Indian Patents. 278195:MIXTURE OF SULFIDE DYES

Title of Invention	MIXTURE OF SULFIDE DYES
Abstract	Disclosed are mixtures of sulfide dyes and dyeing compositions comprising mixtures of sulfide dyes. The dye mixtures are useful for the dyeing of organic materials, such as keratin fibers, preferably human hair.

Full Text	Mixture of sulfide dyes The present invention relates to mixtures of sulfide dyes, compositions thereof, and to their use for the dyeing of organic materials, such as keratin fibers, wool, leather, silk, cellulose or polyamides, especially keratin-containing fibers, cotton or nylon, and preferably hair, more preferably human hair. It is known, for example, from WO 95/01772 that cationic dyes can be used for the dyeing of organic material, for example keratin, silk, cellulose or cellulose derivatives, and also synthetic fibers, for example polyamides. Cationic dyes exhibit very brilliant shades. A disadvantage is their unsatisfactory fastness to washing. The technical problem is to provide dyes that are distinguished by deep dying having good fastness properties with respect to washing, light, shampooing and rubbing. Accordingly, the present invention relates to a dye composition comprising a mixture of dyes selected from the compounds of formula (1) D^—(Z^)^—Y^—S—A , wherein wherein the the mixture comprisies at least two compounds of formula (1), and/or at least two compounds of formula (2) and/or at least one compound of formula (1) and at least one compound of formula (2), wherein R1, R2 and R3 independently from each other hydrogen; halogen; C1-C16alkyl, which is saturated or unsaturated, linear or branched, substituted or unsubstituted, or interrupted or uninterrupted with heteroatoms; phenyl, which substituted or unsubstituted; a carboxylic acid radical; sulfonic acid radical; hydroxy; nitrile; C1-C16alkoxy, (poly)-hydroxy- C2-C4-alkoxy; halogen; SO2NR33R34: SR33; NR33R34; OR33; SO2; COOR33; NR33COR34; or CONR33; Q1 is a bivalent radical selected from -N=N-; -CRd=N-; -N=CRd-; -NRd-N=CRe-; and -RdC=N-NRe-; Ti is a bivalent radical of an aromatic or heteroaromatic substituted or unsubstituted compound; Rd and Re independently from each other are hydrogen; unsubstituted or substituted C1- C14alkyl; C2-C14alkenyl; C5-C10aryt; C1-C10alkyl-C5-C10aryl; or C5-C10aryl-C1-C10alkyl; R33 and R34 independently from each other are hydrogen; C1-C12alkyl, which may be substituted by one or more C1-C5alkyI, C1-C5-alkoxy, hydroxy or -(CO)-H; -(C0)-CrC5alkyl; phenyl or phenyl-CrC4alkyl, wherein the phenyl moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, •'NH2, mono-Cr C5alkylamino, di-C1-C5alkylamino, -NO2, carboxy or hydroxy; R4, R5 and R6 independently from each other are hydrogen; C1-C2oalkyl or C1-C2oalkoxy, which may be substituted by one or more C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5aikylamino. -NO2 or hydroxy; C3-C6cycloalkyl; -C(0)H; -C(0)-C1-C5alkyl; halogen; NO2; OH; phenyl, which may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5aikylamino, -NO2 or hydroxy; or a radical of formula -NR35R36; W1, W2, W3, and W4, independentlay from each other are -CH- or -N-; wherein only one of W1. W2, W3 or W4 is -N; and the radical -(Zi)rYi-S-A is bonded to W1 or W2; R35 and R36 independently from each other are hydrogen; C1-C12alkyl, which may be substituted by one or more C1-C5alkyI, C1-C5-alkoxy, hydroxy or -(CO)-H: -(C0)-C1-C5alkyl; phenyl or phenyl-C1-C4alkyl, wherein the phenyl moiety may be substituted by one or more C1-C5alkyl, C1-C5alkoxy, halogen, -NH2, mono-d- Rf, Rg and Rh independently from each other are hydrogen; C1-C-14alkyl; C2-C14alkenyl; C6-C10aryl; C6-C10aryl-C1-C10alkyI; or C1-C10alkyl{C5-Cioaryl); X2, X3 and X4 independently from each other are C1-C18alkylene; -(CO)-CrCi8alkylene-Ci-Ci8ary!ene; C6-C18arylene-C1-C12alkylene; or -(OCH2CH2)n-Os t is 0; or 1 R37 is hydrogen; or C1-C20oalkyI; R38, R39 and R40 independently from each other are hydrogen, C1-C20oalkyI, C4-Ci2cydoa!kyl, C6-C13aralkyI; phenyl-C1-C5alkyI; or R38 and R39 together with the linking nitrogen atom form a C4-C12-membered heterocyclic ring which may be interrupted by one or more than one -O- or -NH- goups; n1 is is 0 or 1; p isO;or1; s isO;or1; t isO;or1; u isOorl; R11, R12 and R13 independently from each other are hydrogen; C1-C2oalkyl or C1-C2oalkoxy. which may be substituted by one or more C1-C5alkoxy, halogen, -NH2, mono-Cr C5alkylamino, di-C1-C5alkylamino, "NO2 or hydroxy; Cs-CecycloalkyI; -C(0)H; -C(0)-Ci-C5alkyl; -C(0)OH; -C(0)0-C1-C5alkyl; halogen; NO2; OH; SH; phenyl which may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5atkylamino, 'NO2 or hydroxy; or a radical -NR41R42; Q 3 is is -C(0)-; -C(0)0-; -0C0-; -N(R()-X5-; -CON(Ri)-; -(Ri)NC(O}-; -0-; -S-; -S(0)-; or -S(0)2-: I heteroaromatic group; R„ Rk, Ri independently from each other are C1-C14alkyl; C2-Ci4alkeny!; Cg-Cioaryl; C6-C10aryl-C1-C10alkyl; or C1-C10alkyl(C5-Cioaryl); R41 and R42 independently from each other are hydrogen; C1-C12alkyl, which may be substituted by one or more C1-C5alkyI, C1-C5-alkoxy, hydroxy or -(CO)-H; -(CO)-Ci-C5alkyl; phenyl or phenyl-C1-C4alkyl, wherein the phenyl moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy. halogen, -NH2, mono-C1-C5alkylamino, di-Cr at least one of the radicals R11, R12 or R13 is NO2; R43 R44 and R45 independently from each other are hydrogen; Ci-C^alkyl; C2-Ci4alkenyl; Ce- C10aryl; C6-C10aryl-C1-C10alkyl; or C1-C10alkyl(C5-Cioaryl); X5 and X6 independently from each other are the direct bond; C1-C10alkylene; C5- Ciocycloalkylene; C5-C10arylene; or C5-Cioarylene-(C1-C10alkylene); R-14 is N R46R47; R46 and R47 independently from each other are hydrogen; C1-C12alkyl; or phenyl-C1-C4alkyl; or R46 and/or R47 are a bivalent Ca-Cgalkylene radical which is linked to the carbon atoms C^ or C^ in formula (1e) respectively and, together with the linking nitrogen atom form a 6 to 16- membered carbocyclic ring; R15 is is NR4eR49; or OR48; R48and R49, independently from each other are hydrogen; C1-C12alkyl: or phenyl-C1-C4alkyl; or R48and R49are a bivalent C3-C6alkylene radical which is linked to the carbon atoms C3 or C^ in formula (1e) respectively and, together with the linking nitrogen or oxygen atom form a 6 to 16-membered carbocyclic ring; or R4e and R49 together with the linking nitrogen atom form a 4 to 8 membered carbocyclic hng; R52 and R53 independently from each other are hydrogen; or C1-C5alkyt; Hal is a halogen atom; and wherein at least one of R16, R17, R18. R19 and R20 is hydrogen; B2 and B3, independently from each other are C6-C10aryl; or a 5'7-membered heterocyclic compound, which may be substituted by C1-C12alkyl, C1-C12alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or by the radical -NR54R55 or -ORse; B4 is C6-C10arylene, or a bivalent radical of a 5-7-membered heterocyclic compound, which may be substituted by C1-C12alkyl, C1-C12alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or by the radical -NR54R55 or -OR56; R54 R55 and R56 independently from each other are hydrogen; or C1-C12alkyl, which may be substituted by hydroxy or C6-C10aryl; or R54 and R55 together with the linking nitrogen atom form a 5 to 7 membered heterocyclic ring; the asterix() is directed to Zi or Z2 respectively; and the asterix(*) is directed to the linking nitrogen atom; R21 and R22 independently from each other are hydrogen; C1-C2oalkyl; C1-C2oalkoxy; C3- C6cycloalkyI; C5-Cioaryl; anellated aromatic groups; carboxylate; or sulfonate groups; R23, R24 R25 and R26 each independently from each other are hydrogen; unsubstltuted or substituted, straight-chain or branched, monocyclic or polycyclic, interrupted or uninterrupted C1-C14alkyI, C2-C14alkenyl, C6-C10aryl, C6-C10aryl-C1-C10alkyl or C5-Cioalkyl(C5-Cioaryl); or R23 and R24 and/or R25 and R26 together with the linking nitrogen atom form a 5 to 7 membered carbocyclic ring which may contain one or more than one hetero atom; or R23 is linked to C1 together with N"" forming a 5-7 membered carbocyclic ring; or R24 is linked to C2 together with N"" forming a 5-7 membered carbocyclic ring; a 6 to 10 membered carbocyclic ring which may optionally be a condensated aromatic system and may contain one or more than one hetero atom; R57, R58 and R59 independently from each other are hydrogen; or C1-C5alkyI; R29. R30- R31 and R32 independently from each other are hydrogen; hydroxy; -S-H; -S-Ci-C12alkyl; halogen; C1-C12alkyl or C1-C12alkoxy, which may be substituted by one or more C1-C5alkyI, C1-C5-alkoxy, hydroxy, -(CO)-H or-(CO)-C1-C5alkyl; -NRegR/o; -NO2; -(CO)H or (C0)-C1-C5alkyl; C6-Ci2aryl, C6-Ci2aryl-Ci-C4alkyl or C6-Ci2aryl-CrC4alkoxy, wherein the aryl moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy. -(CO)-H or -(C0)-C1-C5alkyl; -NR69R70; -NO2; -(CO)-H; or-(C0)-C1-C5alkyl; R69 and R70 independently from each other are hydrogen; hydroxy; C1-C12alkyl; hydroxy-Ci-C12alkyl; -(CO}-H; -(C0)-C1-C5alkyl; phenyl or phenyl-C1-C5aikyi, wherein the phenyl moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5aikylamino, -NO2, carboxy or hydroxy; Y1 and Y2 independently from each other are unsubstituted or substituted, straight-chain or branched, interrupted or uninterrupted C1-C10alkylene; C5-C10cycloalkylene, C5-C10arylene; or-C5-Cioarylene-(C1-C10alkylene); q is a number from 0 to 5; w is a number from one to 5; r is 0; or 1; and An is an anion. C1-C12alkyl is for example, methyl, ethyl, propyl, isopropyl, n-butyl sec-butyl, tert-butyl, n-pentyl, 2'pentyl, 3-pentyl, 2,2'-ciimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1 1,3,3'-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl,. C1-C12alkylene is for example methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, n»pentylene, 2-pentylene. 3-pentylene or 2,2'-dimethylpropylene, n-hexylene, n-octylene, 1,1',3,3'"tetramethylbutylene, 2-ethylhexylene, nonylene, decylene, undecylene or dodecylene. Alkylene may be straight-chain, branched, or, from CsalkyI upwards, monocyclic or polycyclic, and may be interrupted by hetero atoms, such as such as O, S, -CO- N, NH, NR54, -OCO-, -C0(0R4)-, -CONR4-, -(R5)NC(0)-; for example C1-C10alkylene may be a resisue such as: -CH2CH2-O-CH2CH2-O-CH2CH2-. -CH2CH2-O-CH2CH2--CH2CH2-O-CH2-, -CH2-0'CH2-. -CH2CH2-CH2CH2-0-'CH2-CH2-,-CH2CH2-CH(N(CH3)2)-CH2-CH2-, CH2-NH2-CH2-CH2-, -CH2CH2-NH-CH2CH2-, -CH2CH2-NCH3-CH2CH2-, -CO-CH2-. -CH2CO-, -CH2CH2-NHCO-CH2CH2^-CH2CH2-CONH-CH3-CH2CH2-,-CH2CH2-NCH3CO-CH2CH2-. -CH2CH2-CONCH3-CH3-CH2CH2-.-CH2-NHCO-CH2CH2-,-CH2CH2-NHCO-CH2-, -CH2CH2-CONH-CH2- or -CH2-CONH-CH2CH2-. C5-C10cycloalkylene is for example cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene or cyclodecylene. C5-C10arylene is for example phenylene or naphthylene. Aryl-alkylene is for example C5-C10aryl-C1-C10alkylene. Alkyl-arylene is for example CrCioaikyl-C5-C10arylene. Preferred is a dye mixture, wherein in formula (1) Y1 and Y2 are C1-C5alkylene. Preferred is a composition, wherein D1 is a radical of a cationic aromatic substituted or unsubstituted heterocyclic compound of formulae the asterix indicates the bond to Q1; the asterix indicates the bond to D1; and the heteroaromatic cycles of these radicals may be interrupted by one or more than one -0-, -S-, -(SO2)-, -CrCioalkylene or -(NR82)-; are independently from each other hydrogen; halogen; C1-C14alkyl, which is saturated or unsaturated, linear or branched, substituted or unsubstituted, or interrupted or uninterrupted with heteroatoms; a radical of phenyl, which substituted or unsubstituted; a of carboxylic acid radical; sulfonic acid radical; hydroxy: nitrile; C1-C16alkoxy. (poly)-hydroxy-C2-C4-alkoxy; halogen; SO2NR33R34; SRss, NRSSRSA; ORSSI; SO2; COORsa; NRSSCORSA; or CONR83 and hydrogen; unsubstituted or substituted C1-C14alkyl, C2-C14aikenyl, C5-C10aryl, C5-C10aryl-(C1-Cioalkyl), or -Ci-Cioalkyl(C5-C10aryl). one of W1 or W2 is -N+-, the other is -CH; and the biradical .—(Z,)-Y1-S-S-Y2-(Z,)- is bonded to -N+ and R4, R5, R6- Y1, Y2, Zi and r are defined as in formula (1). Examples for dyes of formula (1), wherein Di and D2 are selected from the radicals of formula (1b) are: Examples for dyes of formula (1), wherein D^ and D^ are selected from the radicals of formula R11, R12 and R13, independently from each other are hydrogen; Ci-CsalkyI; -(CO)-; -C(0)H; ^C(0)-CrC5alkyli -C(0)OH; -C(0)0-CrC5alkyl; NO2; NH2; 01 -NH(C0)-CH3; Y1 is Ci-Cioalkylene; C5-C10cycloalkylene; C5-C10arylene; or C5-Cioarylene-(CrCioalkylene); X6 is the direct bond: or C1-C5alkylene; R1 and R4 each independently from each other are hydrogen; C1-C14alkyi; C2-Ci4alkenyi; Ce-C10aryl; C6-C10aryl-C1-C10alkyI; or C1-C10alkyKCs-Cioaryl). Most preferably compounds of formula (NIT-01) are used, wherein R1., R12 and RT3 independently from each other are hydrogen; NO2; NH2; carboxy; -C(0)OH; or-NhHCO)-CH3; Y, is C1-C5alkylene; Ri and Rk each independently from each other are hydrogen; or Ci-Ci4alkyl. Furthermore, mixtures are preferred wherein the dyes are selected from the compounds of formula (1), wherein D1 and D2 independently from each other are a radical of formula (1e); R14 is N R48R49 R48 and R49 independently from each other are hydrogen; C1-C12alkyl; or phenyl-CrC4alkyl; and R16, R17. R18, R19, R20 and Vi are defined as in formula (1); or compounds of formula (1), wherein D1 and D2 independently from each other are a radical of formula (1e); R15 is NR48R49; or OR48; R48and R49, independently from each other are hydrogen; C1-C12a(kyl; or phenyi-CrC4alkyl; and R16, Ri7, R18, Ri9- R20 and Vi are defined as in formula (1); or compounds of formula (1), wherein D1 and D2 independently from each other are a radical of formula (1e); R14 is N R46R47; R46 and/or R47 independently from each other are hydrogen; C1-C12alkyl; or phenyl-CrC4alkyl; and R16, R17. R18, R19, R20 and Vi are defined as in formula (1); or compounds of formula (1), wherein D1 and D2 independently from each other are a radical of formula (1e); R15 is NR48R49; or OR48; R10 and R11, independently from each other are hydrogen; C1-C12alkyl; or phenyl-Ci-C4alkyl; and Ri6. Ri7, R18. Ri9- R20 and Vi are defined as in formula (1). Furthermore, mixtures are preferred which comprise a dye of formula ; the astenx(') is directed to Z1 or Z2 respectively; and the asterices () are directed to the linking nitrogen atonn of R23/R24 or R25/R26 repectively. Examples for dyes of formula (1), wherein D1 and D2 are a radical of formula (1g) are listed below are: R27 is hydrogen; or C1-C6alkyl; a 6 to 10 membered carbocyclic ring which may optionally be a condensated aromatic system and may contain one or more than one hetero atom; and R57. R58 and R59 independently form each other are hydrogen, or C1-C5alkyI; A1 is H; or a thio ester group of formula E is O; S; or N-Ra; B1 is -ORb; -NRbRc; or -SRb; and Ra, Rb and Rc, independently from each other are hydrogen; C1-C12alkyl; C6-C12aryl; or Ce-C12aryl-C1-C12alkyL R31 is hydrogen; C1-C5-alkoxy; halogen; or-NR69R70, wherein R69 and R70, independently from each other are hydrogen; C1-C12alkyl; "(CO)-H; or -(C0)-Ci-C5alkyl; and An is an anion. Examples of these dyes are listed in the Table below: All compounds of the present invention mentioned above can exist as hydrates or solvates. The mixture of dyes according to the invention are suitable for dyeing organic materials, such as keratin-containing fibers, wool, leather, silk, cellulose or polyamides, cotton or nylon, and preferably human hair. The dyeings obtained are distinguished by their depth of shade and their good fastness properties for example to washing, fastness to light, shampooing and rubbing. The stabilities, in particular the storage stability of the dyes and the dyes in formulations according to the invention are excellent. Gernerally, hair dyeing agents on a synthetic base may be classiefied itnto three groups: temporary dyeing agents semipermanent dyeing agents, and permanent dyeing agents. The multiplicity of shades of the dyes can be increased by combination with other dyes. Therefore the mixture of dyes of the present invention may be combined with dyes of the same or other classes of dyes, especially with direct dyes, oxidation dyes; dye precursor combinations of a coupler compound as well as a diazotized compound, or a capped diazotized compound; and/or cationic reactive dyes. Direct dyes are of natural origin or may be prepared synthetically. They are uncharged, cationic or anionic, such as acid dyes. The mixture of dyes may be used in combination with at least one single direct dye different from the dyes of formula (1) and (2). Direct dyes do not require any addition of an oxidizing agent to develop their dyeing effect. Accordingly the dyeing results are less permanent than those obtained with permanent dyeing compositions. Direct dyes are therefore preferably used for semipermanent hair dyeings. Examples of direct dyes are described in "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, p. 248-250, and in "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. More preferred direct dyes which are useful for the combination with the mixture of dyes of the present invention, especially for semi permanent dyeing, are: 2-amino-3-nitrophenol, 2-amino-4-hydroxyethylamino-anisole sulfate, 2-amino-6-chloro-4-nitrophenol, 2-chloro-5-nitro-N-hydroxyethylene-p-phenylendiamine, 2-hydroxyethyl-picramic acid, 2,6-diamino-3-((pyridine-3yl)-azo)pyridine, 2-nitro-5-glyceryl-methylaniline, 3-methylamino-4-nitro-phenoxyethanol. 4-amino-2-nitrodiphenyleneamine-2'-carboxilic acid, 6-nitro-1,2,3,4,-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis(2'-hydroxyethylamino-2-nitrobenzene hydrochloride, 1-methyl-3-nitro^4-(2'-hydroxyethyl)-aminobenzene, 3-nitro-p-hydroxyethyl-aminophenol, 4-amino-3-nitrophenol, 4-hydroxypropylamine-3-nitrophenol, hydroxyanthrylaminopropylmethyl morpohlino 'mothosulfate, 4-nitrophenyl'aminoethylurea, 6-nitro-p-toluidine, Acid Blue 62, Acid Blue 9, Acid Red 35, Acid Red 87 (Eosin), Acid Violet 43, Acid Yellow 1, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9. Basic Blue 12, Basic Blue 26, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Red 2, Basic Red 22, Basic Red 76, Basic Violet 14, Basic Yellow 57, Basic Yellow 9, Disperse Blue 3, Disperse Orange 3, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Fast Green FCF, HC Blue 2, HC Blue 7, HC Blue 8, HC Blue 12, HC Orange 1, HC Orange 2, HC Red 1. HC Red 10-11, HC Red 13, HC Red 16, HC Red 3, HC Red BN, HC Red 7, HC Violet 1, HC Violet 2, HC Yellow 2, HC Yellow 5. HC Yellow 5, HC Yellow 6, HC Yellow 7, HC Yellow 9, HC Yellow 12. HC Red 8, hydroxyethyl-2-nitro-p-toluidine, N,N-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamJne, HC Violet BS, Picramic Acid, Solvent Green 7. Furthermore, mixture of dyes of the present invention may be combined with at least one cationic azo dye, for example the compounds disclosed in GB-A-2 319 776 as well as the oxazine dyes described in DE-A-299 12 327 and mixtures thereof with the other direct dyes mentioned therein, and even more preferred with cationic dyes such as Basic Yellow 87, Basic Orange 31 or Basic Red 51, or with cationic dyes as described in WO 01/66646, especially example 4, or with cationic dyes as described in WO 02/31056, especially example 6 (compound of formula 106); or the cationic dye of formula (3) as described in EP-A-714,954, benzyl; R3 is hydrogen; Ci-CsalkyI; CrCsalkoxy; cyanide; or halide; preferably hydrogen; and X" is an anion; and preferably a compound of formula (DD1), wherein Ri is methyl; R2 is benzyl; R3 is hydrogen; and X" is an anion; or wherein R1 is benzyl; R2 is benzyl; R3 is hydrogen; and X" is an anion; or wherein R1 is benzyl; R2 is methyl; R3 is hydrogen; and X" is an anion. Furthermore, cationic nitroanlline and anthraquinone dyes are useful for a combination with mixture of dyes of the present invenion, for example the dyes as described in the following patent specifications: US-5 298 029, especially in col 2, I. 33 to col 5, I. 38; US-5 360 930, especially in col 2, I. 38 to col 5, I. 49;.US'5 169 403, especially in col 2, I, 30 to col 5, I. 38; US-5 256 823, especially in col 4, I. 23 to col 5, I. 15; US-5 135 543, especially in col 4, 1. 24 to col 5,1. 16; EP-A-818 193, especially on p. 2,1. 40 to p. 3,1. 26; US-5 486 629, especially in col 2, I. 34 to col 5, I, 29; and EP-A-758 547, especially on p. 7,1. 48 to p. 8, I. 19. The mixture of dyes of the present invention may also be combined with acid dyes, for example the dyes which are known from the international names (Color index), or trade names. Preferred acid dyes which are useful for the combination with the mixture of dyes of the present invention are described in US Patent 6,248,314. They include Red Color No. 120, Yellow Color No. 4, Yellow Color No. 5, Red Color No. 201, Red Color No. 227, Orange Color No. 205, Brown Color No. 201, Red Color No. 502, Red Color No. 503, Red Color No. 504, Red Color No. 506, Orange Color No. 402, Yellow Color No. 402, Yellow Color No. 406, Yellow Color No. 407, Red Color No. 213, Red Color No. 214, Red Color No. 3, Red Color No. 104, Red Color No. 105(1), Red Color No. 106, Green Color No. 2, Green Color No. 3, Orange Color No. 207, Yellow Color No. 202(1), Yellow Color No. 202(2), Blue Color No. 202, Blue Color No. 203, Blue Color No. 205, Blue Color No. 2, Yellow Color No. 203, Blue Color No. 201, Green Color No. 201, Blue Color NO. 1, Red Color No. 230(1), Red Color No. 231, Red Color No. 232, Green Color No. 204, Green Color No. 205, Red Color No. 401, Yellow Color No. 403(1), Green Color No. 401, Green Color No. 402, Black Color No. 401 and Purple Color No. 401, especially Black Color No. 401, Purple Color 401, Orange Color No. 205. These acid dyes may be used either as single component or in any combination thereof. Hair dye compositions comprising an acid dye are known. They are for example described in "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, p. 248-250, especially on p, 253 and 254. Hair dye compositions which comprise an acid dye have a pH of 2-6, preferably 2-5, more preferably 2.5-4.0. The mixture of dyes of the present invention may also readily be used in combination with acid dyes and/or adjuvants, for example - acid dyes and an alkylene carbonate, as described in US patent 6,248,314, especially in examples 1 and 2; - acid hair dye compositions comprising various kinds of organic solvents represented by benzyl alcohol as a penetrant solvent have good penetrability into hair, as described in Japanese Patent Application Laid-Open Nos. 210023/1986 and 101841/1995; - add hair dye compositions with a water-soluble polymer or the like to prevent the drooping of the hair dye composition, as described for example in Japanese Patent Application Laid-Open Nos. 87450/1998, 255540/1997 and 245348/1996; - acid hair dye compositions with a water-soluble polymer of aromatic alcohols, lower alkylene carbonates, or the like as described in Japanese Patent Application Laid-Open No. 53970/1998 and Japanese Patent Invention No. 23911/1973. The mixture of dyes of the present invention may also be combined with uncharged dyes, for example selected from the group of the nitroanilines, nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenois, phenazines, phenothiazines, bispyrazolons, erbispyrazol aza derivatives and methines. Furthermore, the mixture of dyes of the present invention may also be used in combination with oxidation dye systems. Oxidation dyes, which, in the initial state, are not dyes but dye precursors are classified according to their chemical properties into developer and coupler compounds. Suitable oxidation dyes are described for example in DE 19 959 479, especially in col 2.1. 6 to col 3,1.11; - "Dermatology", edited by Oh. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7. Ch. Zviak, The Science of Hair Care, chapter 8, on p. 264 - 267 (oxidation dyes); Preferred developer compounds are for example primary aromatic amines, which are substituted in the para- or ortho- position with a substituted or unsubstituted hydroxy- or amino residue, or diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazol derivatives, 2.4,5,6-tetraaminopyrimidine derivatives, or unsaturated aldehydes as described in DE 19 717 224 esoecially on p. 2. I. 50 to I. 66 and on p. 3 I. 8 to I. 12, or cationic developer compounds as described in WO 00/43367, especially on p., 2 I. 27 to p. 8, I. 24, in particular on p. 9, 1. 22 to p. 11, I. 6, Furthermore, developer compounds in their physiological compatible acid addition salt form, such as hydrochloride or sulfate can be used. Developer compounds, which have aromatic OH radicals are also suitable in their salt form together with a base, such as alkali metal-phenolates. Preferred developer compounds are disclosed in DE 19959479, p. 2,1. 8 - 29, More preferred developer compounds are p-phenylendiamine, p-toluylendiamine, p-, m- o-aminophenol, N,N-biS"(2-hydroxyethyl)-p-phenylenediamine sulfate, 2-amtno-4-hydroxy-ethylaminoanisole sulfate, hydroxyethyl-3,4-methylenedioxyaniline, 1-(2'-hydroxyethyl)-2,5-di-aminobenzene, 2,6-dimethoxy-3,5-diamino-pyridine, hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine) hydrochloride, hydroxyethyl-p-phenylenediamine sulfate, 4-amino-3-me-thylphenol, 4-methylaminophenol sulfate, 2-aminomethyl-4"aminophenol, 4,5-diamino-1-(2-hydroxyethyl)-1H- pyrazol, 4-amino-m-cresol, 6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine or 4-hydroxy-2,5,6-thaminopyrimidine sulfate. Preferred coupler compounds are m-phenylendiamine derivatives, naphthole, resorcine and resorcine derivatives, pyrazolone and m-aminophenol derivatives, and most preferably the coupler compounds disclosed in DE 19959479, p.1,1. 33 to p. 3,1. 11. The mixture of dyes of the present invention may also be used together with unsaturated aldehydes as disclosed in DE 19 717 224 (p. 2, L 50 to 1. 66 and on p. 3 I. 8 to I. 12) which may be used as direct dyes or, alternatively together with oxidation dye precursors. Further preferred for a combination with the mixture of dyes of the present invention are the following oxidation dye precursors: the developer/-coupler combination 2,4,5,6'tetraaminopyrimidine and 2-methylresorcine for assessing of red shades; P-toluenediamine and 4-amino-2-hydroxytoluene for assessing of blue-violet shades; p-to!uenediamine and 2-amino-4-hydroxyethylaminoanisole for assessing of blue shades; P'toluenediamlne and 2,4-diamino-phenoxyethynol for assessing of blue shades; rnethyl-4-aminophenol and 4-amino-2'hydroxytteoluene for assessing of orange shades; p-toluenediamine and resorcine for assessing of brown-green shades; p-toluenediamine and 1-naphthol for assessing of blue-violet shades, or p-toluenediamine and 2-methylresorcine for assessing of brown-gold shades. Furthermore, autooxidizable compounds may be used in combination with the mixture of dyes according to the present invention. Autooxidizable compounds are aromatic compounds with more than two substituents in the aomatic ring, which have a very low redox potential and will therefore be oxidized when ex¬posed to the air. The dyeings obtained with these compounds are very stable and resistant to schampoo. Autooxidizable compounds are for example benzene, indol, or indoline, especially 5,6-dihydro-xyindol or 5,6-dlhydroxyindoline derivatives as described in WO 99/20234, especially on p. 26, I. 10 to p. 28, 1. 15, or in WO 00/28957 on p. 2, third paragraph. Preferred autooxidizable benzene derivatives are 1,2,4-trihydroxybenzene, 1-methyl-2,4,5-trihydroxybenzene, 2,4-diamnio-6-methylphenol, 2-amino-4-methylaminophenol, 2,5-diamino-4-methyl"phenol, 2,6-diaminO"4-diethylaminophenol, 2,6-diamino-1,4-dihydroxybenzene, and the salts of these compounds, which are accessible with acid. Preferred autooxidizable indol derivatives are 5,6-dihydroxyindol, 2-methyl-5,6-dihydroxyindol, 3-methyl'5,6"dihydroxyindole, 1-methyl-5,6-dihydroxyindol, 2,3-dimethyl-5.6-dihydroxyindol, 5-methoxy-6-dihydroxyindol, 5~acetoxy-6-hydroixyindol, 5,6-diacetoxyindol, acid of 5,6-dihydroxyindol-2-carbon acid, and the salts of these compounds, which are accessible with acid. The mixture of dyes of the present invention may also be used in combination with naturally occurring dyes, such as 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 dyeings are described, for example, in EP-A-404 868, especially on p. 3, 1. 55 to p. 4, I. 9. Furthermore, the mixture of dyes of the present invention may also be used in combination with capped dia-zotised compounds. Suitable diazotised compounds are for example the compounds of formulae (1) - (4) in WO 2004/019897 (bridging pages 1 and 2) and the corresponding watersoluble coupling components (I) -(IV) as disclosed in the same reference. Further preferred dyes or dye combinations which are useful for the combination with mixture of dyes of the present invention are described in (DC-01): WO 95/01772. wherein mixtures of at least two cationic dyes are disclosed, especially p. 2,1. 7 to p. 4,1. 1, preferably p, 4, I. 35 to p, 8, I. 21; formulations p. 11, last § - p. 28, I. 19; (DG-02): US 6,843,256, wherein cationic dyes are disclosed, especially the compounds of formulae (1), (2), (3) and (4) (col. 1, L 27 - col. 3, I. 20, and preferably the compounds as prepared in the examples 1 to 4 (col. 10, 1.42 to cot. 13, 1. 37; formulations col. 13, 1. 38 to col. 15,1.8; (DC-03): EP 970 685, wherein direct dyes are described, especially p. 2,1. 44 to p. 9, I. 56 and preferably p. 9,1. 58 to p. 48, I. 12; processes for dyeing of keratin-containing fibers especially p. 50, I. 15 to 43; formulations p. 50, I. 46 to p. 51,1. 40; (DC-04): DE-A-19 713 698, wherein direct dyes are described, especially p. 2, I. 61 to p. 3,1. 43; formulations p. 5, I. 26 to 60; (DC-05): US 6.368.360.. wherein directd dyes (coi 4^ I. 1 to col. 6, I. 31) and oxidizing agents (col. 6, I. 37 -39) are disclosed; formulations col. 7,1. 47 to col. 9, 1. 4; (DC-06): EP 1 166 752, wherein cationic dyes (p. 3, L 22 - p. 4,1. 15) and anionic UV- absorbers (p. 4, I. 27 - 30) are disclosed; formulations p. 7,1. 50 - p. 9, L 56; (DC-07): EP 998,908, wherein oxidation dyeings comprising a cationic direct dye and pyra- zolo-[1,5"a]-pyrimidines (p. 2, L 48 - p. 4 J. 1) are disclosed; dyeing formulations p. 47, I. 25 to p. 50, I. 29; (DC-08): FR-2788432, wherein combinations of cationic dyes with Arianors are disclosed, especially p. 53, 1. 1 to p. 63,1. 23, more especially p. 51 to 52, most especially Basic Brown 17, Basic brown 16, Basic Red 76 and Basic Red 118, and/or at least one Basic Yellow 57. and/or at least one Basic Blue 99; or combinations of arianoren and/or oxidative dyes, especially p. 2, I. 16 to p. 3, L 16; dyeing formulations on p. 53, I. 1 to p. 63, I. 23; (DC-09): DE-A-19 713 698, wherein the combinations of direct dyes and permanent-wave fixing comprising an oxidation agent, an oxidation dye and a direct dye are disclosed; especially p. 4, I. 65 to p. 5, I. 59; (DC-10): EP 850 638, wherein developer compounds and oxidizing agents are disclosed; especially p. 2, I. 27 to p. 7, L 46 and preferably p. 7, 1. 20 to p. 9, 1. 26; dyeing formulations p. 2,1. 3-12 and I. 30 to p. 14, and p. 28, I. 35 - p. 30,1. 20; preferably p. 30,1, 25 - p. 32, I. 30; (DC-11): US 6,190,421 wherein extemporaneous mixtures of a composition (A) containing one or more oxidation dye precursors and optionally one or more couplers, of a composition (B), in powder form, containing one or more direct dyes (col. 5,1. 40 - col. 7,1. 14), optionally dispersed in an organic pulverulent excipient and/or a mineral pulverulent excipient, and a composition (C) containing one or more oxidizing agents are disclosed; formulations col. 8, I. 60 - col. 9, I. 56; (DC-12): US 6,228,129, wherein a ready-to-use composition comprising at least one oxidation base, at least one cationic direct dye and at least one enzyme of the 2-electron oxidoreductase type in the presence of at least one donor for the said enzyme are disclosed; especially col. 8,1. 17 - col. 13, I. 65; dyeing formulations in col. 2,1. 16 to col. 25,1. 55, a multi-compartment dyeing device is described in col. 26,1. 13 - 24; (DC-13): WO 99/20235, wherein compositions of at least one cationic dye and at least one nitrated benzene dye with cationic direct dyes and nitro benzene direct dyes are described; on p. 2, I. 1 to p. 7, I. 9, and p. 39, 1. 1 to p. 40 I. 11. preferably p. 8, I. 12 to p. 25 1. 6. p. 26, !. 7 to p. 30. !. 15: p. 1, I. 25 to p. 8. I. 5. p 30, I. 17 to p. 34 1. 25, p. 8, I. 12 to p. 25 I. 6, p. 35, 1. 21 to 27, especially on p. 36, I. 1 to p. 37; (DC-14): WO 99/20234, wherein compositions comprising at least one direct cationic dye and at least one autooxidisable dye, especially benzene, indol and indoline derivatives are described, preferably direct dyes on p. 2, I. 19 to p. 26, 1. 4, and autooxidisable dyes as dislosed especially on p. 25, I. 10 to p. 28, !. 15; dyeing formulations especially on p. 34, I. 5 to p. 35, li 18; (DC-15): EP 850 636, wherein oxidation dyeing compositions comprising at least one direct dye and at least one meta-aminophenol derivative as coupler component and at least one developer compound and an oxidizing agent are disclosed, especially p. 5, I. 41 to p. 7, I. 52, dyeing formulations p. 19, 1. 50 - p. 22, I. 12; (DC-16): EP-A-850 637, wherein oxidation dyeing compositions comprising at least one oxidation base selected from para-phenylenediamines and bis(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler selected from meta-diphenols, and the acid-addition salts thereof, at least one cationic direct dye, and at least one oxidizing agent are disclosed, especially p. 6, I. 50 to p. 8,1. 44 are discloseded; dyeing formulations p. 21, L 30 - p. 22, I. 57; (DC-17): WO 99/48856, wherein oxidation dyeing compositions comprising cationic couplers are disclosed, especially p. 9, I. 16 - p. 13, 1. 8, and p. 11,1. 20 - p. 12, 1. 13; dyeing formulations p. 36, I. 7 - p. 39, I. 24; (DC-18): DE 197 172 24, wherein dyeing agents comprising unsaturated aldehydes and coupler compounds and primary and secondary amino group compounds, nitrogen-containing heterocyclic compounds, amino acids, oligopeptids, aromatic hydroxy compounds, and/or at least one CH-active compound are disclosed p. 3, I. 42 - p. 5 I. 25; dyeing formulations p. 8. I. 25 - p. 9, 1. 61. In the dye combinations disclosed in the references (DC-01 - DC-18) above, the mixture of dyes of the present invention may be added to the dye combinations or dyeing formulations or may be replaced with the mixture of dyes of the present invention. The present invention also releates to formulations, which are used for the dyeing of organic materials, preferably keratin-containing fibers, and most preferably human hair, comprising mixture of dyes of the present invention. The formulations compnse at least 2 dyes as defined in formula (1) and (2). According to the desired color results the mixtures may comprise 3, 4, 5 or more than 5 dyes of formula (1) and/or (2). Preferably the mixture of dyes of the present invention are incorporated into the composition for treating organic material, preferably for dyeing in amounts of 0.001 - 5% b.w. (hereinafter indicated merely by "%"), particularly 0.005 - 4%, more particularly 0.2 - 3%, based on the total weight of the composition. The formulations mav be applied on the keratin-containing fiber, preferably the human hair in dilterent technical forms. Technical forms of formulations are for example a solution, especially a thickened aqueous or aqueous alcoholic solution, a cream, foam, shampoo, powder, gel, or emulsion. Customary the dyeing compositions are applied to the keratin-containing fiber in an amount of 50 to 100 g. Preferred forms of formulations are ready-to-use compositions or multi-compartment dyeing devices or 'kits' or any of the multi-compartment packaging systems with compartments as described for example in US 6,190,421, col 2, 1. 16 to 31. The pH value of the ready-to-use dyeing compositions is usually from 2 to 11, preferably from 5 to 10. Preferably the dyeing compositions, which are not stable to reduction, are prepared with oxidizing agent free compositions just before the dyeing process. One preferred embodiment of the present invention relates to the formulation of dyes, wherein the mixture of dyes of the present invention are in powder form. Powder formulations are preferably used if stability and/or solubility problems as for example described in DE 197 13 698, p. 2, I. 26 to 54 and p. 3, I. 51 to p, 4, I. 25, and p. 4, I. 41 to p. 5 t 59. Suitable cosmetic hair-care formulations are hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g, pre-treatment preparations or leave-on products such as sprays, creams, gels, lotions, mousses and oils, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for per¬manent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colorants, preparations containing self-oxidizing dyes, or natural hair colorants, such as henna or camomile. For use on human hair, the dyeing compositions of the present invention can usually be incorporated into an aqueous cosmetic carrier. Suitable aqueous cosmetic carriers include, for example W/0, OM, OAA//0, W/OA/V or PIT emulsions and all kinds of microemulsions, creams, sprays, emulsions, gels, powders and also surfactant-containing foaming solutions, e.g. shampoos or other preparations, that are suitable for use on keratin-containing fibers. 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 col 1, I. 70 to col 3,1. 55. The dyeing compositions according to the invention are also excellently suitable for the dyeing method described in DE-A-3 829 870 using a dyeing comb or a dyeing brush. The constituents of the aqueous carrier are present in the dyeing compositions of the present invention in the customary amounts, for example emulsifiers may be present in the dyeing compositions in concentrations from 0.5 to 30 % b.w. and thickeners in concentrations from 0.1 to 25 % b.w. of the total dyeing composition. Further carriers for dyeing compositions are for example described in "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, p. 248-250, especially on p. 243, 1. 1 to p. 244, I. 12. A shampoo has for example, the following composition: 0.01 to 5 % b.w. of mixture of dyes of the present invention; 8 % b.w of disodium PEG-5 laurylcitrate Sulfosuccinate, Sodium Laureth Sulfate; 20 % b.w. of sodium cocoamphoacetate; 0.5 % b.w. of methoxy PEG/PPG-7/3 aminopropyi dimethicone; 0.3 % b.w. of hydroxypropyl guar hydroxypropythmonium chloride; 2.5 % b.w. of PEG-200 hydrogenated glyceryl palmate; PEG-7 glyceryl cocoate; 0.5 % b.w. of PEG-150 distearate; 2.2. % b.w of citric acid; perfume, preservatives; and watered 100 %. The mixture of dyes of the present invention may be stored in a liquid to paste-like preparation (aqueous or non-aqueous) or in the form of a dry powder. When the dyes and adjuvants are stored together in a liquid preparation, the preparation should be substantially anhydrous in order to reduce reaction of the compounds. The dyeing compositions according to the invention may comphse any active ingredients, additives or adjuvants known for such preparations, like surfactants, solvents, bases, acids, perfumes, polymeric adjuvants, thickeners and light stabilisers. The following adjuavents are preferably used in the hair dyeing compositions of the present invention: 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 dimethyldiallyl-ammonium chloride and acrylic acid, as available commercially under the name Merquaf^ 280 and the use thereof in hair dyeing as described, for example, in DE-A-4 421 031, especially p. 2,1. 20 to 49, or EP-A-953 334; acrylamide/dimethyldiallylammonium chloride copolymers, diethyl-sulfate-quaternised dimethylaminoethyl methacrylate/vinylpyrrolidone copolymers, vinylpyrrolidone/-imidazolinium methochloride copolymers; quaternised polyvinyl alcohol: zwitterionic and amphoteric polymer?:, such as acrylamido-propyltrimethylammonium chloride/acrylate copolymers and octylacrylamide/methyl methacry-late/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/isobornyl 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. benfonite or fully synthetic hydrocolloids such as, for example, polyvinyl atcohol; structuring agents, such as glucose and maleic acid; hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin, cephalins, silicone oils, and conditioning compounds, such as those described in DE-A-19 729 080, especially p. 2,1. 20 to 49, EP-A-834 303, especially p. 2 J. 18 - p. 3, 1. 2, orEP-A-312 343, especially p. 2, I. 59 - p. 3, I. 11; 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 cydodextrins, solubilisers, such as ethanol, isopropanol. ethylene glycol, propylene glycol, glycerol and diethylene glycol, anti-dandruff active ingredients, such as ptroctones, olamines and zinc Omadine, substances for adjusting the pH value; panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extracts and vitamins; cholesterol; Furthermore, the following UV absorbers or combinations may be used in the dyeing compositions according to the invention: - cationic benzotriazole UV absorbers as for example descnbed in WO 01/36396 especially on p. 1, I. 20 to p. 2, 1 24, and preferred on p. 3 to 5, and on p. 26 to 37; - cationic benzotriazole UV in combination with antioxidants as described in WO 01/36396, especially on p. 11, I. 14 to p. 18; - UV absorbers in combination with antioxidants as described in US Patent 5 922 310, especially in col 2,1. 1 to 3; - UV absorbers in combination with antioxidants as described in US Patent 4 786 493, especially in col 1, 42 to col 2, I. 7, and preferred in col 3, 43 to col 5, I. 20; - combination of UV absorbers as described in US Patent 5 830 441, especially in col 4, I. 53 to 56; - combination of UV absorbers as descnbed in WO 01/36396, especially on p. 11 J. 9 to 13; or - triazine derivatives as described in WO 98/22447, especially on p. 1, i. 23 to p. 2, 1. 4, and preferred on p. 2, I. 11 to p. 3, I. 15 and most preferred on p. 6 to 7, and 12 to 16. Suitable cosmetic preparations may usually contain 0.05 to 40 % b.w., preferably 0.1 to 20 % b.w., based on the total weight of the composition, of one or more UV absorbers; 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 havinp a molecular weight from 150 to 50 000, for example such as those descnbed in EP-A-BOI 942, especially p. 3, I. 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 p. 27, I. 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; proDeltants, such as propane-butane mixtures. N:;0, dimethyl ether, CO2 and air: antioxidants; preferably the phenolic antioxidants and hindered nitroxyi compounds disclosed in ip.com (IPCOM # 000033153D); sugar-containing polymers, as described in EP-A-970 687; quaternary ammonium salts, as described in WO 00/10517; Bacteria inhibiting agents, like preservatives that have a specific action against gram-positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4'-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties, Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolau-rate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2 % b.w., based on the solids content of the preparations; The dyeing compositions according to the present invention generally comprise at least one surfactant. Suitable surfactants are zwitterionic or ampholytic, or more preferably anionic, non-ionic and/or cationic surfactants. Suitable anionic surfactants in the dyeing compositions according to the present invention include all anionic surface-active substances that are suitable for use on the human body. Such substance? are characterised by an anionic group that imparls water solubility, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having approximately 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 10 to 22 carbon atoms (soaps), ether carboxylic acids of formula R-0-(CH2-CH2-0)x-CH2-COOH, in which R is a linear alkyt group having 10 to 22 carbon atoms and x = 0 or from 1 to 16, acy! sarcosides havinq 10 to 18 carbon atoms in the acyi group, acyl taurldes having 10 to 18 carbon atoms in the acyl group, acyi isothionates having 10 to 18 carbon atoms in the acyl group, sulfosuccinic mono- and di-alkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and from 1 to 6 oxyethyl groups, linear alkane sulfonates having 12 to 18 carbon atoms, linear a-olefin sulfonates having 12 to 18 carbon atoms, a-sulfo fatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of formula R'-0(CH2-CH2-O)x-S03H, in which R' is a preferably iinearar alkyl group having 10 to 18 carbon atoms and x' = 0 or from 1 to 12, mixtures of surface-active hydroxysuifonates according to DE-A-3 725 030; sulfated hydroxyalkylpolyethyiene and/or hydroxyalkylenepropylene glycol ethers according to DE-A-3 723 354, especially p. 4, I. 42 to 62, sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-3 926 344, especially p. 2,1. 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, or anionic surfactants, as described in WO 00/10518, especially p. 45,1. 11 to p. 48,1. 3. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the rnoiecule, and also especially salts of saturated and especially unsaturated Ce-Cazcarboxylic acids, such as oleic acid, stearic acid, isosteahc acid and palmitic acid. Surface-active compounds that carry at least one quaternary ammonium group and at least one -COO' or -SO3" group in the molecule are terminated zwitterionic surfactants. Preference is given the so-called betatnes, such as the N-alky!N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred is the fattv acid amide derivative known by the CTFA name cocoamtdoprcpy! betaine. Amphotytic surfactants are surface-active compounds that, in addition to a Ce-Cig-alkyI or -acyl group and 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-atkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, 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-cocoalkylaminopropionate, cocoacylaminoethylaminopro-pionate and Ci2~Ci8acylsarcosine. Suitable non-ionic surfactants are described in WO 00/10519, especially p. 45, L 11 to p. 50. i. 12. Non-ionic surfactants contain as hydrophilic group, for example, a polyol group, a poly-atkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such com¬pounds are, for example: addition products of 2 to 30 mol of ethylene oxide and/or 0 to 5 mol of propylene oxide with linearar fatty alcohols having 8 to 22 carbon atoms, with fatty acids having 12 to 22 carbon atoms and with alkylphenols having 8 to 15 carbon atoms in the alkyl group, C12-C22 fatty acid mono- and di-esters of addition products of 1 to 30 mol of ethylene oxide with glycerol, C8-C22alkyl-mono -and- -oligo-glycosides and ethoxylated analogues thereof, addition products of 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. The surfactants which 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 are 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 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 cationic surfactants that can be used in the dyeing compositions according to the invention are especially quaternary ammonium compounds. Preference is given to ammonium halides, such as alkyltrimethylammonium chlorides, diaikyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethy-lammonium chloride, lau-ryidimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethyl-ammonium chloride. Further cationic surfactants that can be used in accordance with the invention are quaternised protein hydrolysates. Also suitable are cationic silicone oils, such as, for example, the commercially available pro¬ducts 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 Abj\|®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary potydimethylsiloxanes, quaternium-80), or silicones, as described in WO 00/12057, especially p. 45. I. 9 to p. 55, I. 2. Alkylamidoamines. especially fatty acid amidoamines, such as the stearylamidopropyl-dimethylamine obtainable under the name Tego Amid 18 are alos preffered as surfactants in the present dyeing compositions. They 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 trademark 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 glu-ceth-10 hydroxypropyl dimonium chloride". The alkyi-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 alky! chain lengths according to the particular starting material used. The mixture of dyes of the present invention are suitable for the dyeing of organic materiaL perferably keratin-containig fibers. A further preferred embodiment of the present invention relates to a method of treating keratin-containig fibers with the mixture of dyes of the present invention. The process comprises (a) contacting the keratin fiber with a mixture of dyes of the present invention, (b) leaving the fibers to stand, and (c) then rinsing the fiber. The process for dyeing is for example described in WO 01/66646 on page 15, line 32 to page 16, line 2. A further preferred method comphses treating the hair in the presence of a reduction agent. Preferred reduction agents are for example thioglycol acid or salts therof, gycerine monothio-glycolat, cystein, 2-mercaptopropionic acid, 2-mercaptoethylamine, thiolactic acid, thioglyce- rifie, sodium sulfite, dithionithe, ammonium sulfite, sodium bisulfite, sodium metabisulfife. hydroquinone, phosphines, borhydride, cyanoborohydride, thacetoxy borohydride, trimethoxy borohydride salts (sodium, lithium, potassium, calcium auaternary salts). Furthermore, the present invention relates to a process, comprising treating the hair with (a) optionally a reduction agent, (b) a mixture of dyes of the present invention s defined above, and (c) with an oxidizing agent. The step (a) may be of short duration from o.1 sec to 30 minutes, fro example from 0.1 seconds to 10 minutes with a rducing agent mentioned above. The application of the dye mixture on the hair may be arried out at temperatures ranging from 15° to 100°C. Generally the application is carried out at room temperature. The sequence of the reaction steps is generally not important, the reduction agent can be applied first or in a final step. Usally, the oxidizing agent is applied together with an acid or a base. The acid is for example citric acid, phosphoric acid or tartrate acid. The base is for example sodium hydroxide, ammonia or monoethanolamine. The mixture of dyes of the present invention are suitable for all-over dyeing of the hair, that is to say when dyeing the hair on a first occasion, and also for re-dyeing subsequently, or dyeing of locks or parts of the hair. The mixture of dyes of the present invention is applied on the hair for example by massage with the hand, a comb, a brush, or a bottle, or a bottle, which is combined with a comb or a nozzle. Further preferred is a process for dyeing keratin-containing fibers which compnses treating the keratin-containing fiber with mixture of dyes of the present invention, a base and an oxidizing agent. The oxidation dyeing process usually involves lightening, that is to say that it involves applying to the keratin-containing fibers, at basic pH, a mixture of bases and aqueous hydrogen peroxide solution, leaving the applied mixture to stand on the hair and then rinsing the hair. It allows, particularly in the case of hair dyeing, the melanin to be lightened and the hair to be dyed. Lightening the melanin has the advantageous effect of creating a unified dyeing in the case of grey hair, and, in the case of naluraiiy pigmented hair, of bringing out the color, that is to say of making it more visible. In general, the oxidizing agent containing composition is left on the fiber for 0.1 seconds to 15 minutes, in particular for 0.1 seconds to 5 minutes at 15 to 45°C, usually in amounts of 30 to 200g. Oxidizing agents are for example persulfate or diluted hydrogen peroxide solutions, hydrogen peroxide emulsions or hydrogen peroxide gels, alkaline earth metal peroxides, organic per¬oxides, such as urea peroxides, melamine peroxides. Alkalimetalbromate fixations or enzymes are also appropriate if a shading powder on the basis of semi-permanent, direct hair dyes is used. Further preferred oxidizing agents are oxidizing agents to achieve lightened coloration, as described in WO 97/20545, especially p. 9, I. 5 to 9, oxidizing agents in the form of permanent-wave fixing solution, as described in DE-A-19 713 698 . especially p. 4,1. 