxyethylamιnomethyl)phenol 210(A)'-'" 4-amιno-2-fluoro-phenol Compositions 300(A) ' to 304(A) ' are identical to composition 1 (A), and compositions 300(A) " to 304(A) " are identical to composition 2 (A), and compositions 300(A) '" to 304(A) '" are identical to composition 3 (A), with the proviso that para-am inophenol is replaced by a compound C as given below in table 3. Table 3 Compositions Compound C 300(A)"-' 7 ' 2-amιno-phenol 301(A)'-" 1 2-amιno-5-methylphenol 303(A) '-" 1 2-amιno-6-methylphenol 304(A)'-" 1 5-acetamιdo-2-amιnophenol Compositions 400(A)' to 404(A)' are identical to composition (A), and compositions 400(A)" to 404(A) " are identical to composition 4(A), and compositions 400(A) "' to 404(A) '" are identical to composition 5(A), and compositions 400(A)' V to 404(A) l are identical to composition 6(A), and compositions 400(A) v to 404(A) v are identical to composition 7(A), as given above in example 2 with the proviso that para-phenylenediamine is replaced by a compound C as given below in table 4. Compositions 405(A)' to 409 (A)' are identical to composition 8(A), with the proviso that 2,4- diamino-1-(-(β-hydroxyethyloxy)benzene is replaced by a compound C as given below in table 4. Compositions 410(A)' to 414(A)' are identical to composition 1(A), and compositions 410(A) 1' to 414 (A) π identical to composition 8 (A) as given above in example 2 with the proviso that para-toluylenediamine is replaced by a compound C as given below in table 4. Table 4 Compositions Compound C 400(A)'- V , 405(A)', 410(A)'- 11 2,4,5,6-tetraaminopyrimidine 401 (A)'- v , 406(A)', 411(A)'-" 4-hydroxy-2,5,6-triaminopyrimidine 402(A)'- V , 407(A)', 412(A)'-" 4,5-diamino-1 -methylpyrazole 403(A)'- V , 408(A)', 413(A)' " " 3,4-diaminopyrazole 404(A)'- V , 409(A)', 414(A)'-" 4,5-diamino-1 -(4'-chlorobenzyl) pyrazole Compositions 500 (A) ' to 521 (A) ' are identical to composition 4(A), 9(A) " to 32 (A) " and 400(A) " to 404(A) " with the proviso that 5-amino-2-methylphenol is replaced by a compound C as given below in table 5. Table 5 Compositions Compound C 500(A)' 5-amino-2-methoxyphenol 501 (A) 1 5-amino-2-(.beta.-hydroxyethyloxy)phenol 502(A)' 5-amino-2-methylphenol 503(A)' 5-N-(.beta.-hydroxyethyl)amino-2-methylphenol 504(A)' 5-N-(.beta.-hydroxyethyl)amino-4-methoxy-2-methylphenol 505(A) 1 5-amino-4-methoxy-2-methylphenol 506(A) 1 5-amino-4-chloro-2-methylphenol 507(A)' 5-amino-2,4-dimethoxy-ρhenol 508(A) 1 5-(.gamma.-hydroxypropylamino)-2-methy!phenol 509(A) 1 meta-phenylenediamine 510(A) 1 3,5-diamino-1-ethyl-2-methoxybenzene 511 (A)' 3,5-diamino-2-methoxy-1-methylbenzene 512(A)' 2,4-diamino-1 -ethoxy benzene 513(A)' 1,3-bis(2,4-diaminophenoxy)propane 514(A)' bis(2,4-diaminophenoxy)methane 515(A)' 1-(.beta.-aminoethyloxy)-2,4-diaminobenzene 516(A)' 2-amino-1-(.beta.-hydroxyethyloxy)-4-methylaminobenzene 517(A)' 2,4-diamino-1-ethoxy-5-methylbenzene 518(A) 1 2,4-diamino-5-(.beta.-hydroxyethyloxy)-1-methylbenzene 519(A)' 2,4-diamino-1-(.beta.,.gamma.-dihydroxypropyloxy)benzene 520(A)' 2,4-diamino-1-(.beta.-hydroxyethyloxy)benzene 521(A)' 2-amino4-N-(.beta.-hydroxyethyl)amino-1-methoxybenzene Compositions 600 (A) ' to 615 (A) ' are identical to composition 1-8(A), 9(A) ' "v to 32 (A) μv , 34(A)' to 57 (A)' , 59(A)'-" to 81(A)'-", 100(A) ' " " to 107(A) 1" ", 108(A) '-" to 114(A) '-", 200(A) '-'" to 210(A) ' " ", 300(A)'-'" to 304(A)'-"', 400(A)' "V to 404 (A)' "v , 405(A)" to 409 (A)' , 410(A)' to 414(A)'-" and 500 (A) ' to 521 (A)' with the proviso that the common dye support (*) is replaced by a the common dye support (**) which is identical to the common dye support (*) with the proviso that " aqueous ammonia containing 20% NH 3 ". is replaced by a basifying agent D as given below in table 6. Table 6 common dye support (**) basifying agent D 600(A)' pottassium carbonate 601 (A)' sodium carbonate 602(A)' triethanolamine 603(A)' diethanolamnie 604(A)' monoethaπolamine 605(A)' sodium hydroxide 606(A)' potassium hydroxide 607(A) 1 N,N-dimethyl-N'-ethylenediamine 608(A)' 4-(Ethylamino)-b-butylamine 609(A)' N-(n-Propyl)-1 ,3-propanediamine 610(A)' N,N-diethylenediamine 61 1 (A)' N,N,N',N'-Tetramethylethylenediamine 612(A)' N,N-dimethylhydrazine 613(A)' 2-n-butylaminmoethylamine 614(A)' 1 ,6-diaminohexane 615 (A) ' 2-amino-2-methyl-1 -propanol Example 13: Compositions B (1(B), 2(B) and 3(B)) below, in accordance with the invention, are prepared (contents in grams): 1(B) 2(B) 3(B) 1 ,4-Diaminobenzene 0.40 - - 5-Amino-2-methylphenol 0.45 - - Para-toluylenediamine sulphate - 0.50 0.35 Common dye support (*) as ( * ) O 0 described above in example 12 Demineralized water qs 100 100 100 Cationic dye of example 4 4 4 4 Quaternary polyammonia sold 10 10 10 under trade name CELQUAT SC- 240 by the company National Starch Sawdust qs 100 100 100 Compositions 4(B)' to 29 (B)' are identical to composition 2(B), and compositions 4(B)" to 29 (B) " are identical to composition 3 (B), with the proviso that para-toluylenediamine sulphate is replaced by a compound E as given below in table 1. Compositions 30 (B) ' to 56 (B) ' are identical to composition 1 (B) with the proviso that 1 ,4- diaminobenzene is replaced by a compound E as given below in table 1. Table 1 Compositions Compound E 4(B)'-", 30 (B) ' 2-chloro-para-phenylendiamine 5(B) 1 -" ", 31 (B) ' 2,3-dimethyl-para-phenylenediamine 6(B)'- ".32(B)' 2,6-dimethyl-para-phenylenediamine 7(B)'- 1 ".33(B)' 2,6-diethyl-para-phenylenediamine 8(B)'- 1 ", 34(B)' 2,5-dimethyl-para-phenylenediamine 9(B)'-", 35(B)' N,N-dimethyl-para-phenylenediamine 10(B) 1 -", 37(B)' N.N-diethyl-para-phenylenediamine 11(B)'-", 38(B)' N,N-dipropyl-para-phenylenediamine 12(B)'-", 39(B)' 4-amino-N,N-diethyl-3-methylaniline 13(B)'-", 40(B)' N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine 14(B) 1 -", 41 (B)' 4-amino-N,N-bis(.beta.-hydroxyethyl)-3-methylaniline 15(B)'-", 42(B)' 4-amino-3-chloro-N,N-bis(.beta.-hydroxyethyl)aniline 16(B)'-", 43(B)' 2-.beta.-hydroxyethyl-para-phenylenediamine 17(B) 1 -", 44(B) 1 2-fluoro-para-phenylenediamine 18(B)'-", 45(B)' 2-isopropyl-para-phenylenediamine 19(B)'-", 46(B)' N-(.beta.-hydroxypropyl)-para-phenylenediamine 20(B)'-", 47(B) 1 2-hydroxymethyl-para-phenylenediamine 21(B) 1" ", 48(B)' N,N-dimethyl-3-methyl-para-phenylenediamine 22(B)'-", 49(B)' N,N-(ethyl-.beta.-hydroxyethyl)-para-phenylenediamine 23(B)'-", 50(B)' N-(.beta.,.gamma.-dihydroxypropyl)-ρara-phenylenediamine 24(B)'-", 51 (B)' N-(4'-aminophenyl)-para-phenylenediamine 25(B)'-", 52(B)' N-phenyl-para-phenylenediamine 26(B) 1 -' 1 , 53 (B) ' 2-.beta.-hydroxyethyloxy-para-phenylenediamine 27(B)'-", 54(B)' 2-.beta.-acetylaminoethyloxy-para-phenylenediamine 28(B) 1" ", 55(B)' N-(.beta.-methoxyethyl)-para-phenylenediamine 29(B)'-", 56(B) 1 Para-toluylenediamine Compositions 100 (B)' to 109 (B)' are identical to composition 1(B), 30(B)' to 56 (B) 1 , with the proviso that 5-amino-2-methylphenol is replaced by a compound E as given below in table 2. Table 2 Compositions Compound E 100(B) 1 5-amino-2-methoxyphenol 101(B) 1 5-amino-2-(.beta.-hydroxyethyloxy)phenol 102(B)' 5-amino-2-methylphenol 103(B)' 5-N-(.beta.-hydroxyethyl)amino-2-methylphenol 104(B)' 5-N-(.beta.-hydroxyethyl)amino-4-methoxy-2-methylphenol 105(B)' 5-amino-4-methoxy-2-methylphenol 106(B)' 5-amino-4-chloro-2-methylphenol 107(B)' 5-amino-2,4-dimethoxy-phenol 108(B)' 5-(.gamma.