Cationic azo compounds, their preparation and their use are already known, e. g. from WO 95/01772 and EP-A-714 954.

In hitherto known syntheses of imidazole azo compounds, which are carried out at tempera- tures of from 40°C to 140°C, optionally under pressure and/or under an inert gas atmos- phere in an inert solvent, especially in dimethylformamide or in dimethyl sulfoxide, the synth- esis conditions result in reaction masses that are thermally critical. Such reaction masses give rise to thermal decomposition which, in industrial production, leads to considerable safety problems.

It has now been found that by the selection of a suitable solvent or a solvent mixture and a basic catalyst or a mixture of basic catalysts, such as tertiary amines and/or alcoholates, the synthesis can be carried out at a lower temperature with the same or even improved reaction yield, without at the same time prolonging the reaction time. Alternatively, synthesis at the same temperature proceeds considerably more quickly.

The present invention accordingly relates to a process for the preparation of azo compounds of formula (I) wherein X is-O-or-NR7-, Y is-N= or-CR8=, A is a colourless anion, Ri and R8 each independently of the other are hydrogen; Ct-C4alkyl ; C1-C4alkyl substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyl ; halogen or nitro, R2 and R7 each independently of the other are hydrogen; unsubstituted C1-C4alkyl or C1-C4alkyl substituted by-OH, C1-C4alkoxy, halogen, CN or by phenyl, Ra and R4 each independently of the other are hydrogen; unsubstituted C1-C4alkyl ; C1-C4alkyl substituted by-OH,-Ci-C4alkoxy, halogen,-CN or by phenyl ; unsub- stituted C1-C12alkoxy ; C1-C12alkoxy substituted by -OH, -C1-C4alkoxy, halogen, - CN or by phenyl ; or halogen, R5 is hydrogen; unsubstituted C1 4alkyl ; or Ci-C4alkyl substituted by-OH, -C1-C4alkoxy, halogen, -CN or by phenyl, R6 is hydrogen; unsubstituted C1-4alkyl; C1-C4alkyl substituted by -OH, -C1-C4alkoxy, halogen,-CN or by phenyl ; or a radical of formula (a) or (b) wherein X, Y, A, Ri, R2, R3, R4 and R5 are as defined above, and Rg and Rio each independently of the other are hydrogen; unsubstituted Ci-C4- alkyl ; C1-C4alkyl substituted by -OH, -C1-C4alkoxy, halogen,-CN or by phenyl ;-OR11 ; -NR11R12 or -NR11COR12, wherein Ri, and R12 each independently of the other are hydrogen ;-NH2 ; unsubstituted C1-C12alkyl or Ci-Ci2alkyl substituted by -OH, -C1-C4alkoxy, halogen,-CN or by phenyl, Q is a bridging member, and m is 0 or 1, or R5 and R6 together with the nitrogen atom to which they are bonded form a pyrrolidine, piperidine, morpholine or piperazine ring, by reaction of a compound of formula (II) or a mixture of compounds of formula (II) Ra 1 T I/\ N N OC1-C4alkyl (II) Y-Nr R2 A with a compound of formula (ill) or with a mixture of compounds of formula (III) NHRsRe (III), wherein all the substituents are as defined above, in a solvent or solvent mixture, which process comprises adding to the reaction mixture at least one tertiary amine and/or at least one alcoholate of the formula R13O-Z, wherein R13 is unsubstituted C1-C10alkyl or Ci-Cioaiky) substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyl, and Z is an alkali metal.

Alkyl radicals are to be understood according to the invention generally as being open-chain or branched alkyl radicals, for example methyl, ethyl, n-and iso-propyl and n-, sec-and tert- butyl.

Such alkyl radicals may be mono-or poly-substituted, for example by hydroxy, carboxy, halogen, cyano or C1-C4alkoxy.

The alkoxy radicals preferably have from 1 to 4 carbon atoms and are, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy and n- hexyloxy. The alkoxy groups may likewise be substituted, for example by the radicals listed as possible substituents of alkyl groups, especially by hydroxy or C1-C4alkoxy.

Suitable colourless anions A include 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 or complex anions, such as the anion of a zinc chloride double salt.

The anion is generally governed by the preparation process. Preferably, chlorides, hydrogen sulfates, sulfates, methosulfates, phosphates, formates, lactates or acetates are present.

Halogen is to be understood as being fluorine, bromine, iodine and especially chlorine.

The bridging member Q is especially an unsubstituted C1-C2oalkylene group; a C1-C20alkyl- ene group substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyl ; or a C1-C20alkylene group interrupted by one or more hetero atoms, such as N, O and/or S, which may be unsubstituted or substituted by the above-mentioned groups.

The process is preferred for compounds of formula (I) wherein X is-NR7-, Y is-CR8=, A is a colourless anion, Ri and R8 each independently of the other are hydrogen or unsubstituted C1-C2alkyl, R2 and R7 each independently of the other are unsubstituted C1-C2alkyl or hydroxyethyl, R3 and R4 each independently of the other are hydrogen; methyl ; methoxy or chlorine, R5 is hydrogen; methyl or ethyl, R6 is hydrogen; methyl ; ethyl, or a radical of formula (a) or (b) wherein X, Y, A, R1, R2, R3, R4 and Rr, have the preferred meanings given above, and Rg and Rio each independently of the other are hydrogen; unsubstituted Ci-C4- alkyl ; C1-C4alkyl substituted by -OH, -C1-C4alkoxy, halogen,-CN or by phenyl ;-OR11 ; -NR11R12 or -NR11COR12, wherein R11 and R12 each independently of the other are hydrogen ;-NH2 ; unsubstituted C1-C12alkyl or C1-C12alkyl substituted by -OH, -C1-C4alkoxy, halogen,-CN or by phenyl, Q is unsubstituted C2-C10alkylene or C2-Cloalkylene substituted by -OH, -C1-C4alkoxy, halogen, -CN or by phenyl, and m is 0 or 1.