52 to 55, and 1.60 and 61 or EP-A-1062940, especially p. 6,1. 41 to 47 (and in the equivalent WO 99/40895). Most preferred oxidizing agent is hydrogen peroxide, preferably used in a concentration from about 2 to 30 %, more preferably about 3 to 20% by, and most preferably from 6 to 12% b.w. the corresponding composition. The oxidizing agents may be present in the dyeing compositions according to the invention preferably in an amount from 0.01 % to 6 %, especially from 0.01 % to 1 %, based on the total dyeing composition. In general, the dyeing with an oxidative agent is carried out in the presence of a base, for example ammonia, alkali metal carbonates, earth metal (potassium or lithium) carbonates, alkanol amines, such as mono-, di- or triethanolamlne, alkali metal (sodium) hydroxides, earth metal hydroxides or compounds of the formula R is a propylene residue, which may be substituted with OH or CTC4alkyl, R3, R4, R5 and Re are independently or dependentty from each other hydrogen, Ci-Cdalkyi or hydroxy-(C1-C4)atkyi. The pH-value of the oxidizing agent containing composition is usually about 2 to 7, and in particular about 2 to 5. One preferred method of applying formulations comprising the mixture of dyes of the present invention on the keratin-containing fiber, preferably the hair is by using a multi-compartment dyeing device or "kit" or any other multi-compartment packaging system, as described for example in WO 97/20545 on p. 4, L 19 to I. 27. The first compartment contains for examie the mixture of dyes of the present invention and optionally furhter direct dyes and a basifying agent, and in the second compartment an oxidizing agent; or in the first compartment the mixture of dyes of the present invention and optionally futhter direct dyes, in the second compartment a basifiying agent and in the third compartment an oxidizing agent. A further preferred embodiment of the present invention relates to a method of dyeing hair with oxidative dyes, which comprises (a) mixing at least one dye of formula (1) and optionally at least one coupler compound and at least one developer compound, and an oxidizing agent, which optionally contains a1 least one further dye, and (b) contacting the keratin-containing fibers with the mixture as prepared in step (a). The pH-value of the oxidizing agent free composition is usually from 3 to 11, and in particular from 5 to 10, and most particular about 9 to 10. Preferably, a ready-to-use composition is prepared according to a first preferred embodiment by a process which comprises preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound especially selected from para-phenylenediamines and bis(phenyt)-alkylenediamines. and the acid-addition sails thereot. at least one coupler, especially selected from meta-phenylenediamines and the acid-addition salts thereof, and the mixture of dyes of the present invention, on the other hand, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent and mixing (A) and (B) together immediately before applying this mixture to the keratin-containing fibers. According to a second preferred embodiment for the preparation of the ready-to-use dye composition, the process includes a preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, especially selected from para-phenylenediamines and bis-(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler compound, especially selected from meta-phenylenediamines and the acid-addition salts thereof; on the other hand, a composition (A') comprising, in a medium which is suitable for dyeing, at least one dye of formula (1), and, finally, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent as defined above, and mixing them together at the time of use immediately before applying this mixture to the keratin-containing fibers. The composition (A') used according to this second embodiment may optionally be in powder form, the mixture of dyes of the present invention constituting, in this case, all of the composition (A') or optionally being dispersed in an organic and/or inorganic pulverulent excipient. When present in the composition A', the organic excipient may be of synthetic or natural origin and is selected in particular from crosslinked and non-crosslinked synthetic polymers, polysaccharides such as celluloses and modified or unmodified starches, as well as natural products such as sawdust and plant gums (guar gum, carob gum, xanthan gum, etc.). When present in the composition (A'), the inorganic excipient may contain metal oxides such as titanium oxides, aluminium oxides, kaolin, talc, silicates, mica and silicas. An very suitable excipient in the dyeing compositions according to the invention is sawdust. The powdered composition (A/) may also contain binders or coating products in an amount which preierabiy does not exceed approximately 3% b.vv. relative to the tola! weight of compo^ sition (A'). These binders are preferably selected from oils and liquid fatty substances of inorganic, synthetic, animal or plant ongin. Furthermore, the present invention relates to a process of dyeing of keratin-containig fibers with the mixture of dyes of the present invention and autooxidable compounds and optionally further dyes. Furthermore, the present invention relates to a process for dyeing keratin-containig fibers with the mixture of dyes of the present invention and capped diazotised compounds, which comprises, (a) treating the keratin-containing fibers under alkaline conditions with at least one capped diazotised compound and a coupler compound, and optionally a developer compound ad optionally an oxidizing agent, and optionally in the presence of a further dye, and optionally with the mixture of dyes of the present invention; and (b) adjusting the pH in the range of 6 to 2 by treatment v\/ith an acid, optionally in the presence of a further dye, and optionally with the mixture of dyes of the present invention with the proviso that at least in one step (a) or (b) the mixture of dyes of the present invention is present. The capped diazotised compound and coupler compound and optionally the oxidizing agent and developer compound can be applied in any desired order successively, or simultaneously. Preferably, the capped diazotised compound and the coupler compound are applied simultaneously, in a single composition. "Alkaline conditions" denotes a pH in the range from 8 to 10, preferably 9-10, especially 9.5-10, which are chieved by the addition of bases, for example sodium carbonate, ammonia or sodium hydroxide. The bases may be added to the hair, to the dye precursors, the capped diazotised compound and/or the water-soluble coupling component, or to the dyeing compositions comprising the dye precursors. Acids are for example tartaric acid or cltric acid, a citric acid ge'. a suitabie bufier soluiion witr: optionally an acid dye. The ratio of the amount of alkaline dyeing composition applied in the first stage to that of acid dyeing composition applied in the second stage is preferably about from 1:3 to 3:1, especially about 1:1. Furthermore, the present invention relates to a process for dyeing keratin-containig fibers with the mixture of dyes of the present invention and at least one acid dye. The following Examples serve to illustrate the processes for dyeing without limiting the processes thereto. Unless specified otherwise, parts and percentages relate to weight. The amounts of dye specified are relative to the material being coloured. 12.4 g 4-fluoroanirm are added to a stirred solution of 25 ml water and 25 ml of 32% hydrochloric acid at 295 K. The reaction mixture is cooled to 273 K and 19 ml of a 36% sodium nitrite solution are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. After the addition of the sodium nitrite solution the mixture is stirred for one hour. If no excess of nitrite is detected during one hour (detection by using a potassium iodide paper) further sodium nitrite solution is added. The remaining excess of nitrite is reduced with sulfamic acid. The obtained diazo solution is dropped to a 273 K cold solution of 7.4 g imidazole in 30 ml water, whereby the pH of the solution is maintained in the range of pH 10 to 11 by adding 36% of asodium hydroxide solution. After completing the diazo addition the obtained suspension is warmed up to 295 K, the pH is adjusted to 10.5 with 36% sodium hydroxide solution. After stirring for one hour at this pH and temperature the suspension is filtered off and washed twice with 50 ml water to obtain 55 g of a humid product, which is suspended in 200 ml water and 3 weight equivalents dimethyl sulfate and sodium hydroxide are simultaneously added for maintaining the pH at 10-10.3 and the temperature at 298-303K. The reaction is allowed to stand for one more hour to finish the hydrolysis of excess of dimethyl sulfate. 100 g sodium chloride and 50 g potassium chloride are added at 273K and allowed to stand for 16 hours. The product is separated by filtration and washed with a cold solution of sodium /potassium chloride. About 20g of the compound of formula are obtained 69 G cf cistearnine dihydrochloride are added at 293 K under nitrogen atmosphere to 20 g of the compound of formula (101a) in 120g tsopropanol and 24 g triethylamine. The temperature is raised to 333 K and the reaction mixture is stirred at this temperature during 25 hours. The reaction mass is stirred for 4 hours while the temperature is decreased to 295 K. The reaction mass is filtered off and the filter residue washed with 45 ml of isopropanol and again filtered.300 ml water are added to the humid filter residue and the mixture is stirred for 3 hours at 353 K. Then the temperature is decreased to 295 K and the mixture filtered off. The filter residue is washed with 100 ml water, filtered and dried in vacuum to obtain 16 g of compound of formula (101). hydrochloric acid at 295 K. The reaction mixture is cooled to 273 K and 19 ml 36% sodium nitrite solution are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. After the addition of the sodium nitrite solution the mixture is stirred for one hour. If no excess of nitrite is detected during one hour (detection by using a potassium iodide/starch paper) further amounts of sodium nitrite solution are added. Then the remaining excess of nitrite is destroyed with sulfamic acid. The obtained diazo solution is dropped to a 273 K cold solution of 7.4 g imidazole in 30 ml water, whereby the pH of the solution is maintained in the range of pH 10 to 11 by adding 36% sodium hydroxide solution. After completing the diazo addition the obtained suspension is warmed up to 295 K and the pH os adjusted to 10 5 with 36% sodium hydroxide solution. After stirring for one hour at this pH and temperature the suspension is filtered off and then washed twice witn 50 mi water to obtain 55 g of the humid product, which is suspended in 500 ml water. 0.3 mol dimethyl sulfate and sodium hydroxide are simoultaniously added for maintaining the pH in the range of 10-10.3 and the temperature at 298'303K. The reaction mixture is hold for one hour. Then the water is evaporated. About 40 g humid solid, which gives 27 g of dryed product of the formula 100 g 4>fluoro-3nitroanilin are added to a stirred mass of 80 g methanol and heated to 333 K. 0.1 ml sulfuric acid and 90 ml of acetic anhydride are added during 15 minutes. Heating and boiling are continued for 15 minutes. Then the reaction mixture is cooled slowly to 273 K with stirring. At the final temperature stirring is continued for 30 minutes, then the suspension is filtered off, washed with cold methanol, dryed in the vacuum dryer getting 114 g acetyl derivative which is worked up further. The acetyl derivative is solved in 520 ml ethanol and continuously added to 130 g iron in 35 ml concentrated hydrochloric acid and 220 ml water at 363K during 1 hour. The temperature drops to 353 K. The reaction mixture is stirred for further 3 hours. The hot mass is separated through filtration the residue washed with 100 ml ethanol. The filtrate and wash solution are cooled to 380 K with mixing, when cristallization of the product takes place. The product is separated by filtration, washed with cold ethanol and dryed in a vacuum dryer. The dried material is dissolved in 132 ml water and 110 ml of 32% hydrochloric acid at 295 K. The reaction mixture is cooled to 273 K and 86.4 g 36% sodium nitrite solution are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. The mixture is further stirred for one hour, if no excess of nitrite is detected during one hour (detection by using a potassium iodide/starch paper) further amounts of sodium nitrite solution are added. After this one hour the remaining excess of nitrite is destroyed with sulfamic acid. Then the obtained diazo solution is dropped to a 273 K cold solution of 33.4 g imidazole in 130 mi water, whereby the pH of the solution is maintained in the range of pH 10 to 11 by adding 36% of a sodium hydroxide solution. After completing the diazo addition, the obtained suspension is warmed up to 295 K and the pH is adjusted to 10.5 with 36% sodium hydroxide solution. After stirring for one hour at this pH and temperature the suspension is filtered off and then washed twice with 100 mi water to obtain 200 g of the humid product. The filtercake from the previouse step is suspended in water and 3 weight equivalents dimethylsulfate and sodium hydroxide are simultaniously added for maintaining the pH in the range of 10-10.3 and the temperature at 300 K. Then the reaction mixture is hold for one more hour to finish the hydrolysis of excess of dimethylsulfate. Then the suspension is separated by filtration. About 240 g of a humid solid which gives 140 g dryed product of formula 100 g 4-fluoro-3nitro-anilin is added to a stirred mass of 80 g methanol, heated to 333 K, 0.1 mi sulfuric acid added, and then 90 ml of propionic anhydride dunng 15 minutes. Then heating and boiling is continued for 15 minutes. Then the reaction mixture is cooled slowly to 273 K with stirring- At the final temperature stirring is continued for 30 minutes, then the suspension is filtered, washed with cold methanol, dryed in the vacuum dryer getting 114 g acetyl derivative which is worked up further. Then, the acetyl derivative is solved in 520 ml ethanol and continuously added to 130 g iron in 35 ml concentrated chlorhidric acid and 220 ml water at 363K during 1 hour. The temperature drops to 353 K. The reaction mixture is stirred for further 3 hours. The hot mass is separated through filtration, the residuu washed with 100 ml ethanol. The filtrate and wash solution is cooled to 380 K with mixing, when cristallization of the product takes place. The product is separated by filtration, washed with cold ethanol and dryed in a vacuum dryer. The dried material is dissolved in 132 ml water and 110 ml of 32% hydrochloric acid at 295 K. Then the reaction mixture is cooled to 273 K and 86.4 g 36% sodium nitrite solution is dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. After the addition of the sodium nitrite solution, the mixture is stirred for one hour. If no excess of nitrite is detected dunng one hour (detection by using a potassium iodide/starch paper): further amounts of sodium nitrite solution is added. After this one hour the remaining excess of nitrite is destroyed with sulfamic acid. Then, the obtained diazo solution is dropped to a 273 K cold solution of 33.4 g imidazole in 130 ml water, whereby the pH of the solution is maintained in the range of pH 10 to 11 by adding 36% sodium hydroxide solution. After completing the diazo addition, the obtained suspension is warmed up to 295 K, the pH is adjusted to 10.5 with 36% sodium hydroxide solution. After one hour stirring at this pH and temperature, the ^^uspension is filtrated and then washed twice with 100 ml water to obtain 200 g of the humid product Then, the filtercake from the previouse step is suspended in water and 3 weight equivalents dimethylsulphate and sodium hydroxide simoultaniously added for maintaining the pH in the range of 10-10.3 and the temperature at 300 K. Then, the reaction mixture is hold for one more hour, to finish the hydrolysis of excess of dimethylsulphate. Then, the suspension is separated by filtration. About 240 g humid solid, which gives 140 g dryed product of formula I 100 g 4-fluoro-3nitro-anilin are added to a stirred mass of 80 g methanol and heated to 333 K. 0.1 ml sulfuric acid and 90 ml of benzoyl chloride are added during 15 minutes. Heating and boiling is continued for 15 minutes. The reaction mixture is cooled slowly to 273 K with stirring andcontinued for 30 minutes. The suspension is filtered off, washed with cold methanol, dryed in the vacuum dryer getting 114 g acetyl derivative which is worked up further. The acetyl derivative is dissolved in 520 ml ethanol and continuously added to 130 g iron in 35 ml concentrated chlorhidric acid and 220 ml water at 363K during 1 hour. The temperature drops to 353 K. The reaction mixture is stirred for further 3 hours. The hot mass is separated through filtration, the residue washed with 100 ml ethanol. The filtrate and wash solution are cooled to 380 K with mixing when cristallization of the product takes place. The product is separated by filtration, washed with cold ethanol and dryed in a vacuum dryer. The dried material is dissolved in 132 ml water and 110 ml of 32% hydrochloric acid at 295 K. Then the reaction mixture is cooled to 273 K and 86.4 g of a 36% sodium nitrite solution are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. After the addition of the sodium nitrite solution the mixture is stirred for one hour. If no excess of nitrite is detected during one hour (detection by using a potassium iodide/starch paper) further amounts of sodium nitrite solution are added. The remaining excess of nitrite is destroyed with sulfamic acid. Then the obtained diazo solution is dropped to a 273 K cold solution of 33.4 g imidazole in 130 ml water, whereby the pH of the solution is maintained in the range of p\\ 10 to 11 by adding 36% of a sodium hydroxide solution. After completion of thethe diazo addition the obtained suspension is warmed up to 295 K, the pH adjusted to 10.5 with 36% sodium hydroxide solution. After stirring for one hour at this pH and temperature the suspension is filtered off and then washed twice with 100 ml water to obtain 200 g of the humid product Jrien the filtercake from ihe previouse step is suspended in.water and 3 weight equivalents dimethylsulfate and sodium hydroxide simoultaniously added for maintaining the pH in the range of 10-10.3 and the temperature at 300 K. Then the reaction mixture is hold for one more hour to finish the hydrolysis of excess of dimethylsulfate. Then, the suspension is separated by filtration. About 240 g of a humid solid, which gives 140 g dry product of the following formula t 1. Formation of the Hvdrazone: 14 g sulfuric acid are added to 42 g of water and cooled to 293K. 24 g of N-methyl-phenyl hydrazine (100%) are added with stirring, 24.5 g of 4-pyridine- aldehyde are dropped in during 15 minutes and stirhng is continued for 1 hour. The pH is raised to 2.2 by adding a solution of 36% sodium hydroxide in water. 2.7 g sodium chloride are added at the 333K. Stirhng is continued at this temperature for one hour. The slurry is separated by filtration; the filter cake is dried at 343K in vacuum to yield 42 g of an orange powder. 2. Alkylating agent: A mixture of 15.4g of 2.2-dithiodiethanol in 100 ml chloroform and 24.1 g pyridine are cooled with stirring at 273K and then 41.0 g of tosyl chloride are added in small amounts, maintaining the temperature. After completion of the addition the mixture is left over night In the refrigerator. The reaction mixture is mixed with a water/hydrochlohc acid/Ice slurry. The phases are separated, washed with water and dried. The obtained solution of toluenesulfonate diester is used in the 3. step. S.AIkylation: The foregoing hydrazone is dissolved by stirring with the equivalent amount of diester solution. Temperature is raised to 334K which is maintainedduring the following 48 hours. Crystals separated in the slurry are filtred off. The product is washed with 50 ml chloroform and dried in vacuum to obtain 59 g of an orange solid product. The product is recristallized twice from methanol. 1. Monoazo: 50.0 of g 2-amino-thiazol are added to a stirred solution of 135 ml 60% sulfuric acid at 293-310 K. Then, the reaction mixture is cooled to 273 K and 81 ml of a 40% nitrosilsulfuric acid are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K by cooling. After the addition the mixture is stirred for four hours. The solution is dropped to a well-stirred water ice mixture (400 g) containing 2,5 g amidosulfunc acid. To the obtained diazo solution (at 273 K ice added if need) 60,5 g dimethylaniline are dropped. Then the pH of the solution is raised to the range of 5 to 6 by adding 36% sodium hydroxide solution. After one hour stirring at this pH and temperature the suspension is filtered off and then washed twice with 50 ml water to obtain 155 g of the humid product. After drying 100 monoazo dye is obtained. 2. Alkylating agent: A mixture of 15.4 g of 2,2-dithiodiethanol in 100 ml chloroform and 24,1 g pyridine are cooled with stirring to 273 K and then 41.0 g of tosyl chloride are added in small amounts maintaining the temperature. After completion of the addition the mixture is left over night in the refrigerator. The reaction mixture is mixed with a water/hydrochloric acid/ice slurry, the phases are separated, washed with water and dried. The obtained solution of toluenesuifonate diester is used in the following step 3.Alkvlation: The foregoing monoazo is dissolved by stirring into the diester solution. Temperature is raised to 333K. The temperature is maintained at 333K during the following 60 hours. Crystals separated in the slurry are filtered off. The product is washed with 50 ml of chloroform and dried in vacuum to obtain 59 g of a dark violett solid product. The product is recristallized twice from methanol. 273 to 276 K with cooling and stirred for four hours. The solution is dropped to a well-stirred water ice mixture (400 g) containing 2.5 g amidosulfuric acid. 60,5 g dimethylaniiine are dropped to the obtained diazo solution (at 273 K ice added if need). The pH of the solution is adjusted between 5 and 6 by adding 36% sodium hydroxide solution. After stirring for one hour at this pH and temperature the suspension is filtered off and washed twice with 50 ml water to obtain 255 g of the humid product. After drying 151 monoazo dye is obtained. 2. Alkylating agent: A mixture of 21.4 g of 2.2-dithiodiethanol in 100 ml chloroform and 24.1 g pyridine are cooled with stirring to 273K and then 41,0 g of mesyl anhydride are added in small amounts under constant temperature. After completion of the addition the mixture is left over night in the refrigerator to finish the reaction. The reaction mixture is mixed with a water/hydrochloric acid/ice slurry, the phases are separated, washed with water and dried. The obtained solution of methanesulfonate diester is used in the following step 3.Alkvlation: Two equivalents of the foregoing monoazo are dissolved by stirring into the diester solution. Temperature was raised to 334K. The temperature was maintained at 334K during the following 80 hours. Crystals separated in the slurry are filtered off. The product is washed with 50 ml of chloroform and dried in vacuum to obtain 80 g of a dark violett solid product. The product is recristallized twice from methanol. Characterization by1H-NMR in deuterated methanol (128 scans)/ 360MHz: 19.9 g of N,N'-dimethyl-ethylendiamine are added with stirring to 120g acetonitrjle and compound of the formula of formula {101a) at 293 K under nitrogen atmosphere. The temperature is raised to 333 K while the viscosity of the reaction mixture decreases. The reaction mixture is stirred at this temperature during 25 hours. Then the reaction mass is stirred for 4 hours while the temperature is decreased to 295 K. The reaction mass is filtered off and the filter residue is washed with 45 ml of acetonitrile. Then the material is dried in vacuum to obtain 16 g of product. 2. Alkylaiinq agent: A mixture of 15.4 g of 2.2-dithiodiethanol in 100 fnl chlorolorm and 24,1 g pyridine are cooled with stirring to 273K and then 41,0 g of tosyl chloride are added in small amounts under constant temperature. After completion of the addition the mixture is left over night in the refrigerator. The reaction mixture is mixed with a water/hydrochloric acid/ice slurry, the phases are separated, washed with water and dried. The obtained solution of methane-benzene-sulfonate diester is used in the following step. 3.AIkvlation: Stirring into the diester solution in chloroform dissolves two equivalents of the foregoing monoazo. Temperature is raised to 333K. The temperature is maintained at 333K during the following 20 hours. Crystals separated in the slurry are filtrated. The product is washed with 50 ml of chloroform and dried in vacuum to obtain 80 g ot a dark solid product. The product is recristallized twice from methanol. 1. 16.9 g of ethylenediamine are added to the compound of the formula (101a) (prepared in Example A1) and 120g isopropanol at 293 K under nitrogen atmosphere under stirring. The temperature is raised to 333 K while the viscosity of the reaction mixture decreases. The reaction mixture is stirred at this temperature during 25 hours. Then the reaction mass is stirred for 4 hours while the temperature is decreased to 295 K. The reaction mass is filtered off and the filter residue is washed with 45 ml of isopropanol. Then the filter residue is dried in vacuum to obtain 16 g of the product. 2. Acvlatinq agent: A mixture of 15-4g of 2,2-dithiodipropionic acid and then 41.0 g of thionyl chloride is warmed to 333 K for 2 hours under constant temperature. After completion of the addition the mixture is distilled under vacuum . 3.Alcylatuiun. Two equivalents of the foregoing monoazo are dissolved by stirring into the acid chloride solution in chloroform. The temperature is raised to 333K and maintained during the following 48 hours. Crystals separated in the slurry are filtrated. The product is washed with 50 ml of chloroform and dried in vacuum to obtain 80 g of a dark redish solid product which is re-cristallized twice from methanol. 1 .Formation of the Hydrazone: 14 g sulfuric acid are added to 42 g of water and cooled to 293K. 25 g of N-methyl-phenyl hydrazine (100%) are added with stirring. 24.0 g of 4-pyridine-aldehyde are dropped in dunng 15 minutes and stirnng is continued for i hour. The pH is raised to 2.2 by adding a solution of 36% sodium hydroxide in water. 2.7 g sodium chloride are added at a temperature of 333K and stirred for one more hour at this temperature. The slurry is separated by filtration, the filter cake dried at 343K in vacuum to yield 43 g of an orange powder. 2. Alkylating agent: A solution of 22.5 g of cisteamlne dichlorohydrate in water and 31.4 g bromoacetic chloride are cooled with stirring to 273K and then the pH is kept constant by adding NaOH solution in small amounts under constant temperature. After completion of the addition the mixture is left over night in the refrigerator. The mixture has two phases, which are separated, washed with water and dried. 3. Alkytation: The foregoing hydrazone is dissolved in methanol by stirring with the dibromide solution. The temperature is raised to 60°C and maintained at 60X during the following 24 hours. The crystals separated in the slurry are filtrated. The product is washed with 50 ml of methanol and dried in vacuum to obtain 49 g of an orange solid product. The product is recristallized twice from methanol. 1. 9.9 g of N,N-dimethyl-ethylendiamine are added to 120g acetonitrile and to the compound of the formula (101a) (prepared in example A1) at 293 K under nitrogen atmosphere with stirring. The temperature is raised to 333 K while the viscosity of the reaction mixture decreases. The reaction mixture is stirred at this temperature dunng 25 hours. The reaction mass is stirred for 4 hours while the temperature is decreased to 295 K. The reaction mass is filtered off and the filter residue washed with 45 ml of acetonitrile. Then the material is dried in vacuum to obtain 16 g of product. 2. Alkylating aqent:A mixture of 15.4 g of 2.2-dithiodiethanol in 100 ml chloroform and 24,1 g pyridine is cooled with stirring to 273K and then 41.0 g of tosyl chloride are added in small amounts under constant temperature. After completion of the addition the mixture is left over night in the refrigerator. The reaction mixture is mixed with a water/chiorhidric acid/ice slurry, the phases are separated, washed with water and dried. The obtained solution of methane- benzene-sulfonate diester is used in the following step 3.Alkvlatton: Stirring into the diester solution in chloroform dissolves two equivalents of the foregoing monoazo. The temperature is raised to 333K and maintained at 333K during the following 20 hours. Crystals separated in the slurry are filtrated. The product is washed with 50 ml of chloroform and dried in vacuum to obtain 80 g of a dark solid product, which is recristalJized twice from methanol. The compound of formula (102a) (prepared in example 2) is reacted with N,N-dtmethyl-ethy-lenediamine according to the procedure as described in Example A14. The same alkylating agent is used to give the compound of formula (115). Example AZQ-16: The compound of formula (104a) (prepared in example A 4) is reacted with N,N-dimethyl-ethylendiamine according to the method as described in Example A14. The same alkylating agent is used and the compound of formula (116) is obtained. Example AZO-17: Step 1: 19,9 g of N,N-d(methyl-ethylendiamin is added at 293 K, under nitrogen atmosphere, with stirring to 120g isopropanol and the foregoing compound of the formula (AZO-101a), Then the temperature is raised to 333 K, and viscosity of the reaction mixture decreases. The reaction mixture is stirred at this temperature during 25 hours. Then, the reaction mass is stirred for 4 hours, while the temperature is decreased to 295 K. The reaction mass is filtered and the filter residue is washed with 45 ml of isopropanol. Then the materia! is dried in vacuum to obtain 16 g of the product: 3. Alkylation 4,0 g of Magnesiumoxid is added at 293 K with well-stirring to 100 ml methanol and the foregoing compound of the formula (117a). Then the temperature is raised to 323 K and the reaction mixture is stirred at this temperature for half an hour. After been slowly cooled at room temperature, the reaction mass is filtrated. 14,0 g of the alkylating agent (117b) and 4,0 g of Magnesiumoxid are added at 293 K to the well-stirred foregoing filtrate. A catalytic amount of potassium iodide is added to the reaction mixture. The temperature is then raised to 313 K and the reaction mixture is stirred at this temperature for five days. The reaction mass is then diluted with 100 ml methanol and filtrated. The filtrate is evaporated to dryness and finally the materia! is dried in vacuum to obtain 57.5 g of the product (AZO'117). MS (ES+): m/z 403 (M2+). 1. Monoazo 50.Og of 2-amino-thiazol are added to a stirred solution of 135ml 60% sulfuric acid at 293-31 OK. Then the reaction mixture is cooled to 273K and 81ml of a 40% nitrosilsulfuric acid are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276K by cooling. After the addition the mixture is stirred for four hours. The solution is dropped to a well-stirred water ice mixture (400g) containing 2,5g amidosulfuric acid. To the obtained diazo solution (at 273K ice added if need) 60.5g dimethylaniline are dropped. Then the pH of the solution is raised to the range of 5 to 6 by adding 36% sodium hydroxide solution. After stirring one hour at this pH and temperature the suspension is filtered off and then washed twice with 50ml water to obtain 155g of the humid product. After drying 100g monoazo dye of formula (118a) is obtained. 2. Alkvlation 14.7g of the monoazo dye of formula (118a), 9.9g of the alkylating agent of formula (AZO-117b) and O.lg Kl are stirred for 20h in 100ml tetramethylurea at lOO^'C. After extraction of the crude product with tetrahydrofurane the final product is obtained after crystallization from Methanol/Acetone (7:3 ). Yield after vacuum-drying: 20,5g of the dye of formula (AZO-118). 1. Monoazo 184g of 2-amino-6-methoxy-benzothiazol are added to a well-stirred solution of 270ml 60% sulfuric acid at 293-310 K. Then the reaction mixture is cooled to 266K and 174ml of a 40% nitrosilsulfuric acid are added at such a rate that the temperature of the mixture is maintained in the range of 266 to 268 K by cooling. After the addition the mixture is stirred for 4h at 268K. The solution is poured into to a well-stirred water ice mixture (600g) containing 5g amido-sulfuric acid (at 273K ice added if need). To the obtained diazo solution (at 273K ice added if need) 196.5g of melting N-phenyldiethanolamine are dropped. After the addition the mixture is stirred for 2h. Then the pH of the solution is raised to 7 by adding 36% sodium hydroxide solution (the temperature of the mixture Is maintained under 313K by addition of ice). After 1h stirring at this pH the suspension is filtered off and then washed with water to obtain 1322g of the humid product. After drying 505g monoazo dye of the formula (119a) are obtained. 2. Alkvlation 39.1g of the monoazo dye of the formula (119a) and 13.8g of the alkylating agent (117b) and O.lg Kl are stirred tor 20h in 100ml tetramethylurea at 100°C. The work-up is carried out by extraction of the crude product with tetrahydrofurane. After vacuum-drying 32g of the dye of the formula (AZO-119) are obtained. 1 ■ Monoazo lOOg of 2-amino-thiazol are added to a weli-stirred solution of 270ml 60% sulfuric acid at 293-31 OK. Then the reaction mixture is cooled to 273K and 146ml of a 40% nitrosilsulfuric acid are added at such a rate that the temperature of the mixture is maintained in the range of 273 to 276K by cooling. After the addition the mixture is stirred for four hours. The solution is poured into to a well-stirred water ice mixture (700g) containing 5g amidosulfuric acid (at 273K ice added if need). To the obtained diazo solution (In the range 273-278 K ice added if need) 180g of melting N-Phenyldiethanolamine is dropped. After the addition the mixture is stirred for one hour. Then the pH of the solution is raised to the range of 5 by adding 36% sodium hydroxide solution (The temperature of the mixture is maintained under 303K by addition of ice). After two hours stirring at this pH the suspension is filtered off and then washed with water to obtain 439g of the humid product. After drying 243g monoazo dye of formula (120a) .?_Alkylation 26.6g of the monoazo of formula (120a),15.8g of the alkylating agent (117b) and 0.1g Kl are stirred in 160ml tetramethylutea for 20h at100°C. The solvent is destilled off under reduced pressure and the residue is extracted with tetrahydrofurane (5x500 m!) and vacuum-dried. 1. Alkylating agent A mixture of 15.4 g of 2,2-dithiodiethanol in 100 ml chloroform and 24,1 g pyridine are cooled with stirring to O^C and then 41.0 g of tosyl chloride are added in small amounts, maintaining the temperature at 0°C by cooling externally. After completion of the addition the mixture is left over night in the refrigerator to complete the reaction. The reaction mixture is mixed with a water/ hydrochloric acid and ice slurry, the phases are separated, washed with water and dried. The solution of toluenesulfonate diester is used as starting compound in the 2nd reaction step. 2. Alkylation The alkylation agent obtained in the 1st reaction step is delivered from the solvent, dissolved in two equivalent amounts (18.8 g) of 4-methyl-pyridine. The temperature is raised to 70°C and maintained at 60°C during the following 12 hours. 3. Condensation To the reaction mixture of the foregoing step 50 ml of isopropanoi are added, Then the equivalent amount (30.0 g) of dimethylamino-benzaldehyde and a catalytic amount (3.6 g) of piperidine are added and the reaction mixture is stirred for 24 hours at 70°C. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 45 g of a reddish orange solid product. The product is recristalized twice from methanol. The product is characterized by the following data: - The HPLC-MS gives a main component of a dication of the mass 568 - 1H-NMR data in deuterated chloroform (128 scans)/ 360MHz: A mixture of 15.4g 2,2-dithiodiethanol in 100 ml chloroform and 24.1g pyridine are cooled with stirring to 0°C and then 22.0 g of mesyl chloride are added in small amounts, main-taining the temperature by external cooling. After completion of the addition the mixture is left over night in the refrigerator to complete the reaction. The reaction mixture is mixed with a water/hydrochloric acid and ice slurry, the phases are separated, washed with water and dried. The solution of methanesulfonate diester is used as starting compound in the 2nd reaction step. 2. Alkytation 1 wo equivalents (18.8 g) of 4-methyl-pyridine are dissolved in the foregoing alkyiation agent together with a solvent. The temperature is raised to reflux and maintained at 70°C during the following 12 hours. 3. Condensation The equivalent amount (24.0 g) of amino-benzaldehyde and a catalytic amount (3.6 g) of piperidine are added to the reaction mixture obtained in the 2nd reaction step and the reaction mixture is stirred for 24 hours at 70°C. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 42 g of an orange solid product. The product is recristailized twice from methanol. A mixture of 25.4 g of cisteamine as dichlorohydrate in 100 ml water is cooled with stirring to 0°C and 41.0 g of bromoacetic acid bromide are added in small amounts, maintaining the temperature at O°C by external cooling. The pH is adjusted with sodium hydroxide to 8.0, After completion of the addition the nnixture is left for one hour with agitation to comlete the reaction. The reaction mixture is separated by filtration, the solid washed with water and dried. The alkylating agent used as starting compound in the 2nd reaction step. 2. Alkylation The alkylation agent obtained in the 1st reaction step is added to 50 ml isopropaol and dissolved in two equivalent amounts (18,8 g) of 4-methyl-pyrldine. The temperature is raised to 80°C and maintained during the following 10 hours. 3. Condensation 20 ml of isopropanol are added to the reaction mixture obtained in the 2nd reaction step. Then the equivalent amount (30.0 g) of dimethylamino benzaldehyde and a catylytic amount (3.6g) of piperidine are added and the reaction mixture is stirred for 24 hours at 80°C. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 59 g of an orange solid product. The product is recristallized twice from isopropanol. 1. Acylating agent A mixture of 21.4 g 2,2-dithiodipropionic acid in 100 ml chloroform and 24.0 g thionyl chloride are added in small amounts, maintaining the temperature by external cooling. After completion of the addition the mixture is heated to remove the formed gases and the reaction was finished. The solvent is removed by distillation under low pressure and the acid chloride used as starting compound in the 2^^ reaction step. 2. Alkylation The dimethylsulfate as alkylation agent is used without solvent and mixed with two equivalent amounts (18.8g) 2-methyl-pyridine- The temperature is raised to 80°C and maintained during the following 2 hours. 3. Condensation 50 ml of isopropanol are added to the reaction mixture of the foregoing step. The equivalent amount (24.0 g) of aminobenzaldehyde and a catalytic amount (3.6 g) of piperidine are added and the reaction mixture is stirred for 16 hours at 70°C. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum lo obtain 49 g of an orange solid product. The product is recristallized twice from water. 4. Acylation A mixture of 49 g of the fstyrene compound obtained in the 3rd reaction step and 200 ml water are cooled with stirring to O°C and then 41.0 g of the acid chloride obtained in reaction step 1 dissolved in tetrahydrofurane are added iri small amounts, maintaining the temperature by external cooling. The pH is adjusted to 6.0 by addition of sodium hydroxide. After completion of the addition the mixture is left for one hour with agitation to complete the reaction. The reaction mixture is separated by filtration, the solid washed with water and dried. 1. Alkylating agent A mixture of 25,4 g of 2,2-dithiodiethylamine (cisteamine) as dichlorohydrate and 100 ml water is cooled with stirring to 0°C and then 41.0 g of bromo acetic acid bromide are added in small amounts, maintaining the temperature by cooling externally. The pH is adjusted to 8.0 by addition of sodium hydroxide-After completion of the addition the mixture is left for one hour with agitation to complete the reaction. The reaction mixture is separated by filtration, the solid washed with water and dried. The alkylating agent is used as starting compound in the 2nd reaction step. 2.Alkylation The alkylation agent obtained in the 1st reaction step is delivered from the solvent and dissolved in two equivalents (18.8 g) 2-methyl-pyridine. The temperature is raised to BO'^C and maintained at 60°C during the following 16 hours. 3. Condensation 50 mi ot (sopropanol are added to the reaction mixture obtained in the 2nd reaction step. The equivalent amount (30.0 g) of dimethylamino benzaldehyde and a catalytic amount (3.6 g) of piperidine are added and the reaction mixture is stirred for 24 hours at 70°C. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 57 g of an orange solid product. The product is recristallized twice from methanol. 1. Acylating agent 24.0 g of thionyl chloride are added to a mixture of 21A g of 2,2-dithiodipropionic acid in 100 ml chloroform in small amounts, maintaining the temperature by external cooling. After completion of the addition the mixture is heated to remove the formed gases and the reaction is completed within one hour. The solvent is removed by distillation under low pressure. The acid chloride used as starting compound in the 2nd step 2. Alkyiation The dimethylsulfate as alkyiation agent is used without solvent, with two equivalent amounts (18.8 g) of 4-methyl-pyhdine. The temperature is raised to 80°C and maintained at 80°C during the following 2 hours. 3. Condensation 50 ml of isopropanole are added to the reaction mixture obtained in the 2nd reaction step. Then the equivalent amount (24,0 g) of aminobenzaldehyde and a catalytic amount (3.6 g) of pipehdine are added and the reaction mixture is stirred for 12 hours at 70°C. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 55 g of an orange solid product. The product is recristallized twice from water. 4. Acylatjon A mixture of 55 g of the styrene compound obtained in the 3rd reaction step and 200 ml water is cooled with stirring to 0°C and then 45,0 g of the acid chloride obtained in the 1st reaction step, dissolved in tetrahydrofurane, are added in small amounts, maintaining the temperature at O°C by external cooling. The pH is adjusted to 7,0 by addition of sodium hydroxide. After completion of the addition the mixture is left for one hour with agitation to complete the reaction. The reaction mixture is separated by filtration; the solid washed with water and dried, The product may be used as such for dyeing applications. 1. Acylating agent A mixture of 18.4 g 2,2-dithioglycolic acid in 100 ml chloroform and then 24.0 g of thionyl chloride are added in small amounts, maintaining the temperature by external cooling. After completion of the addition the mixture is heated to remove the formed gases and the reaction is completed within one hour The solvent is removed by distillation under low pressure and the acid chloride is used as such in the 4^ reaction step. 2. Alkylation The dimethylsulfate as alkylation agent is used without solvent with two equivalents (18.8g) 4-methyl-pyridine. The temperature is raised to 70°C and maintained at 80°C during the following 2 hours. 3. Condensation 50 ml of isopropanol are added to the reaction mixture obtained in the 2nd reaction step. The equivalent amount (24.0 g) of amino-benzaldehyde and a catalytic amount (3.6 g) of piperidine are added and the reaction mixture is stirred for 24 hours at 70°C, The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum lo obtain 49 g of an orange solid product. The product is recristallized twice from water. 4. Acylation A mixture of 49g of the styrene compound obtained in the 3nd' reaction step in 200 ml water are cooled with stirring to 0°C and then 35.0 g of the acid chloride obtained in the 1st reaction step, diluted with 30 ml tetrahydrofurane are added in small amounts, maintaining the temperature at O°C by external cooling. The pH is adjusted to 6.0 by addition of sodium hydroxide. After completion of the addition the mixture is left for one hour with agitation to complete the reaction. The reaction mixture is separated by filtration, the solid washed with water and dried. The product may be used as such for dyeing applications. 2. Alkyiation The dimethyisulfate as alkyiation agent is used without solvent, dissolved in two equivalent amounts (18.8g) of 2-methylpyridine. The temperature is raised to 70°C and maintained at 80°'C during the following 2 hours. 3. Condensation 50 ml of isopropanole are added to the reaction mixture obtained in the 2nd reaction step. The equivalent amount (24.Og) amino-benzaldehyde and a catalytic amount (3.6g) of piperidine are added and the reaction mixture is stirred for 24 hours at 70°'C. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 49 g of an orange solid product. The product is recristaJlized twice from isopropanol. 