-hydroxypropylamino)-2-methylphenol 109(B)' meta-phenylenediamine One part by weight of composition B was mixed, at the time of use, with 0.1 part by weight of composition (B') and with one part by weight of a composition (F) comprising a 20-volumes hydrogen peroxide solution (6% by weight). The resulting composition was applied for 30 minutes to locks of natural grey hair containing 90% white hairs. The hair was then rinsed, washed with a standard shampoo and then dried. The hair was dyed in a brilliant red-tinged violet shade with very good endurance properties with respect to subsequent shampooing. Example 14: The ready-to-use dye compositions below are prepared (contents in grams): Compositions 1(G) 2(G) 3(G) 4(G) 5(G) 6(G) Para-phenylenediamine 0.70 - 0.36 0.55 - 0.283 para-Aminophenol 0.187 - 0.147 - 5-N-(β-Hydroxyethyl) 0.21 0.36 - 0.165 0.283 amino-2-methylphenol Cationic dye of example 4 0.6 0.065 0.12 0.47 0.051 0.094 Uricase from Arthrobacter 1.5 1.5 1.5 - - - globiformis, at 20 international units (I.U.)/mg, sold by the company Sigma Uric acid 1.5 1.5 1.5 - - - Laccase issue from Rhus 1.8 1.8 1.8 vernicifere laccase *** at 180 international units (I.U.)/mg sold by the company Sigma Common dye support (*) ( * ) ( * > ( * ) Common dye support (**) ( ** ) r> r> Demineralized water qs 100 100 100 Demineralized water qsq 100 100 100 *** possibility of exchange of Laccase issue de Rhus vernicifere laccase*** at 180 international units (I.U.)/mg sold by the company Sigma with 1 % of pyricularia orizae at 100 units/mg, sold by the company I.CN. (*) Common dye support: Ethanol 20.0 Hydroxyethylcellulose sold under the name Natrosol 1.0 250 HR® by the company Aqualon Poly(C 8 -C 10 )alkylglucoside as an aqueous solution 8.0 g containing 60% active material (A.M.) buffered with ammonium citrate (0.5%), sold under the name Oramix CG110® by the company SEPPIC Monoethanolamine qs pH = 9 (**) Common dve support: Ethanol 20.0 g Poly(C 8 -C 10 )alkylglucoside as an aqueous solution 4.8 g containing 60% active material (A.M.) buffered with ammonium citrate (0.5%), sold under the name Oramix CG110® by the company SEPPIC pH agent Qs pH = 6.5 Compositions 7(G) ' to 32(G) ' are identical to composition 1 (G), and compositions 7(G) " to 32(G) " are identical to composition 3 (G), and compositions 7(G)'" to 32(G) '" are identical to composition 4(G), and compositions 9(G) lv to 32(G) lv are identical to composition 6 (G), as given above in example 4 with the proviso that para-phenylenediamine is replaced by a compound H as given below in table 1. Table 1 Compositions Compound H 7(G) μv para-toluylenediamine 9(G) MV 2-chloro-para-phenylendiamine 10(G)'-' V 2,3-dimethyl-para-phenylenediamine 1 1 (G)'- ,V 2,6-dimethyl-para-phenylenediamine 12(G) IV 2,6-diethyl-para-phenylenediamine 13(G) IV 2,5-dimethyl-para-phenylenediamine 14(G) 1 •IV N,N-dimethyl-para-phenylenediamine 15(G) 1 •IV N,N-diethyl-para-phenylenediamine 16(G) l-IV N,N-dipropyl-para-phenylenediamine 17(G) l-IV 4-amino-N,N-diethyl-3-methylaniline 18(G) l-IV N,N-bis(.beta.-hydroxyethyl)-para-phenylenediamine 19(G) IV 4-amino-N,N-bis(.beta.-hydroxyethyl)-3-methylaniline 20(G) IV 4-amino-3-chloro-N,N-bis(.beta.-hydroxyethyl)aniline 21(G) l-IV 2-.beta.-hydroxyethyl-para-phenylenediamine 22(G) l-IV 2-fluoro-para-phenylenediamine 23(G) IV 2-isopropyl-para-phenylenediamine 24(G)' l-IV N-(.beta.-hydroxypropyl)-para-phenytenediamine 25(G) IV 2-hydroxymethyl-para-phenyIenediamine 26(G) IV N,N-dimethyl-3-methyl-para-phenylenediamine 27(G)' l-IV N,N-(ethyl-.beta.-hydroxyethyl)-para-phenylenediamine 28(G) 1 l-IV N-(.beta.,.gamma.-dihydroxypropyl)-para-phenylenediamine 29(G) MV N-(4'-aminophenyl)-para-phenylenediamine 30(G) IV N-phenyl-para-phenylenediamine 31 (G) IV 2-.beta.-hydroxyethyloxy-para-phenylenediamine 32(G) IV 2-.beta.-acetylaminoethyloxy-para-phenylenediamine Compositions 100(G) 1 to 110(G) 1 are identical to composition 2 (G), and compositions 200(G) " to 210(G) " are identical to composition 5 (G), the proviso that para-aminophenol is replaced by a compound H as given below in table 2. Table 2 Compositions Compound H 200(G)'-" 4-amino-3-methylphenol 203(G) '-" 4-amino-3-fluorophenol 204(G)'-" 4-amino-3-hydroxymethylphenol 205(G) 1 -" 4-amino-2-methylphenol 206(G) 1 -" 4-amino-2-hydroxymethylphenol 207(G) 1 -" 4-amino-2-methoxymethyl-phenol 208(G) 1 -" 4-amino-2-aminomethylphenol 209(G)'-" 4-amino-2-(.beta.-hydroxyethylaminomethyl)phenol 210(G) 1 -" 4-amino-2-fluoro-phenol Each of the ready-to-use dye compositions are applied for 30 minutes. The hair was then rinsed, washed with a standard shampoo and then dried. The locks of hair are dyed in brilliant red-tinged violet shade. Example 15: The ready-to-use dye compositions below were prepared (contents in grams): Compositions 1 (1) 2(l) 3(l) Behenyl-trimethyl- - 2.0 A.M. - ammonimum cloride Cetyl-trimethylammonimum - - 2.0 A.M. cloride Ethanol 10 10 10 Cationic dye of example 1 0.20 0.20 0.10 2-Amino-2-methyl-1 -propanol pH 9 pH 9 pH 9 qs Demineralized water qs 100 100 100 Each of the ready-to-use dye compositions are applied for 30 minutes. The hair was then rinsed, washed with a standard shampoo and then dried. The locks of hair were dyed in brilliant red-tinged violet shade. Compositions 4(l) to 20(l) are identical to composition 2 (I), the proviso that behenyl- trimethylammonimum cloride is replaced by a compound H' as given below in table 2. Table 2 Compositions Compound H' 4(l) tetramethylammonium chloride 5(0 diethyl-dimethylammonium chloride 6(l) methyl-trimethylammonium chloride 7(0 ethyl-trimethylammonium chloride 8(0 distearyl-dimethylammonimum cloride 9(1) oleocetyldimetylhydroxyethylammonium chloride 10(1) oleocetylhydroxyethylammonium chloride 11 (1) stearamidopropyldimetylammonium chloride sold under the name CERAPHYL 70 by the company VAN DYK 12(1) 2-hexyldecylamine -1-metyhl-1'-N-(ethylcarbamaic acid hexyldecylamine)-imidazolium methylsulphate sold under the name REWOQUAT W 7500 by the company REWO 13(1) propylen-1,3-diammonium chloride 14(1) propylen-1,3-diammonium bromide 15(1) propylen-1 ,3-diammonium phosphate 16(1) propylen-1 ,3-diammonium sulphate 17(1) propylen-1 ,3-diammonium acetat 18(1) propylen-1 ,3-di-trimetylammonium chloride 19(1) propylen-1 ,3-di-trimetylammonium sulphate 20(l) propylen-1 ,3-di-trimetylammonium acetate Compositions 1 (I)' to 20 (I)' are identical to compositions 1 (I) to 20(1) , with the proviso that ethanol is replaced by isopropanol. Compositions 1(1)" to 15(1)" are identical to compositions 1(1) to 20(1) and 1(1)' to 20 (I)', with the proviso that 2-amino-2-methyl-1-propanol is replaced by a basifying agent D'. Compositions 1(1)" to 15(1)" basifying agent D' 1 (1)" pottassium carbonate 2(0" sodium carbonate 3(0" triethanolamine 4(0" diethanolamnie 5(0" monoethanolamine 6(0" sodium hydroxide 7(0" potassium hydroxide 8(0" N.N-dimethyl-N'-ethylenediamine 9(0" 4-(Ethylamino)-b-butylamine 10(1)" N-(n-Propyl)-1 ,3-propanediamine 11(0" N,N-diethylenediamine 12(1)" N,N,N',N'-Tetramethylethylenediamine 13(1)" N,N-dimethylhydrazine 14(1)" 2-n-butylaminmoethylamine 15(1)" 1 ,6-diaminohexane Example 16: The ready-to-use dye compositions below are prepared (contents in grams): Composition 1(L) 2(L) 2-Amino-5-hydroxy- 0.35 - nitrobenzene 2-N-(β-Hydroxyethyl) - 0.25 amino-5-aminonitrobenzene Cationic dye* 0.065 0.04 Common dye support (*) ( * ) 0 Demineralized water qs 100 100 (*) Common dve support: Ethanol 20.0 g Nonylphenoloxyethylen with 9 mol oxyethylen 8.0 g sold under the name IGEPAL NR 9 Or by the company RHODIA CHEMIE 2-Amino-2-methyl-1-propanol