The process is especially preferred for compounds of formula (la) wherein Pi and R8 each independently of the other are hydrogen or methyl, R2 and R7 each independently of the other are methyl or ethyl, R5 and R6 each independently of the other are hydrogen; methyl or ethyl and A is a colourless anion.

The process is likewise especially preferred for compounds of formula (lb) wherein Ri and R8 each independently of the other are hydrogen or methyl, R2 and R7 each independently of the other are methyl or ethyl, R5 is hydrogen or methyl, Rg is hydrogen or methyl, Rio is hydrogen; methoxy; ethoxy ;-NH2 ; -NHCOH ;-NHCOCH3 ;-NHCOCH2CH3 or - NHCONH2, Rio preferably being in the 4-position, m is 0 or 1 and A is a colourless anion.

The process is likewise especially preferred for compounds of formula (Ic) R2 R A I In RRX | A NRsC,-C, OalkyleneNRse ¢ 8 t I A wherein R1 and R8 each independently of the other are hydrogen or methyl, R2 and R7 each independently of the other are methyl or ethyl, each R5 independently of the other is hydrogen or methyl, and each A independently of the other is a colourless anion.

In the process according to the invention, from 0.5 to 200 parts, preferably from 1 to 150 parts, especially from 1 to 100 parts, of at least one tertiary amine and/or at least one alcoholate of the formula R130-Z, wherein R13 and Z are as defined above, are used.

The tertiary amines may contain more than one nitrogen atom (diamines, triamines etc.).

The tertiary amines may be aliphatic, aromatic or araliphatic.

The nitrogen atoms of the tertiary amines may be integrated in a ring or the amines may contain a ring.

Such suitable tertiary amines have especially one of the following formulae (c) - (i) wherein R14, R15 and R16 each independently of the others are unsubstituted C1-C10alkyl or C1-10alkyl substituted by-OH,-C,-C4alkoxy, halogen,-CN or by phenyl, R17 is unsubstituted Ci-C4alkyl or C,-C4alkyl substituted by-OH,-Ci-C4alkoxy, halogen,-CN or by phenyl, Rial Rio. Rio, R21, R22, R23, R24 and R25 each independently of the others are hydrogen; un- substituted C1-C4alkyl or C1-C4alkyl substituted by -OH, -C1-C4alkoxy, halogen,-CN or by phenyl, T is N or CH, n is 4, 5 or 6 and n', n"and n"'each independently of the others are 1,2, 3 or 4.

It is preferred to use amines or mixtures thereof wherein R14, R15 and R16 each independently of the others are unsubstituted C-C8alkyl or C1-C8alkyl substituted by-OH,-Ct-C4alkoxy, halogen,-CN or by phenyl, R17 is unsubstituted C1-C2alkyl or C1-C2alkyl substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyl, R18, Pis, R2o, R21, Ræ, R23, R24 and R25 each independently of the others are hydrogen; unsubstituted C1-C2alkyl or C1-C2alkyl substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyi, T is N or CH, n is 5 or 6 and n', n"and n"'each independently of the others are 2 or 3.

Especially preferred amines are above all trimethylamine, triethylamine, trioctylamine, pyrid- ine, N-methylpiperidine, quinuclidine and diaza-bicyclooctane (DABCO).

In preferred alcoholates of the formula RI3O-Z, R13 is unsubstituted C1-C4alkyl or C1-C4alkyl substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyl and Z is an alkali metal, espe- cially sodium.

Suitable solvents for the synthesis include both protic and aprotic solvents, and any mixtures thereof.

Suitable protic solvents are especially water or aliphatic alcohols, preferably Ci-Caaicohois such as methanol, ethanol, isopropanol, propanol, 2-propanol and butanol.

Suitable polar aprotic solvents are especially alkyl nitriles, such as acetonitrile or propio- nitrile ; amides such as dialkylformamides, preferably di-C1-C2alkylformamides, or dialkylacet- amides, preferably di-C1-C2alkylacetamides ; amines from the pyrrolidone series, such as N- alkylpyrrolidones, preferably N-methylpyrrolidone ; or sulfoxides, such as dimethyl sulfoxide.

It is likewise possible to use mixtures of such solvents.

Especially preferred solvents are methanol, 2-propanol, 1-butanol, acetonitrile, dimethyl- formamide and dimethylacetamide.

The process according to the invention is preferably carried out at a temperature of from 40 to 1400C, especially from 50 to 120°C.