4. Acylation A mixture of 49 g of thestyrene compound obtained in the 3rd reaction step and 200 ml water are cooled with stirring to 0°C and then 41,0 g of acid chloride obtained in the 1st reaction step are added in small amounts, maintaining the temperature at by 0°C external cooling. The pH is adjusted to 6.0 by sodium hydroxide addition After completion of the addition the mixture is left for one hour with agitation to complete the reaction. The reaction mixture is separated by filtration, the solid washed with water and dried. The product may be used for dyeing applications. 1. Alkylating agent A mixture of 21.5 g 2-hydroxyethyl-methylamine are neutralized witli hydrochloric acid and evaporated to dryness. The salt is suspended in chlorofornn and cooled under stirring to 0°C and then 41.0 g of thionyl chloride are added in small amounts, maintaining the temperature at byO°C external cooling. After completion of the addition the reaction is completed by heating to reflux and degassing the mixture. The solution is evaporated to dryness, the 2-chloroethyl-methylamine is used as chlorohydrate in the 2nd reaction step. 2. Alkylation The alkylation agent obtained in the 1st reaction stepis dissolved in n-butanol and two equi¬valent amounts (16,8g) 4-methyl-pyridine are added. The temperature is raised to 120°C and maintained during the following 6 hours. Than the temperature is lowered to 70°C. 3. Condensation The equivalent amount (30.Og) of dimethylaminobenzaldehyde and a catalytic amount (3.6g) of piperidine are added to the reaction mixture obtained in the 2nd reaction step and the reaction mixture is stirred for 24 hours at 70°C. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 50 g of an orange solid product. The structure of the compound of formula 4. Alkylating agent A mixture of 15.4 g of 2,2-dithiocliethanol in 100 ml chloroform and 24.1 g pyridine are cooled with stirring to 0°C and then 22.0 g of mesyl chloride are added in small amounts, maintaining the temperature at 0°C by external cooling. After completion of the addition the mixture is left over night in the refrigerator to complete the reaction. The reaction mixture is mixed with a water/hydrochlohc acid and ice slurry, the phases are separated, washed with water and dried. The solution of methanesulfonate diester is used as such in the 5th reaction step. 5. Alkylation Two equivalents (18.8g) of the intermediate dye molecule obtained in the 3rd reaction step are dissolved in alkylation agent obtained in the 4th reaction step with a solvent. The temperature is raised to reflux and maintained at 70°C during the following 12 hours. The reaction mixture is cooled to ambient temperature with agitation and separated through filtration. The solid is washed with chloroform and dryed. 1. Alkylation The alkylation agent 2-chloroethyl-N,N-dimethylamine is dissolved in n-butanol and equivalent amounts (18.028 g) of 4-methyl-pyridine are added. The temperature is raised to 120°C and maintained at 120'C during the following 6 hours. Than the temperature is lowered to TC'C, 2. Condensation The equivalent amount (30.Og) of dimethylamino-benzaldehyde and a catalytic amount (3.6g) of piperidine are added to the reaction mixture obtained in the 1st reaction step and the reaction mixture is stirred for 24 hours at 70°C. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 50 g of an orange solid product. The structure corresponding to formula 3. Alkylating agent A mixture of 15.4 g of 2,2-clithiodiethanol in 100 ml chloroform and 24.1 g pyridine are cooled with stirring to 0°C and then 41 .Og of tosyl chloride are added in small amounts, maintaining the temperature at 0°C by cooling externally. After completion of the addition the mixture is left over night in the refrigerator to complete the reaction. The reaction mixture is mixed with a water/chlorhidric acid and ice slurry, the phases are separated, washed with water and dried. The solution of toluenesulfonate diester is used as starting compound in the 4th reaction step. 4. Alkylation Two equivalents (56g) of the intermediate dye molecule are dissolved in the foregoing alkylation agent obtained in the 4th' reaction step with solvent. The temperature is raised to reflux and maintained at 70°C during the following 12 hours. The reaction mixture is cooled to ambient temperature with agitation and separated through filtration. The solid is washed with chloroform and dryed. Example ANT-01: 2.95 g of 1-(3-dimethylaminopropyl)amino-4-amino-anthraquinone (RN 65274-31-9) and 1.80 g of bis(2-(2-bromoacetamido)ethyl)-disulfide (RN 697755-79-6) are dissolved in 20 ml DMF and stirred for 5 h at 40°C. The dark blue solution is than dropped slowly into 500 ml acetone under vigorous stirring. The precipitate is filtered off, washed with 100ml acetone and dried in a vacuum oven at 50°C to yield 4.06 g of the compound of formula Example ANT~02: 2.06 g of the compound of formula (101) are dissolved in 30 ml NMP and 530µl 4-bromo-butyryl chloride are added under stirhng. After 40 min 10 ml of a 4.2 M solution of trimethyl-amine in ethanol are added and the reaction mixture is stirred at 80°C for 17 h. Then 10 ml of acetone are added and the resulting precipitate is separated by filtration, washed with acetone and dried to give 1.40 g of the compound of formula Example ANT-03: Slept. A solution of 19.39 g 1,3-dibromopropane in 10 ml of chloroform is stirred at room temperature and a solution of 0.50 g N,N'-tetramethylcystamine (RN 1072-11-3) in 10 ml of chloroform is added over a period of 8 h. After additional stirring for 2 days the resulting white precipitate is filtered off, washed with chloroform and dried under vacuum. Step 2: The white solid prepared in step 1 is added to a solution of 1.06 g of 1-(3-dimethyl-aminopropyl)amino-4-amino-anthraquinone (RN 65274-31-9) In 10 ml DMF. The solution is stirred for 3 days at 4^0. After that time the reaction mixture is poured into 200 ml of acetone and the resulting precipitate is collected by filtration. Than the crude product is refluxed for 40 min in 120 ml of acetone. The suspension is filtered off and the collected solid is dried under vacuum at 60'C. Yield: 1.64 g of the compound of formula '^CNMR(DMS0-d6)[ppm]: 6 181.68, 18123, 146.66, 146.58, 134,46, 134.17, 132.80, 132.70, 130.12, 126.13, 126.05, 124.12, 108.76, 108.43, 62.93, 61.93, 60.05, 60.00, 51.19, 51.00. 39.66, 30.86, 23.34, 17.36. Example ANT-04: 5.00 g of 1-(3-dimethylaminopropyl)amino-4-am(no-anthraquinone (RN 65274-31-9) and 3.58 g of the bis(toluolsulfonate) of (2-hydroxyethyl)-'disulfide (RN 69981-39-1; prepared as described in Delacroix et al., Bull Soc. Chim. France (1978), (9-10, Pt. 2), 481-4) are dissolved in 15 ml NMP and stirred at 80°C for 72 h. Then the reaction mixture is poured into 150 ml of acetone and the precipitate is separated from the supernatant liquid. The residue is refluxed for 1 h in 60 ml acetone collected by filtration and dried under high vacuum to obtain 3.55 g of the compound of formula Example ANT-05: Step 1: To a solution of 61.32 g 1-(3-aminopropyl)'imidazole, 5.92 g lithium hydroxide and 1.48 9 Cu(l)CI in 150 ml water. 100 g of sodium 1-amino-4-bromoanthraquinone-2-sulfonate (RN 6258-06-6) are added over a period of 15 min. The reaction mixture is stirred for 30 min at 65°C and then for 1 h at 85°C. After the resulting blue solution had cooled down to room temperature 75 ml concentrated hydrochloric acid are added. The resulting precipitate is filtered off, suspended in 200 ml acetone and stirred for 1h. After filtration the crude product is suspended in 500 ml water and dissolved by addition of 19.98 g of a 4 molar sodium hydroxid solution. Then 18 g of sodium chloride are added and the resulting precipitated is filtered off and dried to yield 44.23 g of the compound of formula Step 2: To a suspension of 30.78 g of the compound of formula (105a) in 300 ml of water 34 ml sodium hydroxid solution (30 %) are added. The mixture is heated to 80°C and a solution of 16.31 g glucose in 90 ml water is added dropwise over a period of 40 min. After 30 min the suspension is cooled to room temperature and filtered. The press cake is stirred in 450 ml 4 molar sodium hydroxid solution, filtered off and washed with water. The residue is dried in a vacuum oven at 50°C to yield 19.69 g of the compound of formula MS (ES+): m/2 463 (M^'). UVA/IS [nm] (water/acetonitrile 1:1): λ1 571 λA2 609. Example ANT-06: Step 1: A mixture of 5.00 g of C.I. Acid Blue 25 (RN 6408-78-2), 7.93 g potassium hydroxide and 20 ml of N,N-dimethyl-ethanotamine is stirred at room temperature for 2 h. Then the reaction mixture is poured into 200 ml of water and the resulting precipitate is collected by filtration. The solid is stirred in 200 mi of water lor 30 min, then filtered off and dried under vacuum at 60C to obtain 1.69 g of the compound of formula step 2/0.50 g of the compound of formula (106a) and 0.29 g of the bis(totuolsulfonate) of (2-hydroxyethyl)-disulfide (RN 69981-39-1) are dissolved in 3 ml of NMP and stirred at 40°C for 72 h. Then the mixture is stirred for additional 72 h at SOX. Then the reaction mixture is dropped into 200 ml of tert-butyl-methyl-ether. The precipitate is separated by filtration, dissolved again in 3 ml of NMP and precipitated by dropping the solution into 50 ml tert-butyl-methyl-ether. After filtration the product is dried under vacuum to obtain 0.32 g of the compound of formula MS (ES+): m/z 332 (M+1). UVA/IS [nm] (water/acetonitrile 1:1):λmax 394. Step 2:1.28 g of the compound of formula (107a) and 0.726 g of bis(2-(2-bromoacetamido)-ethyl)-disulfide (RN 697755-79-6) are mixed in 5 ml dimethylformamide and stirred at 60°C for 24h. The reaction mixture is poured into 150 ml acetone under stirring. The precipitate is 2,0 g (8.1 mmol) of 4-chloro-3,5'dinitro benzoic acid are brought in 6ml acetone. 0.092g (8.1 mmol) of cysteamine hydrochloride dissolved in 10ml H2O is added to the resul¬ting solution. The pH value of this mixture is adjusted to 9 with 10 N sodium hydroxide. The reaction solution is stirred at room temperature under nitrogen atmosphere. The pH value is controlled in distinct intervals by addition of 10 N sodium hydroxide and adjusted to 9. After reaction time of 6h the mixture is acidified with 2 N HCI and the precipitate is filtered off. The filter cake is washed with HCi (10 N) and than with destilled water. The solid is recrystallized from water/acetone. 1.5g of a yellow-orange solid are obtained. Mp: 253-255°C. 5.66g (25.2 mmol) cystamin dihydrochloride are furnished in 40ml dimethylsulfoxide. 8.46g (lOO.8mmol) sodium hydrogen carbonate are added stepwise. Then 10.0g (50.4mmol)4-fluoro-3~nitrophenylacetamide, dissolved in 100ml dimethylsulfoxide are added dropwise at 45'C. The reaction mixture is stirred for 7h at SCC and cooled down to room temperature. The reaction mixture is placed on a water/ice mixture and adjusted to pH 3 by addition of cone. HCI. The resultant precipitate is filtered off, washed with water for several times and dried in vacuo. 12.4g (97%) of a red dye are obtained. Mp: 199-201°C. 20% hydrochloric acid. The obtained suspension is refluxed for 4h, whereupon the color of the reaction mixture changes from red to orange. Then the heterogenic reaction mixture is cooled down to room temperature and the pH is adjusted to 4 with 20% NaOH. The piecipiiate is filtered off and washed with 10% sodium hydrogen carbonate solution aiid then neutral with water. 3.5g (84%) of a violet dye are obtained. Mp.: 193-195"C I b. 34 g of the compound of formula (104a) and 30 g of the bis(toluolsuifonate) of (2--hydroxy-ethyl)-ciisulfide (RN 69981-39-1; prepared as described in Delacroix et al., Bull. Soc. Chim. France (1978), (9-10, Pt 2), 481-4) are suspended in 80 ml of NMP and stirred for 3 days at 45°C. Then 1 I tert.-butyl methyl ether are added slowly to the reaction mixture and the resul¬ting precipitate is collected by filtration. Then the crude product is redissolved in 200 ml ethanol and precipitated again by addition of 150 ml of tert.-butyl methyl ether. The solid is collected by filtration and dried in vacuo to yield 22.6 g of an orange powder which corresponds to the compound of formula (104). MS (ES+): m/z 326 (M2+). UVA/IS [nm] (water): λmax 466. (ai) Condensation 300 ml of chloroform are added to the reaction vessel. 10.5g rhodamine B are introduced with mixing. The equivalent amount (1.54g) of 2,2-dithlodiethanol, 12.0 g dicyclohexylcarbodiimide and a catalytical amount (7.6g) of pyrolidinopyridine are added. The reaction mixture is stirred for 24h at 293°C. The reaction product is separated by washing with 100 ml of a 3% hydrochloric acid solution then with 100ml water with 3% salt. The solution is evaporated to dryness in vacuum to obtain 12g of a reddish blue solid product. (a) Condensation 300 ml chloroform are added to the reaction vessel. 10.5g raw material are introduced with mixing, the equivalent amount (1.54g) of 2,2-dithio- diethanol, 12.0g dicyclohexylcarbodiimide and a catalytical amount (7.6g) of pyrolidinopyridlne are added. The reaction mixture is stirred for 24h at 293'C. The reaction product is separated by washing with 100 ml of a 3% hydrochlonc acid solution, then with 100 ml water with 3% salt. The solution is evaporated to dryness in vacuum to obtain 12g of a reddish blue solid product. 300 ml chloroform are added to the reaction vessel. 10.5 g rhodamine G are introduced with mixing, the equivalent amount (1.54g) 2,2-dithiodi- ethanol ,12.0g dicyclohexylcarbodiimide and a catalytical amount (7,6g) pyrolidinopyridine are added and the reaction mixture is stirred for 24h at 293'C. The reaction product is separated by washing with 100 ml of a 3% hydrochloric acid solution, then with 100 ml water with 3% salt. The solution is evaporated to dryness in vacuum to obtain 12g of a reddish blue solid product. (a) Alkylating agent A mixture of 15.4g 2,2-dithiodiethanoI in 100 ml chloroform and 241g pyridine are cooled with stirnng to 0°C. 22.Og mesyl chloride are added in small amounts, maintaining the temperature by cooling externally. After completion of the addition the mixture is left over night in the refrigerator to finish the reaction. The reaction mixture is mixed with a water/hydrochloric acid and ice slurry, the phases are separated, washed with water and dried. The solution of methanesulfonate diester used for reaction step (b). (b) Alkylation The reaction mixture of 250 g water and 103g of the xanthene precursor obtained in reaction step (a) is adjusted to pH 9.2 with sodium carbonate. 80ml toluene and the equivalent amount (32.0g) of diester and a catalytical amount (0.6g) of tetrabutyl-ammonium bromide are added and the reaction mixture is stirred for 6 hours at 300 K. Tne reaction product is heated to 350 K, the lower water phase is separated, the upper toluene phase washed, then 160 ml water are added and toluene distillated. The precipitate is separated by filtration and dried in vacuum to obtain 90g of-an orange solid product The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/360MHz (a) Condensation 300ml chloroform are added to the reaction vessel. 10.5g Pergascript Orange are introduced with mixing, the equivalent amount (1.54g) 2,2- dithiodiethanol and 12.0g dicyclohexylcarbodiimide and a catalytical amount (7.6g) of pyrolidinopyridine are added and the reaction mixture is stirred for 24h at 293°C. The reaction product is separated by washing with 100 ml of a 3% hydrochlohc acid solution, then with 100 ml water with 3% salt. The solution is evaporated to dryness in vacuum to obtain 12g of a reddish blue solid product. The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/360MHz Example QXA-Q1 (Procedure (a)): Step 1: 6.34g of 1-(3-methoxyphenyl)-piperazine dihydrochloride are suspended in 4 ml and cooled to 0- 5°C, 8.58g of a sodium methylate solution in methanol (1 mol methylate in 179.6 g solution) are added dropwise to this suspension, maintaining the temperature at 0 - 5°C. After completion of the addition the mixture is was stirred for 30min at room temperature. Finallv the solvent is removed by evaporation and the remaining brown oil is dissolved in 40ml dimethyl formamide. 6.58g bis (2-(2-bromoacetamide) ethyl disulfide (RN 697755-79-6) and 4.66 g potassium carbonate are added to this solution and the reaction mixture is stirred for 5 days at 40'C. Then the reaction mass is poured into 50 ml diethyl ether. The product precipitates as an oil, which is dissolved in 100ml dichloromethane and washed with a NaHCO3 solution. The organic phase is dried over sodium sulphate and filtered. Then the solvent is evaporated and the remaining oil is purified by column chromatography (acetone, silica) to obtain 0.64 g of compound of formula Step 2: 0.88g HBr (33%) are added drop wise to a suspension of 0.5g of the compound of formula (1o1a) in 2 g dimethyl formamide and 2.5 g water at 0 -- 5°C. After completion of the addition the yellow solution is warmed up to room temperature and 0.32g of an aqueous sodium nitrite solution (46 w.%) is added slowly. The reaction mixture is stirred at room temperature until the test on nitrite is negative (potassium iodide/starch paper). The dark reaction mixture was used for reaction step 3. Step 3: 0.27g 3-diethylaminophenol are dissolved in 3g dimethyl formamide and after addition of a few drops of HBr (33%) the solution is heated to 70°C, At this temperature the dark reaction mixture obtained in the nitrosation step is added via a dropping funnel over a period of 1h. The resulting blue solution is stirred for an additional hour, then cooled to room temperature and poured into 200 ml of acetone. as a dark blue powder, which can be used for the dyeing of hair. MS (ES+): m/z 453 (M'); UV/VIS ( water): λnax1, 642nm, λmax2 588nm. Example OXA-02 (Procedure (b)): Step 1: A solution of 7.58g of 3-diethylamino-anisole in 37g dimethyl formamide and 45g water is cooled to 0°C. Then 19.5g HBr (33%) are added via a dropping funnel over a period of 1h. during which time the temperature is nsing to 15°C. Then 7.04g of an aqueous sodium nitrite solution (46 % b.w.) is added dropwise over a period of 30min. The reaction mixture is stirred at room temperature until the test on nitrite is negative (potassium iodide/starch paper). The resulting dark solution is used forstep 2. Step 2: A solution of 6.68g 1-(3-hydroxyphenyl) piperazine and 9g HBr (33%) in lOg dimethyl formamide is heated to 70°C. At this temperature the dark solution obtained in step 1 s added via a dropping funnel over a period of 2.5h. The resulting blue solution ios stirred for an additional hour, then cooled to room temperature and poured into 300 ml of acetone. The precipitate is collected by filtration and stirred in 100ml of refluxing acetone two times before it is filtered off and dried In vacuo to obtain 6.97g of the compound of formula MS (ES+): m/z 337 (M'-l); UVA/IS ( water): λmax1 634nm, λmax2 590nm. Step 3: A solution of 0.5g of the compound of formula (102a), 0.24g of bis(2-(2-bromo-acetamide)etnyl)-disulfide (RN 697755-79-6) and 0.08 g of potassium carbonate in SOrnI methanol is stirred at 40°C for 12h. After that time the solvent is removed by evaporation, the remaining solid is dissolved in 5 ml dimethyl formamide and this solution is dropped into 20ml of acetone. The resulting precipitate is collected by filtration and dried to obtain 0.23g of the compound of formula (OXA-101) as a dark blue powder, which can be used for the dyeing of hair. (a) Condensation 35.7g 1,3,3 trimethyl-2-methyleneHndoline are added to 60g acetic acid. The equivalent amount (35.Og) of 2-chloroethyl-methylamino-benzaldehyde is added and the reaction mixture stirred for 6h at 30-40'C, The reaction product is precipitated by cooling, diluted with 375ml water and salted out with 40g sodium chloride, then separated by filtration and dried in vacuum to obtain 65g of a reddish violet solid product. The product is recristallized twice from methanol. (c) Hydrolysis One equivalent (4,0g) sodium hydroxide is dissolved with absolute ethanol as solvent in the compound (101b) as obtained in step (b). The temperature is maintained at 80°C during the following 4 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dryed in vacuum dryer. (a) Alkvlation One equivalent (6.0 g) of thiourea is dissolved with absolute ethanol as solvent in 30 g of the alkylating dye of formula (101a)- The temperature is raised to reflux and maintained at 80°C during the following 48 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in vacuum dryer. One equivalent (14.0g) of ethyl xantogenate is dissolved with absolute ethanol as solvent in the alkylating dye of formula (101a). The temperature is raised to reflux andmaintained at 80°C during the following 8 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dryed in vacuum dryer. 94g dimethylsulfate are introduced into that mixture within one hour. The temperature is maintained at 333 K during the following 1.5 hours. (b) Condensation The equivalent amount (150.0g) 2-chloroethyl-methylamino-benzaldehyde, 250ml ethanol and a catalytical amount (9.6g) of pipehdine are added to the reaction mixture obtained in step (a) and the reaction mixture stirred for 8 hours at, The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 240g of an orange solid product. The product is recristallized twice from methanol. (c): One equivalent (6.0g) thiourea is dissolved with 75 ml absolute ethanol as solvent in 20g alkylating dye of formula (PRO--104a). The temperature is raised to reflux and maintained at 80°C during the following 48 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in the vacuum dryer One equivalent (8.0g) of potasium thioacetate is dissolved with absolute ethanol as solvent to 20g of the alkylating dye of formula (PRO-104a). The temperature is raised to reflux and maintained at 80°C duhng the following 4 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dned in the vacuum dryer. One equivalent (6.0g) thiourea is dissolved in absolute ethanolm the compound of formula (PRO-104a). The temperature is raised to reflux and maintained at SCC during the following 48 hours. The obtaiened product is dissolved in one equivalent (4.0 g) of sodium hydroxide with absolute ethanol. The temperature is maintained at 80°C during the following 4 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in the vacuum dryer. The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/ 360MHz One equivalent (14.0 g) of ethyl xanthogenate is dissolved with 75 ml absolute ethanol in 20 g of the compound of formula (PRO-104a). The temperature is raised to reflux and maintained at 80°C during the following 18 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in thevacuum dryer. The temperatureis raised to reflux andmaintained at 80°C during the following 36 hours. The product is crystallized by cooling to room temperature under mixing, then separated by filtration, washed and dried in the vacuum dryer. (a) Alkvlation 2-methyl-pyridine (68.8g) arere dissolved in 80ml absolute ethanol. The temperature is raised to 333 K. 94g dimethylsulfate are introduced in this mixture within one hour. The temperature is maintained at 333 K during the following 3h. fb) Condensation the equivalent amount (150g) 2-chloroethyl-methylamino-benzaldehyde, 250 ml ethanoi and a catalitical amount (9,6 g) piperidine are added to the reaction mixture obtained In step (a) and is stirred for 18 hours at 343 K. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 220g of an orange solid product of formula One equivalent (6,0 g) of thiourea is dissolved in the compound of formula (107a) with absolute ethanol. The temperature is raised to reflux andmaintained at 80°C during the following 48 hours. (d) Hvdrolvsis One equivalent (4.0g) sodium hydroxide is dissolved to the substance obtained in step (c) with absolute ethanol. The temperature is maintained at 80°'C during the following 4 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in the vacuum dryer. The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/360MHz (a) Alkylation 250g of 4-methyl-quinoline are dissolved in 80 ml absolute ethanol. The temperature was raised to 333 K. 94 g dimethylsulfate are introduced into this mixture within one hour. The temperature is maintained at 333 K during the following 2.5 hours. (b) Condensation The equivalent amount (1500g) of 2-chloroethyl-methylamino-benzaldehyde, 250 ml ethanol and a catalytical amount (9.6g) of piperidine are added to the reaction mixture obtained in step (a) and the reaction mixture stirred for 8 hours. The reaction product is precipitated by cooling, then separated by filtration and dned in vacuum to obtain 340g of an orange solid product of formula The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/ 360MHz and shows a complex spectra. Throught HPLC/MS the identity was proofed, obtaining a single peak with the mass of 337/339 dalton. (cj One equivalent (6.0g) thiourea is dissolved in 30 g of the the compound of formula (108a) with absolute ethanot. The temperature is raised to reflux andmaintained at 80°C during the following 48 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in vacuum dryer. The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/360MHz Throught HPLC/MS the identity was proofed, obtaining a single peak with the mass of 377 dalton The temperature is raised to reflux andmaintained at 80°C during the following"48 hours. (b) Hydrolysis One equivalent (4.0g) sodium hydroxide is dissolved in the substance obtained in step (a) with absolute ethano. The temperature is maintained at 80°C during the following 4 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in the vacuum dryer. Throught HPLC/MS the identity was proofed, obtaining a single peak with the mass of 333 dalton (a) Alkylation 250 g 2-methyl-qu!noline are dissolved in 80 ml absolute ethanol. The temperature is raised to 333 K. 94g dimethylsutfate are introduced within one hour into that mixture. The temperature is maintained at 333 K during the following 2.5 hours. (b) Condensation The equivalent amount (150.0g) of 2-chloroethyl-methylamino-benzaldehyde, 250 ml ethanol and a catalytical amount (9.6g) of piperidine are added to the reaction mixture obtained in step (a) and the reaction mixture stirred for 8 hours. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 340g of an orange solid product of formula compound of formula (PRO-110;. The product is recristallized twice from methanol. The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/360MHz gle One equivalent (6.0g) thiourea is dissolved in 30g of the compound of formula (PRO-112a) with absolute. The temperature is raised to reflux and maintained at 80°C during the following 48 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in vacuum dryer. Throught HPLC/MS the identity was proofed, obtaining a single peak with the mass of 334 datton A mixture of 15.4 g 2,2-dithiodiethanoi in 100 ml chloroform and 24.1 g pyridine are cooled with stirring to 0°C and then 41.0 g of tosyl chloride are added in small amounts, maintaining the temperature. After completion of the addition the mixture is left over night in the refrigerator and the reaction is finished. The reaction mixture is mixed with a water/hydrochloric acid and ice slurry, the phases are separated, washed with water and dried. The solution of totuenesulfonate diester is used for steb (b). (b) Alkylation The alkylation agent obtained in step (a) is freed from the solvent and dissolved in two equivalent amounts of 2-methyl-pyridine. The temperature is raised to 60°C andmaintained at 60°C during the following 24 hours. (c) Condensation 50 ml dimethyl-formamide are added to the reaction mixture obtained in step (b). The equivalent amount of 2-chloroethyl-methylamino-benzaldehyde and a catajytical amount of piperidine are added and the reaction mixture is stirred for 40 hours at 80'C. The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 39g of an orange solid product. The product is recristallized twice from isopropanol. (e) Hydrolysis One equivalent (4,0 g) of sodium hydroxide is dissolved with absolute ethanol as solvent in the substance of step (d). The temperature is maintained at 80°C during the following 4 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in the vacuum dryer. a. Alkylating agent A mixture of 15.4g of 2,2-dithiodiethanol in 100 ml chloroform and 24.1g pyndine are cooled with stirring to 0°C. 41,0 g of tosyl chloride are added in small amounts, maintaining the temperature. After completion of the addition the mixture is left over night in the refrigerator to finish the reaction. The reaction mixture is mixed with a mixture of water/hydrochloric acid and ice slurry, the phases are separated, washed with water and dried. The solution of toluenesulfonate diester is used as starting compound in step b. b. Alkylation The alkylation agent obtained in step a. is delivered from the solvent and dissolved in two equivalent amounts of 2-methyl-pyridine. The temperature is raised to 60°C and maintained at 60°C during the following 24 hours. c. Condensation 50 ml of dimethyl-formamide are added to the reaction mixture obtained in step b. The equivalent amount of dimethylamlno-benzaldehyde and a catalytical amount of piperidine are added and the reaction mixture is stirred for 40 hours at 80°C. The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to obtain 39 g of an orange solid product. The product is recristallized twice from isopropanol. The product is characterized by the following data: - The HPLC-MS gives a main component of a monocation of the mass 283. - 1H-NMR data in deuterated chloroform (128 scans)/ 360MHz: a. Alkylating agent A mixture of 15.4g of 2,2-dithiodiethanol in 100 ml chloroform and 24.1g pyridine are cooled with stirhng to O°C and then 41.0 g of tosyl chloride are added in small amounts, maintaining the temperature. After completion of the addition the mixture is left over night in the refrigerator to finish the reaction. The reaction mixture is mixed with a mixture of water/hydrochloric acid and ice slurry, the phases are separated, washed with water and dried. The solution of toluenesulfonate diester is used as starting compound in the step b. b.Alkylation The alkylation agent obtained in step a. is delivered from the solvent and dissolved in two equivalent amounts of 2-methyl-pyridine. The temperature is raised to 60°C and maintained during the following 24 hours. c. Condensation 50 ml of isopropanol are added to the reaction mixture obtained in step b. The equivalent amount of anisaldehyde and a catalytical amount of anhydrous sodium acetate are added and the reaction mixture is stirred for 40 hours at 80°C. The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to obtain 29 g of a yellowish solid product. The product is recristallized twice from isopropanol. The product is characterized by the following data: - The HPLC-MS gives a main component of a monocation of the mass 270. - 1H-NMR data in deuterated methanol128 scans)/ 360MHz: a. Alkylating agent A mixture of 15.4g of 2,2-dithiodiethanol in 100 ml ethylene and 24.1g pyridine are cooled with stirring to 0°C and then 41.0 g of tosyl chloride are added in small amounts maintaining the temperature. After completion of the addition the mixture is left over night in the refrigerator to finish the reaction. The reaction mixture is mixed with a mixtue of water/hydrochloric acid and ice slurry, the phases are separated, washed with water and dried. The solution of toluenesulfonate diester is used as starting compound in step b. b.Alkylation The alkylation agent obtained in step a. is delivered from the solvent and dissolved in two equivalent amounts of 2-methyl-pyhdine. The temperature is raised to 70°C and maintained during the following 24 hours. c. Condensation 50 ml of toturnr are added to the reaction mixture obtained in step b. The equivalent amounts of amino-benzaldehyde and a catalytical amount of piperidine are added and the reaction mixture is stirred for 30 hours at 80°C. The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to obtain 41 g of an orange solid product. The product is recristallized twice from isopropanol. a. Alkylating agent A mixture of 15.4g of 2,2-dithiodiethanol in 100 ml chloroform and 24.1 g pyridine are cooled with stirring to O°C. 41.0 g of tosyl chtoride are added in small amounts maintaining the temperature-After completion of the addition the mixture is left over night in the refrigerator to finish the reaction. The reaction mixture is mixed with a mixture of water/hydrochloric acid and ice slurry, the phases are separated, washed with water and dried. The solution of toluenesulfonate diester is used as starting compound in step b. b. Alkylation The alkylation agent obtained in step a. is delivered from the solvent dissolved in two equivalent amounts of 2-methyl-pyridine. The temperature is raised to 60X and maintained during the following 24 hours. c. Condensation 50 ml of isopropanol are added to the reaction mixture obtained in step b. The equivalent amounts of 4-fluoro-benzaldehyde and a catalytical amount of piperidine are added and the reaction mixture is stirred for 30 hours at 70°C. The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to obtain 35g of a yellow solid product. The product is recristallized from isopropanol. a. Alkylating agent A mixture of 15.4g of 2,2-dithiocliethanol in 100 ml chloroform and 24.1g pyridine are cooled with stirring to 0°C and then 31.0 g of mesyl chloride are added in small amounts, maintaining the temperature. After completion of the addition the mixture is left over night in the refrigerator to finish the reaction. The reaction mixture is mixed with a mixture ofwater/hydrochloric acid and ice slurry, the phases are separated, washed with water and dried. The solution of methanesulfonate diester is used as starting compound in the step b. b. Alkylation The alkylation agent obtained in step a. is freed from the solvent and dissolved in two equivalent amounts of 2-methyl-pyridine. The temperature is raised to 60°C and maintained during the following 24 hours. c. Condensation 50 ml of dimethyl-formamide are added to the reaction mixture obtained in step b. The equivalent amount of benzaldehyde and a catalytical amount of piperidine are added and the reaction mixture is stirred for 40 hours at 80°C. The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to obtain 33 g of a yellow solid product. The product is recristailized twice from isopropanol. The product is characterized by the following data: - The HPLC-MS gave a main component of a monocation of the mass 240. - 1H-NMR data in deuterated Methanole (128 scans)/ 360MHz: a. Alkylating agent A mixture of 15.4g of 2,2-dithiodiethanol in 100 ml chloroform and 24.1g pyridine are cooled with stirring to 0°C and then 31.Og of mesyl chloride are added in small amounts, maintaining the temperature. After completion of the addition the mixture is left over night in the refrigerator to finish the reaction. The reaction mixture is mixed with a mixture of water/hydrochloric acid and ice slurry, the phases are separated, washed with water and dhed. The solution of methanesulfonate diester is used as starting compound in step b. b. Alkylation The alkylation agent obtained in step b. is delivered from the solvent dissolved in two equivalent amounts of 2-methyl-pyridine. The temperature is raised to 60°C and maintained during the following 24 hours. c. Condensation 50 ml of dimethyl-formamide are added to the reaction mixture obtained in step b. The equivalent amount of acetylamino-benzaldehyde and a catalytical amount of pipehdine are added and the reaction mixture is stirred for 40 hours at 80°C. The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to obtain 44 g of a brown solid product. The product is recristallized twice from isopropanot. The product is characterized by the following data: - The HPLC-MS gave a main component of a monocatlon of the mass 297. - 1H-NMR data in deuterated methanol (128 scans)/ 360MHz: These three compositions (b-1) - (b-3) are applied to hair according to the following the general procedure: A tress of bleached human hair is shampooed. Then the towel dried hair tress is put on the glass plateThe solution (B-1) (permanent solution) is applied to the wet hair tress. After 10 min the hair tress is rinsed under tap water and pressed out with a paper towel. Afterwards the tress is treated with a solution (B-2) containing the dye mixtures described in table 2 for 20 min and then rinsed with water. Then solution (B-3) (permanent fixation) is applied to the towel dhed hair tress. After 10 min. the hair tress is rinsed under tap water again and dried. The color result for each dye mixture is given in tables 2 and 3, In general all tresses showed an intense coloration and a very good wash fastness. Claims_: 1. Mixture of dyes selected from the compounds of formula (1) D—(Zi)r-Y1—S—A, wherein A is hydrogen; a radical of formula (1a) —s—Y2—(Z2)—D2 ; or a thio ester group of wherein the the mixture comprisies at least two compounds of formula (1), and/or at least two compounds of formula (2) and/or at least one compound of formula (1) and at least one compound of formula (2), wherein R1, R2 and R3 independently from each other hydrogen; halogen; C1-C16alkyl, which is saturated or unsaturated, linear or branched, substituted or unsubstituted, or interrupted or uninterrupted with heteroatoms; phenyl, which substituted or unsubstituted; a carboxylic acid radical; sulfonic acid radical; hydroxy; nitrile; CrCiealkoxy, (poly)-hydroxy- C2-C4-alkoxy; halogen; SO2NR33R34; SR33; NR33R34; OR33; SO2; COOR33; NR33COR34; or CONR33; Q1 is a bivalent radical selected from -N=N-; -CRd=N-; -N=CRd-; -NRd-N=CRe-; and -RdC=N'NRe-; T1 is a bivalent radical of an aromatic or heteroaromatic substituted or unsubstituted compound; Rd and Re independently from each other are hydrogen; unsubstituted or substituted Cr C14alkyl: C2-C14alkenyl; C5-C10aryl; C1-C1oaikyl-C5-C10aryl; or C5-C10aryl-C1-C10oalkyl; R33 and R34 independently from each other are hydrogen; C1-C12alkyl, which may be substituted by one or more C1-C5alkyI, C1-C5-alkoxy, hydroxy or -(CO)"H; -(C0)-C1-C5alkyl; phenyl or phenyl-C1-C4alkyl, wherein the phenyl moiety may be substituted by one or more C1-C5alkyl, C1-C5alkoxy, halogen, -NH2, monO'Ci- C5alkylamino, di-C1-C5alkylannino, 'NO2, carboxy or hydroxy; R4, R5 and R6 independently from each other are hydrogen; C1-C20alkyI or C1-C20alkoxy, which may be substituted by one or more C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5alkylamino, -NO2 or hydroxy; C3-C6cycloaikyj; -C(0)H; -C(0)-C1-C5alkyl; halogen; NO2; OH; phenyl, which may be substituted by one or more C1-C5alkyl. C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkyiamino, di-C1-C5alkylamino, -NO2 or hydroxy; or a radical of formula -NR35R36; W1, W2, W3, and W4, independentlay from each other are -CH- or -N+-; wherein only one of Wi, W2, W3 or W4 is -N"; and the radical -(Zi)r-YrS-A is bonded to Wi or W2; R35 and R36 independently from each other are hydrogen; C1-C102alkyl, which may be substituted by one or more C1-C5alkyI, C1-C5-alkoxy. hydroxy or -(CO)-H; -(C0)-C1-C5alkyl; phenyl or phenyl-C1-C4alkyl, wherein the phenyl moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, -NH2, mono-Ci- C5alkyJamino, di-C1-C5alkylamino, -NO2, carboxy or hydroxy; R7 R8. R9 and R10 independently from each other are hydrogen; C1-C20alkyl; C1-C20alkoxy; C3- X?, X3 and X4 independently from each other are C1-C10 alkylene; -(CO)-CrCi8alkylene'CrCi8arylene; C6-C18arylene-C1-C12alkylene; or -(OCH2CH2)n-0-; t is 0; or 1 R37 is hydrogen; or C1-C2oalkyl; R38. R39 and R40 independently from each other are hydrogen, C1-C20alkyl, C4-Ci2cycloalkyl, C6-C13aralkyI; phenyl-C1-C5alkyl; or R38 and R39 together with the linking nitrogen atom form a C4-C12-membered heterocyclic ring which may be interrupted by one or more than one -O- or -NH- goups; n1 is is 0 or 1; p is 0; or 1; s isO;or1; t is 0; or 1; u is 0 or 1; R11, R12 and R13 independently from each other are hydrogen; C1-C20alkyl or Ci-Caoalkoxy, which may be substituted by one or more C1-C5alkoxy, halogen, -NH2. mono-d-C5lkylamino, di-C1-C5alkylamino. -NO2 or hydroxy; C3-C6cycloalkyI; -C(0)H; -C(0)-Cr CsBlkyl; "C(0)OH; -C(0)0-C1-C5alkyl; halogen; NO2; OH; SH; phenyl, which maybe substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, -NH2, mono-Ci-C5alkylamino, di-C1-C5alkylamino, -NO2 or hydroxy; or a radical -NR41R42; Q3 is is -C(0)-; -C(0)0-; -OCO-; -N(Ri)-X5-; -CON(Ri)-; -(Ri)NC(O)- -0-; -S-; ^S(O)-; or -S(0)2- heteroaromatic group; R,, Rk, Ri independently from each other are CrCualkyI; Ca-Cualkenyl; C6-C10aryl; C6-C10aryl-Ci"Cioalkyl; or C1-C10oalkyl(C5-C10aryl); R41 and R42 independently from each other are hydrogen; C1-C12alkyl, which may be substituted by one or more C1-C5aJkyl, C1-C5-alkoxy, hydroxy or -(CO)-H; -(CO)-Ci-Csalkyl; phenyl or phenyl-Ci'-C4aIkyl, wherein the phenyl moiety may be substituted by one or more CrCBalkyI, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-Ci- at least one of the radicals R11, R12 or R13 is NO2; R43, R44 and R45 independently from each other are hydrogen; C1-C104alkyl; C2-C14aikenyl; Ce- Ciosryl; C6-C10aryl-C1-C10alkyl; or C1-C10oalkyl(C5-C10aryl); X5 and X6 independently from each other are the direct bond; C1-C10alkylene; C5- C10cycloalkylene; C5-C10aryjene; or C5-C10arylene-(C1-C10oalkylene); R14 IS N R46R47! R46 and R47 independently from each other are hydrogen; C1-C102alkyl; or phenyl-C1-C4alkyl; or R46 and/or R47 are a bivalent C3-C6alkylene radical which is linked to the carbon atoms C^ or C^ in formula (1e) respectively and, together with the linking nitrogen atom form a 6 to 16- membered carbocyclic ring; Ri5 is is NR48R49; or OR48; R48and R49, independently from each other are hydrogen; C1-C12alkyl; or phenyl-C1-C4alkyl; or R48and R49 are a bivalent C3-C6alkylene radical which is linked to the carbon atoms C^ or C"* in formula (1e) respectively and, together with the linking nitrogen or oxygen atom form a 6 to 16-membered carbocyclic ring; or R48and R49 together with the linking nitrogen atom form a 4 to 8 membered carbocyclic ring; R16, R17, R181 R19 and R20 independently form each other are hydrogen; C1-C102alkyl; halogen; V1 is -0-; or--NR53: R52 and R53 independently from each other are hydrogen; or C1-C5alkyl; Hal is a halogen atom; and wherein at least one of R16, R17. R18, R19 and R20 is hydrogen; B2 and B3, independently from each other are C6-C10aryl; or a 5-7-membered heterocyclic compound, which may be substituted by C1-C12alkyl, C1-C102alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or by the radical -NR54R55 or -OR56; B4 is C8-C10arylene, or a bivalent radical of a 5-7-membered heterocyclic compound, which may be substituted by C1-C12alkyl, C1-C12alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or by the radical -NR54R55 or -OR56; R54 R55 and R56 independently from each other are hydrogen; or C1-C12alkyl, which may be substituted by hydroxy or C6-C10aryl; or R54 and R55 together with the linking nitrogen atom form a 5 to 7 membered heterocyclic ring; the asterix() is directed to Z1 or Z2 respectively; and the asterix() is directed to the linking nitrogen atom; R21 and R22 independently from each other are hydrogen; C1-C20alkyl; C1-C20alkoxy; C3- C6cycloalkyl; C5-C10aryl; anellated aromatic groups; carboxylate; or sulfonate groups; R23 R24 R25 and R26 each independently from each other are hydrogen; unsubstituted or substituted, straight-chain or branched, monocyclic or polycyclic, interrupted or uninterrupted C1-C104alkyl, C2-C14alkenyl, C6-C10aryl, C6-C10aryl-C1-C10oalkyI or C5-C10alkyl(C5-C10aryl); or R23 and R24 and/or R25 and R26 together with the linking nitrogen atom form a 5 to 7 membered carbocyclic ring which may contain one or more than one hetero atom; or R23 is linked to Ci together with N" forming a 5-7 membered carbocyclic ring; or R24 is linked to C2 together with N* forming a 5-7 membered carbocyclic ring; X7 is-0-; or-N(R24)-; or-S-; R27 is hydrogen; or C1-C5alkyl; a 6 to 10 membered carbocyclic ring which may optionally be a condensated aromatic system and may contain one or more than one hetero atom; R57, R58 and R59 independently from each other are hydrogen; or C1-C5alkyl; R29, R30, R31 and R32 independently from each other are hydrogen; hydroxy; -S-H; -S-Ci-Ci2alkyl; halogen; C1-C102alkyl or C1-C102alkoxy, which may be substituted by one or more C1-C5alkyl, C1-C5-alkoxy, hydroxy, -(CO)-H or -(C0)-C1-C5alkyl; -NRegRro; -NO2; -(CO)H or (CO)-C1-C5alkyi; C6-C12aryl, C6-C12aryl-C1-C4alkyl or C6-C12aryl-C1-C4alkoxy, wherein the aryt moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, -(CO)-H or -(CO)-C1-C5alkyl; -NR69R70; -NO2; -(CO)-H; or -(COKi-Cgalkyl; R69 and R70 independently from each other are hydrogen; hydroxy; C1-C102alkyl; hydroxy-Cr C12alkyl; -(CO)-H; -(C0)-C1-C5alky(; phenyl or phenyl-C1-C5alkyI, wherein the phenyl moiety may be substituted by one or more C1-C5alkyl, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5alkylamino, -NO2, carboxy or hydroxy; Y1 and Y2 independently from each other are unsubstituted or substituted, straight-chain or branched, interrupted or uninterrupted C1-C10alkylene; C5-C10cycloalkylene; C5-C10arylene; or-C5-C10arylene-(C1-C10alkylene); the asterix indicates the linkage to Di and/or D2; the asterix ** indicates the linkage to Yi and/or Y2; R60, R61,, R62, R63 and R64 independently from each other are hydrogen; C1-C14alkyl; C2-C14alkenyl; C6-C10aryl; C5-C10aryl-(C1-C10alkyl); or-C1-C10oalkyl(C5-C10aryl); R29, R30. R31 and R32 independently from each other are hydrogen; hydroxy; -S-H; -S-C1-C12alkyl; halogen; C1-C12alkyl or C1-C12alkoxy, which may be substituted by one or more C1-C5alkyl, d-Cg-alkoxy, hydroxy, "(CO)-H or -(C0)-C1-C5alky(; -NR85R66; -NO2; -(CO)H or (C0)-C1-C5alkyl; C6-C12aryl, C6-C12aryl-C1-C4alkyl or C6-C12aryl-C1-C4alkoxy, wherein the aryt moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, -(CO)-H or-(C0)-C1-C5alkyl; -NR67R68; "NO2; -(CO)-H; or-(CO)-C1-C5alkyl; R65, R66.R67 and R68 independently from each other are hydrogen; hydroxy; C1-C102alkyl; hydroxy-C1-C12alkyl; -(CO)-H; -(C0)-C1-C5alkyl; phenyl or phenyl-C1-C5alkyI, wherein the phenyl moiety may be substituted by one or more C1-C5aikyl, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5aikylamino, -NO2, carboxy or hydroxy; q is a number from 0 to 5; w is a number from one to 5; r is 0; or 1; and An is an anion. 2. Mixture according to claim 1, wherein Y1 and Y2 are C1-C5alkylene. An is an anion; and Yi is defined as in claim 1. 7. Mixture according to claim 1, wherein the dyes are selected from the compounds of formula one of W1 or W2 is -N"-. the other is -CH; and the biradical .—(Z1),.Y1.S-S2 Y,-(Z,)-* is bonded to -N+ and R4, R5, R6. Y1, Y2, Z1 and r are defined as in claim 1. 8. Mixture according to claim 7, wherein the dyes are selected from the compounds of formula 9. Mixture according to claim 1, wherein the dyes are selected from the compounds of formula R11, R12 and R13, independently from each other are hydrogen; C1-C5alkyI; -C(0)H; -C(0)-C1-C5alkyl; -C(0)OH; -C(0)0-CrC5alkyl; NO2; or-NH(CO)-CH3; Yi is C1-C10alkylene; C5-C10cycloalkylene; C5-C10arylene; or C5-C1arylene"(C1-C10alkylene); R,and Rk each independently from each other are hydrogen; C1-C14alkyl; C2-C14alkenyl; C6-Cioaryl; C6-C10aryl-C1-C10alkyI; or C1-C10alkyl(C5-C10aryl). 11. Mixture according to claim 1, wherein the dyes are selected from the compounds of Rm is C1-C12alkyl, C1-C12alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or the radical -NRnRo or -ORni and Rn, Ro, B1 and B2 are defined as in claim 1. R31 is hydrogen; C1-C5-alkoxy; halogen; or -NRpRq, wherein Rp and Rq, independently from each other are hydrogen; C1-C12alkyl; -(CO}-H; or -(CO)-Ci-C5alkyl; and An is an anion. 15. A method of dyeing keratin-containing fibers comprising treating the fiber with a mixture as defined in any of claims 1 to 14. 16. A method according to claim 16, wherein the dyeing is carried out in presence of a reducing agent. 17. A method according to claim 15 or 16, wherein the reducing agent is selected from thioglycol acid or salts therof, gycerine monothioglycolate, cystein, 2-mercaptopropionic acid, 2-mercaptoethylamine, thiolactic acid, thioglycerine, sodium sulfite, dithionithe, ammonium sulfite, sodium bisulfite, sodium metabisulfite and hydrochinon. 18. A method according to any of claims 15 to 17, comprising treating the keratin^containing fiber (a) optionally with a reduction agent, and (b) with a mixture of dyes as defined in claim 1, and (c) optionally with an oxidizing agent. 19. A composition comprising a mixture of dyes as defined in claim 1. 20. A composition according to claim 19 in form of a shampoo, conditioner, gel or emulsion, 21. A composition according to claim 19 or 20 comprising mixture of dyes as defined in claim 1 and a direct dye and/or a reactive dye.

