WO2006136617A2 - Mixture of sulfide dyes - Google Patents

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.

Description

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 ) D₁ — (Z₁). — Y₁ — S — A , wherein

A is hydrogen; a radical of formula (1a) * — S-Y₂- — (Z₂)_r — D₂ ; or a thio ester group of

formula (1 b) * — ^. . wherein

E E is O; S; or N-R₃;

B₁ is -OR_b; -NR_bR_c, or -SR_b;

R₃, Rb and R_c, independently from each other are hydrogen; d-C^alkyl; C6-Ci₂aryl; or Ce- Ci₂aryl-Ci-Ci₂alkyl;

D₁ and D₂ independently from each other is a radical of formula (I a₁) ;

An -

and formula

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

Ri, R₂ and R₃ independently from each other hydrogen; halogen; CrCi₆alkyl, 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; CrCi₆alkoxy, (poly)-hydroxy-

C₂-C₄-alkoxy; halogen; SO₂NR₃₃R₃₄; SR₃₃; NR₃₃R₃₄; OR₃₃; SO₂; COOR₃₃; NR₃₃COR₃₄; or

CONR₃₃; Qi is a bivalent radical selected from -N=N-; -CR_d=N-; -N=CR_d-; -NR_d-N=CR_e-; and

T₁ is a bivalent radical of an aromatic or heteroaromatic substituted or unsubstituted compound;

Rd and R_e independently from each other are hydrogen; unsubstituted or substituted C₁- C_i4alkyl; C₂-C₁₄alkenyl; C₅-Ci₀aryl; Ci-Cioalkyl-C₅-Cioaryl; or C₅-Cioaryl-Ci-Ci_Oalkyl;

R₃₃ and R₃₄ independently from each other are hydrogen; CrCi₂alkyl, which may be substituted by one or more CrC₅alkyl, CrC₅-alkoxy, hydroxy or -(CO)-H;

-(CO)-CrC₅alkyl; phenyl or phenyl-CrC₄alkyl, wherein the phenyl moiety may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, halogen, -NH₂, mono-Cr C₅alkylamino, di-Ci-C₅alkylamino, -NO₂, carboxy or hydroxy;

R₄, R₅ and Re independently from each other are hydrogen; Ci-C₂oalkyl or Ci-C₂oalkoxy, which may be substituted by one or more CrC₅alkoxy, halogen, -NH₂, mono-Ci-C₅alkylamino, di-Ci-C₅alkylamino, -NO₂ or hydroxy; C₃-C₆cycloalkyl; -C(O)H; -C(O)-C_rC₅alkyl; halogen;

NO₂; OH; phenyl, which may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, halogen, -NH₂, mono-Ci-C₅alkylamino, di-Ci-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

W₁, W₂, W₃ or W₄ is -N⁺; and the radical ^(Z-OrY₁-S-A is bonded to W₁ or W₂; R₃₅ and R₃₆ independently from each other are hydrogen; CrC₁₂alkyl, which may be substituted by one or more CrC₅alkyl, CrC₅-alkoxy, hydroxy or -(CO)-H;

-(CO)-C-ι-C₅alkyl; phenyl or phenyl-C-ι-C₄alkyl, wherein the phenyl moiety may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, halogen, -NH₂, mono-Cr

C₅alkylamino, di-CrC₅alkylamino, -NO₂, carboxy or hydroxy; R₇, R₈, Rg and R₁₀ independently from each other are hydrogen; CrC₂₀alkyl; CrC₂₀alkoxy; C₃-

Cβcycloalkyl; halogen; NO₂; OH; SH; or a radical of formula (I c₁) '

- A -

X₁ is CrCi₈alkylene; -(CO)-CrCi₈alkylene CrCi₈arylene; C₆-Ci8arylene-Ci-Ci₂alkylene; or -(OCH₂CH₂)_n2-O-;

O

T₂ is a radical of formula (I c₂) * — ^{N "} -x,- ; or -0-(X₃)Si

Q₂ is a cationic biradical of a saturated, aromatic or heteroaromatic group; or a radical of

formula (I c₃)

R_f, R_g and R_h independently from each other are hydrogen; Ci-Ci₄alkyl; C₂-Ci₄alkenyl; C₆-Ci₀aryl; C₆-Cioaryl-Ci-Ci_Oalkyl; or Ci-Cioalkyl(C₅-Cioaryl);