A preferred embodiment of the present invention is the preparation of compounds of formula (la) wherein R, and R8 each independently of the other are hydrogen or methyl, R2 and R7 each independently of the other are methyl or ethyl, R5 and R6 each independently of the other are hydrogen; methyl or ethyl and A is a colourless anion, by reaction of a compound of formula (Ila) or a mixture of compounds of formula (IIa) Ruz "1 J p ; N/ß7 <-OC-C4ikoxy (lla) Fizz R8 R2 A with a compound of formula (III) or with a mixture of compounds of formula (III) NHR5R6 (III) wherein all the substituents have the preferred meanings given above, in a protic solvent, especially in water or in aliphatic alcohols, preferably in Ci-Ceaicohois such as methanol, ethanol, isopropanol, propanol, 2-propanol or butanol or in a polar aprotic solvent, especially in alkyl nitriles, such as acetonitrile or propionitrile ; in amides such as dialkylformamides, preferably di-C1-C2alkylformamides, or in dialkylacet- amides, preferably di-Ci-C2alkylacetamides ; in amines from the pyrrolidone series, such as N-alkylpyrrolidones, preferably N-methylpyrrolidone ; or in sulfoxides, such as dimethyl sulf- oxide, optionally under an inert atmosphere, such as a nitrogen atmosphere, at a temperature of from 40 to 140°C, preferably from 50 to 120°C, which process comprises adding from 0.5 to 200 parts, preferably from 1 to 150 parts, especially from 1 to 100 parts, of at least one amine of one of formulae (c) - (i) and/or at least one alcoholate of the formula R130-Z, wherein Pis is unsubstituted C1-C10alkyl or C1-C10alkyl substituted by-OH,-C1-C4alkoxy, halogen, - CN or by phenyl, and Z is an alkali metal, R14, Pis and Rie each independently of the others are unsubstituted C1-C10alkyl or C1- Cioalkyl substituted by -OH, -C1-C4alkoxy, halogen, -CN or by phenyl, preferably unsubstituted Ci-C8alkyl or C1-C8alkyl substituted by -OH, -C1-C4alkoxy, halogen,-CN or by phenyl, R17 is unsubstituted C1-C4alkyl or Ci-C4alkyl substituted by -OH, -c1-C4alkoxy, halogen, -CN or by phenyl, preferably unsubstituted C1-C2alkyl or C1-C2alkyl substituted by-OH, -C1-C4alkoxy, halogen, -CN or by phenyl, Pis. R19, R20, R21, R22, R23, R24 and R25 each independently of the others are hydrogen; unsubstituted Ci-C4alkyl or C1-C4alkyl substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyl ; preferably hydrogen, unsubstituted Ci-C2alkyl or C1-C2alkyl substituted by-OH, -C1-C4alkoxy, halogen, -CN or by phenyl, T is N or CH, n is 4,5 or 6, preferably 5 or 6, and n', n"and n"'each independently of the others are 1,2, 3 or 4, preferably 2 or 3.

A likewise preferred embodiment of the present invention is the preparation of compounds of formula (lb) wherein R1 and Ra each independently of the other are hydrogen or methyl, R2 and R7 each independently of the other are methyl or ethyl, R5 is hydrogen or methyl, Rg is hydrogen or methyl, Rio is hydrogen; methoxy; ethoxy ;-NH2 ; -NHCOH ;-NHCOCH3 ;-NHCOCH2CH3 or - NHCONH2, R1o preferably being in the 4-position, m is 0 or 1 and A is a colourless anion, by reaction of a compound of formula (alb) or a mixture of compounds of formula (llb) R1 R7 N tN/OC1-C4alkyl (llb nu+ () R R2 A with a compound of formula (Illb) or with a mixture of compounds of formula (Illb) wherein all the substituents have the definitions and preferred meanings given above, in a protic solvent, especially in water or in aliphatic alcohols, preferably in C1-C8alcohols such as methanol, ethanol, isopropanol, propanol, 2-propanol or butanol or in a polar aprotic solvent, especially in alkyl nitriles, such as acetonitrile or propionitrile ; in amides such as dialkylformamides, preferably di-Ci-C2alkylformamides, or in dialkylacet- amides, preferably di-C1-C2alkylacetamides ; in amines from the pyrrolidone series, such as N-alkylpyrrolidones, preferably N-methylpyrrolidone ; or in sulfoxides, such as dimethyl sulf- oxide, optionally under an inert atmosphere, such as a nitrogen atmosphere, at a temperature of from 40 to 140°C, preferably from 50 to 120°C, which process comprises adding from 0.5 to 200 parts, preferably from 1 to 150 parts, especially from 1 to 100 parts, of at least one amine of one of formulae (c) - (i) and/or at least one alcoholate of the formula R13O-Z, wherein Ri3 is unsubstituted Ci-Cloalkyl or Ci-Cioalkyl substituted by -OH, -C1-C4alkoxy, halogen, - CN or by phenyl, and Z is an alkali metal, R14, Ris and R16 each independently of the others are unsubstituted Ci-Cioalkyl or Ci- Cioaikyi substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyl, preferably unsubstituted Ci-Caalkyl or Ci-C8alkyl substituted by -OH, -C1-C4alkoxy, halogen,-CN or by phenyl, R17 is unsubstituted Ci-C4alkyl or C1-C4alkyl substituted by-OH,-Ci-C4alkoxy, halogen,-CN or by phenyl, preferably unsubstituted C1-C2alkyl or C1-C2alkyl substituted by-OH, -C1-C4alkoxy, halogen, -CN or by phenyl, Pie. Pie. R2o, R21, R22, R23, R24 and R25 each independently of the others are hydrogen; unsubstituted C1-C4alkyl or C1-C4alkyl substituted by -OH, -C1-C4alkoxy, halogen, -CN or by phenyl ; preferably hydrogen, unsubstituted Ci-C2alkyl or Ci-C2alkyl substituted by-OH, -C1-C4alkoxy, halogen, -CN or by phenyl, T is N or CH, n is 4,5 or 6, preferably 5 or 6, and n', n"and n''' each independently of the others are 1,2, 3 or 4, preferably 2 or 3.