Full Text

Mixture of sulfide dyes
The present invention relates to mixtures of sulfide dyes, compositions thereof, and to their use for the dyeing of organic materials, such as keratin fibers, wool, leather, silk, cellulose or polyamides, especially keratin-containing fibers, cotton or nylon, and preferably hair, more preferably human hair.
It is known, for example, from WO 95/01772 that cationic dyes can be used for the dyeing of organic material, for example keratin, silk, cellulose or cellulose derivatives, and also synthetic fibers, for example polyamides. Cationic dyes exhibit very brilliant shades. A disadvantage is their unsatisfactory fastness to washing.
The technical problem is to provide dyes that are distinguished by deep dying having good fastness properties with respect to washing, light, shampooing and rubbing.
Accordingly, the present invention relates to a dye composition comprising a mixture of dyes selected from the compounds of formula (1) D^—(Z^)^—Y^—S—A , wherein

wherein the the mixture comprisies at least two compounds of formula (1), and/or at least two compounds of formula (2) and/or at least one compound of formula (1) and at least one compound of formula (2), wherein R1, R2 and R3 independently from each other hydrogen; halogen; C1-C16alkyl, which is
saturated or unsaturated, linear or branched, substituted or unsubstituted, or interrupted

or uninterrupted with heteroatoms; phenyl, which substituted or unsubstituted; a
carboxylic acid radical; sulfonic acid radical; hydroxy; nitrile; C1-C16alkoxy, (poly)-hydroxy-
C2-C4-alkoxy; halogen; SO2NR33R34: SR33; NR33R34; OR33; SO2; COOR33; NR33COR34; or
CONR33; Q1 is a bivalent radical selected from -N=N-; -CRd=N-; -N=CRd-; -NRd-N=CRe-; and
-RdC=N-NRe-; Ti is a bivalent radical of an aromatic or heteroaromatic substituted or unsubstituted
compound; Rd and Re independently from each other are hydrogen; unsubstituted or substituted C1-
C14alkyl; C2-C14alkenyl; C5-C10aryt; C1-C10alkyl-C5-C10aryl; or C5-C10aryl-C1-C10alkyl; R33 and R34 independently from each other are hydrogen; C1-C12alkyl, which may be
substituted by one or more C1-C5alkyI, C1-C5-alkoxy, hydroxy or -(CO)-H;
-(C0)-CrC5alkyl; phenyl or phenyl-CrC4alkyl, wherein the phenyl moiety may be
substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, •'NH2, mono-Cr
C5alkylamino, di-C1-C5alkylamino, -NO2, carboxy or hydroxy; R4, R5 and R6 independently from each other are hydrogen; C1-C2oalkyl or C1-C2oalkoxy, which
may be substituted by one or more C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino,
di-C1-C5aikylamino. -NO2 or hydroxy; C3-C6cycloalkyl; -C(0)H; -C(0)-C1-C5alkyl; halogen;
NO2; OH; phenyl, which may be substituted by one or more C1-C5alkyI, C1-C5alkoxy,
halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5aikylamino, -NO2 or hydroxy; or a radical
of formula -NR35R36; W1, W2, W3, and W4, independentlay from each other are -CH- or -N*-; wherein only one of
W1. W2, W3 or W4 is -N*; and the radical *-(Zi)rYi-S-A is bonded to W1 or W2; R35 and R36 independently from each other are hydrogen; C1-C12alkyl, which may be substituted by one or more C1-C5alkyI, C1-C5-alkoxy, hydroxy or -(CO)-H: -(C0)-C1-C5alkyl; phenyl or phenyl-C1-C4alkyl, wherein the phenyl moiety may be substituted by one or more C1-C5alkyl, C1-C5alkoxy, halogen, -NH2, mono-d-