X₂, X₃ and X₄ independently from each other are CrC₁₈alkylene;

-(CO)-Ci-Ci₈alkylene-Ci-Ci₈arylene; C₆-Ci₈arylene-Ci-Ci₂alkylene; or -(OCH₂CH₂)_n-O-; t is O; or 1

R₃₇ is hydrogen; or CrC₂₀alkyl;

R₃₈, R₃g and R₄₀ independently from each other are hydrogen, CrC₂₀alkyl, C₄-Ci₂cycloalkyl, C₆-Ci₃aralkyl; phenyl-CrC₅alkyl; or R₃₈ and R₃g together with the linking nitrogen atom form a C₄-Ci₂-membered heterocyclic ring which may be interrupted by one or more than one -O- or -NH- goups; n-[ is is 0 or 1 ; p is 0; or 1 ; s is 0; or 1 ; t is O; or 1 ; u is O or i ;

R₁₁, R₁₂ and R₁₃ independently from each other are hydrogen; CrC₂oalkyl or CrC₂oalkoxy, which may be substituted by one or more CrC₅alkoxy, halogen, -NH₂, mono-d- C₅alkylamino, di-CrC₅alkylamino, -NO₂ or hydroxy; C₃-Cecycloalkyl; -C(O)H; -C(O)-C₁- C₅alkyl; -C(O)OH; -C(O)O-C_rC₅alkyl; halogen; NO₂; OH; SH; phenyl, which may be substituted by one or more C-ι-C₅alkyl, C-ι-C₅alkoxy, halogen, -NH₂, mono-Cr

C₅alkylamino, di-CrC₅alkylamino, -NO₂ or hydroxy; or a radical -NR₄₁R₄₂;

Q₃ is is -C(O)-; -C(O)O-; -OCO-; -N(R)-X₅-; -CON(R)-; -(R)NC(O)-; -0-; -S-; -S(O)-; or -S(O)₂-; T₃ is the direct bond; *— N— * ; or a cationic biradical of a saturated, aromatic or

R, heteroaromatic group; R₁, R_k, Ri independently from each other are CrCi₄alkyl; C₂-Ci₄alkenyl; C₆-Ci₀aryl; C₆-Ci₀aryl- d-Cioalkyl; or Ci-Cioalkyl(C₅-Cioaryl); R₄i and R₄₂ independently from each other are hydrogen; d-C^alkyl, which may be substituted by one or more CrC₅alkyl, CrC₅-alkoxy, hydroxy or -(CO)-H; -(CO)-Cr C₅alkyl; phenyl or phenyl-Ci-C₄alkyl, wherein the phenyl moiety may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, halogen, -NH₂, mono-Ci-C₅alkylamino, di-Cr

^R43

C₅alkylamino, -NO₂, carboxy or hydroxy; or a radical of formula *— -X-N-R₄₄ ; wherein

R₄₅ at least one of the radicals Rn, Ri₂ or R₁₃ is NO₂;

R₄₃, R₄₄ and R₄₅ independently from each other are hydrogen; Ci-Ci₄alkyl; C₂-Ci₄alkenyl; C₆-

Cioaryl; C₆-Cioaryl-Ci-Ci_Oalkyl; or Ci-Cioalkyl(C₅-Cioaryl); X₅ and X₆ independently from each other are the direct bond; CrCi_Oalkylene; C₅-

Ciocycloalkylene; C₅-Ci₀arylene; or C₅-Cioarylene-(Ci-Ci_Oalkylene); R_i4 is N⁺R₄₆R₄₇;

R₄₆ and R₄₇ independently from each other are hydrogen; Ci-Ci₂alkyl; or phenyl-Ci-C₄alkyl; or R₄₆ and/or R₄₇ are a bivalent C₃-C₆alkylene radical which is linked to the carbon atoms C¹ or C² in formula (1 e) respectively and, together with the linking nitrogen atom form a 6 to 16- membered carbocyclic ring; Ris is is NR₄₈R₄₉; or OR₄₈;