A likewise preferred embodiment of the present invention is the preparation of compounds of formula (Ic) 2 R R1 R A + N zizi N-&NRg-C4-Cloalkylene-NR 5 &N/N N S R2 R I A 8 R2 I 2 wherein R, and R8 each independently of the other are hydrogen or methyi, R2 and R7 each independently of the other are methyl or ethyl, each R5 independently of the other is hydrogen or methyl, each A independently of the other is a colourless anion. by reaction of a compound of formula (IIc) or a mixture of compounds of formula (IIc) Ri R7 N kS OC1-C4alkyl (llc) zon R$ R A R I A with a compound of formula (Ilic) or with a mixture of compounds of formula (Illc) A R2 R +N HNR5 C4-C10alkylenc NR5t (Illc) R7 R1 Ruz wherein all the substituents have the definitions and preferred meanings given above, in a protic solvent, especially in water or in aliphatic alcohols, preferably in Ci-C8alcohols such as methanol, ethanol, isopropanol, propanol, 2-propanol or butanol or in a polar aprotic solvent, especially in alkyl nitriles, such as acetonitrile or propionitrile ; in amides such as dialkylformamides, preferably di-C1-C2alkylformamides, or in dialkylacet- amides, preferably kylacetam ides ; in amines from the pyrrolidone series, such as N-alkylpyrrolidones, preferably N-methylpyrrolidone ; or in sulfoxides, such as dimethyl sulf- oxide, optionally under an inert atmosphere, such as a nitrogen atmosphere, at a temperature of from 40 to 140°C, preferably from 50 to 120°C, which process comprises adding from 0.5 to 200 parts, preferably from 1 to 150 parts, especially from 1 to 100 parts, of at least one amine of one of formulae (c) - (i), and/or at least one alcoholate of the formula R130-Z, wherein Pis is unsubstituted C1-C10alkyl or Ci-Cioatky) substituted by-OH,-C1-C4alkoxy, halogen, - CN or by phenyl, and Z is an alkali metal, R14, Ris and R16 each independently of the others are unsubstituted C1-C10alkyl or C1- C10alkyl substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyl, preferably unsubstituted C1-C8alkyl or C1-C8alkyl substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyl, R17 is unsubstituted C,-C4alkyl or C1-C4alkyl substituted by-OH,-C1-C4alkoxy, halogen,-CN or by phenyl, preferably unsubstituted C1-C2alkyl or C1-C2alkyl substituted by-OH, -C1-C4alkoxy, halogen, -CN or by phenyl, R18, R19, R20, R21, R22, R23, R24 and R25 each independently of the others are hydrogen; unsubstituted C1-C4alkyl or C1-C4alkyl substituted by-OH,-Ci-C4alkoxy, halogen,-CN or by phenyl ; preferably hydrogen, unsubstituted C1-C2alkyl or C1-C2alkyl substituted by-OH, - Ci-C4alkoxy, halogen,-CN or by phenyl, T is N or CH, n is 4,5 or 6, preferably 5 or 6, and n', n"and n''' each independently of the others are 1,2, 3 or 4, preferably 2 or 3.

The azo compounds prepared by the preparation process according to the invention are suitable for dyeing materials customarily dyed using cationic dyes, for example polyacrylo- nitrile, wood pulp and hair, especially living human hair.

The invention relates also to compositions for dyeing keratin-containing material, which compositions comprise the dyes prepared according to the invention.

The compounds of formula (I) prepared according to the invention 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 range of shades and the colour fastness of the dyes of formula (I) used according to the invention can be extended by combination with other dyes used in the field of hair-dyeing compositions. They can very readily be combined with oxidation dyes and with direct dyes, it being possible for the latter to be of cationic nature or uncharged. Solely in the case of anionic direct dyes is a degree of caution advisable, because in that case precipitation in the formulation may occur under certain circumstances.

In all dyeing compositions it is also possible for a plurality of different colouring substances to be used together; likewise, it is also possible for a plurality of different oxidation dye precursors from the group of developer and coupler compounds to be used together, 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 DE-A1-197 17224.

In a further embodiment, in addition to comprising the dyes of formula (I) according to the invention the dyeing compositions according to the invention may, for the purpose of further modification of colour shades, also comprise customary direct dyes, for example from the group of the nitroanilines, nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenols, phenazines, phenothiazines, methines and the compounds known as Arianors, for example the compounds known by the international denominations or trade names HC 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 and Basic Brown 17, and picramic acid, 2-amino-6-chloro- 4-nitrophenol, 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2, 3,4-tetrahydro- quinoxaline, 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 prepared according to the invention are cationised nitroaniline and anthraquinone dyes, for example those described in the following Patent Specifications: US-5 298 029, US-5 360 930, US-5 169 403, US-5 256 823, US-5 135 543, EP-A-818 193, US-5 486 629 and EP-A-758 547.

Also readily capable of combination are cationic azo dyes, for example according to GB-A- 2 319 776, and the oxazine dyes described in DE-A-299 12 327 and mixtures thereof with the further direct dyes indicated therein.

The compositions of the invention according to that embodiment contain the dyes preferably in an amount of from 0.01 to 5 % by weight, based on the total dyeing composition.

Furthermore, the dyeing compositions according to the invention may also comprise naturally occurring dyes, 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. Suitable dyeing methods are described, for example, in EP-A-404 868.

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 Körperpflegemittel e. V. , Mannheim.