Rf, Rg and Rh independently from each other are hydrogen; C1-C-14alkyl; C2-C14alkenyl; C6-C10aryl; C6-C10aryl-C1-C10alkyI; or C1-C10alkyl{C5-Cioaryl);
X2, X3 and X4 independently from each other are C1-C18alkylene;
-(CO)-CrCi8alkylene-Ci-Ci8ary!ene; C6-C18arylene-C1-C12alkylene; or -(OCH2CH2)n-Os
t is 0; or 1
R37 is hydrogen; or C1-C20oalkyI;
R38, R39 and R40 independently from each other are hydrogen, C1-C20oalkyI, C4-Ci2cydoa!kyl, C6-C13aralkyI; phenyl-C1-C5alkyI; or R38 and R39 together with the linking nitrogen atom form a C4-C12-membered heterocyclic ring which may be interrupted by one or more than one -O- or -NH- goups;
n1 is is 0 or 1;
p isO;or1;
s isO;or1;
t isO;or1;
u isOorl;
R11, R12 and R13 independently from each other are hydrogen; C1-C2oalkyl or C1-C2oalkoxy. which may be substituted by one or more C1-C5alkoxy, halogen, -NH2, mono-Cr C5alkylamino, di-C1-C5alkylamino, "NO2 or hydroxy; Cs-CecycloalkyI; -C(0)H; -C(0)-Ci-C5alkyl; -C(0)OH; -C(0)0-C1-C5alkyl; halogen; NO2; OH; SH; phenyl which may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5atkylamino, 'NO2 or hydroxy; or a radical -NR41R42;
Q 3 is is -C(0)-; -C(0)0-; -0C0-; -N(R()-X5-; -CON(Ri)-; -(Ri)NC(O}-; -0-; -S-; -S(0)-; or -S(0)2-:

I
heteroaromatic group;
R„ Rk, Ri independently from each other are C1-C14alkyl; C2-Ci4alkeny!; Cg-Cioaryl; C6-C10aryl-C1-C10alkyl; or C1-C10alkyl(C5-Cioaryl);
R41 and R42 independently from each other are hydrogen; C1-C12alkyl, which may be substituted by one or more C1-C5alkyI, C1-C5-alkoxy, hydroxy or -(CO)-H; -(CO)-Ci-C5alkyl; phenyl or phenyl-C1-C4alkyl, wherein the phenyl moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy. halogen, -NH2, mono-C1-C5alkylamino, di-Cr

at least one of the radicals R11, R12 or R13 is NO2; R43 R44 and R45 independently from each other are hydrogen; Ci-C^alkyl; C2-Ci4alkenyl; Ce-
C10aryl; C6-C10aryl-C1-C10alkyl; or C1-C10alkyl(C5-Cioaryl); X5 and X6 independently from each other are the direct bond; C1-C10alkylene; C5-
Ciocycloalkylene; C5-C10arylene; or C5-Cioarylene-(C1-C10alkylene); R-14 is N R46R47;
R46 and R47 independently from each other are hydrogen; C1-C12alkyl; or phenyl-C1-C4alkyl; or R46 and/or R47 are a bivalent Ca-Cgalkylene radical which is linked to the carbon atoms C^ or
C^ in formula (1e) respectively and, together with the linking nitrogen atom form a 6 to 16-
membered carbocyclic ring;
R15 is is NR4eR49; or OR48;
R48and R49, independently from each other are hydrogen; C1-C12alkyl: or phenyl-C1-C4alkyl; or
R48and R49are a bivalent C3-C6alkylene radical which is linked to the carbon atoms C3 or C^ in
formula (1e) respectively and, together with the linking nitrogen or oxygen atom form a 6
to 16-membered carbocyclic ring; or R4e and R49 together with the linking nitrogen atom form a 4 to 8 membered carbocyclic hng;

R52 and R53 independently from each other are hydrogen; or C1-C5alkyt;
Hal is a halogen atom; and wherein at least one of R16, R17, R18. R19 and R20 is hydrogen;
B2 and B3, independently from each other are C6-C10aryl; or a 5'7-membered heterocyclic
compound, which may be substituted by C1-C12alkyl, C1-C12alkoxy, phenyl, hydroxy,
halogen, sulfonic acid, carboxylate, or by the radical -NR54R55 or -ORse; B4 is C6-C10arylene, or a bivalent radical of a 5-7-membered heterocyclic compound, which
may be substituted by C1-C12alkyl, C1-C12alkoxy, phenyl, hydroxy, halogen, sulfonic acid,
carboxylate, or by the radical -NR54R55 or -OR56; R54 R55 and R56 independently from each other are hydrogen; or C1-C12alkyl, which may be
substituted by hydroxy or C6-C10aryl; or R54 and R55 together with the linking nitrogen atom form a 5 to 7 membered heterocyclic ring;

the asterix(*) is directed to Zi or Z2 respectively; and
the asterix(**) is directed to the linking nitrogen atom;
R21 and R22 independently from each other are hydrogen; C1-C2oalkyl; C1-C2oalkoxy; C3-
C6cycloalkyI; C5-Cioaryl; anellated aromatic groups; carboxylate; or sulfonate groups; R23, R24 R25 and R26 each independently from each other are hydrogen; unsubstltuted or
substituted, straight-chain or branched, monocyclic or polycyclic, interrupted or
uninterrupted C1-C14alkyI, C2-C14alkenyl, C6-C10aryl, C6-C10aryl-C1-C10alkyl or
C5-Cioalkyl(C5-Cioaryl); or R23 and R24 and/or R25 and R26 together with the linking nitrogen atom form a 5 to 7 membered
carbocyclic ring which may contain one or more than one hetero atom; or R23 is linked to C1 together with N"" forming a 5-7 membered carbocyclic ring; or R24 is linked to C2 together with N"" forming a 5-7 membered carbocyclic ring;

a 6 to 10 membered carbocyclic ring which may optionally be a condensated aromatic system and may contain one or more than one hetero atom;
R57, R58 and R59 independently from each other are hydrogen; or C1-C5alkyI;
R29. R30- R31 and R32 independently from each other are hydrogen; hydroxy; -S-H; -S-Ci-C12alkyl; halogen; C1-C12alkyl or C1-C12alkoxy, which may be substituted by one or more C1-C5alkyI, C1-C5-alkoxy, hydroxy, -(CO)-H or-(CO)-C1-C5alkyl; -NRegR/o; -NO2; -(CO)H or (C0)-C1-C5alkyl; C6-Ci2aryl, C6-Ci2aryl-Ci-C4alkyl or C6-Ci2aryl-CrC4alkoxy, wherein the aryl moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy. -(CO)-H or -(C0)-C1-C5alkyl; -NR69R70; -NO2; -(CO)-H; or-(C0)-C1-C5alkyl;
R69 and R70 independently from each other are hydrogen; hydroxy; C1-C12alkyl; hydroxy-Ci-C12alkyl; -(CO}-H; -(C0)-C1-C5alkyl; phenyl or phenyl-C1-C5aikyi, wherein the phenyl moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5aikylamino, -NO2, carboxy or hydroxy;
Y1 and Y2 independently from each other are unsubstituted or substituted, straight-chain or branched, interrupted or uninterrupted C1-C10alkylene; C5-C10cycloalkylene, C5-C10arylene; or-C5-Cioarylene-(C1-C10alkylene);

q is a number from 0 to 5;
w is a number from one to 5;
r is 0; or 1; and
An is an anion.
C1-C12alkyl is for example, methyl, ethyl, propyl, isopropyl, n-butyl sec-butyl, tert-butyl, n-pentyl, 2'pentyl, 3-pentyl, 2,2'-ciimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1 1,3,3'-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl,.

C1-C12alkylene is for example methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, n»pentylene, 2-pentylene. 3-pentylene or 2,2'-dimethylpropylene, n-hexylene, n-octylene, 1,1',3,3'"tetramethylbutylene, 2-ethylhexylene, nonylene, decylene, undecylene or dodecylene.
Alkylene may be straight-chain, branched, or, from CsalkyI upwards, monocyclic or polycyclic, and may be interrupted by hetero atoms, such as such as O, S, -CO- N, NH, NR54, -OCO-, -C0(0R4)-, -CONR4-, -(R5)NC(0)-; for example C1-C10alkylene may be a resisue such as: -CH2CH2-O-CH2CH2-O-CH2CH2-. -CH2CH2-O-CH2CH2--CH2CH2-O-CH2-, -CH2-0'CH2-. -CH2CH2-CH2CH2-0-'CH2-CH2-,-CH2CH2-CH(N(CH3)2)-CH2-CH2-, CH2-NH2-CH2-CH2-, -CH2CH2-NH-CH2CH2-, -CH2CH2-NCH3-CH2CH2-, -CO-CH2-. -CH2CO-, -CH2CH2-NHCO-CH2CH2^-CH2CH2-CONH-CH3-CH2CH2-,-CH2CH2-NCH3CO-CH2CH2-. -CH2CH2-CONCH3-CH3-CH2CH2-.-CH2-NHCO-CH2CH2-,-CH2CH2-NHCO-CH2-, -CH2CH2-CONH-CH2- or -CH2-CONH-CH2CH2-.
C5-C10cycloalkylene is for example cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene or cyclodecylene.
C5-C10arylene is for example phenylene or naphthylene.
Aryl-alkylene is for example C5-C10aryl-C1-C10alkylene.
Alkyl-arylene is for example CrCioaikyl-C5-C10arylene.
Preferred is a dye mixture, wherein in formula (1) Y1 and Y2 are C1-C5alkylene.

Preferred is a composition, wherein D1 is a radical of a cationic aromatic substituted or unsubstituted heterocyclic compound of formulae

the asterix * indicates the bond to Q1;
the asterix ** indicates the bond to D1; and
the heteroaromatic cycles of these radicals may be interrupted by one or more than one -0-, -S-, -(SO2)-, -CrCioalkylene or -(NR82)-;
are independently from each other hydrogen; halogen; C1-C14alkyl, which is saturated or unsaturated, linear or branched, substituted or unsubstituted, or interrupted or uninterrupted with heteroatoms; a radical of phenyl, which substituted or unsubstituted; a of carboxylic acid radical; sulfonic acid radical; hydroxy: nitrile; C1-C16alkoxy. (poly)-hydroxy-C2-C4-alkoxy; halogen; SO2NR33R34; SRss, NRSSRSA; ORSSI; SO2; COORsa; NRSSCORSA; or CONR83 and

hydrogen; unsubstituted or substituted C1-C14alkyl, C2-C14aikenyl, C5-C10aryl, C5-C10aryl-(C1-Cioalkyl), or -Ci-Cioalkyl(C5-C10aryl).

one of W1 or W2 is -N+-, the other is -CH; and
the biradical .—(Z,)-Y1-S-S-Y2-(Z,)- is bonded to -N+ and
R4, R5, R6- Y1, Y2, Zi and r are defined as in formula (1).

Examples for dyes of formula (1), wherein Di and D2 are selected from the radicals of formula (1b) are:

Examples for dyes of formula (1), wherein D^ and D^ are selected from the radicals of formula

R11, R12 and R13, independently from each other are hydrogen; Ci-CsalkyI; -(CO)-; -C(0)H;
^C(0)-CrC5alkyli -C(0)OH; -C(0)0-CrC5alkyl; NO2; NH2; 01 -NH(C0)-CH3; Y1 is Ci-Cioalkylene; C5-C10cycloalkylene; C5-C10arylene; or C5-Cioarylene-(CrCioalkylene); X6 is the direct bond: or C1-C5alkylene;

R1 and R4 each independently from each other are hydrogen; C1-C14alkyi; C2-Ci4alkenyi; Ce-C10aryl; C6-C10aryl-C1-C10alkyI; or C1-C10alkyKCs-Cioaryl).
Most preferably compounds of formula (NIT-01) are used, wherein

R1., R12 and RT3 independently from each other are hydrogen; NO2; NH2; carboxy; -C(0)OH; or-NhHCO)-CH3;
Y, is C1-C5alkylene;

Ri and Rk each independently from each other are hydrogen; or Ci-Ci4alkyl.

Furthermore, mixtures are preferred wherein the dyes are selected from the compounds of
formula (1), wherein
D1 and D2 independently from each other are a radical of formula (1e);
R14 is N R48R49
R48 and R49 independently from each other are hydrogen; C1-C12alkyl; or phenyl-CrC4alkyl;
and
R16, R17. R18, R19, R20 and Vi are defined as in formula (1); or
compounds of formula (1), wherein
D1 and D2 independently from each other are a radical of formula (1e);
R15 is NR48R49; or OR48;
R48and R49, independently from each other are hydrogen; C1-C12a(kyl; or phenyi-CrC4alkyl;
and
R16, Ri7, R18, Ri9- R20 and Vi are defined as in formula (1); or

compounds of formula (1), wherein
D1 and D2 independently from each other are a radical of formula (1e);
R14 is N R46R47;
R46 and/or R47 independently from each other are hydrogen; C1-C12alkyl; or phenyl-CrC4alkyl;
and
R16, R17. R18, R19, R20 and Vi are defined as in formula (1); or
compounds of formula (1), wherein
D1 and D2 independently from each other are a radical of formula (1e);
R15 is NR48R49; or OR48;
R10 and R11, independently from each other are hydrogen; C1-C12alkyl; or phenyl-Ci-C4alkyl;
and
Ri6. Ri7, R18. Ri9- R20 and Vi are defined as in formula (1).

Furthermore, mixtures are preferred which comprise a dye of formula ;

the astenx(') is directed to Z1 or Z2 respectively; and
the asterices (**) are directed to the linking nitrogen atonn of R23/R24 or R25/R26 repectively.

Examples for dyes of formula (1), wherein D1 and D2 are a radical of formula (1g) are listed below are:

R27 is hydrogen; or C1-C6alkyl;

a 6 to 10 membered carbocyclic ring which may optionally be a condensated aromatic system and may contain one or more than one hetero atom; and
R57. R58 and R59 independently form each other are hydrogen, or C1-C5alkyI; A1 is H; or a thio ester group of formula

E is O; S; or N-Ra; B1 is -ORb; -NRbRc; or -SRb; and
Ra, Rb and Rc, independently from each other are hydrogen; C1-C12alkyl; C6-C12aryl; or Ce-C12aryl-C1-C12alkyL

R31 is hydrogen; C1-C5-alkoxy; halogen; or-NR69R70, wherein
R69 and R70, independently from each other are hydrogen; C1-C12alkyl; "(CO)-H; or
-(C0)-Ci-C5alkyl; and An is an anion.
Examples of these dyes are listed in the Table below:

All compounds of the present invention mentioned above can exist as hydrates or solvates.
The mixture of dyes according to the invention are suitable for dyeing organic materials, such as keratin-containing fibers, wool, leather, silk, cellulose or polyamides, cotton or nylon, and preferably human hair. The dyeings obtained are distinguished by their depth of shade and their good fastness properties for example to washing, fastness to light, shampooing and rubbing. The stabilities, in particular the storage stability of the dyes and the dyes in formulations according to the invention are excellent.
Gernerally, hair dyeing agents on a synthetic base may be classiefied itnto three groups: temporary dyeing agents semipermanent dyeing agents, and permanent dyeing agents.

The multiplicity of shades of the dyes can be increased by combination with other dyes.
Therefore the mixture of dyes of the present invention may be combined with dyes of the same or other classes of dyes, especially with direct dyes, oxidation dyes; dye precursor combinations of a coupler compound as well as a diazotized compound, or a capped diazotized compound; and/or cationic reactive dyes.
Direct dyes are of natural origin or may be prepared synthetically. They are uncharged, cationic or anionic, such as acid dyes.
The mixture of dyes may be used in combination with at least one single direct dye different from the dyes of formula (1) and (2).
Direct dyes do not require any addition of an oxidizing agent to develop their dyeing effect. Accordingly the dyeing results are less permanent than those obtained with permanent dyeing compositions. Direct dyes are therefore preferably used for semipermanent hair dyeings.
Examples of direct dyes are described in "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, p. 248-250, and in "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.
More preferred direct dyes which are useful for the combination with the mixture of dyes of the present invention, especially for semi permanent dyeing, are: 2-amino-3-nitrophenol, 2-amino-4-hydroxyethylamino-anisole sulfate, 2-amino-6-chloro-4-nitrophenol, 2-chloro-5-nitro-N-hydroxyethylene-p-phenylendiamine, 2-hydroxyethyl-picramic acid, 2,6-diamino-3-((pyridine-3yl)-azo)pyridine, 2-nitro-5-glyceryl-methylaniline, 3-methylamino-4-nitro-phenoxyethanol. 4-amino-2-nitrodiphenyleneamine-2'-carboxilic acid, 6-nitro-1,2,3,4,-tetrahydroquinoxaline, 4-N-ethyl-1,4-bis(2'-hydroxyethylamino-2-nitrobenzene hydrochloride, 1-methyl-3-nitro^4-(2'-hydroxyethyl)-aminobenzene, 3-nitro-p-hydroxyethyl-aminophenol, 4-amino-3-nitrophenol, 4-hydroxypropylamine-3-nitrophenol, hydroxyanthrylaminopropylmethyl morpohlino

'mothosulfate, 4-nitrophenyl'aminoethylurea, 6-nitro-p-toluidine, Acid Blue 62, Acid Blue 9, Acid Red 35, Acid Red 87 (Eosin), Acid Violet 43, Acid Yellow 1, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9. Basic Blue 12, Basic Blue 26, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Red 2, Basic Red 22, Basic Red 76, Basic Violet 14, Basic Yellow 57, Basic Yellow 9, Disperse Blue 3, Disperse Orange 3, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Fast Green FCF, HC Blue 2, HC Blue 7, HC Blue 8, HC Blue 12, HC Orange 1, HC Orange 2, HC Red 1. HC Red 10-11, HC Red 13, HC Red 16, HC Red 3, HC Red BN, HC Red 7, HC Violet 1, HC Violet 2, HC Yellow 2, HC Yellow 5. HC Yellow 5, HC Yellow 6, HC Yellow 7, HC Yellow 9, HC Yellow 12. HC Red 8, hydroxyethyl-2-nitro-p-toluidine, N,N-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamJne, HC Violet BS, Picramic Acid, Solvent Green 7.
Furthermore, mixture of dyes of the present invention may be combined with at least one cationic azo dye, for example the compounds disclosed in GB-A-2 319 776 as well as the oxazine dyes described in DE-A-299 12 327 and mixtures thereof with the other direct dyes mentioned therein, and even more preferred with cationic dyes such as Basic Yellow 87, Basic Orange 31 or Basic Red 51, or with cationic dyes as described in WO 01/66646, especially example 4, or with cationic dyes as described in WO 02/31056, especially example 6 (compound of formula 106); or the cationic dye of formula (3) as described in EP-A-714,954,

benzyl; R3 is hydrogen; Ci-CsalkyI; CrCsalkoxy; cyanide; or halide; preferably hydrogen; and X" is an anion; and preferably a compound of formula (DD1), wherein Ri is methyl; R2 is benzyl; R3 is hydrogen; and X" is an anion; or wherein R1 is benzyl; R2 is benzyl; R3 is hydrogen; and X" is an anion; or wherein R1 is benzyl; R2 is methyl; R3 is hydrogen; and X" is an anion.
Furthermore, cationic nitroanlline and anthraquinone dyes are useful for a combination with mixture of dyes of the present invenion, for example the dyes as described in the following

patent specifications: US-5 298 029, especially in col 2, I. 33 to col 5, I. 38; US-5 360 930, especially in col 2, I. 38 to col 5, I. 49;.US'5 169 403, especially in col 2, I, 30 to col 5, I. 38; US-5 256 823, especially in col 4, I. 23 to col 5, I. 15; US-5 135 543, especially in col 4, 1. 24 to col 5,1. 16; EP-A-818 193, especially on p. 2,1. 40 to p. 3,1. 26; US-5 486 629, especially in col 2, I. 34 to col 5, I, 29; and EP-A-758 547, especially on p. 7,1. 48 to p. 8, I. 19.
The mixture of dyes of the present invention may also be combined with acid dyes, for example the dyes which are known from the international names (Color index), or trade names.
Preferred acid dyes which are useful for the combination with the mixture of dyes of the present invention are described in US Patent 6,248,314. They include Red Color No. 120, Yellow Color No. 4, Yellow Color No. 5, Red Color No. 201, Red Color No. 227, Orange Color No. 205, Brown Color No. 201, Red Color No. 502, Red Color No. 503, Red Color No. 504, Red Color No. 506, Orange Color No. 402, Yellow Color No. 402, Yellow Color No. 406, Yellow Color No. 407, Red Color No. 213, Red Color No. 214, Red Color No. 3, Red Color No. 104, Red Color No. 105(1), Red Color No. 106, Green Color No. 2, Green Color No. 3, Orange Color No. 207, Yellow Color No. 202(1), Yellow Color No. 202(2), Blue Color No. 202, Blue Color No. 203, Blue Color No. 205, Blue Color No. 2, Yellow Color No. 203, Blue Color No. 201, Green Color No. 201, Blue Color NO. 1, Red Color No. 230(1), Red Color No. 231, Red Color No. 232, Green Color No. 204, Green Color No. 205, Red Color No. 401, Yellow Color No. 403(1), Green Color No. 401, Green Color No. 402, Black Color No. 401 and Purple Color No. 401, especially Black Color No. 401, Purple Color 401, Orange Color No. 205.
These acid dyes may be used either as single component or in any combination thereof.
Hair dye compositions comprising an acid dye are known. They are for example described in "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, p. 248-250, especially on p, 253 and 254.
Hair dye compositions which comprise an acid dye have a pH of 2-6, preferably 2-5, more preferably 2.5-4.0.

The mixture of dyes of the present invention may also readily be used in combination with acid dyes and/or adjuvants, for example
- acid dyes and an alkylene carbonate, as described in US patent 6,248,314, especially in examples 1 and 2;
- acid hair dye compositions comprising various kinds of organic solvents represented by benzyl alcohol as a penetrant solvent have good penetrability into hair, as described in Japanese Patent Application Laid-Open Nos. 210023/1986 and 101841/1995;
- add hair dye compositions with a water-soluble polymer or the like to prevent the drooping of the hair dye composition, as described for example in Japanese Patent Application Laid-Open Nos. 87450/1998, 255540/1997 and 245348/1996;
- acid hair dye compositions with a water-soluble polymer of aromatic alcohols, lower alkylene carbonates, or the like as described in Japanese Patent Application Laid-Open No. 53970/1998 and Japanese Patent Invention No. 23911/1973.
The mixture of dyes of the present invention may also be combined with uncharged dyes, for example selected from the group of the nitroanilines, nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenois, phenazines, phenothiazines, bispyrazolons, erbispyrazol aza derivatives and methines.
Furthermore, the mixture of dyes of the present invention may also be used in combination with oxidation dye systems.
Oxidation dyes, which, in the initial state, are not dyes but dye precursors are classified according to their chemical properties into developer and coupler compounds.
Suitable oxidation dyes are described for example in DE 19 959 479, especially in col 2.1. 6 to col 3,1.11; - "Dermatology", edited by Oh. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7. Ch. Zviak, The Science of Hair Care, chapter 8, on p. 264 - 267 (oxidation dyes); Preferred developer compounds are for example primary aromatic amines, which are substituted in the para- or ortho- position with a substituted or unsubstituted hydroxy- or amino residue, or diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazol derivatives, 2.4,5,6-tetraaminopyrimidine derivatives, or unsaturated aldehydes as described in DE

19 717 224 esoecially on p. 2. I. 50 to I. 66 and on p. 3 I. 8 to I. 12, or cationic developer compounds as described in WO 00/43367, especially on p., 2 I. 27 to p. 8, I. 24, in particular on p. 9, 1. 22 to p. 11, I. 6,
Furthermore, developer compounds in their physiological compatible acid addition salt form, such as hydrochloride or sulfate can be used. Developer compounds, which have aromatic OH radicals are also suitable in their salt form together with a base, such as alkali metal-phenolates.
Preferred developer compounds are disclosed in DE 19959479, p. 2,1. 8 - 29,
More preferred developer compounds are p-phenylendiamine, p-toluylendiamine, p-, m- o-aminophenol, N,N-biS"(2-hydroxyethyl)-p-phenylenediamine sulfate, 2-amtno-4-hydroxy-ethylaminoanisole sulfate, hydroxyethyl-3,4-methylenedioxyaniline, 1-(2'-hydroxyethyl)-2,5-di-aminobenzene, 2,6-dimethoxy-3,5-diamino-pyridine, hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine) hydrochloride, hydroxyethyl-p-phenylenediamine sulfate, 4-amino-3-me-thylphenol, 4-methylaminophenol sulfate, 2-aminomethyl-4"aminophenol, 4,5-diamino-1-(2-hydroxyethyl)-1H- pyrazol, 4-amino-m-cresol, 6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine or 4-hydroxy-2,5,6-thaminopyrimidine sulfate.
Preferred coupler compounds are m-phenylendiamine derivatives, naphthole, resorcine and resorcine derivatives, pyrazolone and m-aminophenol derivatives, and most preferably the coupler compounds disclosed in DE 19959479, p.1,1. 33 to p. 3,1. 11.
The mixture of dyes of the present invention may also be used together with unsaturated aldehydes as disclosed in DE 19 717 224 (p. 2, L 50 to 1. 66 and on p. 3 I. 8 to I. 12) which may be used as direct dyes or, alternatively together with oxidation dye precursors.
Further preferred for a combination with the mixture of dyes of the present invention are the following oxidation dye precursors:
the developer/-coupler combination 2,4,5,6'tetraaminopyrimidine and 2-methylresorcine
for assessing of red shades;
P-toluenediamine and 4-amino-2-hydroxytoluene for assessing of blue-violet shades;

p-to!uenediamine and 2-amino-4-hydroxyethylaminoanisole for assessing of blue shades; P'toluenediamlne and 2,4-diamino-phenoxyethynol for assessing of blue shades; rnethyl-4-aminophenol and 4-amino-2'hydroxytteoluene for assessing of orange shades; p-toluenediamine and resorcine for assessing of brown-green shades; p-toluenediamine and 1-naphthol for assessing of blue-violet shades, or p-toluenediamine and 2-methylresorcine for assessing of brown-gold shades.
Furthermore, autooxidizable compounds may be used in combination with the mixture of dyes according to the present invention.
Autooxidizable compounds are aromatic compounds with more than two substituents in the aomatic ring, which have a very low redox potential and will therefore be oxidized when ex¬posed to the air. The dyeings obtained with these compounds are very stable and resistant to schampoo.
Autooxidizable compounds are for example benzene, indol, or indoline, especially 5,6-dihydro-xyindol or 5,6-dlhydroxyindoline derivatives as described in WO 99/20234, especially on p. 26, I. 10 to p. 28, 1. 15, or in WO 00/28957 on p. 2, third paragraph.
Preferred autooxidizable benzene derivatives are 1,2,4-trihydroxybenzene, 1-methyl-2,4,5-trihydroxybenzene, 2,4-diamnio-6-methylphenol, 2-amino-4-methylaminophenol, 2,5-diamino-4-methyl"phenol, 2,6-diaminO"4-diethylaminophenol, 2,6-diamino-1,4-dihydroxybenzene, and the salts of these compounds, which are accessible with acid.
Preferred autooxidizable indol derivatives are 5,6-dihydroxyindol, 2-methyl-5,6-dihydroxyindol, 3-methyl'5,6"dihydroxyindole, 1-methyl-5,6-dihydroxyindol, 2,3-dimethyl-5.6-dihydroxyindol, 5-methoxy-6-dihydroxyindol, 5~acetoxy-6-hydroixyindol, 5,6-diacetoxyindol, acid of 5,6-dihydroxyindol-2-carbon acid, and the salts of these compounds, which are accessible with
acid.
The mixture of dyes of the present invention may also be used in combination with naturally occurring dyes, such as 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 dyeings are described, for example, in EP-A-404 868, especially on p. 3, 1. 55 to p. 4, I. 9.
Furthermore, the mixture of dyes of the present invention may also be used in combination with capped dia-zotised compounds.
Suitable diazotised compounds are for example the compounds of formulae (1) - (4) in WO 2004/019897 (bridging pages 1 and 2) and the corresponding watersoluble coupling components (I) -(IV) as disclosed in the same reference.
Further preferred dyes or dye combinations which are useful for the combination with mixture
of dyes of the present invention are described in
(DC-01): WO 95/01772. wherein mixtures of at least two cationic dyes are disclosed,
especially p. 2,1. 7 to p. 4,1. 1, preferably p, 4, I. 35 to p, 8, I. 21; formulations p. 11, last § - p.
28, I. 19;
(DG-02): US 6,843,256, wherein cationic dyes are disclosed, especially the compounds of
formulae (1), (2), (3) and (4) (col. 1, L 27 - col. 3, I. 20, and preferably the compounds as
prepared in the examples 1 to 4 (col. 10, 1.42 to cot. 13, 1. 37; formulations col. 13, 1. 38 to col.
15,1.8;
(DC-03): EP 970 685, wherein direct dyes are described, especially p. 2,1. 44 to p. 9, I. 56 and
preferably p. 9,1. 58 to p. 48, I. 12; processes for dyeing of keratin-containing fibers
especially p. 50, I. 15 to 43; formulations p. 50, I. 46 to p. 51,1. 40; (DC-04): DE-A-19 713 698, wherein direct dyes are described, especially p. 2, I. 61 to p. 3,1.
43; formulations p. 5, I. 26 to 60; (DC-05): US 6.368.360.. wherein directd dyes (coi 4^ I. 1 to col. 6, I. 31) and oxidizing agents
(col. 6, I. 37 -39) are disclosed; formulations col. 7,1. 47 to col. 9, 1. 4; (DC-06): EP 1 166 752, wherein cationic dyes (p. 3, L 22 - p. 4,1. 15) and anionic UV-
absorbers (p. 4, I. 27 - 30) are disclosed; formulations p. 7,1. 50 - p. 9, L 56; (DC-07): EP 998,908, wherein oxidation dyeings comprising a cationic direct dye and pyra-
zolo-[1,5"a]-pyrimidines (p. 2, L 48 - p. 4 J. 1) are disclosed; dyeing formulations p. 47,
I. 25 to p. 50, I. 29; (DC-08): FR-2788432, wherein combinations of cationic dyes with Arianors are disclosed,
especially p. 53, 1. 1 to p. 63,1. 23, more especially p. 51 to 52, most especially Basic
Brown 17, Basic brown 16, Basic Red 76 and Basic Red 118, and/or at least one Basic

Yellow 57. and/or at least one Basic Blue 99; or combinations of arianoren and/or oxidative dyes, especially p. 2, I. 16 to p. 3, L 16; dyeing formulations on p. 53, I. 1 to p. 63, I. 23;
(DC-09): DE-A-19 713 698, wherein the combinations of direct dyes and permanent-wave fixing comprising an oxidation agent, an oxidation dye and a direct dye are disclosed; especially p. 4, I. 65 to p. 5, I. 59;
(DC-10): EP 850 638, wherein developer compounds and oxidizing agents are disclosed; especially p. 2, I. 27 to p. 7, L 46 and preferably p. 7, 1. 20 to p. 9, 1. 26; dyeing formulations p. 2,1. 3-12 and I. 30 to p. 14, and p. 28, I. 35 - p. 30,1. 20; preferably p. 30,1, 25 - p. 32, I. 30;
(DC-11): US 6,190,421 wherein extemporaneous mixtures of a composition (A) containing one or more oxidation dye precursors and optionally one or more couplers, of a composition (B), in powder form, containing one or more direct dyes (col. 5,1. 40 - col. 7,1. 14), optionally dispersed in an organic pulverulent excipient and/or a mineral pulverulent excipient, and a composition (C) containing one or more oxidizing agents are disclosed; formulations col. 8, I. 60 - col. 9, I. 56;
(DC-12): US 6,228,129, wherein a ready-to-use composition comprising at least one oxidation base, at least one cationic direct dye and at least one enzyme of the 2-electron oxidoreductase type in the presence of at least one donor for the said enzyme are disclosed; especially col. 8,1. 17 - col. 13, I. 65; dyeing formulations in col. 2,1. 16 to col. 25,1. 55, a multi-compartment dyeing device is described in col. 26,1. 13 - 24;
(DC-13): WO 99/20235, wherein compositions of at least one cationic dye and at least one nitrated benzene dye with cationic direct dyes and nitro benzene direct dyes are described; on p. 2, I. 1 to p. 7, I. 9, and p. 39, 1. 1 to p. 40 I. 11. preferably p. 8, I. 12 to p. 25 1. 6. p. 26, !. 7 to p. 30. !. 15: p. 1, I. 25 to p. 8. I. 5. p 30, I. 17 to p. 34 1. 25, p. 8, I. 12 to p. 25 I. 6, p. 35, 1. 21 to 27, especially on p. 36, I. 1 to p. 37;
(DC-14): WO 99/20234, wherein compositions comprising at least one direct cationic dye and at least one autooxidisable dye, especially benzene, indol and indoline derivatives are described, preferably direct dyes on p. 2, I. 19 to p. 26, 1. 4, and autooxidisable dyes as dislosed especially on p. 25, I. 10 to p. 28, !. 15; dyeing formulations especially on p. 34, I. 5 to p. 35, li 18;
(DC-15): EP 850 636, wherein oxidation dyeing compositions comprising at least one direct dye and at least one meta-aminophenol derivative as coupler component and at least one

developer compound and an oxidizing agent are disclosed, especially p. 5, I. 41 to p. 7, I. 52, dyeing formulations p. 19, 1. 50 - p. 22, I. 12;
(DC-16): EP-A-850 637, wherein oxidation dyeing compositions comprising at least one oxidation base selected from para-phenylenediamines and bis(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler selected from meta-diphenols, and the acid-addition salts thereof, at least one cationic direct dye, and at least one oxidizing agent are disclosed, especially p. 6, I. 50 to p. 8,1. 44 are discloseded; dyeing formulations p. 21, L 30 - p. 22, I. 57;
(DC-17): WO 99/48856, wherein oxidation dyeing compositions comprising cationic couplers are disclosed, especially p. 9, I. 16 - p. 13, 1. 8, and p. 11,1. 20 - p. 12, 1. 13; dyeing formulations p. 36, I. 7 - p. 39, I. 24;
(DC-18): DE 197 172 24, wherein dyeing agents comprising unsaturated aldehydes and coupler compounds and primary and secondary amino group compounds, nitrogen-containing heterocyclic compounds, amino acids, oligopeptids, aromatic hydroxy compounds, and/or at least one CH-active compound are disclosed p. 3, I. 42 - p. 5 I. 25; dyeing formulations p. 8. I. 25 - p. 9, 1. 61.
In the dye combinations disclosed in the references (DC-01 - DC-18) above, the mixture of dyes of the present invention may be added to the dye combinations or dyeing formulations or may be replaced with the mixture of dyes of the present invention.
The present invention also releates to formulations, which are used for the dyeing of organic materials, preferably keratin-containing fibers, and most preferably human hair, comprising mixture of dyes of the present invention.
The formulations compnse at least 2 dyes as defined in formula (1) and (2). According to the desired color results the mixtures may comprise 3, 4, 5 or more than 5 dyes of formula (1)
and/or (2).
Preferably the mixture of dyes of the present invention are incorporated into the composition for treating organic material, preferably for dyeing in amounts of 0.001 - 5% b.w. (hereinafter indicated merely by "%"), particularly 0.005 - 4%, more particularly 0.2 - 3%, based on the total weight of the composition.