qs. pH = 9.5 • *Cationic dye is mixed with the other components of the oxidative dye composition shortly before the applying to the hair. • "Cationic dye is a single cationic dye or composition of cationic dyes as given above ' Cationic dye compositions (V 1 ) compositions (V)'= composition 1L + composition 2L + 'cationic dye 'cationic dye Cationic dye of example 1 10(V) io(Vy Cationic dye of example 2 11(V') 11(V')' Cationic dye of example 3 12(V') 12(V)' Cationic dye of example 4 13(V) 13(V')' compositions (V) = composition 1 L + "cationic dye + ** dye ("cationic dye/**dye in a ratio of 1 :1) * Dye cationic dye of cationic dye cationic dye cationic dye of example 1 of example 2 of example 3 example 4 HC Yellow 2 14(V) 15(V) 16(V) 17(V) HC Yellow 4 18(V) 19(V) 20(V) 21(V) HC Yellow 6 22(V') 23(V) 24(V) 25(V') Basic Yellow 57 26(V) 27(V) 28(V) 29(V) Basic Yellow 9 30(V) 31 (V) 32(V) 33(V') Disperse Orange 3 34(V') 35(V) 36(V) 37(V) HC Red 3 38(V') 39(V') 40(V) 41 (V) HC Red BN 42(V) 43(V') 44(V) 45(V') Basic Red 76 46(V') 47(V') 48(V) 49(V') Basic Red 2 50(V) 51 (V 1 ) 52(V) 53(V) Basic Violet 14 54(V') 55(V) 56(V') 57(V) Basic Blue 3 58(V) 59(V') 60(V) 61 (V 1 ) Basic Blue 6 62(V') 63(V') 64(V) 65(V) Basic Blue 7 66(V') 67(V') 68(V) 69(V') Basic Blue 9 70(V') 71 (V 1 ) 72(V) 73(V') Basic Blue 12 74(V') 75(V) 76(V) 77(V') Basic Blue 26 78(V') 79(V') 80(V) 81 (V 1 ) HC Blue 2 82(V') 83(V') 84(V') 85(V') HC Blue 7 86(V') 87(V) 88(V') 89(V) HC Blue 12 90(V') 91 (V) 92(V') 93(V) Disperse Blue 3 94(V') 95(V') 96(V') 97(V) HC Violet 1 98(V') 99(V') lOOfV 1 ) 101(V') Disperse Violet 1 102(V') 103(V') 104(V) 105(V') Disperse Black 9 106(V') 107(V') 108(V) 109(V') Basic Brown 16 110(V') 111(V') 112(V) 113(V') Basic Brown 17 114(V) 115(V') 116(V) 117(V) 2-amino-6-chloro-4-nitrophenol 118{V l ) 119(V') 120(V) 121(V) 4-amino-2-nitrodiphenylamine-2'-carboxylic acid 122(V) 123(V') 124(V) 125(V) 6-nitro-1 ,2,3,4-tetrahydroquinoxaline 126(V) 127(V') 128(V) 129(V') 4-N-ethyl-1 ,4-bis(2'-hydroxyethylamino)-2-nitrobenzene 130(V') 131(V') 132(V) 133(V) hydrochloride 1-methyl-3-nitro-4-(2'-hydroxyethyl)-aminobenzene 135(V') 136(V') 137(V) 138(V') compositions (V 1 ) = composition 1 L + *cationic dye + * ** dyes ("cationic dye ***dye in a ratio of 1:1) Dyes *** cationic dye cationic dye cationic dye cationic dye of example 1 of example 2 of example 3 of example 4 HC Yellow 2, HC Yellow 4 139(V') 140(V) 141 (V) 142(V) Basic Red 76, HC Red BN, 143(V') 144(V') 145(V) 146(V') HC Red BN, Basic Violet 14 147(V') 148(V') 149(V) 150(V') Basic Blue 12, Basic Blue 6 151 (V) 152(V) 153(V) 154(V) 4-N-ethyl-1 ,4-bis(2'-hydroxyethylamino)-2-nitrobenzene 155(V') 156(V) 157(V) 158(V) hydrochloride, 6-nitro-1 ,2,3,4-tetrahydroquinoxaline Basic Brown 16, Disperse Black 9 159(V') 160(V) 162(V) 163(V') compositions (V) = composition 1L + 'cationic dye + * "*dyes (*cationic dye/ * ***dye in a ratio of 1:1) Dyes ' cationic dye cationic dye cationic dye cationic dye of example 1 of example 2 of example 3 of example 4 HC Yellow 2, HC Yellow 4, Basic Red 2 164(V) 165(V') 166(V) 167(V) Basic Red 76, HC Red BN, Basic Red 2 168(V) 169(V) 170(V') 171(V) HC Red BN, Basic Violet 14, Disperse Violet 1 172(V') 173(V) 174(V') 175(V') Basic Blue 12, Basic Blue 6, Disperse Violet 1 176(V) 177(V) 178(V) 179(V') 2-amino-6-chloro-4-nitrophenol, 6-nitro- 180(V) 181(V) 182(V) 183(V) 1 ,2,3,4-tetrahydroquinoxaliπe, Basic Brown 17 Basic Brown 16, Disperse Black 9, Basic Brown 17 184(V') 185(V') 186(V) 187(V') compositions (V) = composition 1L + "cationic dye + ******dyes ('cationic dye/*****dye in a ratio of 1:1) Dyes cationic dye cationic dye cationic dye cationic dye of example 1 of example 2 of example 3 of example 4 HC Yellow 2, Basic Red 76, Basic Red 2, Disperse Orange 3 188(V') 189(V) 190(V) 191(V) Basic Red 76, HC Red BN, Basic Red 2, Basic Violet 14 192(V') 193(V) 194(V') 195(V) HC Red BN, Basic Violet 14, Disperse Violet 1 , HC Red 3 196(V') 197(V') 197(V') 198(V') Basic Blue 12, Basic Blue 6, Disperse Violet 1, Basic Blue 9 199(V') 200(V') 201 (V) 202(V) 2-amino-6-chloro-4-nitrophenol, 6-nitro- 203(V') 204(V) 205(V) 206(V') 1 ,2,3,4-tetrahydroquinoxaline, Basic Brown 17, HC Red BN Basic Brown 16, Disperse Black 9, Basic Brown 17, Basic Red 207(V') 208(V') 209(V) 210(V') 76 Each of the ready-to-use dye compositions are applied for 30 minutes. The hair is then rinsed, washed with a standard shampoo and then dried. The locks of hair are dyed in brilliant shades. Example 17: The powdery dye composition 1 (M) is prepared as given below: Composition 1(M) (%-by weight) Hydroxypropyl-Guar-triamoniumchloride 20.00 Cycloocatamylose 4.00 PEG-150/PPG 301 16.00 Polyethylenglycol (MW 10000) 48.20 Corn proteine hydrolysate 5.00 Honey dried extract 2.00 Potassium sorbat 2.00 Cationic dye of formula (I) of example 1 0.2 An oxidative dye powder for hair, composition 2(M), is prepared as given below: Composition 2(M) (%-by weight) p-Toluylendiaminsulphate 3.0 Resorcine 1.0 3-Aminophenolsulphate 0.3 m-Phenylendiamine hydrochloride 0.2 Silicon dioxide 0.5 sodium lauryl sulphate 0.2 sodium alginate 3.5 sodium meta silica 0.4 potassium sulphite 0.1 Compositions 2(M)' to 33 ( )' are identical to composition 2(M), with the proviso that resorcine is replaced by a compound M' as given in the table below. Compositions 2(M)" to 33 (M)" are identical to composition 2(M), with the proviso that m- phenylendiamine hydrochloride is replaced by a compound M' as given in the table below. Compositions 2(M)'" to 33 (M)'" are identical to composition 2(M), with the proviso that 3- aminophenolsulphate is replaced by a compound M' as given in the table below. Compositions 2(M) ιv to 33 (M) lv are identical to composition 2(M), with the proviso that 3- aminophenolsulphate, m-phenylendiamine hydrochloride and resorcine is replaced by 1.5%- by weight of a compound M' as given in the table below. Composition 2(M) compound M' 1 (M)'" l 2-methylresorcine 2(M) l_IV 4-chloroesorcine 3( ) M 2-amino-4-chlorophenol 4(M) '-' v 4-(N-methyl)aminophenol 5( ) '' lV 2-aminophenol 6(M) M 3-aminophenol 7(M) l lV 1-methyl-2-hydroxy-4-aminobenzene 8(M) '" lV 3-N,N-dimethylaminophenol 9(M) '-' V 4-amino-3-methylphenol 10(M) '"' V 5-amino-2-methylphenol 11 (M) l-IV 6-amιno-3-methylphenol 12(M) l-IV 3-amιno-2-methylamιno-6-methoxypyrιdιπe 13(M) l-IV 2-amιno-3-hydroxypyrιdιne 14(M) l-IV 4-amιnodιphenylamιne 15(M) l-IV 4,4'-dιamιnodophenylamιne 16(M) l-IV 2-dιmethylamιno-5-amιnopyrιdιne 17(M) l-IV 2,6-dιamιnopyπdιne 18(M) l-IV 1 ,3-dιamιnobenzol 19(M) l-IV 1-amιno-3-(2'-hydroxyethylamιno)benzene 20(M l-IV 1-amιno-3-[bιs(2'-hydroxyethyl)amιno]benzene 21 (M] l-IV 1 ,3-dιamιnotoluene 22(M; I l-IV -naphthol 23(M; I l-IV 1 ,4-dιamιno-2-chlorobenzene 24(M; l-IV 4,6-dιchlororesorcιne 25(M I l-IV 4-hydroxy-1 ,2-methylendιoxybenzene 26(M, l-IV 1 ,5-dιhydroxynaphthalιne 27(M > I-1V 1 ,7-dιhydroxynaphthalιne 28(M i l-IV 2,7-dιhydroxynaphthalιne 29(M i l-IV 1 -hydroxy naphthaline 30(M v l-IV 4-hydroxy-1 ,2-methylenedιoxybenzene 31 (M i l-IV 2,4-dιammo-3-chlorophenol 32(M v l-IV 1-methoxy-2-amιno-4-(2'-hydroxyethylamιno)-benzene 33(M v l-IV 2,4-dιamιno-3-chlorophenol and 1-methoxy-2-amιno-4-(2'- hydroxyethylamιno)-benzene Dying process a) Bleached human hair is pretreated with a common permanent wave on the basis of thioglycolic acid at a pH value in the range of 9.0 to 9.5 and then rinsed with water. Afterwards, the hair is treated with the powdery dye composition 1 (M) or 1 (M) V