It is not necessary for the oxidation dye precursors, where present, or for the dyes each to be single compounds, but rather the dyeing compositions according to the invention may additionally comprise, depending on the preparation procedures for the individual dyes, lesser amounts of further components, provided such components do not have an adverse effect on the dyeing result or do not need to be excluded for other reasons, for example on toxicological grounds.

The dyes of formula (I) according to the invention may also readily be used in combination with other dyes and/or adjuvants used in the dyeing of hair, for example with oxidising agents for achieving lightened dyeings, as described in EP-A-810 851, oxidising agents in the form of permanent-wave fixing solutions, as described in DE-A- 197 13 698 or WO 99/40895, oxidation dyeing compositions, as described in EP-A-850 636, EP-A-850 637, EP-A-850 638 and EP-A-852 135, oxidation dyeing compositions containing cationic couplers, as described in WO 99/48856 and WO 99/48875, oxidation dyes in the presence of oxidoreductase enzyme, as described in WO 99/17730 and WO 99/36034, autooxidisable oxidation dyes, as described in WO 99/20234, nitrobenzene derivatives, as described in WO 99/20235, 'po) polyols or polyethers, as described in EP-A-962 219, thickening polymers, as described in EP-A-970 684, sugar-containing polymers, as described in EP-A-970 687, quaternary ammonium salts, as described in WO 00/10517, anionic surfactants, as described in WO 00/10518, non-ionic surfactants, as described in WO 00/10519 or silicones, as described in WO 00/12057.

The dyeing compositions according to the invention produce intense dyeings even at physiologically tolerable temperatures of less than 45°C. They are accordingly suitable espe- cially for dyeing 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 modes of application 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. The dyeing compositions according to the invention are also outstandingly suitable for the dyeing method described in DE-A-3 829 870 using a dyeing comb or dyeing 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 preparations according to the invention include any anionic surface-active substance that is suitable for use on the human body. Such a substance is 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.

Examples of suitable anionic surfactants, each in the form of sodium, potassium or ammon- ium salts or mono-, di-or tri-alkanolammonium salts having 2 or 3 carbon atoms in the alkanol group, are: - linear fatty acids having from 10 to 22 carbon atoms (soaps), - ether carboxylic acids of formula R-O-(CH2-CH2-O) X-CH2-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 acid mono-and di-alkyl esters having from 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethyl esters having from 8 to 18 carbon atoms in the alkyl group and from 1 to 6 oxyethyl groups, - linear alkanesulfonates having from 12 to 18 carbon atoms, - linear a-olefin sulfonates having from 12 to 18 carbon atoms, - a-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 (CH2-CH2-O),-SOSH, 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-37 25 030, sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropylene glycol ethers accord- ing to DE-A-37 23 354, sulfonate of unsaturated fatty acids having from 12 to 24 carbon atoms and from 1 to 6 double bonds according to DE-A-39 26 344, - esters of tartaric acid and citric acid with alcohols that are addition products of approx- imately 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 unsatura- ted C8-C22carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

The term"zwitterionic surfactants"denotes surface-active compounds that carry at least one quaternary ammonium group and at least one-COO () or-SO3 () group in the molecule.

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 cocoacylamino- propyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacyl- aminoethylhydroxyethylcarboxymethyl 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 containing a C8-C,8-alkyl or-acyl group, contain at least one free amino group and at least one-COOH or-SO3H 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-alkyl- amidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each having approximately from 8 to 18 carbon atoms in the alkyl group. Especially preferred ampholytic surfactants are N-cocoalkylaminopropionate, coco- acylaminoethylaminopropionate and 8acylsarcosine.

Non-ionic surfactants contain as the hydrophilic group, for example, a polyol group, a poly- alkylen 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 propyl- ene 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, - C12-C22 fatty acid mono-and di-esters of addition products of from 1 to 30 mol of ethylene oxide with glycerol, - C8-C22alkyl-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 suitable for use in the hair treatment preparations according to the invention are especially quaternary ammonium compounds. Preference is given to ammonium halides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e. g. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethyl- ammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants suitable for use according to the invention are the quaternised protein hydrolysates.

Also suitable according to the invention are cationic silicone oils, for example the commerc- ially available products Q2-7224 (manufacturer: Dow Corning ; a stabilised trimethylsilyl- amodimethicone), Dow Corning 929 Emulsion (comprising a hydroxylamino-modified silicone, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and 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 especially by their good biodegradability, in addition to their good conditioning action.

Likewise highly biodegradable are quaternary ester compounds, so-called"esterquats", such as the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates sold under the trade mark Stepantext.

An example of a quaternary sugar derivative that can be used as a 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 it is usually preferred to use natural raw materials of vegetable or animal origin as starting materials in the preparation of such substances, with the result that the substance mixtures obtained have different alkyl chain lengths according to the particular raw material used. The surfactants that are addition products of ethylene oxide and/or propylene oxide with fatty alcohols or are 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 alkylen 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, or 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: - non-ionic polymers, for example vinylpyrrolidone/vinyl acrylate copolymers, polyvinyl- pyrrolidone and vinylpyrrolidone/vinyl acetate copolymers and polysiloxanes, - cationic polymers, such as quaternised cellulose ethers, polysiloxanes having quaternary groups, dimethyldiallylammonium chloride polymers, copolymers of dimethyidiailyl- ammonium chloride and acrylic acid that are commercially available under the name Merquat 280 and the use of which in hair-dyeing is described, for example, in DE-A 4 421 031 or EP-A-953 334, acrylamide/dimethyidiallylammonium chloride copolymers, dimethylaminoethyl methacrylate/vinylpyrrolidone copolymers quaternised with diethyl sulfate, vinylpyrrolidone/imidazolinium methochloride copolymers, - quaternised polyvinyl alcohol, - zwitterionic and amphoteric polymers, for example acrylamidopropyl-trimethylammonium chloride/acrylate copolymers and octylacrylamide/methyl methacrylate/tert-butylamino- ethyl methacrylate/2-hydroxypropyl methacrylate copolymers, - anionic polymers, for example polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butylacrylamide 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 as amylose, amylopectin and dextrins, clays, e. g. bentonite, or fully synthetic hydro- colloids 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 cephalin, silicone oils, and also conditioning compounds, for example such as those described in DE-A-197 29 080, EP-A-834 303 or EP-A-312 343, protein hydrolysates, especially elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolysates, condensation products thereof with fatty acids and also quaternised 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 piroctone, lamines and Zinc Omadine, further substances for adjusting the pH, 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, 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 acid 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, 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, 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, N20, dimethyl ether, C02 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 of the ready-to-use dyeing compositions is usually from 2 to 11, preferably from 5 to 10.