The formulations mav be applied on the keratin-containing fiber, preferably the human hair in dilterent technical forms.
Technical forms of formulations are for example a solution, especially a thickened aqueous or aqueous alcoholic solution, a cream, foam, shampoo, powder, gel, or emulsion.
Customary the dyeing compositions are applied to the keratin-containing fiber in an amount of 50 to 100 g.
Preferred forms of formulations are ready-to-use compositions or multi-compartment dyeing devices or 'kits' or any of the multi-compartment packaging systems with compartments as described for example in US 6,190,421, col 2, 1. 16 to 31.
The pH value of the ready-to-use dyeing compositions is usually from 2 to 11, preferably from 5 to 10.
Preferably the dyeing compositions, which are not stable to reduction, are prepared with oxidizing agent free compositions just before the dyeing process.
One preferred embodiment of the present invention relates to the formulation of dyes, wherein the mixture of dyes of the present invention are in powder form.
Powder formulations are preferably used if stability and/or solubility problems as for example described in DE 197 13 698, p. 2, I. 26 to 54 and p. 3, I. 51 to p, 4, I. 25, and p. 4, I. 41 to p. 5
t 59.
Suitable cosmetic hair-care formulations are hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g, pre-treatment preparations or leave-on products such as sprays, creams, gels, lotions, mousses and oils, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for per¬manent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or

oils, temporary, semi-permanent or permanent hair colorants, preparations containing self-oxidizing dyes, or natural hair colorants, such as henna or camomile.
For use on human hair, the dyeing compositions of the present invention can usually be incorporated into an aqueous cosmetic carrier. Suitable aqueous cosmetic carriers include, for example W/0, OM, OAA//0, W/OA/V or PIT emulsions and all kinds of microemulsions, creams, sprays, emulsions, gels, powders and also surfactant-containing foaming solutions, e.g. shampoos or other preparations, that are suitable for use on keratin-containing fibers. 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 col 1, I. 70 to col 3,1. 55. The dyeing compositions according to the invention are also excellently suitable for the dyeing method described in DE-A-3 829 870 using a dyeing comb or a dyeing brush.
The constituents of the aqueous carrier are present in the dyeing compositions of the present invention in the customary amounts, for example emulsifiers may be present in the dyeing compositions in concentrations from 0.5 to 30 % b.w. and thickeners in concentrations from 0.1 to 25 % b.w. of the total dyeing composition.
Further carriers for dyeing compositions are for example described in "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, p. 248-250, especially on p. 243, 1. 1 to p. 244, I.
12.
A shampoo has for example, the following composition:
0.01 to 5 % b.w. of mixture of dyes of the present invention;
8 % b.w of disodium PEG-5 laurylcitrate Sulfosuccinate, Sodium Laureth Sulfate;
20 % b.w. of sodium cocoamphoacetate;
0.5 % b.w. of methoxy PEG/PPG-7/3 aminopropyi dimethicone;
0.3 % b.w. of hydroxypropyl guar hydroxypropythmonium chloride;
2.5 % b.w. of PEG-200 hydrogenated glyceryl palmate; PEG-7 glyceryl cocoate;
0.5 % b.w. of PEG-150 distearate;
2.2. % b.w of citric acid;
perfume, preservatives; and

watered 100 %.
The mixture of dyes of the present invention may be stored in a liquid to paste-like preparation (aqueous or non-aqueous) or in the form of a dry powder.
When the dyes and adjuvants are stored together in a liquid preparation, the preparation should be substantially anhydrous in order to reduce reaction of the compounds.
The dyeing compositions according to the invention may comphse any active ingredients,
additives or adjuvants known for such preparations, like surfactants, solvents, bases, acids,
perfumes, polymeric adjuvants, thickeners and light stabilisers.
The following adjuavents are preferably used in the hair dyeing compositions of the present
invention:
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 dimethyldiallyl-ammonium chloride and acrylic acid, as available commercially under the name Merquaf^ 280 and the use thereof in hair dyeing as described, for example, in DE-A-4 421 031, especially p. 2,1. 20 to 49, or EP-A-953 334;
acrylamide/dimethyldiallylammonium chloride copolymers, diethyl-sulfate-quaternised dimethylaminoethyl methacrylate/vinylpyrrolidone copolymers, vinylpyrrolidone/-imidazolinium methochloride copolymers; quaternised polyvinyl alcohol:
zwitterionic and amphoteric polymer?:, such as acrylamido-propyltrimethylammonium chloride/acrylate copolymers and octylacrylamide/methyl methacry-late/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/isobornyl 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. benfonite or fully synthetic hydrocolloids
such as, for example, polyvinyl atcohol;
structuring agents, such as glucose and maleic acid;
hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg
lecithin, cephalins, silicone oils, and conditioning compounds, such as those described in
DE-A-19 729 080, especially p. 2,1. 20 to 49, EP-A-834 303, especially p. 2 J. 18 - p. 3, 1.
2, orEP-A-312 343, especially p. 2, I. 59 - p. 3, I. 11;
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 cydodextrins,
solubilisers, such as ethanol, isopropanol. ethylene glycol, propylene glycol, glycerol and
diethylene glycol,
anti-dandruff active ingredients, such as ptroctones, olamines and zinc Omadine,
substances for adjusting the pH value;
panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and salts thereof, plant
extracts and vitamins;
cholesterol;

Furthermore, the following UV absorbers or combinations may be used in the dyeing compositions according to the invention:
- cationic benzotriazole UV absorbers as for example descnbed in WO 01/36396 especially on p. 1, I. 20 to p. 2, 1 24, and preferred on p. 3 to 5, and on p. 26 to 37;
- cationic benzotriazole UV in combination with antioxidants as described in WO 01/36396, especially on p. 11, I. 14 to p. 18;
- UV absorbers in combination with antioxidants as described in US Patent 5 922 310, especially in col 2,1. 1 to 3;
- UV absorbers in combination with antioxidants as described in US Patent 4 786 493, especially in col 1, 42 to col 2, I. 7, and preferred in col 3, 43 to col 5, I. 20;
- combination of UV absorbers as described in US Patent 5 830 441, especially in col 4, I. 53 to 56;

- combination of UV absorbers as descnbed in WO 01/36396, especially on p. 11 J. 9 to 13; or
- triazine derivatives as described in WO 98/22447, especially on p. 1, i. 23 to p. 2, 1. 4, and preferred on p. 2, I. 11 to p. 3, I. 15 and most preferred on p. 6 to 7, and 12 to 16.
Suitable cosmetic preparations may usually contain 0.05 to 40 % b.w., preferably 0.1 to 20 % b.w., based on the total weight of the composition, of one or more UV absorbers; 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 havinp a molecular weight from 150 to 50 000, for example such as those descnbed in EP-A-BOI 942, especially p. 3, I. 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 p. 27, I. 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;

proDeltants, such as propane-butane mixtures. N:;0, dimethyl ether, CO2 and air: antioxidants; preferably the phenolic antioxidants and hindered nitroxyi compounds disclosed in ip.com (IPCOM # 000033153D); sugar-containing polymers, as described in EP-A-970 687; quaternary ammonium salts, as described in WO 00/10517;
Bacteria inhibiting agents, like preservatives that have a specific action against gram-positive bacteria, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di(4-chlorophenyl-biguanido)hexane) or TCC (3,4,4'-trichlorocarbanilide). A large number of aromatic substances and ethereal oils also have antimicrobial properties, Typical examples are the active ingredients eugenol, menthol and thymol in clove oil, mint oil and thyme oil. A natural deodorising agent of interest is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil. Glycerol monolau-rate has also proved to be a bacteriostatic agent. The amount of the additional bacteria-inhibiting agents present is usually from 0.1 to 2 % b.w., based on the solids content of the preparations;
The dyeing compositions according to the present invention generally comprise at least one
surfactant.
Suitable surfactants are zwitterionic or ampholytic, or more preferably anionic, non-ionic and/or cationic surfactants.
Suitable anionic surfactants in the dyeing compositions according to the present invention include all anionic surface-active substances that are suitable for use on the human body. Such substance? are characterised by an anionic group that imparls water solubility, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having approximately 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 10 to 22 carbon atoms (soaps),
ether carboxylic acids of formula R-0-(CH2-CH2-0)x-CH2-COOH, in which R is a linear
alkyt group having 10 to 22 carbon atoms and x = 0 or from 1 to 16,

acy! sarcosides havinq 10 to 18 carbon atoms in the acyi group, acyl taurldes having 10 to 18 carbon atoms in the acyl group, acyi isothionates having 10 to 18 carbon atoms in the acyl group,
sulfosuccinic mono- and di-alkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having 8 to 18 carbon atoms in the alkyl group and from 1 to 6 oxyethyl groups, linear alkane sulfonates having 12 to 18 carbon atoms, linear a-olefin sulfonates having 12 to 18 carbon atoms, a-sulfo fatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates of formula R'-0(CH2-CH2-O)x-S03H, in which R' is a preferably iinearar alkyl group having 10 to 18 carbon atoms and x' = 0 or from 1 to 12, mixtures of surface-active hydroxysuifonates according to DE-A-3 725 030; sulfated hydroxyalkylpolyethyiene and/or hydroxyalkylenepropylene glycol ethers according to DE-A-3 723 354, especially p. 4, I. 42 to 62,
sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-3 926 344, especially p. 2,1. 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, or anionic surfactants, as described in WO 00/10518, especially p. 45,1. 11 to p. 48,1. 3.
Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether
groups in the rnoiecule, and also especially salts of saturated and especially unsaturated Ce-Cazcarboxylic acids, such as oleic acid, stearic acid, isosteahc acid and palmitic acid.
Surface-active compounds that carry at least one quaternary ammonium group and at least one -COO' or -SO3" group in the molecule are terminated zwitterionic surfactants. Preference is given the so-called betatnes, such as the N-alky!N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred

is the fattv acid amide derivative known by the CTFA name
cocoamtdoprcpy! betaine.
Amphotytic surfactants are surface-active compounds that, in addition to a Ce-Cig-alkyI or -acyl group and 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-atkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, 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-cocoalkylaminopropionate, cocoacylaminoethylaminopro-pionate and Ci2~Ci8acylsarcosine.
Suitable non-ionic surfactants are described in WO 00/10519, especially p. 45, L 11 to p. 50. i. 12. Non-ionic surfactants contain as hydrophilic group, for example, a polyol group, a poly-atkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such com¬pounds are, for example:
addition products of 2 to 30 mol of ethylene oxide and/or 0 to 5 mol of propylene oxide
with linearar fatty alcohols having 8 to 22 carbon atoms, with fatty acids having 12 to 22
carbon atoms and with alkylphenols having 8 to 15 carbon atoms in the alkyl group,
C12-C22 fatty acid mono- and di-esters of addition products of 1 to 30 mol of ethylene
oxide with glycerol,
C8-C22alkyl-mono -and- -oligo-glycosides and ethoxylated analogues thereof,
addition products of 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.
The surfactants which 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 are 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

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 cationic surfactants that can be used in the dyeing compositions according to the invention are especially quaternary ammonium compounds. Preference is given to ammonium halides, such as alkyltrimethylammonium chlorides, diaikyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethy-lammonium chloride, lau-ryidimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethyl-ammonium chloride. Further cationic surfactants that can be used in accordance with the invention are quaternised protein hydrolysates.
Also suitable are cationic silicone oils, such as, for example, the commercially available pro¬ducts 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 Abj|®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary potydimethylsiloxanes, quaternium-80), or silicones, as described in WO 00/12057, especially p. 45. I. 9 to p. 55, I. 2.
Alkylamidoamines. especially fatty acid amidoamines, such as the stearylamidopropyl-dimethylamine obtainable under the name Tego Amid 18 are alos preffered as surfactants in
the present dyeing compositions. They 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 trademark 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 glu-ceth-10 hydroxypropyl dimonium chloride".

The alkyi-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 alky! chain lengths according to the particular starting material used.
The mixture of dyes of the present invention are suitable for the dyeing of organic materiaL perferably keratin-containig fibers.
A further preferred embodiment of the present invention relates to a method of treating keratin-containig fibers with the mixture of dyes of the present invention.
The process comprises
(a) contacting the keratin fiber with a mixture of dyes of the present invention,
(b) leaving the fibers to stand, and
(c) then rinsing the fiber.
The process for dyeing is for example described in WO 01/66646 on page 15, line 32 to page 16, line 2.
A further preferred method comphses treating the hair in the presence of a reduction agent.
Preferred reduction agents are for example thioglycol acid or salts therof, gycerine monothio-glycolat, cystein, 2-mercaptopropionic acid, 2-mercaptoethylamine, thiolactic acid, thioglyce-
rifie, sodium sulfite, dithionithe, ammonium sulfite, sodium bisulfite, sodium metabisulfife. hydroquinone, phosphines, borhydride, cyanoborohydride, thacetoxy borohydride, trimethoxy borohydride salts (sodium, lithium, potassium, calcium auaternary salts).
Furthermore, the present invention relates to a process, comprising treating the hair with
(a) optionally a reduction agent,
(b) a mixture of dyes of the present invention s defined above, and
(c) with an oxidizing agent.

The step (a) may be of short duration from o.1 sec to 30 minutes, fro example from 0.1 seconds to 10 minutes with a rducing agent mentioned above.
The application of the dye mixture on the hair may be arried out at temperatures ranging from 15° to 100°C. Generally the application is carried out at room temperature.
The sequence of the reaction steps is generally not important, the reduction agent can be applied first or in a final step.
Usally, the oxidizing agent is applied together with an acid or a base.
The acid is for example citric acid, phosphoric acid or tartrate acid.
The base is for example sodium hydroxide, ammonia or monoethanolamine.
The mixture of dyes of the present invention are suitable for all-over dyeing of the hair, that is to say when dyeing the hair on a first occasion, and also for re-dyeing subsequently, or dyeing of locks or parts of the hair.
The mixture of dyes of the present invention is applied on the hair for example by massage with the hand, a comb, a brush, or a bottle, or a bottle, which is combined with a comb or a nozzle.
Further preferred is a process for dyeing keratin-containing fibers which compnses treating the
keratin-containing fiber with mixture of dyes of the present invention, a base and an oxidizing agent.
The oxidation dyeing process usually involves lightening, that is to say that it involves applying to the keratin-containing fibers, at basic pH, a mixture of bases and aqueous hydrogen peroxide solution, leaving the applied mixture to stand on the hair and then rinsing the hair. It allows, particularly in the case of hair dyeing, the melanin to be lightened and the hair to be dyed.

Lightening the melanin has the advantageous effect of creating a unified dyeing in the case of
grey hair, and, in the case of naluraiiy pigmented hair, of bringing out the color, that is to say of making it more visible.
In general, the oxidizing agent containing composition is left on the fiber for 0.1 seconds to 15 minutes, in particular for 0.1 seconds to 5 minutes at 15 to 45°C, usually in amounts of 30 to 200g.
Oxidizing agents are for example persulfate or diluted hydrogen peroxide solutions, hydrogen peroxide emulsions or hydrogen peroxide gels, alkaline earth metal peroxides, organic per¬oxides, such as urea peroxides, melamine peroxides. Alkalimetalbromate fixations or enzymes are also appropriate if a shading powder on the basis of semi-permanent, direct hair dyes is used.
Further preferred oxidizing agents are
oxidizing agents to achieve lightened coloration, as described in WO 97/20545, especially p. 9, I. 5 to 9,
oxidizing agents in the form of permanent-wave fixing solution, as described in DE-A-19 713 698 . especially p. 4,1. 52 to 55, and 1.60 and 61 or EP-A-1062940, especially p. 6,1. 41 to 47 (and in the equivalent WO 99/40895).
Most preferred oxidizing agent is hydrogen peroxide, preferably used in a concentration from about 2 to 30 %, more preferably about 3 to 20% by, and most preferably from 6 to 12% b.w. the corresponding composition.
The oxidizing agents may be present in the dyeing compositions according to the invention preferably in an amount from 0.01 % to 6 %, especially from 0.01 % to 1 %, based on the total dyeing composition.
In general, the dyeing with an oxidative agent is carried out in the presence of a base, for example ammonia, alkali metal carbonates, earth metal (potassium or lithium) carbonates, alkanol amines, such as mono-, di- or triethanolamlne, alkali metal (sodium) hydroxides, earth metal hydroxides or compounds of the formula

R is a propylene residue, which may be substituted with OH or CTC4alkyl,
R3, R4, R5 and Re are independently or dependentty from each other hydrogen, Ci-Cdalkyi or hydroxy-(C1-C4)atkyi.
The pH-value of the oxidizing agent containing composition is usually about 2 to 7, and in particular about 2 to 5.
One preferred method of applying formulations comprising the mixture of dyes of the present invention on the keratin-containing fiber, preferably the hair is by using a multi-compartment dyeing device or "kit" or any other multi-compartment packaging system, as described for example in WO 97/20545 on p. 4, L 19 to I. 27.
The first compartment contains for examie the mixture of dyes of the present invention and optionally furhter direct dyes and a basifying agent, and in the second compartment an oxidizing agent; or in the first compartment the mixture of dyes of the present invention and optionally futhter direct dyes, in the second compartment a basifiying agent and in the third compartment an oxidizing agent.
A further preferred embodiment of the present invention relates to a method of dyeing hair
with oxidative dyes, which comprises
(a) mixing at least one dye of formula (1) and optionally at least one coupler compound and
at least one developer compound, and an oxidizing agent, which optionally contains a1 least one further dye, and (b) contacting the keratin-containing fibers with the mixture as prepared in step (a).
The pH-value of the oxidizing agent free composition is usually from 3 to 11, and in particular
from 5 to 10, and most particular about 9 to 10.
Preferably, a ready-to-use composition is prepared according to a first preferred embodiment by a process which comprises preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one

developer compound especially selected from para-phenylenediamines and bis(phenyt)-alkylenediamines. and the acid-addition sails thereot. at least one coupler, especially selected from meta-phenylenediamines and the acid-addition salts thereof, and the mixture of dyes of the present invention, on the other hand, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent and mixing (A) and (B) together immediately before applying this mixture to the keratin-containing fibers.
According to a second preferred embodiment for the preparation of the ready-to-use dye composition, the process includes a preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, especially selected from para-phenylenediamines and bis-(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler compound, especially selected from meta-phenylenediamines and the acid-addition salts thereof; on the other hand, a composition (A') comprising, in a medium which is suitable for dyeing, at least one dye of formula (1), and, finally, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent as defined above, and mixing them together at the time of use immediately before applying this mixture to the keratin-containing fibers.
The composition (A') used according to this second embodiment may optionally be in powder form, the mixture of dyes of the present invention constituting, in this case, all of the composition (A') or optionally being dispersed in an organic and/or inorganic pulverulent excipient.
When present in the composition A', the organic excipient may be of synthetic or natural origin
and is selected in particular from crosslinked and non-crosslinked synthetic polymers, polysaccharides such as celluloses and modified or unmodified starches, as well as natural products such as sawdust and plant gums (guar gum, carob gum, xanthan gum, etc.).
When present in the composition (A'), the inorganic excipient may contain metal oxides such as titanium oxides, aluminium oxides, kaolin, talc, silicates, mica and silicas.
An very suitable excipient in the dyeing compositions according to the invention is sawdust.

The powdered composition (A/) may also contain binders or coating products in an amount which preierabiy does not exceed approximately 3% b.vv. relative to the tola! weight of compo^ sition (A'). These binders are preferably selected from oils and liquid fatty substances of inorganic, synthetic, animal or plant ongin.
Furthermore, the present invention relates to a process of dyeing of keratin-containig fibers with the mixture of dyes of the present invention and autooxidable compounds and optionally
further dyes.
Furthermore, the present invention relates to a process for dyeing keratin-containig fibers with the mixture of dyes of the present invention and capped diazotised compounds, which comprises,
(a) treating the keratin-containing fibers under alkaline conditions with at least one capped diazotised compound and a coupler compound, and optionally a developer compound ad optionally an oxidizing agent, and optionally in the presence of a further dye, and optionally with the mixture of dyes of the present invention; and
(b) adjusting the pH in the range of 6 to 2 by treatment v\/ith an acid, optionally in the presence of a further dye, and optionally with the mixture of dyes of the present invention
with the proviso that at least in one step (a) or (b) the mixture of dyes of the present invention is present.
The capped diazotised compound and coupler compound and optionally the oxidizing agent and developer compound can be applied in any desired order successively, or simultaneously.
Preferably, the capped diazotised compound and the coupler compound are applied simultaneously, in a single composition.
"Alkaline conditions" denotes a pH in the range from 8 to 10, preferably 9-10, especially 9.5-10, which are chieved by the addition of bases, for example sodium carbonate, ammonia or sodium hydroxide.
The bases may be added to the hair, to the dye precursors, the capped diazotised compound and/or the water-soluble coupling component, or to the dyeing compositions comprising the dye precursors.

Acids are for example tartaric acid or cltric acid, a citric acid ge'. a suitabie bufier soluiion witr: optionally an acid dye.
The ratio of the amount of alkaline dyeing composition applied in the first stage to that of acid dyeing composition applied in the second stage is preferably about from 1:3 to 3:1, especially about 1:1.
Furthermore, the present invention relates to a process for dyeing keratin-containig fibers with the mixture of dyes of the present invention and at least one acid dye.
The following Examples serve to illustrate the processes for dyeing without limiting the processes thereto. Unless specified otherwise, parts and percentages relate to weight. The amounts of dye specified are relative to the material being coloured.

12.4 g 4-fluoroanirm are added to a stirred solution of 25 ml water and 25 ml of 32% hydrochloric acid at 295 K. The reaction mixture is cooled to 273 K and 19 ml of a 36% sodium nitrite solution are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. After the addition of the sodium nitrite solution the mixture is stirred for one hour. If no excess of nitrite is detected during one hour (detection by using a potassium iodide paper) further sodium nitrite solution is added. The remaining excess of nitrite is reduced with sulfamic acid. The obtained diazo solution is dropped to a 273 K cold solution of 7.4 g imidazole in 30 ml water, whereby the pH of the solution is maintained in the range of pH 10 to 11 by adding 36% of asodium hydroxide solution. After completing the diazo addition the obtained suspension is warmed up to 295 K, the pH is adjusted to 10.5 with 36% sodium hydroxide solution. After stirring for one hour at this pH and temperature the suspension is filtered off and washed twice with 50 ml water to obtain 55 g of a humid product, which is suspended in 200 ml water and 3 weight equivalents dimethyl sulfate and sodium hydroxide are simultaneously added for maintaining the pH at 10-10.3 and the temperature at 298-303K.
The reaction is allowed to stand for one more hour to finish the hydrolysis of excess of dimethyl sulfate.
100 g sodium chloride and 50 g potassium chloride are added at 273K and allowed to stand for 16 hours. The product is separated by filtration and washed with a cold solution of sodium /potassium chloride. About 20g of the compound of formula

are obtained
69 G cf cistearnine dihydrochloride are added at 293 K under nitrogen atmosphere to 20 g of the compound of formula (101a) in 120g tsopropanol and 24 g triethylamine. The temperature is raised to 333 K and the reaction mixture is stirred at this temperature during 25 hours. The reaction mass is stirred for 4 hours while the temperature is decreased to 295 K. The reaction mass is filtered off and the filter residue washed with 45 ml of isopropanol and again filtered.300 ml water are added to the humid filter residue and the mixture is stirred for 3 hours at 353 K. Then the temperature is decreased to 295 K and the mixture filtered off. The filter residue is washed with 100 ml water, filtered and dried in vacuum to obtain 16 g of compound of formula (101).

hydrochloric acid at 295 K. The reaction mixture is cooled to 273 K and 19 ml 36% sodium nitrite solution are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. After the addition of the sodium nitrite solution the mixture is stirred for one hour. If no excess of nitrite is detected during one hour (detection by using a potassium iodide/starch paper) further amounts of sodium nitrite solution are added. Then the remaining excess of nitrite is destroyed with sulfamic acid. The obtained diazo solution is dropped to a 273 K cold solution of 7.4 g imidazole in 30 ml water, whereby the pH of the solution is maintained in the range of pH 10 to 11 by adding 36% sodium hydroxide solution. After completing the diazo addition the obtained suspension is warmed up to 295 K and the

pH os adjusted to 10 5 with 36% sodium hydroxide solution. After stirring for one hour at this pH and temperature the suspension is filtered off and then washed twice witn 50 mi water to obtain 55 g of the humid product, which is suspended in 500 ml water. 0.3 mol dimethyl sulfate and sodium hydroxide are simoultaniously added for maintaining the pH in the range of 10-10.3 and the temperature at 298'303K. The reaction mixture is hold for one hour. Then the water is evaporated. About 40 g humid solid, which gives 27 g of dryed product of the formula

100 g 4>fluoro-3nitroanilin are added to a stirred mass of 80 g methanol and heated to 333 K. 0.1 ml sulfuric acid and 90 ml of acetic anhydride are added during 15 minutes. Heating and boiling are continued for 15 minutes. Then the reaction mixture is cooled slowly to 273 K with stirring. At the final temperature stirring is continued for 30 minutes, then the suspension is filtered off, washed with cold methanol, dryed in the vacuum dryer getting 114 g acetyl derivative which is worked up further. The acetyl derivative is solved in 520 ml ethanol and continuously added to 130 g iron in 35 ml concentrated hydrochloric acid and 220 ml water at 363K during 1 hour. The temperature drops to 353 K. The reaction mixture is stirred for further 3 hours. The hot mass is separated through filtration the residue washed with 100 ml ethanol. The filtrate and wash solution are cooled to 380 K with mixing, when cristallization of the product takes place. The product is separated by filtration, washed with cold ethanol and dryed in a vacuum dryer.
The dried material is dissolved in 132 ml water and 110 ml of 32% hydrochloric acid at 295 K. The reaction mixture is cooled to 273 K and 86.4 g 36% sodium nitrite solution are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. The mixture is further stirred for one hour, if no excess of nitrite is detected during one hour (detection by using a potassium iodide/starch paper) further amounts of sodium nitrite solution are added. After this one hour the remaining excess of nitrite is destroyed with sulfamic acid. Then the obtained diazo solution is dropped to a 273 K cold solution of 33.4 g imidazole in 130 mi water, whereby the pH of the solution is maintained in the range of pH 10 to 11 by adding 36% of a sodium hydroxide solution. After completing the diazo addition, the obtained suspension is warmed up to 295 K and the pH is adjusted to 10.5 with 36% sodium hydroxide

solution. After stirring for one hour at this pH and temperature the suspension is filtered off and then washed twice with 100 mi water to obtain 200 g of the humid product. The filtercake from the previouse step is suspended in water and 3 weight equivalents dimethylsulfate and sodium hydroxide are simultaniously added for maintaining the pH in the range of 10-10.3 and the temperature at 300 K. Then the reaction mixture is hold for one more hour to finish the hydrolysis of excess of dimethylsulfate. Then the suspension is separated by filtration. About 240 g of a humid solid which gives 140 g dryed product of formula

100 g 4-fluoro-3nitro-anilin is added to a stirred mass of 80 g methanol, heated to 333 K, 0.1 mi sulfuric acid added, and then 90 ml of propionic anhydride dunng 15 minutes. Then heating and boiling is continued for 15 minutes. Then the reaction mixture is cooled slowly to 273 K with stirring- At the final temperature stirring is continued for 30 minutes, then the suspension is filtered, washed with cold methanol, dryed in the vacuum dryer getting 114 g acetyl derivative which is worked up further. Then, the acetyl derivative is solved in 520 ml ethanol and continuously added to 130 g iron in 35 ml concentrated chlorhidric acid and 220 ml water at 363K during 1 hour. The temperature drops to 353 K. The reaction mixture is stirred for further 3 hours. The hot mass is separated through filtration, the residuu washed with 100 ml ethanol. The filtrate and wash solution is cooled to 380 K with mixing, when cristallization of the product takes place. The product is separated by filtration, washed with cold ethanol and dryed in a vacuum dryer. The dried material is dissolved in 132 ml water and 110 ml of 32% hydrochloric acid at 295 K.
Then the reaction mixture is cooled to 273 K and 86.4 g 36% sodium nitrite solution is dropped
at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K.
After the addition of the sodium nitrite solution, the mixture is stirred for one hour. If no excess
of nitrite is detected dunng one hour (detection by using a potassium iodide/starch paper):
further amounts of sodium nitrite solution is added. After this one hour the remaining excess of
nitrite is destroyed with sulfamic acid. Then, the obtained diazo solution is dropped to a 273 K
cold solution of 33.4 g imidazole in 130 ml water, whereby the pH of the solution is maintained
in the range of pH 10 to 11 by adding 36% sodium hydroxide solution. After completing the
diazo addition, the obtained suspension is warmed up to 295 K, the pH is adjusted to 10.5 with
36% sodium hydroxide solution. After one hour stirring at this pH and temperature, the

^^uspension is filtrated and then washed twice with 100 ml water to obtain 200 g of the humid
product
Then, the filtercake from the previouse step is suspended in water and 3 weight equivalents dimethylsulphate and sodium hydroxide simoultaniously added for maintaining the pH in the range of 10-10.3 and the temperature at 300 K. Then, the reaction mixture is hold for one more hour, to finish the hydrolysis of excess of dimethylsulphate. Then, the suspension is separated by filtration. About 240 g humid solid, which gives 140 g dryed product of formula

I
100 g 4-fluoro-3nitro-anilin are added to a stirred mass of 80 g methanol and heated to 333 K. 0.1 ml sulfuric acid and 90 ml of benzoyl chloride are added during 15 minutes. Heating and boiling is continued for 15 minutes. The reaction mixture is cooled slowly to 273 K with stirring andcontinued for 30 minutes. The suspension is filtered off, washed with cold methanol, dryed in the vacuum dryer getting 114 g acetyl derivative which is worked up further. The acetyl derivative is dissolved in 520 ml ethanol and continuously added to 130 g iron in 35 ml concentrated chlorhidric acid and 220 ml water at 363K during 1 hour. The temperature drops to 353 K. The reaction mixture is stirred for further 3 hours. The hot mass is separated through filtration, the residue washed with 100 ml ethanol. The filtrate and wash solution are cooled to 380 K with mixing when cristallization of the product takes place. The product is separated by filtration, washed with cold ethanol and dryed in a vacuum dryer. The dried material is dissolved in 132 ml water and 110 ml of 32% hydrochloric acid at 295 K. Then the reaction mixture is cooled to 273 K and 86.4 g of a 36% sodium nitrite solution are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276 K. After the addition of the sodium nitrite solution the mixture is stirred for one hour. If no excess of nitrite is detected during one hour (detection by using a potassium iodide/starch paper) further amounts of sodium nitrite solution are added. The remaining excess of nitrite is destroyed with sulfamic acid. Then the obtained diazo solution is dropped to a 273 K cold solution of 33.4 g imidazole in 130 ml water, whereby the pH of the solution is maintained in the range of p\\ 10 to 11 by adding 36% of a sodium hydroxide solution. After completion of thethe diazo addition the obtained suspension is warmed up to 295 K, the pH adjusted to 10.5 with 36% sodium hydroxide solution. After stirring for one hour at this pH and temperature the suspension is

filtered off and then washed twice with 100 ml water to obtain 200 g of the humid product Jrien the filtercake from ihe previouse step is suspended in.water and 3 weight equivalents dimethylsulfate and sodium hydroxide simoultaniously added for maintaining the pH in the range of 10-10.3 and the temperature at 300 K. Then the reaction mixture is hold for one more hour to finish the hydrolysis of excess of dimethylsulfate. Then, the suspension is separated by filtration. About 240 g of a humid solid, which gives 140 g dry product of the following formula

t
1. Formation of the Hvdrazone: 14 g sulfuric acid are added to 42 g of water and cooled to
293K. 24 g of N-methyl-phenyl hydrazine (100%) are added with stirring, 24.5 g of 4-pyridine-
aldehyde are dropped in during 15 minutes and stirhng is continued for 1 hour. The pH is
raised to 2.2 by adding a solution of 36% sodium hydroxide in water. 2.7 g sodium chloride are
added at the 333K. Stirhng is continued at this temperature for one hour. The slurry is
separated by filtration; the filter cake is dried at 343K in vacuum to yield 42 g of an orange
powder.
2. Alkylating agent: A mixture of 15.4g of 2.2-dithiodiethanol in 100 ml chloroform and 24.1 g
pyridine are cooled with stirring at 273K and then 41.0 g of tosyl chloride are added in small
amounts, maintaining the temperature.
After completion of the addition the mixture is left over night In the refrigerator. The reaction mixture is mixed with a water/hydrochlohc acid/Ice slurry. The phases are separated, washed with water and dried. The obtained solution of toluenesulfonate diester is used in the 3. step.
S.AIkylation: The foregoing hydrazone is dissolved by stirring with the equivalent amount of
diester solution. Temperature is raised to 334K which is maintainedduring the following 48 hours. Crystals separated in the slurry are filtred off. The product is washed with 50 ml chloroform and dried in vacuum to obtain 59 g of an orange solid product. The product is recristallized twice from methanol.

1. Monoazo: 50.0 of g 2-amino-thiazol are added to a stirred solution of 135 ml 60% sulfuric
acid at 293-310 K. Then, the reaction mixture is cooled to 273 K and 81 ml of a 40%
nitrosilsulfuric acid are dropped at such a rate that the temperature of the mixture is
maintained in the range of 273 to 276 K by cooling. After the addition the mixture is stirred for
four hours. The solution is dropped to a well-stirred water ice mixture (400 g) containing 2,5 g
amidosulfunc acid. To the obtained diazo solution (at 273 K ice added if need) 60,5 g
dimethylaniline are dropped. Then the pH of the solution is raised to the range of 5 to 6 by
adding 36% sodium hydroxide solution. After one hour stirring at this pH and temperature the
suspension is filtered off and then washed twice with 50 ml water to obtain 155 g of the humid
product. After drying 100 monoazo dye is obtained.
2. Alkylating agent: A mixture of 15.4 g of 2,2-dithiodiethanol in 100 ml chloroform and 24,1 g
pyridine are cooled with stirring to 273 K and then 41.0 g of tosyl chloride are added in small
amounts maintaining the temperature.
After completion of the addition the mixture is left over night in the refrigerator. The reaction mixture is mixed with a water/hydrochloric acid/ice slurry, the phases are separated, washed

with water and dried. The obtained solution of toluenesuifonate diester is used in the following step
3.Alkvlation: The foregoing monoazo is dissolved by stirring into the diester solution. Temperature is raised to 333K. The temperature is maintained at 333K during the following 60 hours. Crystals separated in the slurry are filtered off. The product is washed with 50 ml of chloroform and dried in vacuum to obtain 59 g of a dark violett solid product. The product is recristallized twice from methanol.

273 to 276 K with cooling and stirred for four hours. The solution is dropped to a well-stirred water ice mixture (400 g) containing 2.5 g amidosulfuric acid. 60,5 g dimethylaniiine are dropped to the obtained diazo solution (at 273 K ice added if need). The pH of the solution is adjusted between 5 and 6 by adding 36% sodium hydroxide solution. After stirring for one hour at this pH and temperature the suspension is filtered off and washed twice with 50 ml water to obtain 255 g of the humid product. After drying 151 monoazo dye is obtained.
2. Alkylating agent: A mixture of 21.4 g of 2.2-dithiodiethanol in 100 ml chloroform and 24.1 g pyridine are cooled with stirring to 273K and then 41,0 g of mesyl anhydride are added in small amounts under constant temperature.
After completion of the addition the mixture is left over night in the refrigerator to finish the reaction. The reaction mixture is mixed with a water/hydrochloric acid/ice slurry, the phases are separated, washed with water and dried. The obtained solution of methanesulfonate diester is used in the following step
3.Alkvlation: Two equivalents of the foregoing monoazo are dissolved by stirring into the diester solution. Temperature was raised to 334K. The temperature was maintained at 334K during the following 80 hours. Crystals separated in the slurry are filtered off. The product is washed with 50 ml of chloroform and dried in vacuum to obtain 80 g of a dark violett solid product. The product is recristallized twice from methanol. Characterization by1H-NMR in deuterated methanol (128 scans)/ 360MHz:

19.9 g of N,N'-dimethyl-ethylendiamine are added with stirring to 120g acetonitrjle and compound of the formula of formula {101a) at 293 K under nitrogen atmosphere.
The temperature is raised to 333 K while the viscosity of the reaction mixture decreases. The reaction mixture is stirred at this temperature during 25 hours. Then the reaction mass is stirred for 4 hours while the temperature is decreased to 295 K. The reaction mass is filtered off and the filter residue is washed with 45 ml of acetonitrile. Then the material is dried in vacuum to obtain 16 g of product.
2. Alkylaiinq agent: A mixture of 15.4 g of 2.2-dithiodiethanol in 100 fnl chlorolorm and 24,1 g pyridine are cooled with stirring to 273K and then 41,0 g of tosyl chloride are added in small amounts under constant temperature.
After completion of the addition the mixture is left over night in the refrigerator. The reaction mixture is mixed with a water/hydrochloric acid/ice slurry, the phases are separated, washed with water and dried. The obtained solution of methane-benzene-sulfonate diester is used in the following step.
3.AIkvlation: Stirring into the diester solution in chloroform dissolves two equivalents of the foregoing monoazo. Temperature is raised to 333K. The temperature is maintained at 333K

during the following 20 hours. Crystals separated in the slurry are filtrated. The product is washed with 50 ml of chloroform and dried in vacuum to obtain 80 g ot a dark solid product. The product is recristallized twice from methanol.