to 33(M) ' " ιv and 40 ml stabilized peroxide solution (6% by weight). The powdery dye composition is applied for 5 to 10 minutes and then rinsed with water and in following, dried. The hair is dyed in a brilliant red-tinged violet shade with very good endurance properties with respect to subsequent shampooing. b) A fixing solution, composition 3(M), is prepared as given below: fixing solution, composition 3(M) (%-by weight) Peroxide solution 4.8 PPG30/PEG150 1.0 Cocosamineoκide 0.6 Coco fatty acid/collagen hydrolysate, potassium salt 0.5 Polyquaternium-35 0.5 Sodiumphosphate 0.4 Phosphore acid 0.3 Citronic acid 0.3 Demineralized Water qs 00 10 g of composition 2(M) is mixed with 80 ml of composition 3(M). The resulting mixture is applied on bleached human hair, which was pretreated with a common permanent wave on the basis of thioglycolic acid at a pH value in the range of 9.0 to 9.5 for 10 minutes. Afterwars the hair is rinsed and dried. The hair is dyed in a brilliant red-tinged violet shade with very good endurance properties with respect to subsequent shampooing. This oxidative dying process is also applicable if it is divided in two steps: step 1 : prefixing with peroxide, and then the removal of rollers step 2: after fixing with dying. Example 18: The ready-to-use dye compositions below are prepared (contents in grams): Compositions 1(N) 2(N) 3(N) 4(N) Hydroxyethylcellulose sold 1.0 A.M. under the name NATROSOL 250 HHR by the company AQUALON Carboxymethylcellulose sold 1.0 under the name A.M. BLANOSE 7M by the company AQUALON Resin of guar sold under the 1.0 name VIDOGUM GH175 by A.M. the company UNIPECTINE Resin of scleroglucane sold 1.0 under the name AMIGEL by A.M. the company ALBAN MULLER INTERNATINAL Ethanol 10 10 10 10 2-Amine-2-methy 1-1 -propanol pH 9 pH 9 pH 9 pH 9 Cationic dye of formula (I) of 0.2 0.2 0.2 0.2 example 1 Demineralized water qs 100 100 100 100 Each of the ready-to-use dye compositions are applied for 30 minutes to locks of natural grey hair containing 90% white hairs. The hair is then rinsed, washed with a standard shampoo and then dried. The locks of hair are dyed in brilliant red-tinged violet shade. Compositions 5(N)" to 19(N)" are identical to compositions 1(N) to 4(N), with the proviso that 2-amino-2-methyl-1 -propanol is replaced by a basifying agent N'. compositions basifying agent N' 5(N)" potassium carbonate Q/ SJΛ" sodium carbonate 7(N)" triethanolamine 8(N) diethanolamine 9(N)" monoethanolamine 10(N)" sodium hydroxide 1 1 (|sjy potassium hydroxide 12(N)" N,N-dimethyl-N'-ethylenediamine ■ \ 3(N)" 4-(efhylamino)-b-butylamine 14(N)" N-(n-propyl)-1,3-propanediamine 15(N)" N,N-diethylenediamine 16(N)" N,N,N',N'-Tetramethylethylenediamine • j 7(N) M N,N-dimethylhydrazine 18(N)" 2-n-butylaminmoethylamine 19(N)" 1 ,6-diaminohexane Composition 20(N)' is identical to compositions 1(N) and 5(N)" to 19(N)", with the proviso that hydroxyethylcellulose is replaced by a hydroxypropylcellulose. Example 19: Permanent wave composition consisting of two compositions O, 1 (O)-5(O), and P, 1(P)-5(P). Compositions O and P are prepared according to common processes. Composition 1(0) % by weight Cationic dye of formula (I) 02 35-volumes hydrogen peroxide solution 4.3 Cetanol 0.5 Hydrated lanoline 0.35 Actealdehyde 0.02 Sodiumpyrophphate 0.025 Phosphoric acid, purified water(with phosphoric acid adjusted 100 to pH 6.5 Composition 1 (P) % by weight . Ammoniumthioglycolate solution (50% by volumes thioglycolic 13.6 acid) Ammoniumcicarbonate 3.5 Disodiumedetat 0.1 Monoethanolamine, purified water(with monoethanolamine 100 adjusted to pH 6.5) Process: According to common processes, white hair, which tips are wrapped up in paper, is rolled up on a stick of synthetic material (stick with 1.5 cm in diameter). This stick is then dipped in the composition 1(P) for 15 minutes at 30° C, and afterwards rinsed with water for 1 minute. Then the stick is dipped in the composition 01 for 15 minutes at 30° C and afterwards rinsed with water, washed with a standard shampoo and then dried. In this way the white hair is homogeneously dyed and waved from the roots up to the tips. Composition 2(O) % by weight Cationic dye of formula (I) of example 1 02 Potassiumbromate 10.2 Lauryldimethylacetic acid betain 1.0 Cetyltrimethylammoniumchloride 0.6 Sodiumbenzoate 0.3 Salicylacid 0.05 Trisodiumphosphate 0.27 Phosphoric acid, purified water(with phosphoric acid adjusted 100 to pH 6.5 Composition 2(P) % by weight L-Cysteine hydrochloride 7.0 Cetanol 0.5 Oleylalcohol 0.5 Polyoxyethylenethter (10 UO) 1.0 Polyoxyetheylencetylether (15 UO) 1.0 Sodiumedetat 0.1 Monoethanolamine, purified water (with monoethanolamine 100 adjusted to pH 9) White hair is treated in the same way as given above in the process of example 9 with the proviso that 1(P) is replaced by 2(P) and 1(O) is replaced by 2(O). Composition 3(O) % by weight Cationic dye of formula (I) of example 1 0.2 Uricase (20 U/mg) 1.0 Uric acid 1.0 Glycerine 3.0 Purified water qs 100 Composition 3(P) % by weight Ammoniumthioglycolate solution (50% by volumes thioglycolic 7.0 acid) Polyoxyethylenether (10 UO) 1.0 Polyoxyetheylencetylether (15 UO) 1.0 Sodiumlaurylsulphate 0.5 Collagen hydrolysate solution 0.4 Disodiumedetat 0.1 Ammonia water, purified water(with Ammonia water, adjusted 100 to pH 9) White hair is treated in the same way as given above in the process of example 9 with the proviso that 1 (P) is replaced by 3(P) and 1 (O) is replaced by 3(O). Composition 4(0) % by weight Cationic dye of formula (1) of example 1 0.4 Monoethanolamine, purified water (with monoethanolamine 100 adjusted to pH 8) Composition 4(P)/oxiative fixing formulation % by weight Sodiumbromate 17.0 Lauryldimethylaceticacidbetain 1.5 Cetyltrimethylammoniachloride 1.0 Sodiumbenzoate 0.6 Salicylicacid 0.1 Trisodiumphophate 0.54 Phosphoric acid, purified water(with phosphoric acid adjusted 100 to pH 6.5 White hair is treated in the same way as given above in the process of example 9 with the proviso that 1 (P) is replaced by 3(P) and 1 (O) is replaced by a mixture of the two compositions 4(O) and 4(P) in a ratio of 1:1. Composition 5(O) % by weight Cationic dye of formula (I) of example 1 0.2 % by weight in relation to the composition P5 Composition 5(P)/oxidative fixing formulation % by weight Sodiumbromate 8.5 Lauryldimethylaceticacidbetain 1.0 Cetyltrimethylammoniachloride 0.6 Sodiumbenzoate 0.3 Salicylicacid 0.05 Trisodiumphophate 0.27 Phosphoric acid, purified water(with phosphoric acid adjusted 100 to pH 6.5 White hair is treated in the same way as given above in the process of example 9 with the proviso that 1 (P) is replaced by 3(P) and 1 (O) is replaced by a mixture of the two compositions 5(O) and 5(P) in a ratio of 1:10. Composition 6(O) % by weight Cationic dye of formula (I) of example 1 " " 02 Hydroxyethylcellulose 2.5 Triethanolamine, purified water( with triethanolamine adjusted 100 to pH 8.0) qs White hair which is treated with the above cited compositions is homogeneously waved and dyed in a brilliant red-tinged violet shade. Example 20: The ready-to-use dye compositions below are prepared (contents in grams): Compositions 1 (Q) 2(Q) 3(Q) 4(Q) 5(Q) Cationic dye of 0.2 0.2 0.15 0.12 0.1 formula (I) of example 1 Cocoglutamate of 5.0 A.M. triethanolamine sold under the name ACYGLUTAMATE CT12 by the company AJINOMOTO Laurylsarcorsinate 5.0 A.M. of sodium sold under the name ORAMIX L30 by the company SEPPIC Cocoylicethionate of 5.0 