For dyeing keratin-containing fibres, especially for dyeing human hair, the dyeing compo- sitions, generally in the form of the aqueous cosmetic carrier, are applied to the hair in an amount of from 50 to 100 g, are left on the hair for approximately 30 minutes and are then rinsed off or washed off with a commercially available hair shampoo.

The compounds used in accordance with the invention and, where used, the oxidation dye precursors may be applied to the keratin-containing fibres either simultaneously or success- ively, the order in which they are applied being unimportant.

The compounds used in accordance with the invention and, where used, the oxidation dye precursors of the compositions according to the invention may be stored either 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 compo- nents. 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 usually a defined amount of hot water (from 50 to 80°C) is added and a homogeneous mixture prepared.

The following Examples serve to illustrate the invention but the scope of the invention is not limited thereto. The temperature is given in degrees Celsius. Parts and percentages relate to weight, unless otherwise indicated.

Example 1 (Comparison test) 45 g of dimethylformamide are introduced into a vessel and, under nitrogen, 54 g of 4- anisidine are dissolved therein. Then, at room temperature, 50 g of 1, 3-dimethyl-2- (4'- methoxyphenylazo)-imidazole, having a titre of about 85 %, are added. With stirring, a viscous mass is formed, which is heated to a temperature of 92°C. After 3 hours a further 54 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)-imidazole are added. The relatively fluid mass is stirred under nitrogen at an internal temperature of 92°C for 45 hours. The conversion is 85%.

Then in the course of 1.5 hours, without heating, 170 g of dimethylformamide are added, the temperature falling to about 60°C. When the addition is complete, the mixture is cooled to 25°C in the course of 4 hours. The highly fluid suspension is separated by suction filtration.

The filtration residue is thoroughly drained under suction and washed with dimethyl- formamide and then purified.

About 78 g of the product of formula (IV) are obtained, in a yield of 63 % calculated on the basis of the amount of starting material used.

Example 2 The procedure is similar to that in Example 1.10 g of triethylamine are additionally added to the reaction mass as catalyst. After the same reaction time of 45 hours, but at 80°C, a conversion of 95 % is ascertained. Working-up is carried out in identical manner, there being obtained a yield of 88.6 g of the product of formula (IV), that is to say 71.6 % calculated on the basis of the amount of starting material used.

Example 3 The procedure is similar to that in Example 1.2 g of di-aza-bicyclooctane (DABCO) are added to the reaction mass as catalyst. After the same reaction time of 45 hours, but at 80°C, the conversion is virtually quantitative. Working-up is carried out in identical manner, there being obtained a yield of 107 g of the product of formula (IV), that is to say 86.6 % calculated on the basis of the amount of starting material used.

Example 4 50 g of dimethylacetamide are introduced into a vessel and, under nitrogen, 54 g of 4- anisidine are dissolved therein. Then, at room temperature, 50 g of 1, 3-dimethyl-2- (4'- methoxyphenylazo)-imidazole, having a titre of about 85 %, and 10 g of triethylamine as catalyst are added. With stirring, a viscous mass is formed, which is heated to a temperature of 80°C. After 3 hours a further 54 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)-imidazole are added. The relatively fluid mass is stirred under nitrogen at an internal temperature of 92°C for 20 hours. The conversion is 95 %.

Then in the course of 1.5 hours, without heating, 170 g of dimethylacetamide are added, the temperature falling to about 60°C. When the addition is complete, the mixture is cooled to 25°C in the course of 4 hours. The highly fluid suspension is separated by suction filtration, the filtration residue is thoroughly drained under suction and washed with 45 ml of dimethylacetamide and then purified.

About 74.6 g of the product of formula (IV) are obtained, in a yield of 60 % calculated on the basis of the amount of starting material used.

Example 5 (Comparison test) 200 g of 2-propanol are introduced into a vessel and, under nitrogen, 52 g of 1,4- phenyienediamine are dissolved therein. Then, at room temperature, 50 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)-imidazole, having a titre of about 85 %, are added. With stirring, a viscous mass is formed, which is heated under reflux to a temperature of 80°C. After 3 hours a further 54 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)-imidazole are added. The relatively fluid mass is stirred under nitrogen at an internal temperature of 90°C for a further 34 hours.

The conversion is 70 %.

At the end of the reaction time, the mixture is cooled to 25°C in the course of 4 hours. The highly fluid suspension is separated by suction filtration, the filtration residue is thoroughly drained under suction and washed with 45 ml of 2-propanol and then purified.