R₄₈ and R₄₉, independently from each other are hydrogen; Ci-Ci₂alkyl; or phenyl-Ci-C₄alkyl; or R₄₈ and R₄₉are a bivalent C₃-C₆alkylene radical which is linked to the carbon atoms C³ or C⁴ in formula (1e) respectively and, together with the linking nitrogen or oxygen atom form a 6 to 16-membered carbocyclic ring; or R₄₈ and R₄₉ together with the linking nitrogen atom form a 4 to 8 membered carbocyclic ring; Ri₆, Ri₇, Ri₈, Ri₉ and R₂₀ independently form each other are hydrogen; Ci-Ci₂alkyl; halogen;

0-R₅₂

NR₅oR₅i; or a radical of formula (1 ei) * — / ; o R_5O and R₅i independently from each other are hydrogen; d-C^alkyl; phenyl-Ci-C₄alkyl; or a

radical of formula (I e₂)

V₁ is -O-; Or -NR₅₃;

R₅₂ and R₅₃ independently from each other are hydrogen; or Ci-C₅alkyl; Hal is a halogen atom; and wherein at least one of Ri₆, R₁7, R₁8, R₁9 and R₂₀ is hydrogen; B₂ and B₃, independently from each other are C6-Cioaryl; or a 5-7-membered heterocyclic compound, which may be substituted by Ci-Ci₂alkyl, Ci-Ci₂alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or by the radical -NR₅₄R₅₅ or -OR₅6; B₄ is C₆-Ci₀arylene, or a bivalent radical of a 5-7-membered heterocyclic compound, which may be substituted by CrCi₂alkyl, Ci-Ci₂alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or by the radical -NR₅₄R₅₅ or -OR₅₆; Rs₄ R55 and R₅₆ independently from each other are hydrogen; or Ci-Ci₂alkyl, which may be substituted by hydroxy or C₆-Ci₀aryl; or

R₅₄ and R₅₅ together with the linking nitrogen atom form a 5 to 7 membered heterocyclic ring; or

R₅₅ and R₅₆ together with the linking nitrogen atom form a piperidine ring of

formula (If₁) , wherein

the asterix(*) is directed to Z₁ or Z₂ respectively; and the asterix(**) is directed to the linking nitrogen atom; R₂i and R₂₂ independently from each other are hydrogen; CrC₂₀alkyl; CrC₂₀alkoxy; C₃-

C₆cycloalkyl; C₅-Cioaryl; 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 CrCi₄alkyl, C₂-Ci₄alkenyl, C₆-Ci₀aryl, C₆-Cioaryl-Ci-Ci_Oalkyl 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 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 -O-; Or -N(R₂₄)-; or -S-; R₂₇ is hydrogen; or d-C₅alkyl;

R₂S is a radical of formula (Ig₁) ; (ig₂) or

(Ig₃) or R₂₇ and R₂₈ together with the linking carbon atom ¹C form

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 Ci-C₅alkyl; R₂g, R₃₀, R3₁ and R₃₂ independently from each other are hydrogen; hydroxy; -S-H; -S-Cr

Ci₂alkyl; halogen; Ci-Ci₂alkyl or Ci-Ci₂alkoxy, which may be substituted by one or more CrC₅alkyl, C_rC₅-alkoxy, hydroxy, -(CO)-H or -(CO)-C_rC₅alkyl; -NR₆₉R₇₀; -NO₂; -(CO)H or

(CO)-CrC₅alkyl; C₆-Ci₂aryl, C₆-Ci₂aryl-Ci-C₄alkyl or C₆-Ci₂aryl-Ci-C₄alkoxy, wherein the aryl moiety may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, -(CO)-H or -(CO)-CrC₅alkyl; -NR₆₉R₇₀; -NO₂; -(CO)-H; or -(CO)-C_rC₅alkyl;

R₆₉ and R₇₀ independently from each other are hydrogen; hydroxy; CrCi₂alkyl; hydroxy-Cr C_i2alkyl; -(CO)-H; -(CO)-C_rC₅alkyl; phenyl or phenyl-C_rC₅alkyl, wherein the phenyl moiety may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, halogen, -NH₂, mono- Ci-C₅alkylamino, di-Ci-C₅alkylamino, -NO₂, carboxy or hydroxy; Yi and Y₂ independently from each other are unsubstituted or substituted, straight-chain or branched, interrupted or uninterrupted CrCi_Oalkylene; C₅-Ci₀cycloalkylene; C₅-Ci₀arylene; or-C₅-Ci₀arylene-(Ci-Ci₀alkylene);