A.M. sodium sold under the name JORDAPON POWDER by the company PPG Laurylether 5.0 A.M. carboxilic acid (10 UO) sold under the name AKYPO RLM 100 by the company KAO Sodium salt of 5.0 A.M. Tartaric ester of cocoylpolyglycoside sold under the name GUCAROL AGE ET by the company CESALPINE Ethanol 10 10 10 10 10 2-Amine-2-methyl- pH 9 pH 9 pH 9 pH 9 pH 9 1 -propanol qs Demineralized 100 100 100 100 100 water qsq The resulting compositions are applied for 30 minutes to locks of natural grey hair containing 90% white hairs. The hair is then rinsed, washed with a standard shampoo and then dried. The hair is dyed in a brilliant red-tinged violet shade with very good endurance properties with respect to subsequent shampooing. Compositions 6(Q)" to 20(Q)" are identical to compositions 1(Q) to 5(Q), with the proviso that 2-amino-2-methyl-1 -propanol is replaced by a basifying agent Q'. compositions basifying agent Q' 6(Q)" potassium carbonate 7(Q)" sodium carbonate 8(Q)" triethanolamine 9(Q)" diethanolamiπe 10(Q)" monoethanolamine -] 1 (QV 1 sodium hydroxide 12(Q)" potassium hydroxide 13(Q)" N,N-dimethyl-N'-ethylenediamine 14(Q)" 4-(ethylamino)-b-butylamine 15(Q)" N-(n-propyl)-1 ,3-propanediamine 16(Q)" N,N-diethylenediamine 17(Q)" N,N,N',N'-Tetramethylethyleπediamine 18(Q)" N,N-dimethylhydrazine 19(Q)" 2-n-butylaminmoethylamine 20(Q)" 1,6-diaminohexane Composition 21 (Q)' is identical to compositions (Q) and (Q)", with the proviso that ethanol is replaced by a isopropanol. Example 21: The ready-to-use dye compositions below are prepared (contents in grams): Compositions 1( R) 2( R) 3( R) 4( R) 5( R) 6( R) 7 R) 8( R) Cationic dye 0.12 0.1 0.11 0.12 0.20 0.10 0.20 0.15 of formula (I) of example 1 Alkylpoly- 8.0 8.0 glucoside sold under the name ORAMIX CGHO by the company SEPPIC N-Decanonyl- 8.0 8.0 N-methyl- glucamine** O-Hexa- 8.0 8.0 decanoyl- 6- D-glucose N-Cocolacto- 8.0 8.0 bionamide Ethanol 10 10 10 10 10 10 10 10 2-Amine-2- pH 9 pH 9 pH 9 pH 9 pH 9 pH 9 pH 9 pH 9 methyl-1- propanol qs Demineralized 100 100 100 100 100 100 100 100 water qsq **N-decanoyl-N-methylglucamine (acid amide of polyhydroxy of the formula C 9 H 19 -CO- N(CH 3 )-CH 2 -(CHOH) 4 -CH 2 OH) The resulting compositions are applied for 30 minutes to locks of natural grey hair containing 90% white hairs. The hair is then rinsed, washed with a standard shampoo and then dried. The hair is dyed in a brilliant red-tinged violet shade with very good endurance properties with respect to subsequent shampooing. Compositions 10(R)' to 24(R)' are identical to compositions 1(R) to 8(R), with the proviso that 2-amino-2-methyl-1 -propanol is replaced by a basifying agent R'. compositions basifying agent R' 10(R)' potassium carbonate 11 (R)' sodium carbonate 12(R)' triethanolamine 13(R)' diethanolamine 14(R)' monoethanolamine 15(R)' sodium hydroxide 16(R)' potassium hydroxide 17(R)' N,N-dimethyl-N'-ethylenediamine 18(R)' 4-(ethylamino)-b-butylamine 19(R)' N-(n-propyl)-1 ,3-propanediamine 20(R) r N,N-diethylenediamine 21 (R) 1' N,N,N',N'-Tetramethylethylenediamine 22(R) P N,N-dimethylhydrazine 23(R) 2-n-butylaminmoethylamine 24(R) r 1 ,6-diaminohexane Compositions 26(R)" to 39(R)" are identical to compositions 1(R) to 8(R), with the proviso that alkylpolyglucoside is replaced by a compound R". compositions compound R" 26(R)" APG 300 * 27(R)" APG 350 * 28(R)" APG 500* 29(R)" APG 550* 30(R)" APG 625* 31 (R)" APG base 10-12* sold by company HENKEL 32(RV ORAMIX CG 110' 33(R)" ORAMIX NS 10** ** sold by company SEPPIC 34(R)" LUTENSOL GD 70 sold by compny BASF 35(R)" PLANTAREN 1200 *** 36(R)" PLANTAREN 1300 ** * 37(R)" PLANTAREN 2000*** 38(R)" PLANTACARE 818*** 39(R)" PLANTACARE 1200* * * ***sold by company HENKEL Compositions 40 (R)"' to 52(R)'" are identical to compositions (R ), (R )' and (R )" with the proviso that O-hexadecanoyl-6-αD-glucose is replaced by a compound R "'. compositions compound R '" 40(R)'" O-Octanoyl-6-D-glucose 41 (R) 1 " O-Oleyl-6-D-glucose 42(R)'" O-Linoleyl-6-D-giucose 43(R)'" monostearate methylglucoside 44(R)'" sesquistearate methylglucoside 45(R)'" decanoate ethyl-6-glucoside 46(R)'" mono and dicocoate(82/7) ethyl-6-glucoside sold under the name BIOSURF COCO by the company NOVO 47(R)"' moπo and di'aurate (84/8) ethyl-6-glucoside sold under the name BIOSURF 12 by the company NOVO 48(R)'" monococoate butylglucoside polyoxyethylene with 3 mol oxygen/ethylen sold under the name REWOPOL V3122 by the company REWO 49(R)'" monococoate butylglucoside sold under the name REWOPOL V3101 by the company NOVO REWOSAN V 3101 by the company NOVO 50(R)'" monococoate butylglucoside sold under the name REWOSAN V 3101 by the company NOVO 51 (R)" monolaurate of saccharose 52(R)" monococoate of saccharose Composition 25(R)' is identical to any of a composition (R) (R )" and (R)'", with the proviso that ethanol is replaced by a isopropanol. Example 22: The dye compositions below are prepared (contents in grams): Compositions Ϊ(S) 2(S) Cationic dye of formula (I) of example 1 0.2 0.2 Propylene gylcol 0.0 2-Amine-2-methyl-1 -propanol qs pH 9 Demineralized water qsq 100 100 Monomethylether of propylene glycol 10.0 The resulting compositions 1 or 2 are applied for 30 minutes to locks of natural grey hair containing 90% white hairs. The hair is then rinsed, washed with a standard shampoo and then dried. The hair is dyed in a brilliant red-tinged violet shade with very good endurance properties with respect to subsequent shampooing. Compositions 3(S)' to 17(S)'are identical to compositions 1(S), with the proviso that propylene glycol is replaced by a compound S'. compositions compound S' 3(S)' glycerine 4(S)' 1 ,3-propanediol 5(S)' 2-butene-1,4-diol 6(S)' pentane-1 ,5-diol 7(S)' 2,2-dimethyl-propane-1 ,3-diol 8(S)' 3-methyl-pentane-1 ,5-diol 9(S)< potassium hydroxide ιo(sy pentane-1 ,2-diol ii (sy 2,2,4-trimethyl-pentane-1 ,3-diol i2(sy 2-methylpropane-1 ,3-diol 13(S)' hexyleneglycol -| 4(S)' 1 ,3-butyleneglycol 15(S)' dipropyleneglycol 16(S)' diethylenglcol -j 7(S)' triethylenglycol Compositions 18(S)" to 29(S)" are identical to compositions 2(S), with the proviso that monomethylether of propylene glycol is replaced by a compound S". compositions compound S II 18(S)" monoethylether of propylene glycol 19(S)" dimethylether of isopropylene glycol 20(S) 11 monomethylether of diethylen glycol 2 -| (S)" monomethylether of dipropylen glycol 22(S)" monomethylether of tripropylen glycol 23(S)" monomethylether of dimethylen glycol 24(S)" monomethylether of diethylen glycol 25(S)" monophenylether of ethylen glycol 26(S)" monobenylether of ethylen glycol 27(S)" monophenylether of propylene glycol 28(S)" monophenylether of diethylen glycol 29(S)" monobenylether of diethylen glycol Compositions 30 (S)" 1 to 44(S)"' are identical to compositions 1(S), (S)' and (S) with the proviso that 2-amino-2-methyl-1 -propanol is replaced by a basifying agent S'". compositions basifying agent S '" 30(S)'" pottassium carbonate 31 (S)"' sodium carbonate 33(S)'" triethanolamine 34(S)'" diethanolamnie 35(S)'" monoethanolamine 36(S)'" sodium hydroxide 37(S)'" potassium hydroxide 38(S)'" N,N-dimethyl-N'-ethylenediamine 39(S)'" 4-(ethylamino)-b-butylamine 40(S)"' N-(n-propyl)-1 ,3-propanediamine 41 (S)'" N,N-diethylenediamine 42(S)'" N,N,N',N'-tetramethylethylenediamine 43(S)"' N,N-dimethylhydrazine 44(S)'" 2-n-butylaminmoethylamine 45(S)'" 1 ,6-diaminohexane Example 23: The ready-to-use dye compositions below are prepared (contents in grams): Compositions