About 77 g of the product of formula (V) are obtained, in a yield of 63 % calculated on the basis of the amount of starting material used.

Example 6 The procedure is similar to that in Example 5.4 g of DABCO are added to the reaction mass as catalyst. After a reaction time of 15 hours, a conversion of 95 % is ascertained. Working- up is carried out in identical manner, there being obtained a yield of 89 g of the product, that is to say 72 % calculated on the basis of the amount of starting material used.

Example 7 145 g of 1-butanol are introduced into a vessel and, under nitrogen, 64 g of 4- acetamidoaniline are dissolved therein. Then, at room temperature, 4 g (36 parts) of DABCO as catalyst and 50 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)-imidazole, having a titre of about 85 %, are added. With stirring, a viscous mass is formed, which is heated to a temperature of 90°C. After 3 hours a further 54 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)- imidazole are added. The relatively fluid mass is stirred under nitrogen at an internal temperature of 92°C for 25 hours. The conversion is 95 %.

Then in the course of 1.5 hours, without heating, 170 g of 1-butanol are added, the temperature falling to about 60°C. When the addition is complete, the mixture is cooled to 25°C in the course of 4 hours. The highly fluid suspension is separated by suction filtration, the filtration residue is thoroughly drained under suction and washed with 45 ml of 1-butanol and then purified.

About 108 g of the product of formula (VI) are obtained, in a yield of 83 % calculated on the basis of the amount of starting material used.

Example 8 (Comparison test) The procedure is similar to that in Example 7, but no catalyst is added to the reaction mass.

After a reaction time of 45 hours, a conversion of 70 % is ascertained. Working-up is carried out in identical manner, there being obtained a yield of 78.3 g of the product of formula (VI), that is to say 60 % calculated on the basis of the amount of starting material used.

Example 9 50 g of acetonitrile are introduced into a vessel and, under nitrogen, 54 g of 4-anisidine are dissolved therein. Then, at room temperature, 50 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)- imidazole, having a titre of about 85 %, and 2 g of DABCO as catalyst are added. With stirring, a viscous mass is formed, which is heated to the boiling temperature of 85°C. After a further 3 hours a further 54 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)-imidazole are added.

The relatively fluid mass is stirred under nitrogen at an internal temperature of 80-85°C for a further 45 hours. The conversion is 90 %.

Then in the course of 1.5 hours, without heating, 170 g of acetonitrile are added, the temperature falling to about 60°C. When the addition is complete, the mixture is cooled to 25°C in the course of 4 hours. The highly fluid suspension is separated by suction filtration, the filtration residue is thoroughly drained under suction and washed with 45 ml of aceto- nitrile and then purified.

About 86.8 g of the product of formula (IV) are obtained, in a yield of 70 % calculated on the basis of the amount of starting material used.

Example 10 (Comparison test) The procedure is similar to that in Example 9, but no catalyst is added to the reaction mass.

After a reaction time of 45 hours, the conversion is 60 %. Working-up is carried out in identical manner, there being obtained a yield of 62 g of the product of formula (IV), that is to say 50 % calculated on the basis of the amount of starting material used.

Example 11 50 g of acetonitrile are introduced into a vessel and, under nitrogen, 65 g of 4-formamido- aniline are dissolved therein. Then, at room temperature, 104 g of 1, 3-dimethyl-2- (4'- methoxyphenylazo)-imidazole, having a titre of about 85 %, and 2 g of DABCO are added.

With stirring, a viscous mass is formed, which is heated to the boiling temperature of 85°C.

The relatively fluid mass is stirred under nitrogen at an internal temperature of 80-85°C for a further 15 hours. The conversion is 90 %.

Then in the course of 1.5 hours, without heating, 170 g of acetonitrile are added, the temperature falling to about 60°C. When the addition is complete, the mixture is cooled to 25°C in the course of 4 hours. The highly fluid suspension is separated by suction filtration, the filtration residue is thoroughly drained under suction and washed with 45 ml of aceto- nitrile and drained under suction.

The moist filtration residue is slurried in 300 ml of water and stirred at 80°C for 3 hours. The slurry is then cooled to room temperature and separated by suction filtration. The filtration residue is washed with 100 mi of a 3 % salt solution, thoroughly drained under suction and then dried. About 96.8 g of the product of formula (VII) are obtained, in a yield of 75 % calculated on the basis of the amount of starting material used.

Example 12 100 g of acetonitrile are introduced into a vessel and, under nitrogen, 58 g of benzylamine are dissolved therein. Then, at room temperature, 104g of 1, 3-dimethyl-2- (4'-methoxy- phenylazo)-imidazole, having a titre of about 85 %, and 2 g of DABCO are added. With stirring, a viscous mass is formed, which is heated to the boiling temperature of 65°C. The relatively fluid mass is stirred under nitrogen at an internal temperature of 60-65°C for a further 10 hours. The conversion is about 95 %.

Then in the course of 1.5 hours, without heating, 70 g of acetonitrile are poured in, the temperature falling to about 50°C. When the addition is complete, the mixture is cooled to 25°C in the course of 4 hours. The highly fluid suspension is separated by suction filtration, the filtration residue is thoroughly drained under suction and washed with 45 mi of acetonitrile and drained under suction.

The moist filtration residue is slurried in 300 ml of water and stirred at 70°C for 3 hours. The slurry is then cooled to room temperature and separated by suction filtration. The filtration residue is washed with 100 mi of a 3 % salt solution, thoroughly drained under suction and then dried. About 86. 8 g of the product of formula (Viil) are obtained, in a yield of 80 % calculated on the basis of the amount of starting material used.