Z₁ and Z₂ independently from each other are *-(CH₂)_q-C(O)-**; *-(CH₂CH₂-O)_w-**;

*-(CH₂)_q-C(O)O-**; -(CH₂VOCO-**; *-(CH₂)_q-N(R₆₀)-**; ;

*-(CH₂)_q-CON(R₆₀)-**; *-(CH₂)_q-(R₆₀)NC(O)-**; -0-; -S-; -S(O)-; -S(O)₂-; or a cationic biradical of a substituted or unsubstituted aromatic or heteroaromatic compound of the formula (1a)

(1 d) ; wherein

G₁ and G₂ independently from each other are N; -O-; -S-; or a radical of CRe₄; the asterix * indicates the linkage to D₁ and/or D₂; the asterix ** indicates the linkage to Y₁ and/or Y₂ ; R₆O, R₆i, Rβ₂, Rβ3 and R₆₄ independently from each other are hydrogen; CrC₁₄alkyl; C₂-

C₁₄alkenyl; C₆-C₁₀aryl;

R₂g, R₃₀, R₃₁ and R₃₂ independently from each other are hydrogen; hydroxy; -S-H; -S-C-ι-C₁₂alkyl; halogen; CrC₁₂alkyl or CrC₁₂alkoxy, which may be substituted by one or more C_rC₅alkyl, C_rC₅-alkoxy, hydroxy, -(CO)-H or -(CO)-C_rC₅alkyl; -NR₆₅R₆₆; -NO₂; -(CO)H or (CO)-C_rC₅alkyl; C₆-C₁₂aryl, C₆-C₁₂aryl-C_rC₄alkyl or Ce-C^aryl-d-C^lkoxy, wherein the aryl moiety may be substituted by one or more CrC₅alkyl, C-ι-C₅alkoxy, -(CO)-H or -(CO)-C_rC₅alkyl; -NR₆₇R₆₈; -NO₂; -(CO)-H; or -(CO)-C_rC₅alkyl; R₆₅, R₆₆, R₆₇ and R₆₈ independently from each other are hydrogen; hydroxy; CrC₁₂alkyl; hydroxy-CrC₁₂alkyl; -(CO)-H; -(COJ-d-Csalkyl; phenyl or phenyl-CrC₅alkyl, wherein the phenyl moiety may be substituted by one or more CrC₅alkyl, C-ι-C₅alkoxy, halogen, -NH₂, mono-CrC₅alkylamino, di-CrC₅alkylamino, -NO₂, carboxy or hydroxy; q is a number from O to 5; w is a number from one to 5; r is O; or 1 ; and An is an anion.

CrC₁₂alkyl is for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2'-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1 ,1 ',3,3'-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl,. Ci-Ci₂alkylene 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 C₅alkyl upwards, monocyclic or polycyclic, and may be interrupted by hetero atoms, such as such as O, S, -CO-, N, NH, NR₅₄ -OCO-, - CO(OR₄)-, -CONR₄-, -(R₅)NC(O)-; for example C-i-C-ioalkylene may be a resisue such as: - CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂- -CH₂CH₂-O-CH₂CH₂- -CH₂CH₂-O-CH₂-, -CH₂-O-CH₂-, - CH₂CH₂-CH₂CH₂-O-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-Ciocycloalkylene is for example cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene or cyclodecylene.

C₅-Ci₀arylene is for example phenylene or naphthylene.

Aryl-alkylene is for example C₅-Cioaryl-Ci-Ci_Oalkylene.

Alkyl-arylene is for example Ci-Cioalkyl-C₅-Ci_Oarylene.

Preferred is a dye mixture, wherein in formula (1 ) Yi and Y₂ are Ci-C₅alkylene.

Furthermore, a composition is preferred, wherein in formula (1 )

Z₁ and Z₂ independently from each are other -N(R₆₀)-; — N— ; -CON(R₆₀)-; -(CH₂)_qNC(0)-;

^R61 -0-; or -S-; and

R₆₀ R₆i and q are defined as in formula (1 ).. Preferred is a composition, wherein D₁ is a radical of a cationic aromatic substituted or unsubstituted heterocyclic compound of formulae

Prreferably, D₁ and D₂ independently from each other are a radical of formula

(I a₁₁) or (I a₁₂) ; wherein

R₁, R₂, Q₁ and T₁ independently from each other are defined as in formula (1 ).