KT) 2(T) 3(T) Monobro ohydrate of 5,6- 0.7 dihydroxy indoline 5.6-dihydroxy indole 0.5 1 ,2,4-Trihydroxy benzene 1.2 Cationic dye of formula (I) of 0.1 0.07 0.05 example 1 Common dye support (*) O (*) O Demineralized water q.s.q 100 100 100 ( * ) Common dve suDDOrt: Ethanol 20.0 g Nonylphenoloxyethylen with 9 mol oxyethylen 8.0 g sold under the name IGEPAL NR 9 Or by the company RHODIA CHEMIE 2-Amino-2-methyl-1 -propanol qs. pH = 8.0 Each of the ready-to-use dye compositions are applied for 30 minutes to locks of natural grey hair containing 90% white hairs. The hair is then rinsed, washed with a standard shampoo and then dried. The hair is dyed in a brilliant red-tinged violet shade with very good endurance properties with respect to subsequent shampooing. Compositions 4(T)' to 9(T)' are identical to compositions 3(T), with the proviso that 1 ,2,4- trihydroxy benzene is replaced by a compound T'. Compositions compound T' 4(T)' 1 -methyl-2,4,5-trihydroxy benzene 5(T)' 2, 4-diamino-6-methyl phenol 6(T)' 2-amino-4-methylamino phenol 7(τy 2, 4-diamino-4-methyl phenol 8(T)' 2, 6-diamino-4-diethylamino phenol 9(τy 2, 6-diamino-1 ,4-dihydroxy benzene Compositions 10(T)" to 17(T)" are identical to compositions 2(T), with the proviso that 5.6- dihydroxy indole is replaced by a compound T". compositions compound T" 10(T)" ' 2-methyl-5,6-dihydroxy indole 11(T)" 3-methyl-5,6-dihydroxy indole 12(T)" ' 1-methyl-5,6-dihydroxy indole 13(T)" 2, 3-dimethyl-5,6-dihydroxy indole 14(T)" 5-methoxy-6-hydroxy indole 15(T)" ' 5-acetoxy-6-hydroxy indole 16(T)" 5,6-diacetoxy indole 17(T)" ' 5,6-dihydroxy indole carbonic acid Compositions 18(T)'" to 20(T)"' are identical to compositions 1(T), with the proviso that monobromohydrate of 5,6-dihydroxy indoline is replaced by a compound T'". compositions compound T'" 18(T)'" 5,6-dihydroxy indoline 19(T)'" 1-methyI-5,6-dihydroxy indoline 20(T)'" 1-ethyl-5,6-dihydroxy indoline Example 24: Dying compositions possessing pH 9.8 are prepared by mixing identical percentages of weight of a hydrogen peroxide solution (6% by weight) and a oxidative precursor dye composition prepared as given below in table 1 : Table 1 : Oxidative precursor dye CθmpθSitiθn(contents in percentage by weight) 1(V) 2(V) 3(V) 4(V) Oxidative dye compositions 2,5,6-Triarnino-4-hydroxypyrimidine 0.01 0.2 0.2 0.01 sulphate 4-Amino-2-hydroxytoluene 0.5 0.5 2,5-Diaminotoluene sulphate 0.55 0.7 0.7 0.55 "common dye support 4-Chlororesorcine 0.17 0.17 Resorcine 0.05 0.05 Ascorbic acid 0.5 0.5 Cationic dye * in % by weight 1.0 1.0 3-Aminophenol 0.03 0.03 Demineralized water qs. 100 100 100 100 for for for for *common dye support 1(V) 2(V) 3(V) 4(V) Cetylstearylalcohol 11.00 11.00 Oleth-5 5.0 5.00 Oleic acid 2.5 10.0 10.0 2.50 Stearic acid monoethanolamide 2.5 2.50 Coco fatty acid monoethanolamide 2.5 2.5 Sodium laurylsuphate 1.7 1.7 Sodiumsulphite 1.0 1.00 1.00 1.00 1,2-Propanediol 1.0 1.00 Ammoniumchloride 0.5 0.50 EDTA, Tetrasodiumsalt 0.2 0.20 Perfume 0.4 0.40 Cornproteinhydrolysate 0.2 0.20 Silica 0.1 0.10 • 'Cationic dye is mixed with the other components of the oxidative dye composition shortly before the applying to the hair. • 'Cationic dye is a single cationic dye or composition of cationic dyes as given above * Cationic dye compositions (V ) = compositions (V )' = composition 4(V) + composition 3(V) + 'cationic dye *cationic dye Cationic dye of example 1 10(V) 10(V')' Cationic dye of example 2 11(V') 11(V')' Cationic dye of example 3 12(V) 12(V')' Cationic dye of example 4 13(V) ISf 1 )' compositions (V 1 ) = composition 4(V) + 'cationic dye + dye** (*cationic dye/ **dye in a ratio of 1 :1) dye " cationic dye cationic dye cationic dye cationic dye of of example 1 of example 2 of example 3 example 4 HC Yellow 2 14(V) 15(V) 16(V) 17(V') HC Yellow 4 18(V) 19(V') 20(V) 21 (V 1 ) HC Yellow 6 22(V') 23(V) 24(V) 25(V) Basic Yellow 57 26(V') 27(V') 28(V) 29(V') Basic Yellow 9 30(V) 31 (V 1 ) 32(V') 33(V') Disperse Orange 3 34(V) 35(V) 36(V) 37(V') HC Red 3 38(V') 39(V') 40(V) 41 (V 1 ) HC Red BN 42(V) 43(V') 44(V) 45(V) Basic Red 76 46(V) 47(V') 48(V') 49(V) Basic Red 2 50(V) 51 (V 1 ) 52(V) 53(V') Basic Violet 14 54(V) 55(V') 56(V) 57(V') Basic Blue 3 58(V) 59(V) 60(V) 61 (V 1 ) Basic Blue 6 62(V) 63(V') 64(V) 65(V') Basic Blue 7 66(V) 67(V) 68(V) 69(V) Basic Blue 9 70(V') 71 (V 1 ) 72(V) 73(V) Basic Blue 12 74(V') 75(V) 76(V) 77(V) Basic Blue 26 78(V) 79(V') 80(V) 81 (V) HC Blue 2 82(V) 83(V') 84(V') 85(V') HC Blue 7 86(V') 87(V) 88(V) 89(V) HC Blue 12 90(V') 91 (V 1 ) 92(V) 93(V') Disperse Blue 3 94(V) 95(V') 96(V') 97(V) HC Violet 1 98(V) 99(V') 100(V') ιoi(V) Disperse Violet 1 102(V') 103(V') 104(V') 105(V) Disperse Black 9 106(V) 107(V') 108(V) 109(V) Basic Brown 16 110(V) 111 (V 1 ) 112(V) 113(V) Basic Brown 17 114(V) 115(V) 116(V') 117(V) 2-amino-6-chloro-4-nitrophenol 118(V) 119(V) 120(V) 121(V) 4-amino-2-nitrodiphenylamine-2'-carboxylic acid 122(V) 123(V) 124(V) 125(V) 6-nitro-1 ,2,3,4-tetrahydroquinoxaline 126(V) 127(V) 128(V) 129(V) 4-N-ethyl-1 ,4-bis(2'-hydroxyethylamino)-2-nitrobenzene 130(V) 131 (V) 132(V) 133(V) hydrochloride 1 -methyl-3-nitro-4-(2'-hydroxyethy l)-aminobenzene 135(V) 136(V) 137(V') 138(V) compositions (V ) = composition 4(V) + "cationic dye + dye* ('cationic dye/***dye in a ratio of 1:1) dyes ' cationic dye cationic dye cationic dye of cationic dye of example 1 of example 2 example 3 of example 4 HC Yellow 2, HC Yellow 4 139(V) 140(V) 141(V) 142(V') Basic Red 76, HC Red BN, 143(V) 144(V) 145(V) 146(V) HC Red BN, Basic Violet 14 147(V') 148(V') 149(V') 150(V) Basic Blue 12, Basic Blue 6 151(V') 152(V') 153(V') 154(V) 4-N-ethyl-1,4-bis(2'-hydroxyethylamino)-2-nitrobenzene 155(V) 156(V) 157(V) 158(V) hydrochloride, 6-nitro-1 ,2,3,4-tetrahydroquinoxaline Basic Brown 16, Disperse Black 9 159(V) 160(V') 162(V') 163(V') compositions (V ) = composition 4(V) + *cationic dye + dye* ('cationic dye/****dye in a ratio of 1:1) dyes ' cationic dye cationic dye cationic dye of cationic dye of of example 1 of example 2 example 3 example 4 HC Yellow 2, HC Yellow 4, Basic Red 2 164(V) 165(V') 166(V') 167(V') Basic Red 76, HC Red BN, Basic Red 2 168(V) 169(V') 170(V') 171(V) HC Red BN, Basic Violet 14, Disperse Violet 1 172(V) 173(V') 174(V') 175(V) Basic Blue 12, Basic Blue 6, Disperse Violet 1 176(V) 177(V) 178(V) 179(V') 2-amino-6-chloro-4-nitrophenol, 6-nitro- 180(V) 181(V) 182(V) 183(y) 1 ,2,3,4-tetrahydroquinoxaline, Basic Brown 17 Basic Brown 16, Disperse Black 9, Basic Brown 17 184(V) 185(V) 186(V) 187(V) compositions (V ) = composition 4(V) + "cationic dye + dye***** fcationic dye/*****dye in a ratio of 1 :1) dye ***** cationic dye cationic dye cationic dye cationic dye of example 1 of example 2 of example 3 of example 4 HC Yellow 2, Basic Red 76, Basic Red 2, Disperse Orange 3 188(V) 189(V) 190(V) 191 (V) Basic Red 76, HC Red BN, Basic Red 2, Basic Violet 14 192(V') 193(V) 194(V) 195(V) HC Red BN, Basic Violet 14, Disperse Violet 1 , HC Red 3 196(V) 197(V) 197(V) 198(V) Basic Blue 12, Basic Blue 6, Disperse Violet 1, Basic Blue 9 199(V) 200(V) 201 (V) 202(V) 2-amino-6-chloro-4-nitrophenol, 6-nitro- 203(V) 204(V) 205(V) 206(V) 1 ,2,3,4-tetrahydroquinoxaline, Basic Brown 17, HC Red BN Basic Brown 16, Disperse Black 9, Basic Brown 17, Basic Red 207(V) 208(V) 209(V) 210(V) 76 Each of the oxidative precursor dye compositions 1 (V), 2(V), 3(V) and 4(V) are applied for 15 minutes to locks of bleached hair. The hair is then not rinsed, but treated for 15 minutes