1. 16.9 g of ethylenediamine are added to the compound of the formula (101a) (prepared in
Example A1) and 120g isopropanol at 293 K under nitrogen atmosphere under stirring. The
temperature is raised to 333 K while the viscosity of the reaction mixture decreases. The
reaction mixture is stirred at this temperature during 25 hours. Then the reaction mass is
stirred for 4 hours while the temperature is decreased to 295 K. The reaction mass is filtered
off and the filter residue is washed with 45 ml of isopropanol. Then the filter residue is dried in
vacuum to obtain 16 g of the product.
2. Acvlatinq agent: A mixture of 15-4g of 2,2-dithiodipropionic acid and then 41.0 g of thionyl
chloride is warmed to 333 K for 2 hours under constant temperature.

After completion of the addition the mixture is distilled under vacuum . 3.Alcylatuiun. Two equivalents of the foregoing monoazo are dissolved by stirring into the acid chloride solution in chloroform. The temperature is raised to 333K and maintained during the following 48 hours. Crystals separated in the slurry are filtrated. The product is washed with 50 ml of chloroform and dried in vacuum to obtain 80 g of a dark redish solid product which is re-cristallized twice from methanol.

1 .Formation of the Hydrazone: 14 g sulfuric acid are added to 42 g of water and cooled to 293K. 25 g of N-methyl-phenyl hydrazine (100%) are added with stirring. 24.0 g of 4-pyridine-aldehyde are dropped in dunng 15 minutes and stirnng is continued for i hour. The pH is raised to 2.2 by adding a solution of 36% sodium hydroxide in water. 2.7 g sodium chloride are added at a temperature of 333K and stirred for one more hour at this temperature. The slurry is separated by filtration, the filter cake dried at 343K in vacuum to yield 43 g of an orange
powder.
2. Alkylating agent: A solution of 22.5 g of cisteamlne dichlorohydrate in water and 31.4 g
bromoacetic chloride are cooled with stirring to 273K and then the pH is kept constant by
adding NaOH solution in small amounts under constant temperature.
After completion of the addition the mixture is left over night in the refrigerator. The mixture
has two phases, which are separated, washed with water and dried.

3. Alkytation: The foregoing hydrazone is dissolved in methanol by stirring with the dibromide solution. The temperature is raised to 60°C and maintained at 60X during the following 24 hours. The crystals separated in the slurry are filtrated. The product is washed with 50 ml of methanol and dried in vacuum to obtain 49 g of an orange solid product. The product is recristallized twice from methanol.

1. 9.9 g of N,N-dimethyl-ethylendiamine are added to 120g acetonitrile and to the compound
of the formula (101a) (prepared in example A1) at 293 K under nitrogen atmosphere with
stirring. The temperature is raised to 333 K while the viscosity of the reaction mixture
decreases. The reaction mixture is stirred at this temperature dunng 25 hours.
The reaction mass is stirred for 4 hours while the temperature is decreased to 295 K. The reaction mass is filtered off and the filter residue washed with 45 ml of acetonitrile. Then the material is dried in vacuum to obtain 16 g of product.
2. Alkylating aqent:A mixture of 15.4 g of 2.2-dithiodiethanol in 100 ml chloroform and 24,1 g
pyridine is cooled with stirring to 273K and then 41.0 g of tosyl chloride are added in small
amounts under constant temperature. After completion of the addition the mixture is left over
night in the refrigerator. The reaction mixture is mixed with a water/chiorhidric acid/ice slurry,
the phases are separated, washed with water and dried. The obtained solution of methane-
benzene-sulfonate diester is used in the following step

3.Alkvlatton: Stirring into the diester solution in chloroform dissolves two equivalents of the foregoing monoazo. The temperature is raised to 333K and maintained at 333K during the following 20 hours. Crystals separated in the slurry are filtrated. The product is washed with 50 ml of chloroform and dried in vacuum to obtain 80 g of a dark solid product, which is recristalJized twice from methanol.

The compound of formula (102a) (prepared in example 2) is reacted with N,N-dtmethyl-ethy-lenediamine according to the procedure as described in Example A14. The same alkylating agent is used to give the compound of formula (115).
Example AZQ-16:

The compound of formula (104a) (prepared in example A 4) is reacted with N,N-dimethyl-ethylendiamine according to the method as described in Example A14.
The same alkylating agent is used and the compound of formula (116) is obtained. Example AZO-17:

Step 1:
19,9 g of N,N-d(methyl-ethylendiamin is added at 293 K, under nitrogen atmosphere, with
stirring to 120g isopropanol and the foregoing compound of the formula (AZO-101a),
Then the temperature is raised to 333 K, and viscosity of the reaction mixture decreases. The reaction mixture is stirred at this temperature during 25 hours. Then, the reaction mass is

stirred for 4 hours, while the temperature is decreased to 295 K. The reaction mass is filtered and the filter residue is washed with 45 ml of isopropanol. Then the materia! is dried in vacuum to obtain 16 g of the product:

3. Alkylation
4,0 g of Magnesiumoxid is added at 293 K with well-stirring to 100 ml methanol and the foregoing compound of the formula (117a). Then the temperature is raised to 323 K and the reaction mixture is stirred at this temperature for half an hour. After been slowly cooled at room temperature, the reaction mass is filtrated. 14,0 g of the alkylating agent (117b) and 4,0 g of Magnesiumoxid are added at 293 K to the well-stirred foregoing filtrate. A catalytic amount of potassium iodide is added to the reaction mixture. The temperature is then raised to 313 K and the reaction mixture is stirred at this temperature for five days. The reaction mass is then diluted with 100 ml methanol and filtrated. The filtrate is evaporated to dryness and finally the materia! is dried in vacuum to obtain 57.5 g of the product (AZO'117). MS (ES+): m/z 403 (M2+).

1. Monoazo
50.Og of 2-amino-thiazol are added to a stirred solution of 135ml 60% sulfuric acid at 293-31 OK. Then the reaction mixture is cooled to 273K and 81ml of a 40% nitrosilsulfuric acid are dropped at such a rate that the temperature of the mixture is maintained in the range of 273 to 276K by cooling. After the addition the mixture is stirred for four hours. The solution is dropped to a well-stirred water ice mixture (400g) containing 2,5g amidosulfuric acid. To the obtained diazo solution (at 273K ice added if need) 60.5g dimethylaniline are dropped. Then the pH of the solution is raised to the range of 5 to 6 by adding 36% sodium hydroxide solution. After stirring one hour at this pH and temperature the suspension is filtered off and then washed twice with 50ml water to obtain 155g of the humid product. After drying 100g monoazo dye of formula (118a) is obtained.

2. Alkvlation
14.7g of the monoazo dye of formula (118a), 9.9g of the alkylating agent of formula
(AZO-117b) and O.lg Kl are stirred for 20h in 100ml tetramethylurea at lOO^'C. After extraction
of the crude product with tetrahydrofurane the final product is obtained after crystallization
from Methanol/Acetone (7:3 ).
Yield after vacuum-drying: 20,5g of the dye of formula (AZO-118).

1. Monoazo
184g of 2-amino-6-methoxy-benzothiazol are added to a well-stirred solution of 270ml 60% sulfuric acid at 293-310 K. Then the reaction mixture is cooled to 266K and 174ml of a 40% nitrosilsulfuric acid are added at such a rate that the temperature of the mixture is maintained in the range of 266 to 268 K by cooling. After the addition the mixture is stirred for 4h at 268K. The solution is poured into to a well-stirred water ice mixture (600g) containing 5g amido-sulfuric acid (at 273K ice added if need). To the obtained diazo solution (at 273K ice added if need) 196.5g of melting N-phenyldiethanolamine are dropped. After the addition the mixture is stirred for 2h. Then the pH of the solution is raised to 7 by adding 36% sodium hydroxide solution (the temperature of the mixture Is maintained under 313K by addition of ice). After 1h stirring at this pH the suspension is filtered off and then washed with water to obtain 1322g of the humid product. After drying 505g monoazo dye of the formula (119a) are obtained.

2. Alkvlation
39.1g of the monoazo dye of the formula (119a) and 13.8g of the alkylating agent (117b) and O.lg Kl are stirred tor 20h in 100ml tetramethylurea at 100°C. The work-up is carried out by extraction of the crude product with tetrahydrofurane. After vacuum-drying 32g of the dye of the formula (AZO-119) are obtained.

1 ■ Monoazo
lOOg of 2-amino-thiazol are added to a weli-stirred solution of 270ml 60% sulfuric acid at 293-31 OK. Then the reaction mixture is cooled to 273K and 146ml of a 40% nitrosilsulfuric acid are added at such a rate that the temperature of the mixture is maintained in the range of 273 to 276K by cooling. After the addition the mixture is stirred for four hours. The solution is poured into to a well-stirred water ice mixture (700g) containing 5g amidosulfuric acid (at 273K ice added if need). To the obtained diazo solution (In the range 273-278 K ice added if need) 180g of melting N-Phenyldiethanolamine is dropped. After the addition the mixture is stirred for one hour. Then the pH of the solution is raised to the range of 5 by adding 36% sodium hydroxide solution (The temperature of the mixture is maintained under 303K by addition of ice). After two hours stirring at this pH the suspension is filtered off and then washed with water to obtain 439g of the humid product. After drying 243g monoazo dye of formula (120a)

.?_Alkylation
26.6g of the monoazo of formula (120a),15.8g of the alkylating agent (117b) and 0.1g Kl are stirred in 160ml tetramethylutea for 20h at100°C. The solvent is destilled off under reduced pressure and the residue is extracted with tetrahydrofurane (5x500 m!) and vacuum-dried.

1. Alkylating agent
A mixture of 15.4 g of 2,2-dithiodiethanol in 100 ml chloroform and 24,1 g pyridine are cooled with stirring to O^C and then 41.0 g of tosyl chloride are added in small amounts, maintaining the temperature at 0°C by cooling externally.
After completion of the addition the mixture is left over night in the refrigerator to complete the reaction. The reaction mixture is mixed with a water/ hydrochloric acid and ice slurry, the phases are separated, washed with water and dried.
The solution of toluenesulfonate diester is used as starting compound in the 2nd reaction step.
2. Alkylation
The alkylation agent obtained in the 1st reaction step is delivered from the solvent, dissolved in two equivalent amounts (18.8 g) of 4-methyl-pyridine. The temperature is raised to 70°C and maintained at 60°C during the following 12 hours.
3. Condensation
To the reaction mixture of the foregoing step 50 ml of isopropanoi are added, Then the
equivalent amount (30.0 g) of dimethylamino-benzaldehyde and a catalytic amount (3.6 g) of
piperidine are added and the reaction mixture is stirred for 24 hours at 70°C.
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum to obtain 45 g of a reddish orange solid product.
The product is recristalized twice from methanol.
The product is characterized by the following data:
- The HPLC-MS gives a main component of a dication of the mass 568
- 1H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

A mixture of 15.4g 2,2-dithiodiethanol in 100 ml chloroform and 24.1g pyridine are cooled with
stirring to 0°C and then 22.0 g of mesyl chloride are added in small amounts, main-taining the
temperature by external cooling.
After completion of the addition the mixture is left over night in the refrigerator to complete the
reaction.
The reaction mixture is mixed with a water/hydrochloric acid and ice slurry, the phases are separated, washed with water and dried.
The solution of methanesulfonate diester is used as starting compound in the 2nd reaction step.

2. Alkytation
1 wo equivalents (18.8 g) of 4-methyl-pyridine are dissolved in the foregoing alkyiation agent together with a solvent. The temperature is raised to reflux and maintained at 70°C during the following 12 hours.
3. Condensation
The equivalent amount (24.0 g) of amino-benzaldehyde and a catalytic amount (3.6 g) of
piperidine are added to the reaction mixture obtained in the 2nd reaction step and the reaction
mixture is stirred for 24 hours at 70°C.
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum to obtain 42 g of an orange solid product.
The product is recristailized twice from methanol.

A mixture of 25.4 g of cisteamine as dichlorohydrate in 100 ml water is cooled with stirring to 0°C and 41.0 g of bromoacetic acid bromide are added in small amounts, maintaining the temperature at O°C by external cooling. The pH is adjusted with sodium hydroxide to 8.0,

After completion of the addition the nnixture is left for one hour with agitation to comlete the reaction.
The reaction mixture is separated by filtration, the solid washed with water and dried. The alkylating agent used as starting compound in the 2nd reaction step.
2. Alkylation
The alkylation agent obtained in the 1st reaction step is added to 50 ml isopropaol and dissolved in two equivalent amounts (18,8 g) of 4-methyl-pyrldine. The temperature is raised to 80°C and maintained during the following 10 hours.
3. Condensation
20 ml of isopropanol are added to the reaction mixture obtained in the 2nd reaction step. Then the equivalent amount (30.0 g) of dimethylamino benzaldehyde and a catylytic amount (3.6g) of piperidine are added and the reaction mixture is stirred for 24 hours at 80°C.
The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 59 g of an orange solid product. The product is recristallized twice from isopropanol.

1. Acylating agent
A mixture of 21.4 g 2,2-dithiodipropionic acid in 100 ml chloroform and 24.0 g thionyl chloride are added in small amounts, maintaining the temperature by external cooling. After completion of the addition the mixture is heated to remove the formed gases and the reaction was finished. The solvent is removed by distillation under low pressure and the acid chloride used as starting compound in the 2^^ reaction step.
2. Alkylation
The dimethylsulfate as alkylation agent is used without solvent and mixed with two equivalent amounts (18.8g) 2-methyl-pyridine- The temperature is raised to 80°C and maintained during the following 2 hours.
3. Condensation
50 ml of isopropanol are added to the reaction mixture of the foregoing step. The equivalent
amount (24.0 g) of aminobenzaldehyde and a catalytic amount (3.6 g) of piperidine are added
and the reaction mixture is stirred for 16 hours at 70°C.
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum lo obtain 49 g of an orange solid product.
The product is recristallized twice from water.
4. Acylation
A mixture of 49 g of the fstyrene compound obtained in the 3rd reaction step and 200 ml water are cooled with stirring to O°C and then 41.0 g of the acid chloride obtained in reaction step 1 dissolved in tetrahydrofurane are added iri small amounts, maintaining the temperature by external cooling. The pH is adjusted to 6.0 by addition of sodium hydroxide. After completion of the addition the mixture is left for one hour with agitation to complete the reaction. The reaction mixture is separated by filtration, the solid washed with water and dried.

1. Alkylating agent
A mixture of 25,4 g of 2,2-dithiodiethylamine (cisteamine) as dichlorohydrate and 100 ml water is cooled with stirring to 0°C and then 41.0 g of bromo acetic acid bromide are added in small amounts, maintaining the temperature by cooling externally. The pH is adjusted to 8.0 by addition of sodium hydroxide-After completion of the addition the mixture is left for one hour with agitation to complete the reaction.
The reaction mixture is separated by filtration, the solid washed with water and dried. The alkylating agent is used as starting compound in the 2nd reaction step.
2.Alkylation
The alkylation agent obtained in the 1st reaction step is delivered from the solvent and dissolved in two equivalents (18.8 g) 2-methyl-pyridine. The temperature is raised to BO'^C and maintained at 60°C during the following 16 hours.

3. Condensation
50 mi ot (sopropanol are added to the reaction mixture obtained in the 2nd reaction step. The
equivalent amount (30.0 g) of dimethylamino benzaldehyde and a catalytic amount (3.6 g) of
piperidine are added and the reaction mixture is stirred for 24 hours at 70°C.
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum to obtain 57 g of an orange solid product.
The product is recristallized twice from methanol.

1. Acylating agent
24.0 g of thionyl chloride are added to a mixture of 21A g of 2,2-dithiodipropionic acid in 100
ml chloroform in small amounts, maintaining the temperature by external cooling.

After completion of the addition the mixture is heated to remove the formed gases and the
reaction is completed within one hour.
The solvent is removed by distillation under low pressure.
The acid chloride used as starting compound in the 2nd step
2. Alkyiation
The dimethylsulfate as alkyiation agent is used without solvent, with two equivalent amounts (18.8 g) of 4-methyl-pyhdine. The temperature is raised to 80°C and maintained at 80°C during the following 2 hours.
3. Condensation
50 ml of isopropanole are added to the reaction mixture obtained in the 2nd reaction step.
Then the equivalent amount (24,0 g) of aminobenzaldehyde and a catalytic amount (3.6 g) of
pipehdine are added and the reaction mixture is stirred for 12 hours at 70°C.
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum to obtain 55 g of an orange solid product.
The product is recristallized twice from water.
4. Acylatjon
A mixture of 55 g of the styrene compound obtained in the 3rd reaction step and 200 ml water is cooled with stirring to 0°C and then 45,0 g of the acid chloride obtained in the 1st reaction step, dissolved in tetrahydrofurane, are added in small amounts, maintaining the temperature at O°C by external cooling. The pH is adjusted to 7,0 by addition of sodium hydroxide. After completion of the addition the mixture is left for one hour with agitation to complete the reaction.
The reaction mixture is separated by filtration; the solid washed with water and dried, The product may be used as such for dyeing applications.

1. Acylating agent
A mixture of 18.4 g 2,2-dithioglycolic acid in 100 ml chloroform and then 24.0 g of thionyl chloride are added in small amounts, maintaining the temperature by external cooling. After completion of the addition the mixture is heated to remove the formed gases and the reaction is completed within one hour
The solvent is removed by distillation under low pressure and the acid chloride is used as such in the 4*^ reaction step.
2. Alkylation
The dimethylsulfate as alkylation agent is used without solvent with two equivalents (18.8g) 4-methyl-pyridine. The temperature is raised to 70°C and maintained at 80°C during the following 2 hours.
3. Condensation
50 ml of isopropanol are added to the reaction mixture obtained in the 2nd reaction step. The
equivalent amount (24.0 g) of amino-benzaldehyde and a catalytic amount (3.6 g) of piperidine
are added and the reaction mixture is stirred for 24 hours at 70°C,
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum lo obtain 49 g of an orange solid product.
The product is recristallized twice from water.

4. Acylation
A mixture of 49g of the styrene compound obtained in the 3nd' reaction step in 200 ml water are cooled with stirring to 0°C and then 35.0 g of the acid chloride obtained in the 1st reaction step, diluted with 30 ml tetrahydrofurane are added in small amounts, maintaining the temperature at O°C by external cooling. The pH is adjusted to 6.0 by addition of sodium hydroxide. After completion of the addition the mixture is left for one hour with agitation to complete the reaction. The reaction mixture is separated by filtration, the solid washed with water and dried. The product may be used as such for dyeing applications.

2. Alkyiation
The dimethyisulfate as alkyiation agent is used without solvent, dissolved in two equivalent amounts (18.8g) of 2-methylpyridine. The temperature is raised to 70°C and maintained at 80°'C during the following 2 hours.
3. Condensation
50 ml of isopropanole are added to the reaction mixture obtained in the 2nd reaction step. The
equivalent amount (24.Og) amino-benzaldehyde and a catalytic amount (3.6g) of piperidine
are added and the reaction mixture is stirred for 24 hours at 70°'C.
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum to obtain 49 g of an orange solid product.
The product is recristaJlized twice from isopropanol.
4. Acylation
A mixture of 49 g of thestyrene compound obtained in the 3rd reaction step and 200 ml water
are cooled with stirring to 0°C and then 41,0 g of acid chloride obtained in the 1st reaction
step are added in small amounts, maintaining the temperature at by 0°C external cooling.
The pH is adjusted to 6.0 by sodium hydroxide addition
After completion of the addition the mixture is left for one hour with agitation to complete the
reaction.
The reaction mixture is separated by filtration, the solid washed with water and dried.
The product may be used for dyeing applications.

1. Alkylating agent
A mixture of 21.5 g 2-hydroxyethyl-methylamine are neutralized witli hydrochloric acid and
evaporated to dryness. The salt is suspended in chlorofornn and cooled under stirring to 0°C
and then 41.0 g of thionyl chloride are added in small amounts, maintaining the temperature at
byO°C external cooling.
After completion of the addition the reaction is completed by heating to reflux and degassing
the mixture.
The solution is evaporated to dryness, the 2-chloroethyl-methylamine is used as chlorohydrate
in the 2nd reaction step.
2. Alkylation
The alkylation agent obtained in the 1st reaction stepis dissolved in n-butanol and two equi¬valent amounts (16,8g) 4-methyl-pyridine are added. The temperature is raised to 120°C and maintained during the following 6 hours. Than the temperature is lowered to 70°C.
3. Condensation
The equivalent amount (30.Og) of dimethylaminobenzaldehyde and a catalytic amount (3.6g)
of piperidine are added to the reaction mixture obtained in the 2nd reaction step and the
reaction mixture is stirred for 24 hours at 70°C.
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum to obtain 50 g of an orange solid product.
The structure of the compound of formula

4. Alkylating agent
A mixture of 15.4 g of 2,2-dithiocliethanol in 100 ml chloroform and 24.1 g pyridine are cooled
with stirring to 0°C and then 22.0 g of mesyl chloride are added in small amounts, maintaining
the temperature at 0°C by external cooling.
After completion of the addition the mixture is left over night in the refrigerator to complete the
reaction.
The reaction mixture is mixed with a water/hydrochlohc acid and ice slurry, the phases are
separated, washed with water and dried.
The solution of methanesulfonate diester is used as such in the 5th reaction step.
5. Alkylation
Two equivalents (18.8g) of the intermediate dye molecule obtained in the 3rd reaction step are
dissolved in alkylation agent obtained in the 4th reaction step with a solvent. The temperature
is raised to reflux and maintained at 70°C during the following 12 hours.
The reaction mixture is cooled to ambient temperature with agitation and separated through
filtration.
The solid is washed with chloroform and dryed.

1. Alkylation
The alkylation agent 2-chloroethyl-N,N-dimethylamine is dissolved in n-butanol and equivalent amounts (18.028 g) of 4-methyl-pyridine are added. The temperature is raised to 120°C and maintained at 120'C during the following 6 hours. Than the temperature is lowered to TC'C,
2. Condensation
The equivalent amount (30.Og) of dimethylamino-benzaldehyde and a catalytic amount (3.6g)
of piperidine are added to the reaction mixture obtained in the 1st reaction step and the
reaction mixture is stirred for 24 hours at 70°C.
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum to obtain 50 g of an orange solid product.
The structure corresponding to formula

3. Alkylating agent
A mixture of 15.4 g of 2,2-clithiodiethanol in 100 ml chloroform and 24.1 g pyridine are cooled
with stirring to 0°C and then 41 .Og of tosyl chloride are added in small amounts, maintaining
the temperature at 0°C by cooling externally.
After completion of the addition the mixture is left over night in the refrigerator to complete the
reaction.
The reaction mixture is mixed with a water/chlorhidric acid and ice slurry, the phases are
separated, washed with water and dried.
The solution of toluenesulfonate diester is used as starting compound in the 4th reaction step.
4. Alkylation
Two equivalents (56g) of the intermediate dye molecule are dissolved in the foregoing
alkylation agent obtained in the 4th' reaction step with solvent. The temperature is raised to
reflux and maintained at 70°C during the following 12 hours.
The reaction mixture is cooled to ambient temperature with agitation and separated through
filtration.
The solid is washed with chloroform and dryed.

Example ANT-01:
2.95 g of 1-(3-dimethylaminopropyl)amino-4-amino-anthraquinone (RN 65274-31-9) and 1.80 g of bis(2-(2-bromoacetamido)ethyl)-disulfide (RN 697755-79-6) are dissolved in 20 ml DMF and stirred for 5 h at 40°C. The dark blue solution is than dropped slowly into 500 ml acetone under vigorous stirring. The precipitate is filtered off, washed with 100ml acetone and dried in a vacuum oven at 50°C to yield 4.06 g of the compound of formula

Example ANT~02:
2.06 g of the compound of formula (101) are dissolved in 30 ml NMP and 530µl 4-bromo-butyryl chloride are added under stirhng. After 40 min 10 ml of a 4.2 M solution of trimethyl-amine in ethanol are added and the reaction mixture is stirred at 80°C for 17 h. Then 10 ml of acetone are added and the resulting precipitate is separated by filtration, washed with acetone and dried to give 1.40 g of the compound of formula

Example ANT-03:
Slept. A solution of 19.39 g 1,3-dibromopropane in 10 ml of chloroform is stirred at room temperature and a solution of 0.50 g N,N'-tetramethylcystamine (RN 1072-11-3) in 10 ml of chloroform is added over a period of 8 h. After additional stirring for 2 days the resulting white precipitate is filtered off, washed with chloroform and dried under vacuum.
Step 2: The white solid prepared in step 1 is added to a solution of 1.06 g of 1-(3-dimethyl-aminopropyl)amino-4-amino-anthraquinone (RN 65274-31-9) In 10 ml DMF. The solution is stirred for 3 days at 4^0. After that time the reaction mixture is poured into 200 ml of acetone and the resulting precipitate is collected by filtration. Than the crude product is refluxed for 40 min in 120 ml of acetone. The suspension is filtered off and the collected solid is dried under vacuum at 60'C. Yield: 1.64 g of the compound of formula

'^CNMR(DMS0-d6)[ppm]: 6 181.68, 18123, 146.66, 146.58, 134,46, 134.17, 132.80, 132.70, 130.12, 126.13, 126.05, 124.12, 108.76, 108.43, 62.93, 61.93, 60.05, 60.00, 51.19, 51.00. 39.66, 30.86, 23.34, 17.36.
Example ANT-04:
5.00 g of 1-(3-dimethylaminopropyl)amino-4-am(no-anthraquinone (RN 65274-31-9) and 3.58 g of the bis(toluolsulfonate) of (2-hydroxyethyl)-'disulfide (RN 69981-39-1; prepared as described in Delacroix et al., Bull Soc. Chim. France (1978), (9-10, Pt. 2), 481-4) are dissolved in 15 ml NMP and stirred at 80°C for 72 h. Then the reaction mixture is poured into 150 ml of acetone and the precipitate is separated from the supernatant liquid. The residue is refluxed for 1 h in 60 ml acetone collected by filtration and dried under high vacuum to obtain 3.55 g of the compound of formula

Example ANT-05:
Step 1: To a solution of 61.32 g 1-(3-aminopropyl)'imidazole, 5.92 g lithium hydroxide and 1.48 9 Cu(l)CI in 150 ml water. 100 g of sodium 1-amino-4-bromoanthraquinone-2-sulfonate (RN 6258-06-6) are added over a period of 15 min. The reaction mixture is stirred for 30 min at 65°C and then for 1 h at 85°C. After the resulting blue solution had cooled down to room temperature 75 ml concentrated hydrochloric acid are added. The resulting precipitate is filtered off, suspended in 200 ml acetone and stirred for 1h. After filtration the crude product is suspended in 500 ml water and dissolved by addition of 19.98 g of a 4 molar sodium hydroxid solution. Then 18 g of sodium chloride are added and the resulting precipitated is filtered off and dried to yield 44.23 g of the compound of formula

Step 2: To a suspension of 30.78 g of the compound of formula (105a) in 300 ml of water 34 ml sodium hydroxid solution (30 %) are added. The mixture is heated to 80°C and a solution of 16.31 g glucose in 90 ml water is added dropwise over a period of 40 min. After 30 min the suspension is cooled to room temperature and filtered. The press cake is stirred in 450 ml 4
molar sodium hydroxid solution, filtered off and washed with water. The residue is dried in a vacuum oven at 50°C to yield 19.69 g of the compound of formula

MS (ES+): m/2 463 (M^'). UVA/IS [nm] (water/acetonitrile 1:1): λ1 571 λA2 609.
Example ANT-06:
Step 1: A mixture of 5.00 g of C.I. Acid Blue 25 (RN 6408-78-2), 7.93 g potassium hydroxide and 20 ml of N,N-dimethyl-ethanotamine is stirred at room temperature for 2 h. Then the reaction mixture is poured into 200 ml of water and the resulting precipitate is collected by
filtration. The solid is stirred in 200 mi of water lor 30 min, then filtered off and dried under vacuum at 60*C to obtain 1.69 g of the compound of formula

step 2/0.50 g of the compound of formula (106a) and 0.29 g of the bis(totuolsulfonate) of (2-hydroxyethyl)-disulfide (RN 69981-39-1) are dissolved in 3 ml of NMP and stirred at 40°C for 72 h. Then the mixture is stirred for additional 72 h at SOX. Then the reaction mixture is dropped into 200 ml of tert-butyl-methyl-ether. The precipitate is separated by filtration, dissolved again in 3 ml of NMP and precipitated by dropping the solution into 50 ml tert-butyl-methyl-ether. After filtration the product is dried under vacuum to obtain 0.32 g of the compound of formula

MS (ES+): m/z 332 (M+1). UVA/IS [nm] (water/acetonitrile 1:1):λmax 394.
Step 2:1.28 g of the compound of formula (107a) and 0.726 g of bis(2-(2-bromoacetamido)-ethyl)-disulfide (RN 697755-79-6) are mixed in 5 ml dimethylformamide and stirred at 60°C for 24h. The reaction mixture is poured into 150 ml acetone under stirring. The precipitate is

2,0 g (8.1 mmol) of 4-chloro-3,5'dinitro benzoic acid are brought in 6ml acetone. 0.092g (8.1 mmol) of cysteamine hydrochloride dissolved in 10ml H2O is added to the resul¬ting solution. The pH value of this mixture is adjusted to 9 with 10 N sodium hydroxide. The reaction solution is stirred at room temperature under nitrogen atmosphere. The pH value is controlled in distinct intervals by addition of 10 N sodium hydroxide and adjusted to 9. After reaction time of 6h the mixture is acidified with 2 N HCI and the precipitate is filtered off. The filter cake is washed with HCi (10 N) and than with destilled water. The solid is recrystallized from water/acetone. 1.5g of a yellow-orange solid are obtained. Mp: 253-255°C.

5.66g (25.2 mmol) cystamin dihydrochloride are furnished in 40ml dimethylsulfoxide.
8.46g (lOO.8mmol) sodium hydrogen carbonate are added stepwise.
Then 10.0g (50.4mmol)4-fluoro-3~nitrophenylacetamide, dissolved in 100ml dimethylsulfoxide
are added dropwise at 45'C.
The reaction mixture is stirred for 7h at SCC and cooled down to room temperature. The
reaction mixture is placed on a water/ice mixture and adjusted to pH 3 by addition of cone.
HCI.
The resultant precipitate is filtered off, washed with water for several times and dried in vacuo.
12.4g (97%) of a red dye are obtained.
Mp: 199-201°C.

20% hydrochloric acid.
The obtained suspension is refluxed for 4h, whereupon the color of the reaction mixture
changes from red to orange.
Then the heterogenic reaction mixture is cooled down to room temperature and the pH is
adjusted to 4 with 20% NaOH.
The piecipiiate is filtered off and washed with 10% sodium hydrogen carbonate solution aiid
then neutral with water.
3.5g (84%) of a violet dye are obtained.
Mp.: 193-195"C

I
b. 34 g of the compound of formula (104a) and 30 g of the bis(toluolsuifonate) of (2--hydroxy-ethyl)-ciisulfide (RN 69981-39-1; prepared as described in Delacroix et al., Bull. Soc. Chim. France (1978), (9-10, Pt 2), 481-4) are suspended in 80 ml of NMP and stirred for 3 days at 45°C. Then 1 I tert.-butyl methyl ether are added slowly to the reaction mixture and the resul¬ting precipitate is collected by filtration. Then the crude product is redissolved in 200 ml ethanol and precipitated again by addition of 150 ml of tert.-butyl methyl ether. The solid is collected by filtration and dried in vacuo to yield 22.6 g of an orange powder which corresponds to the compound of formula (104).
MS (ES+): m/z 326 (M2+). UVA/IS [nm] (water): λmax 466.

(ai) Condensation
300 ml of chloroform are added to the reaction vessel.
10.5g rhodamine B are introduced with mixing.
The equivalent amount (1.54g) of 2,2-dithlodiethanol, 12.0 g dicyclohexylcarbodiimide and a
catalytical amount (7.6g) of pyrolidinopyridine are added.
The reaction mixture is stirred for 24h at 293°C.
The reaction product is separated by washing with 100 ml of a 3% hydrochloric acid solution
then with 100ml water with 3% salt.
The solution is evaporated to dryness in vacuum to obtain 12g of a reddish blue solid product.

(a) Condensation
300 ml chloroform are added to the reaction vessel.
10.5g raw material are introduced with mixing, the equivalent amount (1.54g) of 2,2-dithio-
diethanol, 12.0g dicyclohexylcarbodiimide and a catalytical amount (7.6g) of pyrolidinopyridlne
are added.
The reaction mixture is stirred for 24h at 293'C.
The reaction product is separated by washing with 100 ml of a 3% hydrochlonc acid solution,
then with 100 ml water with 3% salt.
The solution is evaporated to dryness in vacuum to obtain 12g of a reddish blue solid product.

300 ml chloroform are added to the reaction vessel.
10.5 g rhodamine G are introduced with mixing, the equivalent amount (1.54g) 2,2-dithiodi-
ethanol ,12.0g dicyclohexylcarbodiimide and a catalytical amount (7,6g) pyrolidinopyridine are
added and the reaction mixture is stirred for 24h at 293'C.
The reaction product is separated by washing with 100 ml of a 3% hydrochloric acid solution,
then with 100 ml water with 3% salt.
The solution is evaporated to dryness in vacuum to obtain 12g of a reddish blue solid product.

(a) Alkylating agent
A mixture of 15.4g 2,2-dithiodiethanoI in 100 ml chloroform and 241g pyridine are cooled with
stirnng to 0°C.
22.Og mesyl chloride are added in small amounts, maintaining the temperature by cooling
externally.
After completion of the addition the mixture is left over night in the refrigerator to finish the
reaction.
The reaction mixture is mixed with a water/hydrochloric acid and ice slurry, the phases are
separated, washed with water and dried.
The solution of methanesulfonate diester used for reaction step (b).
(b) Alkylation
The reaction mixture of 250 g water and 103g of the xanthene precursor obtained in reaction
step (a) is adjusted to pH 9.2 with sodium carbonate.
80ml toluene and the equivalent amount (32.0g) of diester and a catalytical amount (0.6g) of
tetrabutyl-ammonium bromide are added and the reaction mixture is stirred for 6 hours at 300
K.
Tne reaction product is heated to 350 K, the lower water phase is separated, the upper
toluene phase washed, then 160 ml water are added and toluene distillated.
The precipitate is separated by filtration and dried in vacuum to obtain 90g of-an orange solid
product
The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/360MHz

(a) Condensation
300ml chloroform are added to the reaction vessel.
10.5g Pergascript Orange are introduced with mixing, the equivalent amount (1.54g) 2,2-
dithiodiethanol and 12.0g dicyclohexylcarbodiimide and a catalytical amount (7.6g) of
pyrolidinopyridine are added and the reaction mixture is stirred for 24h at 293°C.
The reaction product is separated by washing with 100 ml of a 3% hydrochlohc acid solution,
then with 100 ml water with 3% salt.
The solution is evaporated to dryness in vacuum to obtain 12g of a reddish blue solid product.
The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/360MHz

Example QXA-Q1 (Procedure (a)):
Step 1: 6.34g of 1-(3-methoxyphenyl)-piperazine dihydrochloride are suspended in 4 ml and
cooled to 0- 5°C,
8.58g of a sodium methylate solution in methanol (1 mol methylate in 179.6 g solution) are
added dropwise to this suspension, maintaining the temperature at 0 - 5°C.
After completion of the addition the mixture is was stirred for 30min at room temperature.
Finallv the solvent is removed by evaporation and the remaining brown oil is dissolved in 40ml
dimethyl formamide.