T₁ is preferablya bivalent radical of formulae ; or

, wherein

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 -O-, -S-, -(SO₂)-, -d-Cioalkylene or -(NR₈₂)-; are independently from each other hydrogen; halogen; CrC₁₄alkyl, 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; CrC₁₆alkoxy, (poly)- hydroxy-C₂-C₄-alkoxy; halogen; SO₂NR₃₃R₃₄; SR₈₃, NR₈₃R₈₄; OR₈₃₁; SO₂; COOR₈₃; NR₈₃COR₈₄; or CONR₈₃; and R₇4 R75 R₇₆ R77 R78, R79, Rβo, Rβi, Rβ2 and R₈3 and R₈₄ are each independently of the other hydrogen; unsubstituted or substituted CrCi₄alkyl, C₂-Ci₄alkenyl, C₅-Cioaryl, C₅-Ci₀aryl-(Ci- Cioalkyl), or -Ci-Cioalkyl(C₅-Ci_Oaryl).

More preferably, the dyes are selected from the compounds of formula

(AZO-01 ) , wherein

R₆9, R70, R7₂ and R₇₃ independently from each other are hydrogen; unsubstituted or substituted CrCi₄alkyl; C₅-Ci₀cycloalkyl; C₂-Ci₄alkenyl; C₅-Cioaryl-(Ci-Ci_Oalkyl); C_rCioalkyl-(C₅- Cioaryl); C₅-Ci₀aryl;

,0 R₇i is hydrogen; or a radical of formula (2a) ^"NR₇^

V3

An is an anion; and

Yi is defined as in formula (1 ).

More preferably, the dyes are selected from the compounds of formula

, wherein

More preferably, the dyes are selected from the compounds of formula

(AZO-03) , wherein

R₁ and R₂ independently from each other are hydrogen; unsubstituted or substituted Cr Ci₄alkyl; C₅-Ci₀cycloalkyl; C₂-Ci₄alkenyl; C₅-Ci₀aryl; Ci-Cioalkyl-(C₅-Cioaryl); C₅-Ci₀aryl-

(d-doalkyl). Examples for dyes of formula (1), wherein D₁ and D₂ are selected from the radicals of formula (Ia₁) - (Ia₇) are:

Further preferred dyes are selected from the compounds of formula (STY-01 ) , wherein

one of W₁ or W₂ is -N⁺- the other is -CH; and the biradical .-(Z₁J_n-Y₁-S-S-Y₂-(Z₁)-* j_s bonded to -N⁺; and

R₄, R₅, Re, Y-i, Y₂, Z₁ and r are defined as in formula (1 ).

Preferred are also dyes of formula

(STY-04) . or

wherein

R₄, R₅, R₆, Z₁, Y₁, Y₂, An and r are defined as in formula (1 ).

Examples for dyes of formula (1 ), wherein D₁ and D₂ are selected from the radicals of formula (1 b) are:

Preferred are also compositions, wherein the dyes are selected from the compounds of formula

(ANT-01 ) ; wherein

FL O T₂ is a radical of formula * N- -C- -XO ; or -O-(X₂)_S;

Re is hydrogen; Ci-C₂oalkyl; NH₂; or hydroxy; and R_f, Q₂, Z₁, Y₁, X₂, p and r are defined as in formula (1 ).

Examples for dyes of formula (1 ), wherein D₁ and D₂ are selected from the radicals of formula (1 c) are:

Preferred are also mixtures, wherein the dyes are selected from the compounds of formula

(N IT-01 ) , wherein

R₁₁, R₁₂ and R₁₃, independently from each other are hydrogen; CrC₅alkyl; -(CO)-; -C(O)H;

-C(O)-C_rC₅alkyl; -C(O)OH; -C(O)O-C_rC₅alkyl; NO₂; NH₂; Or -NH(CO)-CH₃; Y₁ is CrC₁₀alkylene; C₅-C₁₀cycloalkylene; C₅-C₁₀arylene; or Cs-doarylene-^rdoalkylene); Xe is the direct bond: or C-ι-C₅alkylene;

T₃ is the direct bond; or

R_ι and R_k each independently from each other are hydrogen; Ci-Ci₄alkyl; C₂-C-i₄alkenyl; Ce- C₁₀aryl; Ce-C^aryl-d-doalkyl; or Crdoalky^Cs-C^aryl).