Example 13 200 g of 2-propanol are introduced into a vessel and, under nitrogen, 50 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)-imidazole, having a titre of about 85 %, are added at room temperature. With stirring, a viscous mass is formed, which is heated to a temperature of 80°C (reflux), the mass becoming considerably more fluid. 1 g of sodium methoxide 30 % in methanol and ammonia are introduced into the reaction mass. After a maintenance period of a further 3 hours, a further 50 g of the same starting material is added and further ammonia is introduced. The relatively fluid mass is stirred under nitrogen at an internal temperature of 82°C for a further 34 hours. The conversion is 90 %.

At the end of the reaction time, the mixture is cooled to 25°C in the course of 4 hours. The highly fluid suspension is separated by suction filtration, the filtration residue is thoroughly drained under suction and washed with 45 mi of 2-propanol and drained under suction.

The moist filtration residue is slurried in 300 ml of water and stirred at 80°C for 3 hours. The slurry is then cooled to room temperature and separated by suction filtration. The filtration residue is washed with 100 ml of a 3 % sodium chloride solution, thoroughly drained under suction and then dried. About 67 g of the product of formula (IX) are obtained, in a yield of 73 % calculated on the basis of the amount of starting material used.

Example 14 200 g of 2-propanol are introduced into a vessel and, under nitrogen, 50 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)-imidazole, having a titre of about 85 %, are added at room temperature. With stirring, a viscous mass is formed, which is heated to a temperature of 80°C (reflux), the mass becoming considerably more fluid. 1 g of sodium methoxide 30 % in methanol and dimethylamine are introduced into the reaction mass. After a maintenance period of a further 3 hours, a further 50 g of the same starting material are added and further dimethylamine is introduced. The relatively fluid mass is stirred under nitrogen at an internal temperature of 82°C for a further 4 hours. The conversion is 95 %.

At the end of the reaction time, the mixture is cooled to 25°C in the course of 4 hours. The highly fluid suspension is separated by suction filtration, the filtration residue is thoroughly drained under suction and washed with 45 mi of 2-propanol and drained under suction.

The moist filtration residue is slurried in 300 ml of water and stirred at 80°C for 3 hours.

Salting-out is then carried out with 30 g of sodium chloride, followed by cooling to room temperature and separation by suction filtration The filtration residue is washed with 100 ml of a 10 % sodium chloride solution, thoroughly drained under suction and then dried. About 77 g of the product of formula (X) are obtained, in a yield of 83 % calculated on the basis of the amount of starting material used.

Example 15 53.2 g of 1, 3-dimethyl-2- (4'-methoxyphenylazo)-imidazole are slurried in 200 g of methanol at room temperature. The temperature is then raised to 45-50°C and 10.3 g (90 parts) of 1,6-diamino-hexane are added. 1 g of a 30 % solution of sodium methoxide is added. The mixture is stirred for 7 hours. Then the reaction mass is diluted with 140 g of methanol, cooled during 5 hours to room temperature, when crystallization occurs. The crystal suspension is separated by filtration, washed twice with 20 g of isopropanol and dried to yield 50 g of a dark powder of the compound of formula (XI) which is used as such in tinctorial applications.

Application Example A A 0.1 % solution of the dye of formula (VIII) prepared according to the invention (Example 12) in a surfactant base, consisting of 10 % cocoamphoglycinate and 90 % water, is applied for 20 minutes to one strand each of bleached and unbleached white human hair ("Italian white virgin"IMHAIR Ltd. ), rinsed and shampooed once. Very intense, brilliant scarlet dyeings of identical shade are obtained on both hair qualities. Surprisingly, both the tinctorial strength and the fastness to washing are excellent and very similar on both hair qualities, which testifies to the good levelling capacity of this product.

Application Example B A 10 % solution of a non-ionic surfactant (Plantarens registered trade mark of the Henkel company) is adjusted to pH 9.5 with citric acid, and 0.06 % of the dye of Example 7 prepared according to the invention is dissolved therein. 2 g of the resulting solution are applied to a strand (1 g) of undamaged white human hair ("Italian white virgin"IMHAIR Ltd. ), rinsed and shampooed once. A very intense violet dyeing, which remains clearly visible even after eight hairwashes, is obtained. The dyeing is also very lightfast.

Application Example C A 10 % solution of a non-ionic surfactant (Plantarene registered trade mark of the Henkel company) is adjusted to pH 5.5 with citric acid. To 100 g of that solution there are added 0.20 g of the dye according to Example 1 of WO 95/01772 (yellow dye) and 0.05 g of the dye of Example 7 prepared according to the invention.

2 g of the resulting solution are applied to a strand (1 g) of undamaged white human hair ("Italian white virgin"IMHAIR Ltd. ), rinsed and shampooed once. A very intense copper- coloured dyeing is obtained, which is distinguished by excellent fastness to washing, to rubbing and to light.

Application Examnle D A 10 % solution of a non-ionic surfactant (Plantarene registered trade mark of the Henkel company) is adjusted to pH 5.5 with citric acid. To 100 g of that solution there are added 0.25 g of the dye according to Example 1 from WO 95/01772 (yellow dye), 0.08 g of the dye according to Example 46 of WO 95/01772 (orange dye) and 0.11 g of the dye of Example 1 prepared according to the invention.

4 g of the resulting solution are applied to a strand (1 g) of bleached human hair, rinsed and shampooed once. A very intense black dyeing is obtained, which is distinguished by excellent fastness to washing and to rubbing.