6.58g bis (2-(2-bromoacetamide) ethyl disulfide (RN 697755-79-6) and 4.66 g potassium
carbonate are added to this solution and the reaction mixture is stirred for 5 days at 40'C.
Then the reaction mass is poured into 50 ml diethyl ether.
The product precipitates as an oil, which is dissolved in 100ml dichloromethane and washed
with a NaHCO3 solution.
The organic phase is dried over sodium sulphate and filtered.
Then the solvent is evaporated and the remaining oil is purified by column chromatography
(acetone, silica) to obtain 0.64 g of compound of formula

Step 2: 0.88g HBr (33%) are added drop wise to a suspension of 0.5g of the compound of
formula (1o1a) in 2 g dimethyl formamide and 2.5 g water at 0 -- 5°C.
After completion of the addition the yellow solution is warmed up to room temperature and
0.32g of an aqueous sodium nitrite solution (46 w.%) is added slowly.
The reaction mixture is stirred at room temperature until the test on nitrite is negative
(potassium iodide/starch paper).
The dark reaction mixture was used for reaction step 3.
Step 3: 0.27g 3-diethylaminophenol are dissolved in 3g dimethyl formamide and after addition
of a few drops of HBr (33%) the solution is heated to 70°C,
At this temperature the dark reaction mixture obtained in the nitrosation step is added via a
dropping funnel over a period of 1h.
The resulting blue solution is stirred for an additional hour, then cooled to room temperature
and poured into 200 ml of acetone.

as a dark blue powder, which can be used for the dyeing of hair. MS (ES+): m/z 453 (M'); UV/VIS ( water): λnax1, 642nm, λmax2 588nm.
Example OXA-02 (Procedure (b)):
Step 1: A solution of 7.58g of 3-diethylamino-anisole in 37g dimethyl formamide and 45g water
is cooled to 0°C. Then 19.5g HBr (33%) are added via a dropping funnel over a period of 1h.
during which time the temperature is nsing to 15°C.
Then 7.04g of an aqueous sodium nitrite solution (46 % b.w.) is added dropwise over a period
of 30min.
The reaction mixture is stirred at room temperature until the test on nitrite is negative
(potassium iodide/starch paper).
The resulting dark solution is used forstep 2.
Step 2: A solution of 6.68g 1-(3-hydroxyphenyl) piperazine and 9g HBr (33%) in lOg dimethyl
formamide is heated to 70°C.
At this temperature the dark solution obtained in step 1 s added via a dropping funnel over a
period of 2.5h.
The resulting blue solution ios stirred for an additional hour, then cooled to room temperature
and poured into 300 ml of acetone.
The precipitate is collected by filtration and stirred in 100ml of refluxing acetone two times
before it is filtered off and dried In vacuo to obtain 6.97g of the compound of formula

MS (ES+): m/z 337 (M'-l); UVA/IS ( water): λmax1 634nm, λmax2 590nm.
Step 3: A solution of 0.5g of the compound of formula (102a), 0.24g of bis(2-(2-bromo-acetamide)etnyl)-disulfide (RN 697755-79-6) and 0.08 g of potassium carbonate in SOrnI methanol is stirred at 40°C for 12h.
After that time the solvent is removed by evaporation, the remaining solid is dissolved in 5 ml dimethyl formamide and this solution is dropped into 20ml of acetone.

The resulting precipitate is collected by filtration and dried to obtain 0.23g of the compound of formula (OXA-101) as a dark blue powder, which can be used for the dyeing of hair.

(a) Condensation
35.7g 1,3,3 trimethyl-2-methyleneHndoline are added to 60g acetic acid.
The equivalent amount (35.Og) of 2-chloroethyl-methylamino-benzaldehyde is added and the
reaction mixture stirred for 6h at 30-40'*C,
The reaction product is precipitated by cooling, diluted with 375ml water and salted out with
40g sodium chloride, then separated by filtration and dried in vacuum to obtain 65g of a
reddish violet solid product.
The product is recristallized twice from methanol.

(c) Hydrolysis
One equivalent (4,0g) sodium hydroxide is dissolved with absolute ethanol as solvent in the
compound (101b) as obtained in step (b).
The temperature is maintained at 80°C during the following 4 hours.
The product is crystallized by cooling to room temperature under mixing, than separated by
filtration, washed and dryed in vacuum dryer.

(a) Alkvlation
One equivalent (6.0 g) of thiourea is dissolved with absolute ethanol as solvent in 30 g of the
alkylating dye of formula (101a)-
The temperature is raised to reflux and maintained at 80°C during the following 48 hours. The
product is crystallized by cooling to room temperature under mixing, than separated by
filtration, washed and dried in vacuum dryer.

One equivalent (14.0g) of ethyl xantogenate is dissolved with absolute ethanol as solvent in the alkylating dye of formula (101a).
The temperature is raised to reflux andmaintained at 80°C during the following 8 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dryed in vacuum dryer.

94g dimethylsulfate are introduced into that mixture within one hour. The temperature is maintained at 333 K during the following 1.5 hours.
(b) Condensation
The equivalent amount (150.0g) 2-chloroethyl-methylamino-benzaldehyde, 250ml ethanol and
a catalytical amount (9.6g) of pipehdine are added to the reaction mixture obtained in step (a)
and the reaction mixture stirred for 8 hours at,
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum to obtain 240g of an orange solid product.
The product is recristallized twice from methanol.

(c):
One equivalent (6.0g) thiourea is dissolved with 75 ml absolute ethanol as solvent in 20g
alkylating dye of formula (PRO--104a).
The temperature is raised to reflux and maintained at 80°C during the following 48 hours. The
product is crystallized by cooling to room temperature under mixing, than separated by
filtration, washed and dried in the vacuum dryer

One equivalent (8.0g) of potasium thioacetate is dissolved with absolute ethanol as solvent to 20g of the alkylating dye of formula (PRO-104a).
The temperature is raised to reflux and maintained at 80°C duhng the following 4 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dned in the vacuum dryer.

One equivalent (6.0g) thiourea is dissolved in absolute ethanolm the compound of formula
(PRO-104a).
The temperature is raised to reflux and maintained at SCC during the following 48 hours.
The obtaiened product is dissolved in one equivalent (4.0 g) of sodium hydroxide with
absolute ethanol.
The temperature is maintained at 80°C during the following 4 hours.
The product is crystallized by cooling to room temperature under mixing, than separated by
filtration, washed and dried in the vacuum dryer.
The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/ 360MHz

One equivalent (14.0 g) of ethyl xanthogenate is dissolved with 75 ml absolute ethanol in 20 g of the compound of formula (PRO-104a).
The temperature is raised to reflux and maintained at 80°C during the following 18 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in thevacuum dryer.

The temperatureis raised to reflux andmaintained at 80°C during the following 36 hours. The product is crystallized by cooling to room temperature under mixing, then separated by filtration, washed and dried in the vacuum dryer.

(a) Alkvlation
2-methyl-pyridine (68.8g) arere dissolved in 80ml absolute ethanol.
The temperature is raised to 333 K.
94g dimethylsulfate are introduced in this mixture within one hour.
The temperature is maintained at 333 K during the following 3h.
fb) Condensation
the equivalent amount (150g) 2-chloroethyl-methylamino-benzaldehyde, 250 ml ethanoi and a
catalitical amount (9,6 g) piperidine are added to the reaction mixture obtained In step (a) and
is stirred for 18 hours at 343 K.
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum to obtain 220g of an orange solid product of formula

One equivalent (6,0 g) of thiourea is dissolved in the compound of formula (107a) with
absolute ethanol.
The temperature is raised to reflux andmaintained at 80°C during the following 48 hours.
(d) Hvdrolvsis
One equivalent (4.0g) sodium hydroxide is dissolved to the substance obtained in step (c) with
absolute ethanol.
The temperature is maintained at 80°'C during the following 4 hours.
The product is crystallized by cooling to room temperature under mixing, than separated by
filtration, washed and dried in the vacuum dryer.
The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/360MHz

(a) Alkylation
250g of 4-methyl-quinoline are dissolved in 80 ml absolute ethanol. The temperature was raised to 333 K.
94 g dimethylsulfate are introduced into this mixture within one hour. The temperature is maintained at 333 K during the following 2.5 hours.
(b) Condensation
The equivalent amount (1500g) of 2-chloroethyl-methylamino-benzaldehyde, 250 ml ethanol and a catalytical amount (9.6g) of piperidine are added to the reaction mixture obtained in step (a) and the reaction mixture stirred for 8 hours.
The reaction product is precipitated by cooling, then separated by filtration and dned in vacuum to obtain 340g of an orange solid product of formula

The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/ 360MHz and shows a complex spectra. Throught HPLC/MS the identity was proofed, obtaining a single peak with the mass of 337/339 dalton.
(cj
One equivalent (6.0g) thiourea is dissolved in 30 g of the the compound of formula (108a) with
absolute ethanot.
The temperature is raised to reflux andmaintained at 80°C during the following 48 hours.
The product is crystallized by cooling to room temperature under mixing, than separated by
filtration, washed and dried in vacuum dryer.
The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/360MHz Throught HPLC/MS the identity was proofed, obtaining a single peak with the mass of 377
dalton

The temperature is raised to reflux andmaintained at 80°C during the following"48 hours.
(b) Hydrolysis
One equivalent (4.0g) sodium hydroxide is dissolved in the substance obtained in step (a) with
absolute ethano.
The temperature is maintained at 80°C during the following 4 hours.
The product is crystallized by cooling to room temperature under mixing, than separated by
filtration, washed and dried in the vacuum dryer.
Throught HPLC/MS the identity was proofed, obtaining a single peak with the mass of 333 dalton

(a) Alkylation
250 g 2-methyl-qu!noline are dissolved in 80 ml absolute ethanol. The temperature is raised to 333 K.
94g dimethylsutfate are introduced within one hour into that mixture. The temperature is maintained at 333 K during the following 2.5 hours.
(b) Condensation
The equivalent amount (150.0g) of 2-chloroethyl-methylamino-benzaldehyde, 250 ml ethanol and a catalytical amount (9.6g) of piperidine are added to the reaction mixture obtained in step (a) and the reaction mixture stirred for 8 hours.
The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 340g of an orange solid product of formula compound of formula (PRO-110;. The product is recristallized twice from methanol.
The product is characterized by 1H-NMR data in deuterated chloroform (128 scans)/360MHz

gle
One equivalent (6.0g) thiourea is dissolved in 30g of the compound of formula (PRO-112a) with absolute.
The temperature is raised to reflux and maintained at 80°C during the following 48 hours. The product is crystallized by cooling to room temperature under mixing, than separated by filtration, washed and dried in vacuum dryer.
Throught HPLC/MS the identity was proofed, obtaining a single peak with the mass of 334 datton

A mixture of 15.4 g 2,2-dithiodiethanoi in 100 ml chloroform and 24.1 g pyridine are cooled
with stirring to 0°C and then 41.0 g of tosyl chloride are added in small amounts, maintaining
the temperature.
After completion of the addition the mixture is left over night in the refrigerator and the reaction
is finished.
The reaction mixture is mixed with a water/hydrochloric acid and ice slurry, the phases are
separated, washed with water and dried.
The solution of totuenesulfonate diester is used for steb (b).

(b) Alkylation
The alkylation agent obtained in step (a) is freed from the solvent and dissolved in two
equivalent amounts of 2-methyl-pyridine.
The temperature is raised to 60°C andmaintained at 60°C during the following 24 hours.
(c) Condensation
50 ml dimethyl-formamide are added to the reaction mixture obtained in step (b).
The equivalent amount of 2-chloroethyl-methylamino-benzaldehyde and a catajytical amount
of piperidine are added and the reaction mixture is stirred for 40 hours at 80*'C.
The reaction product is precipitated by cooling, then separated by filtration and dried in
vacuum to obtain 39g of an orange solid product.
The product is recristallized twice from isopropanol.

(e) Hydrolysis
One equivalent (4,0 g) of sodium hydroxide is dissolved with absolute ethanol as solvent in the
substance of step (d).
The temperature is maintained at 80°C during the following 4 hours.
The product is crystallized by cooling to room temperature under mixing, than separated by
filtration, washed and dried in the vacuum dryer.

a. Alkylating agent
A mixture of 15.4g of 2,2-dithiodiethanol in 100 ml chloroform and 24.1g pyndine are cooled
with stirring to 0°C.
41,0 g of tosyl chloride are added in small amounts, maintaining the temperature.
After completion of the addition the mixture is left over night in the refrigerator to finish the
reaction.
The reaction mixture is mixed with a mixture of water/hydrochloric acid and ice slurry, the
phases are separated, washed with water and dried.

The solution of toluenesulfonate diester is used as starting compound in step b.
b. Alkylation
The alkylation agent obtained in step a. is delivered from the solvent and dissolved in two equivalent amounts of 2-methyl-pyridine. The temperature is raised to 60°C and maintained at 60°C during the following 24 hours.
c. Condensation
50 ml of dimethyl-formamide are added to the reaction mixture obtained in step b.
The equivalent amount of dimethylamlno-benzaldehyde and a catalytical amount of piperidine
are added and the reaction mixture is stirred for 40 hours at 80°C.
The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to
obtain 39 g of an orange solid product.
The product is recristallized twice from isopropanol.
The product is characterized by the following data:
- The HPLC-MS gives a main component of a monocation of the mass 283.
- 1H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

a. Alkylating agent
A mixture of 15.4g of 2,2-dithiodiethanol in 100 ml chloroform and 24.1g pyridine are cooled
with stirhng to O°C and then 41.0 g of tosyl chloride are added in small amounts, maintaining
the temperature.
After completion of the addition the mixture is left over night in the refrigerator to finish the
reaction.
The reaction mixture is mixed with a mixture of water/hydrochloric acid and ice slurry, the
phases are separated, washed with water and dried.
The solution of toluenesulfonate diester is used as starting compound in the step b.
b.Alkylation
The alkylation agent obtained in step a. is delivered from the solvent and dissolved in two
equivalent amounts of 2-methyl-pyridine.
The temperature is raised to 60°C and maintained during the following 24 hours.
c. Condensation
50 ml of isopropanol are added to the reaction mixture obtained in step b.
The equivalent amount of anisaldehyde and a catalytical amount of anhydrous sodium acetate
are added and the reaction mixture is stirred for 40 hours at 80°C.
The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to
obtain 29 g of a yellowish solid product.
The product is recristallized twice from isopropanol.
The product is characterized by the following data:
- The HPLC-MS gives a main component of a monocation of the mass 270.
- 1H-NMR data in deuterated methanol128 scans)/ 360MHz:

a. Alkylating agent
A mixture of 15.4g of 2,2-dithiodiethanol in 100 ml ethylene and 24.1g pyridine are cooled with
stirring to 0°C and then 41.0 g of tosyl chloride are added in small amounts maintaining the
temperature.
After completion of the addition the mixture is left over night in the refrigerator to finish the
reaction.
The reaction mixture is mixed with a mixtue of water/hydrochloric acid and ice slurry, the
phases are separated, washed with water and dried.
The solution of toluenesulfonate diester is used as starting compound in step b.
b.Alkylation
The alkylation agent obtained in step a. is delivered from the solvent and dissolved in two
equivalent amounts of 2-methyl-pyhdine.
The temperature is raised to 70°C and maintained during the following 24 hours.
c. Condensation
50 ml of toturnr are added to the reaction mixture obtained in step b.

The equivalent amounts of amino-benzaldehyde and a catalytical amount of piperidine are
added and the reaction mixture is stirred for 30 hours at 80°C.
The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to
obtain 41 g of an orange solid product.
The product is recristallized twice from isopropanol.

a. Alkylating agent
A mixture of 15.4g of 2,2-dithiodiethanol in 100 ml chloroform and 24.1 g pyridine are cooled with stirring to O°C.
41.0 g of tosyl chtoride are added in small amounts maintaining the temperature-After completion of the addition the mixture is left over night in the refrigerator to finish the reaction.

The reaction mixture is mixed with a mixture of water/hydrochloric acid and ice slurry, the
phases are separated, washed with water and dried.
The solution of toluenesulfonate diester is used as starting compound in step b.
b. Alkylation
The alkylation agent obtained in step a. is delivered from the solvent dissolved in two
equivalent amounts of 2-methyl-pyridine.
The temperature is raised to 60X and maintained during the following 24 hours.
c. Condensation
50 ml of isopropanol are added to the reaction mixture obtained in step b.
The equivalent amounts of 4-fluoro-benzaldehyde and a catalytical amount of piperidine are
added and the reaction mixture is stirred for 30 hours at 70°C.
The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to
obtain 35g of a yellow solid product.
The product is recristallized from isopropanol.

a. Alkylating agent
A mixture of 15.4g of 2,2-dithiocliethanol in 100 ml chloroform and 24.1g pyridine are cooled
with stirring to 0°C and then 31.0 g of mesyl chloride are added in small amounts, maintaining
the temperature.
After completion of the addition the mixture is left over night in the refrigerator to finish the
reaction.
The reaction mixture is mixed with a mixture ofwater/hydrochloric acid and ice slurry, the
phases are separated, washed with water and dried.
The solution of methanesulfonate diester is used as starting compound in the step b.
b. Alkylation
The alkylation agent obtained in step a. is freed from the solvent and dissolved in two
equivalent amounts of 2-methyl-pyridine.
The temperature is raised to 60°C and maintained during the following 24 hours.
c. Condensation
50 ml of dimethyl-formamide are added to the reaction mixture obtained in step b.
The equivalent amount of benzaldehyde and a catalytical amount of piperidine are added and
the reaction mixture is stirred for 40 hours at 80°C.
The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to
obtain 33 g of a yellow solid product.
The product is recristailized twice from isopropanol.
The product is characterized by the following data:
- The HPLC-MS gave a main component of a monocation of the mass 240.
- 1H-NMR data in deuterated Methanole (128 scans)/ 360MHz:

a. Alkylating agent
A mixture of 15.4g of 2,2-dithiodiethanol in 100 ml chloroform and 24.1g pyridine are cooled
with stirring to 0°C and then 31.Og of mesyl chloride are added in small amounts, maintaining
the temperature.
After completion of the addition the mixture is left over night in the refrigerator to finish the
reaction.
The reaction mixture is mixed with a mixture of water/hydrochloric acid and ice slurry, the
phases are separated, washed with water and dhed.
The solution of methanesulfonate diester is used as starting compound in step b.
b. Alkylation
The alkylation agent obtained in step b. is delivered from the solvent dissolved in two equivalent amounts of 2-methyl-pyridine. The temperature is raised to 60°C and maintained during the following 24 hours.
c. Condensation
50 ml of dimethyl-formamide are added to the reaction mixture obtained in step b.
The equivalent amount of acetylamino-benzaldehyde and a catalytical amount of pipehdine
are added and the reaction mixture is stirred for 40 hours at 80°C.

The reaction product is precipitated by cooling, separated by filtration and dried in vacuum to
obtain 44 g of a brown solid product.
The product is recristallized twice from isopropanot.
The product is characterized by the following data:
- The HPLC-MS gave a main component of a monocatlon of the mass 297.
- 1H-NMR data in deuterated methanol (128 scans)/ 360MHz:

These three compositions (b-1) - (b-3) are applied to hair according to the following the general procedure:
A tress of bleached human hair is shampooed. Then the towel dried hair tress is put on the glass plateThe solution (B-1) (permanent solution) is applied to the wet hair tress. After 10 min the hair tress is rinsed under tap water and pressed out with a paper towel. Afterwards the tress is treated with a solution (B-2) containing the dye mixtures described in table 2 for 20 min and then rinsed with water. Then solution (B-3) (permanent fixation) is applied to the towel dhed hair tress. After 10 min. the hair tress is rinsed under tap water again and dried.
The color result for each dye mixture is given in tables 2 and 3, In general all tresses showed an intense coloration and a very good wash fastness.

Claims_:
1. Mixture of dyes selected from the compounds of formula (1) D—(Zi)r-Y1—S—A, wherein
A is hydrogen; a radical of formula (1a) *—s—Y2—(Z2)—D2 ; or a thio ester group of

wherein the the mixture comprisies at least two compounds of formula (1), and/or at least two compounds of formula (2) and/or at least one compound of formula (1) and at least one compound of formula (2), wherein R1, R2 and R3 independently from each other hydrogen; halogen; C1-C16alkyl, which is
saturated or unsaturated, linear or branched, substituted or unsubstituted, or interrupted
or uninterrupted with heteroatoms; phenyl, which substituted or unsubstituted; a
carboxylic acid radical; sulfonic acid radical; hydroxy; nitrile; CrCiealkoxy, (poly)-hydroxy-
C2-C4-alkoxy; halogen; SO2NR33R34; SR33; NR33R34; OR33; SO2; COOR33; NR33COR34; or
CONR33; Q1 is a bivalent radical selected from -N=N-; -CRd=N-; -N=CRd-; -NRd-N=CRe-; and
-RdC=N'NRe-; T1 is a bivalent radical of an aromatic or heteroaromatic substituted or unsubstituted
compound; Rd and Re independently from each other are hydrogen; unsubstituted or substituted Cr
C14alkyl: C2-C14alkenyl; C5-C10aryl; C1-C1oaikyl-C5-C10aryl; or C5-C10aryl-C1-C10oalkyl; R33 and R34 independently from each other are hydrogen; C1-C12alkyl, which may be
substituted by one or more C1-C5alkyI, C1-C5-alkoxy, hydroxy or -(CO)"H;
-(C0)-C1-C5alkyl; phenyl or phenyl-C1-C4alkyl, wherein the phenyl moiety may be

substituted by one or more C1-C5alkyl, C1-C5alkoxy, halogen, -NH2, monO'Ci-
C5alkylamino, di-C1-C5alkylannino, 'NO2, carboxy or hydroxy; R4, R5 and R6 independently from each other are hydrogen; C1-C20alkyI or C1-C20alkoxy, which
may be substituted by one or more C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino,
di-C1-C5alkylamino, -NO2 or hydroxy; C3-C6cycloaikyj; -C(0)H; -C(0)-C1-C5alkyl; halogen;
NO2; OH; phenyl, which may be substituted by one or more C1-C5alkyl. C1-C5alkoxy,
halogen, -NH2, mono-C1-C5alkyiamino, di-C1-C5alkylamino, -NO2 or hydroxy; or a radical
of formula -NR35R36; W1, W2, W3, and W4, independentlay from each other are -CH- or -N+-; wherein only one of
Wi, W2, W3 or W4 is -N"; and the radical *-(Zi)r-YrS-A is bonded to Wi or W2; R35 and R36 independently from each other are hydrogen; C1-C102alkyl, which may be
substituted by one or more C1-C5alkyI, C1-C5-alkoxy. hydroxy or -(CO)-H;
-(C0)-C1-C5alkyl; phenyl or phenyl-C1-C4alkyl, wherein the phenyl moiety may be
substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, -NH2, mono-Ci-
C5alkyJamino, di-C1-C5alkylamino, -NO2, carboxy or hydroxy; R7 R8. R9 and R10 independently from each other are hydrogen; C1-C20alkyl; C1-C20alkoxy; C3-

X?, X3 and X4 independently from each other are C1-C10 alkylene;
-(CO)-CrCi8alkylene'CrCi8arylene; C6-C18arylene-C1-C12alkylene; or -(OCH2CH2)n-0-;
t is 0; or 1
R37 is hydrogen; or C1-C2oalkyl;
R38. R39 and R40 independently from each other are hydrogen, C1-C20alkyl, C4-Ci2cycloalkyl, C6-C13aralkyI; phenyl-C1-C5alkyl; or R38 and R39 together with the linking nitrogen atom form a C4-C12-membered heterocyclic ring which may be interrupted by one or more than one -O- or -NH- goups;
n1 is is 0 or 1;
p is 0; or 1;
s isO;or1;
t is 0; or 1;
u is 0 or 1;
R11, R12 and R13 independently from each other are hydrogen; C1-C20alkyl or Ci-Caoalkoxy, which may be substituted by one or more C1-C5alkoxy, halogen, -NH2. mono-d-C5lkylamino, di-C1-C5alkylamino. -NO2 or hydroxy; C3-C6cycloalkyI; -C(0)H; -C(0)-Cr CsBlkyl; "C(0)OH; -C(0)0-C1-C5alkyl; halogen; NO2; OH; SH; phenyl, which maybe substituted by one or more C1-C5alkyI, C1-C5alkoxy, halogen, -NH2, mono-Ci-C5alkylamino, di-C1-C5alkylamino, -NO2 or hydroxy; or a radical -NR41R42;
Q3 is is -C(0)-; -C(0)0-; -OCO-; -N(Ri)-X5-; -CON(Ri)-; -(Ri)NC(O)- -0-; -S-; ^S(O)-; or -S(0)2-

heteroaromatic group;
R,, Rk, Ri independently from each other are CrCualkyI; Ca-Cualkenyl; C6-C10aryl; C6-C10aryl-Ci"Cioalkyl; or C1-C10oalkyl(C5-C10aryl);
R41 and R42 independently from each other are hydrogen; C1-C12alkyl, which may be substituted by one or more C1-C5aJkyl, C1-C5-alkoxy, hydroxy or -(CO)-H; -(CO)-Ci-Csalkyl; phenyl or phenyl-Ci'-C4aIkyl, wherein the phenyl moiety may be substituted by one or more CrCBalkyI, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-Ci-

at least one of the radicals R11, R12 or R13 is NO2; R43, R44 and R45 independently from each other are hydrogen; C1-C104alkyl; C2-C14aikenyl; Ce-
Ciosryl; C6-C10aryl-C1-C10alkyl; or C1-C10oalkyl(C5-C10aryl); X5 and X6 independently from each other are the direct bond; C1-C10alkylene; C5-
C10cycloalkylene; C5-C10aryjene; or C5-C10arylene-(C1-C10oalkylene); R14 IS N R46R47!
R46 and R47 independently from each other are hydrogen; C1-C102alkyl; or phenyl-C1-C4alkyl; or R46 and/or R47 are a bivalent C3-C6alkylene radical which is linked to the carbon atoms C^ or
C^ in formula (1e) respectively and, together with the linking nitrogen atom form a 6 to 16-
membered carbocyclic ring; Ri5 is is NR48R49; or OR48;
R48and R49, independently from each other are hydrogen; C1-C12alkyl; or phenyl-C1-C4alkyl; or R48and R49 are a bivalent C3-C6alkylene radical which is linked to the carbon atoms C^ or C"* in
formula (1e) respectively and, together with the linking nitrogen or oxygen atom form a 6
to 16-membered carbocyclic ring; or R48and R49 together with the linking nitrogen atom form a 4 to 8 membered carbocyclic ring; R16, R17, R181 R19 and R20 independently form each other are hydrogen; C1-C102alkyl; halogen;

V1 is -0-; or--NR53:
R52 and R53 independently from each other are hydrogen; or C1-C5alkyl;
Hal is a halogen atom; and wherein at least one of R16, R17. R18, R19 and R20 is hydrogen;
B2 and B3, independently from each other are C6-C10aryl; or a 5-7-membered heterocyclic compound, which may be substituted by C1-C12alkyl, C1-C102alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or by the radical -NR54R55 or -OR56;

B4 is C8-C10arylene, or a bivalent radical of a 5-7-membered heterocyclic compound, which may be substituted by C1-C12alkyl, C1-C12alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or by the radical -NR54R55 or -OR56;
R54 R55 and R56 independently from each other are hydrogen; or C1-C12alkyl, which may be substituted by hydroxy or C6-C10aryl; or
R54 and R55 together with the linking nitrogen atom form a 5 to 7 membered heterocyclic ring;

the asterix(*) is directed to Z1 or Z2 respectively; and
the asterix(**) is directed to the linking nitrogen atom;
R21 and R22 independently from each other are hydrogen; C1-C20alkyl; C1-C20alkoxy; C3-
C6cycloalkyl; C5-C10aryl; anellated aromatic groups; carboxylate; or sulfonate groups; R23* R24 R25 and R26 each independently from each other are hydrogen; unsubstituted or
substituted, straight-chain or branched, monocyclic or polycyclic, interrupted or
uninterrupted C1-C104alkyl, C2-C14alkenyl, C6-C10aryl, C6-C10aryl-C1-C10oalkyI or
C5-C10alkyl(C5-C10aryl); or R23 and R24 and/or R25 and R26 together with the linking nitrogen atom form a 5 to 7 membered
carbocyclic ring which may contain one or more than one hetero atom; or R23 is linked to Ci together with N" forming a 5-7 membered carbocyclic ring; or R24 is linked to C2 together with N* forming a 5-7 membered carbocyclic ring; X7 is-0-; or-N(R24)-; or-S-; R27 is hydrogen; or C1-C5alkyl;

a 6 to 10 membered carbocyclic ring which may optionally be a condensated aromatic system and may contain one or more than one hetero atom;
R57, R58 and R59 independently from each other are hydrogen; or C1-C5alkyl;
R29, R30, R31 and R32 independently from each other are hydrogen; hydroxy; -S-H; -S-Ci-Ci2alkyl; halogen; C1-C102alkyl or C1-C102alkoxy, which may be substituted by one or more C1-C5alkyl, C1-C5-alkoxy, hydroxy, -(CO)-H or -(C0)-C1-C5alkyl; -NRegRro; -NO2; -(CO)H or (CO)-C1-C5alkyi; C6-C12aryl, C6-C12aryl-C1-C4alkyl or C6-C12aryl-C1-C4alkoxy, wherein the aryt moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, -(CO)-H or -(CO)-C1-C5alkyl; -NR69R70; -NO2; -(CO)-H; or -(COKi-Cgalkyl;
R69 and R70 independently from each other are hydrogen; hydroxy; C1-C102alkyl; hydroxy-Cr C12alkyl; -(CO)-H; -(C0)-C1-C5alky(; phenyl or phenyl-C1-C5alkyI, wherein the phenyl moiety may be substituted by one or more C1-C5alkyl, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5alkylamino, -NO2, carboxy or hydroxy;
Y1 and Y2 independently from each other are unsubstituted or substituted, straight-chain or branched, interrupted or uninterrupted C1-C10alkylene; C5-C10cycloalkylene; C5-C10arylene; or-C5-C10arylene-(C1-C10alkylene);

the asterix indicates the linkage to Di and/or D2;
the asterix ** indicates the linkage to Yi and/or Y2;
R60, R61,, R62, R63 and R64 independently from each other are hydrogen; C1-C14alkyl; C2-C14alkenyl; C6-C10aryl; C5-C10aryl-(C1-C10alkyl); or-C1-C10oalkyl(C5-C10aryl);
R29, R30. R31 and R32 independently from each other are hydrogen; hydroxy; -S-H;
-S-C1-C12alkyl; halogen; C1-C12alkyl or C1-C12alkoxy, which may be substituted by one or more C1-C5alkyl, d-Cg-alkoxy, hydroxy, "(CO)-H or -(C0)-C1-C5alky(; -NR85R66; -NO2; -(CO)H or (C0)-C1-C5alkyl; C6-C12aryl, C6-C12aryl-C1-C4alkyl or C6-C12aryl-C1-C4alkoxy, wherein the aryt moiety may be substituted by one or more C1-C5alkyI, C1-C5alkoxy, -(CO)-H or-(C0)-C1-C5alkyl; -NR67R68; "NO2; -(CO)-H; or-(CO)-C1-C5alkyl;
R65, R66.R67 and R68 independently from each other are hydrogen; hydroxy; C1-C102alkyl;
hydroxy-C1-C12alkyl; -(CO)-H; -(C0)-C1-C5alkyl; phenyl or phenyl-C1-C5alkyI, wherein the phenyl moiety may be substituted by one or more C1-C5aikyl, C1-C5alkoxy, halogen, -NH2, mono-C1-C5alkylamino, di-C1-C5aikylamino, -NO2, carboxy or hydroxy;
q is a number from 0 to 5;
w is a number from one to 5;
r is 0; or 1; and
An is an anion.
2. Mixture according to claim 1, wherein Y1 and Y2 are C1-C5alkylene.

An is an anion; and
Yi is defined as in claim 1.
7. Mixture according to claim 1, wherein the dyes are selected from the compounds of formula

one of W1 or W2 is -N"-. the other is -CH; and
the biradical .—(Z1),.Y1.S-S2 Y,-(Z,)-* is bonded to -N+ and
R4, R5, R6. Y1, Y2, Z1 and r are defined as in claim 1.
8. Mixture according to claim 7, wherein the dyes are selected from the compounds of formula

9. Mixture according to claim 1, wherein the dyes are selected from the compounds of formula

R11, R12 and R13, independently from each other are hydrogen; C1-C5alkyI; -C(0)H;
-C(0)-C1-C5alkyl; -C(0)OH; -C(0)0-CrC5alkyl; NO2; or-NH(CO)-CH3; Yi is C1-C10alkylene; C5-C10cycloalkylene; C5-C10arylene; or C5-C1arylene"(C1-C10alkylene);

R,and Rk each independently from each other are hydrogen; C1-C14alkyl; C2-C14alkenyl; C6-Cioaryl; C6-C10aryl-C1-C10alkyI; or C1-C10alkyl(C5-C10aryl).
11. Mixture according to claim 1, wherein the dyes are selected from the compounds of

Rm is C1-C12alkyl, C1-C12alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or the radical -NRnRo or -ORni and

Rn, Ro, B1 and B2 are defined as in claim 1.

R31 is hydrogen; C1-C5-alkoxy; halogen; or -NRpRq, wherein
Rp and Rq, independently from each other are hydrogen; C1-C12alkyl; -(CO}-H; or
-(CO)-Ci-C5alkyl; and An is an anion.
15. A method of dyeing keratin-containing fibers comprising treating the fiber with a mixture as
defined in any of claims 1 to 14.
16. A method according to claim 16, wherein the dyeing is carried out in presence of a reducing agent.
17. A method according to claim 15 or 16, wherein the reducing agent is selected from thioglycol acid or salts therof, gycerine monothioglycolate, cystein, 2-mercaptopropionic acid,

2-mercaptoethylamine, thiolactic acid, thioglycerine, sodium sulfite, dithionithe, ammonium sulfite, sodium bisulfite, sodium metabisulfite and hydrochinon.
18. A method according to any of claims 15 to 17, comprising treating the keratin^containing
fiber
(a) optionally with a reduction agent, and
(b) with a mixture of dyes as defined in claim 1, and
(c) optionally with an oxidizing agent.

19. A composition comprising a mixture of dyes as defined in claim 1.
20. A composition according to claim 19 in form of a shampoo, conditioner, gel or emulsion,
21. A composition according to claim 19 or 20 comprising mixture of dyes as defined in claim
1 and a direct dye and/or a reactive dye.

Documents:

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Patent Number

278195

Indian Patent Application Number

1771/CHENP/2008

PG Journal Number

53/2016

Publication Date

23-Dec-2016

Grant Date

16-Dec-2016

Date of Filing

09-Apr-2008

Name of Patentee

BASF SE,

Applicant Address

Klybeckstrasse 141, Basel CH-4057, Switzerland; a german Company

Inventors:

#	Inventor's Name	Inventor's Address
1	WALLQUIST, OLOF	ROSENWEG 6 CH-4103 BOTTMINGEN
2	CREMER, CHRISTIAN	IM SAND 29 79540 LORRACH
3	ELIU, VICTOR, PAUL	IM LOGELHARDT 2 79539 LORRACH

PCT International Classification Number

C09B 67/22, A61K 8/46

PCT International Application Number

PCT/EP06/66325

PCT International Filing date

2006-09-13

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	05109445.6	2005-10-11	EUROPEAN UNION