Most preferably compounds of formula (NIT-01 ) are used, wherein R₁₁, R₁₂ and R-₁3 independently from each other are hydrogen; NO₂; NH₂; carboxy; -C(O)OH;

Or -NH(CO)-CH₃; Y₁ is CrC₅alkylene;

T₃ is the direct bond; or

R₁ and R_k each independently from each other are hydrogen; or CrC₁₄alkyl.

The nitro-sulfide dyes (NIT-01 ) used in the present invention are derived form nitro-dyes, ie.

the phenyl moieties correspond to nitro dyes well known in the literature, for

example the following nitro dyes listed in the table below:

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

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);

R₄₈ and R₄₉ independently from each other are hydrogen; CrC₁₂alkyl; or phenyl-CrC₄alkyl; and

R₁₆, R , R₁₈, R₁Ci, R20 and V₁ 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;

R₄₈ and R₄₉, independently from each other are hydrogen; CrC₁₂alkyl; or phenyl-CrC₄alkyl; and

R₁₆, R , R₁₈, R₁₉, R₂o and V₁ 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; CrC₁₂alkyl; or phenyl-CrC₄alkyl; and

R₁₆, R₁₇, R₁S, Ri9, R20 and V₁ 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; R_1O and R₁₁, independently from each other are hydrogen; CrC₁₂alkyl; or phenyl-C-ι-C₄alkyl; and R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and V₁ are defined as in formula (1 ).

More preferred are mixtures comprising a compound of formula (1 ), wherein D₁ and D₂ independently from each other are a radical of formula

wherein

Ri5, Ri₆, Ri7, R18, Ri₉, R20, R₄₆ and R₄₈ and V₁ are defined as in formula (1 ).

Most preferred are compounds of formula

(XAN-01 ) , wherein

Ri4, Ri5, Rr₁₆, Ri7, R₁S, R19, R20, Yi, Y2 and V₁ are defined as in formula (1 ).

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

Furthermore, mixtures are preferred which comprise a dye of formula

(TRI-01 ) , wherein

R_m is CrCi₂alkyl, CrCi₂alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or the radical -NR_nR₀ or -OR_n; and R_n, R₀, B₁ and B₂ are defined as in formula (1 ).

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

Furthermore, mixtures are preferred which comprise a dye of formula (1 ), wherein D₁ and D₂ independently from each other are a radical of formula (1g), wherein R₂3 and R₂₄ and R₂₅ and R₂6 together with the linking nitrogen atom form a piperidine ring of

formula (Ig₁) *— N , wherein

the asterix(^*) is directed to Z₁ or Z₂ respectively; and the asterices (^**) are directed to the linking nitrogen atom of R₂β/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:

Furrthermore, mixtures are preferred, which comprise a dye of formula

(PRO-01 ) ¹ N ^WS \ wherein Rp

R_p is hydrogen; CrC₁₂alkyl; or phenyl-CrC₄alkyl;

Yi is CrCi₂alkylene; C₂-Ci₂alkenylene; C₅-Ci₀cycloalkylene; C₅-Ci₀arylene; or C₅-

Ci_Oarylene-Ci-Ci_Oalkylene; D₁ is the residue of an organic dye which corresponds to the formula

(1 h) , wherein

R₂₇ is hydrogen; or Ci-C₅alkyl;

R₂₈ is a radical of formula (I h₁) or

(I h₃) ; or R₂₇ and R₂₈ together with the linking carbon atom ¹C form

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 R₅g independently form each other are hydrogen, or CrC₅alkyl;

A₁ is H; or a thio ester group of formula (1 b) -f- wherein

E is O; S; or N-R₃; B₁ is -OR_b; -NR_bR_c, or -SR_b; and

R₃, Rb and R_c, independently from each other are hydrogen; d-C^alkyl; C6-Ci₂aryl; or Ce- Ci₂aryl-Ci-Ci₂alkyl.

Preferred are compounds of formula

(PRO-02) , wherein

A₁, Y₁, Rp and B₁ are defined as in formula (PRO-01 ).