with a oxidative precursor dye compositions(V") which is prepared as given in table 2 below: Table 2: oxidative precursor dye compositions(V") oxidative precursor dye compositions(V") oxidative precursor dye composition 1(V) and 1(V") a cationic dye of example 1 as solution (1.0 % by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dye composition 1(V) and 2 (V") a cationic dye of example 2 as solution (1.0 % by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dye composition 1(V) and 3(V") a cationic dye of example 3 as solution (1.0 % by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dye composition 1(V) and 4(V") a cationic dye of example 4 as solution (1.0 % by weight) with pH 9.8; in a ratio of 1:1 oxidative precursor dye composition 1(V) and a 4/14(V") to cationic dye composition 14(V)-210(V) as solution (1.0 % by weight) with 4/210(V") pH 9.8; in a ratio of 1:1 oxidative precursor dye composition 2(V) and 50/") a cationic dye of example 1 as solution (1.0 % by weight) with pH 9.8; in a ratio of 1 :1 oxidative precursor dye composition 2(V) and 6(V") a cationic dye of example 2 as solution (1.0 % by weight) with pH 9.8; in a ratio of 1 :1 oxidative precursor dye composition 2(V) and 7(V") a cationic dye of example 3 as solution (1.0 % by weight) with pH 9.8; in a ratio of 1 :1 oxidative precursor dye composition 2(V) and 8(V") a cationic dye of example 4 as solution (1.0 % by weight) with pH 9.8; in a ratio of 1 :1 oxidative precursor dye composition 2(V) and 8/14(V") to a cationic dye composition 14(V')-210(V) as solution (1.0 % by weight) with 8/210(V") pH 9.8; in a ratio of 1:1 oxidative precursor dye composition 1(V) and 11 (V") a cationic dye of example 1 as solution (1.0 % by weight) with pH 5 (adjusted with citric acid) ; in a ratio of 1 :1 oxidative precursor dye composition 1(V) and 12(V") a cationic dye of example 2 as solution (1.0 % by weight) with pH 5 (adjusted with citric acid) ; in a ratio of 1 :1 oxidative precursor dye composition 1(V) and 13(V") a cationic dye of example 3 as solution (1.0 % by weight) with pH 5 (adjusted with citric acid) ; in a ratio of 1 :1 oxidative precursor dye composition 1(V) and 14(V") a cationic dye of example 4 as solution (1.0 % by weight) with pH 5 (adjusted with citric acid) ; in a ratio of 1:1 oxidative precursor dye composition 1(V) and 14/14(V") to a cationic dye composition 14(V')-210(V) solution (1.0 % by weight) with 14/210(V") pH 5 (adjusted with citric acid) ; in a ratio of 1 :1 oxidative precursor dye composition 2(V) and 15(V") a cationic dye of example 1 as solution (1.0 % by weight) with pH 5 (adjusted with citric acid) ; in a ratio of 1:1 oxidative precursor dye composition 2(V) and 16(V") a cationic dye of example 2 as solution (1.0 % by weight) with pH 5 (adjusted with citric acid) ; in a ratio of 1:1 oxidative precursor dye composition 2(V) and 17(V") a cationic dye of example 3 as solution (1.0 % by weight) with pH 5 (adjusted with citric acid) ; in a ratio of 1 :1 oxidative precursor dye composition 2(V) and 18(V") a cationic dye of example 4 as solution (1.0 % by weight) with pH 5 (adjusted with citric acid) ; in a ratio of 1:1 oxidative precursor dye composition 2(V) and 18/14(V") to a cationic dye composition 14(V')-210(V') as solution (1.0 % by weight) with 18/210(V") pH 5 (adjusted with citric acid) ; in a ratio of 1 :1 oxidative precursor dye composition 3(V) with pH 5 (adjusted with citric acid) 19(V") oxidative precursor dye composition 4(V) with pH 5 (adjusted with citric acid) 20(V") oxidative precursor dye composition 3(V) comprising cationic dye composition 14(V')- 20/14(V") to 210(V') with pH 5 (adjusted with citric acid) 20/210(V") oxidative precursor dye composition 4(V) comprising cationic dye composition 14(V')- 21/14(V") tO 210(V') with pH 5 (adjusted with citric acid) 21/210(V") cationic dye of example 1 in a watery citric gel (12.5% by weight) with pH 5; 22(V") in an equimolar weight portion to the weight of composition 3(V) cationic dye of example 2 in a watery citric gel (12.5% by weight) with pH 5; 23(V") in an equimolar weight portion to the weight of composition 3(V) cationic dye of example 3 in a watery citric gel (12.5% by weight) with pH 5; 24(V") in an equimolar weight portion to the weight of composition 3(V) cationic dye of example 4 in a watery citric gel (12.5% by weight) with pH 5; 25(V") in an equimolar weight portion to the weight of composition 3(V) cationic dye composition 14(V')-210(V') a watery citric gel (12.5% by weight) with pH 5; 25/14(V") tO in an equimolar weight portion to the weight of composition 3(V) 25/2 0(V") cationic dye of example 1 as solution (1.0 % by weight) with pH 9.8; 26(V") in an equimolar weight portion to composition 3(V) cationic dye of example 2 as solution (1.0 % by weight) with pH 9.8; 27(V") in an equimolar weight portion to composition 3(V) cationic dye of example 3 as solution (1.0 % by weight) with pH 9.8; 28(V") in an equimolar weight portion to composition 3(V) cationic dye of example 4 as solution (1.0 % by weight) with pH 9.8; 29(V") in an equimolar weight portion to composition 3(V) cationic dye composition 14(V')-210(V) as solution (1.0 % by weight) with pH 9.8; 29/14(V") to in an equimolar weight portion to composition 3(V) 29/210(V") Each of the oxidative precursor dye compositions 3(V) and 4(V) are applied for 15 minutes to locks of bleached hair. The hair is then not rinsed, but treated for 15 minutes with a oxidative precursor dye compositions(V") which is prepared as given in table 3 below: Table 3: oxidative precursor dye compositions(V") oxidative precursor dye compositions(V") oxidative precursor dye composition 2(V) with pH 9.8; in a ratio of 1:1 9(V") oxidative precursor dye composition 1(V) with pH 9.8; in a ratio of 1 :1 10(V") Then the hair is rinsed, washed with a standard shampoo and afterwards dried. The hair is dyed in a brilliant shades with very good endurance properties with respect to subsequent shampooing and fastness to rubbing and lightness. Example 25: Example 25 is identical to example 24 with the proviso that the dying compositions do not possess pH 9.8, but pH 5 (pH value is adjusted with citric acid) Example 26: Example 26 is identical to example 24 with the proviso that the oxidative precursor dye compositions (V") are replaced by the oxidative precursor dye compositions (W") which are prepared as given in table 1 below. Table 1 dye compositions (W) Oxidative precursor dye compositions 1 (W) and hydrogen peroxide 1 (W") solution (6% by weight); with pH 5 (adjusted with citric acid) ; in a ratio of 1 :1 Oxidative precursor dye compositions 2(W") and hydrogen peroxide 2(W") solution (6% by weight); with pH 9.8 ; in a ratio of 1:1 Oxidative precursor dye compositions 1 (W") and hydrogen peroxide 3(W") solution (6% by weight); with pH 9.8 ; in a ratio of 1:1 Oxidative precursor dye compositions 2(W") and hydrogen peroxide 4(W") solution (6% by weight); with pH 5 ; in a ratio of 1 :1 Cationic dye of example 1 (1.0 % by weight) in a watery citric gel 5(W") (12.5% by weight) with pH 5; in a ratio of weight of 1:1 to composition 3(W) Cationic dye of example 2 (1.0 % by weight) in a watery citric gel 6(W") (12.5% by weight) with pH 5; in a ratio of weight of 1:1 to composition 3(W) Dye of example 4 with pH 9.8; in a ratio of weight of 1 :1 to 7(W") composition 3(W) Dye of example 4 ) with pH 9.8 and hydrogen peroxide solution (6% 8(W") by weight); in a ratio of weight of 1:1 to composition 3( ) Cationic dye of example 3 (1.0 % by weight) in a watery citric gel 9(W") (12.5% by weight) and hydrogen peroxide solution (6% by weight); with pH 5 (adjusted with citric acid) ; in a ratio of 1 :1 Cationic dye of example 3 (1.0 % by weight) in a watery citric gel 10(W") (12.5% by weight) with pH 5; in a ratio of weight of 1:1 to composition 3(W) Cationic dye of example 4 (1.0 % by weight) in a watery citric gel 11 (W 11 ) (12.5% by weight) with pH 5; in a ratio of weight of 1:1 to composition 3(W) Then the locks of bleached hair is treated till of 7 is adjusted. After 15 minutes at pH 7 the hair is rinsed, washed with a standard shampoo and then dried. The hair is dyed in a brilliant red-tinged violet shade with very good endurance properties with respect to subsequent shampooing and fastness to rubbing and lightness. Example 27: Example 27 is identical to example 26 with the proviso that the oxidative precursor dye compositions (W") are applied to the locks of bleached hair by a comb. Example 28: Example 28 is identical to example 25 with the proviso that the oxidative precursor dye compositions are applied to the locks of bleached hair by a comb. Examples 29-32 Example 29 is identical to example 24, and Example 30 is identical to example 25, and Example 31 is identical to example 26, and Example 32 is identical to example 27, and Example 33 is identical to example 28, with the proviso that the dying concerns not "locks of bleached hair", but "locks of middle blonde hair". Examples 33-37 Example 33 is identical to example 24, and Example 34 is identical to example 25, and Example 35 is identical to example 26, and Example 36 is identical to example 27, and Example 37 is identical to example 28, with the proviso that the dying concerns not "locks of bleached hair", but "bleached hair". Examples 38-42 Example 38 is identical to example 24, and Example 39 is identical to example 25, and Example 40 is identical to example 26, and Example 41 is identical to example 27, and Example 42 is identical to example 28, with the proviso that the dying concerns not "locks of bleached hair", but "middle blonde hair". All of the forgoing examples can also be carried out without the use of a common dye support. In all of the forgoing examples the identified common dye support can be replaced by the following dye support: (*) Common dye support: Ethanol 20.0 g Poly(C 8 -C 10 )alkylglucoside as an aqueous solution 4.8 g containing 60% active material (A.M.) buffered with ammonium citrate (0.5%), sold under the name Oramix CG110® by the company SEPPIC pH agent Qs pH = 6.5 or by In all of the forgoing examples the identified common dye support can be replaced by the following dye support: Common dye support: Ethanol 20.0 g Nonylphenoloxyethylen with 9 mol oxyethylen 8.0 g sold under the name IGEPAL NR 9 Or by the company RHODIA CHEMIE 2-Amino-2-methyl-1 -propanol qs. pH = 8.0 or by Common dye support: Oleic acid 10.0 Sodiumsulphite 1.00

Claims: What is claimed is: 1. A method of colouring keratin-containing fibres that comprises treating the fibres with a dye of formula wherein Y, and Y 2 are each independently of the other hydrogen, unsubstituted or substituted C r C 4 - alkyl, or halogen, R, and R 2 are each independently of the other hydrogen or unsubstituted or substituted C,-C 4 alkyl, R 3 and R 4 are each independently of the other hydrogen, unsubstituted or substituted C,-C 4 - alkyl, C,-C 4 alkoxy or halogen, R s is hydrogen, C,-C 4 alkyl, C,-C 4 alkoxy or halogen, X is C,-C 12 alkoxy or a group of formula -N(R 6 )-CO-R 7 , wherein R 6 is hydrogen or C 1 -C 4 alkyl and R 7 is hydrogen, C,-C 4 alkyl or -NH 2 and A- is an anion. 2. A method of colouring keratin-containing fibres acoording to claim 1 comprising a1) treating the fibres with a composition, possessing a pH value of pH >7, and comprising a developing substance and at least one coupling substance and an oxidation agent, or a2)treating the fibres with a composition, possessing a pH value of pH <7, comprising a developing substance and at least one coupling substance and an oxidation agent, or a3) treating the fibres with a dye of formula (1) according to claim 1 , or with a dye of formula (4) according to claim 3, or with a composition according to claim 5 and a composition, possessing a pH value of pH >7, and comprising a developing substance and at least one coupling substance and an oxidation agent, or a4) treating the fibres with a dye of formula (1) according to claim 1 , or with a dye of formula (4) according to claim 3, or with a composition according to claim 5 and a composition, possessing a pH value of pH <7, and comprising a developing substance and at least one coupling substance and an oxidation agent, and b) then applying without intermediary rinsing for 5 to 30 minutes, and d )then applying to the treated fibres a composition, possessing a pH value of pH < 7, and comprising a developing substance and at least one coupling substance, or c2)then applying to the treated fibres a composition, possessing a pH value of pH > 7, and comprising a developing substance and at least one coupling substance, or c3)then applying to the treated fibres a dye of formula (1) according to claim 1, or a dye of formula (4) according to claim 3, or a composition according to claim 5, and a composition, possessing a pH value of pH < 7, and comprising a developing substance and at least one coupling substance, or c4)then applying to the treated fibres a dye of formula (1) according to claim 1, or a dye of formula (4) according to claim 2, or a composition according to claim 4, composition, possessing a pH value of pH > 7, and comprising a developing substance and at least one coupling substance, or c5)then applying to the treated fibres a composition, possessing a pH value of pH > 7, and comprising a dye of formula (1) according to claim 1 , or a dye of formula (4) according to claim 3, or a composition according to claim 5, or c6)then applying to the treated fibres a composition, possessing a pH value of pH < 7, and comprising a dye of formula (1) according to claim 1, or a dye of formula (4) according to claim 3, or a composition according to claim 5, with the proviso that least one dye of formula (1) according to claim 1 , or a dye of formula (4) according to claim 2, or a composition according to claim 4 is applied to the hair. 3. A dye of formula wherein R, and R 2 are each methyl or ethyl, X is unsubstituted C r C 4 alkoxy or a radical -NH-CO-R 7 , wherein R 7 is hydrogen, methyl, ethyl or -NH 2 , and A " is an anion. 4. A process for the preparation of a dye of formula (1), which comprises acylating the free amino group in a compound of formula NH, wherein Y,, Y 2 , R,, R 2 , R 3 , R 4 , R 5 and A " are as defined for formula (1), in a manner known per se, or reacting a compound of formula wherein Y,, Y 2 , R,, R 2 , R 3 and R 4 are as defined for formula (1) and R 8 is C,-C 4 alkyl with a p- alkoxy-aniline under reaction conditions known per se. 5.A composition for colouring keratin-containing fibres, which comprises at least one dye of formula (1) according to claim 1.

Inventors: FROEHLING BEATE SUSANNE, MOECKLI PETER, FROEHLING, BEATE, SUSANNE, MOECKLI, PETER
Applicants: CIBA SC HOLDING AG, FROEHLING BEATE SUSANNE, MOECKLI PETER, CIBA SPECIALTY CHEMICALS HOLDING INC., FROEHLING, BEATE, SUSANNE, MOECKLI, PETER
Application year: 2001
Main classification: C09B44
IPC codes: A61K8, A61Q5, C09B44