Preferred are dyes of formula (PRO-01 ), wherein

D₁ is selected from the radicals of formulae (1 h₃)

Examples of compounds of the present invention are represented in the Table below:

Exemplified compounds of the present invention

Compound R₂ R₁ X of formula

(PRO-60) CH₃ -CH2-CH2- -(CS)S-CH₃

(PRO-61 ) CH₃ -CH2-CH2- -(CS)S-CH₃

(PRO-62) CH₃ -CH2-CH2- -(CS)S-CH₃

¹C

Furthermore, mixtures are preferred which comprise a dye of formula (2), wherein R30, R31 and R₃₂ are hydrogen; or d-C^alkyl; and R₃₂ is defiend as formula (2).

Preferred are dyes of formula

(PYR-02) , wherein

R₃₁ is hydrogen; Ci-C₅-alkoxy; halogen; or -NR₆gR7o, wherein

R₆g and R₇₀, independently from each other are hydrogen; Ci-Ci₂alkyl; -(CO)-H; or

-(CO)-CrC₅alkyl; 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.

Generally, 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 methosulfate, 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-phenylendiamine, 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, or with a yellow cationic dye of formula

(DD1) . wherein

R₁ and R₂ are each independently of the other a Ci-Cβalkyl; or an unsubstituted or substituted benzyl;

R3 is hydrogen; d-Cβalkyl; d-Cβalkoxy; cyanide; or halide; preferably hydrogen; and X^" is an anion; and preferably a compound of formula (DD1 ), wherein R₁ 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 nitroaniline 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, 1. 33 to col 5, 1. 38; US-5 360 930, especially in col 2, I. 38 to col 5, I. 49; US-5 169 403, especially in col 2, 1. 30 to col 5, I. 38; US-5 256 823, especially in col 4, 1. 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, 1. 29; and EP-A-758 547, especially on p. 7, 1. 48 to p. 8, 1. 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;

- acid 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. 2391 1/1973.

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, indophenols, phenazines, phenothiazines, bispyrazolons, θ^bispyrazol 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, I. 6 to col 3, 1. 1 1 ;

- "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 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, especially 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, 1. 24, in particular on p. 9, I. 22 to p. 1 1 , 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, I. 8 - 29.

More preferred developer compounds are p-phenylendiamine, p-toluylendiamine, p-, m- o- aminophenol, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine sulfate, 2-amino-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)-1 H- 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- triaminopyrimidine 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, I. 1 1.

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, 1. 50 to I. 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-toluenediamine and 2-amino-4-hydroxyethylaminoanisole for assessing of blue shades; p-toluenediamine and 2,4-diamino-phenoxyethynol for assessing of blue shades; methyl-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 exposed 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-dihydroxyindoline derivatives as described in WO 99/20234, especially on p. 26, I. 10 to p. 28, I. 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, I. 55 to p. 4, 1. 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, 1. 35 to p. 8, 1. 21 ; formulations p. 1 1 , last § - p. 28, 1. 19;

(DC-02): US 6,843,256, wherein cationic dyes are disclosed, especially the compounds of formulae (1 ), (2), (3) and (4) (col. 1 , 1. 27 - col. 3, 1. 20, and preferably the compounds as prepared in the examples 1 to 4 (col. 10, 1.42 to col. 13, 1. 37; formulations col. 13, I. 38 to col. 15, 1. 8; (DC-03): EP 970 685, wherein direct dyes are described, especially p. 2, 1. 44 to p. 9, 1. 56 and preferably p. 9, I. 58 to p. 48, 1. 12; processes for dyeing of keratin-containing fibers especially p. 50, 1. 15 to 43; formulations p. 50, I. 46 to p. 51 , I. 40; (DC-04): DE-A-19 713 698, wherein direct dyes are described, especially p. 2, 1. 61 to p. 3, 1.

43; formulations p. 5, 1. 26 to 60; (DC-05): US 6,368,360, wherein directd dyes (col. 4, 1. 1 to col. 6, 1. 31 ) and oxidizing agents

(col. 6, I. 37 -39) are disclosed; formulations col. 7, I. 47 to col. 9, 1. 4; (DC-06): EP 1 166 752, wherein cationic dyes (p. 3, 1. 22 - p. 4, 1. 15) and anionic UV- absorbers (p. 4, 1. 27 - 30) are disclosed; formulations p. 7, 1. 50 - p. 9, I. 56; (DC-07): EP 998,908, wherein oxidation dyeings comprising a cationic direct dye and pyra- zolo-[1 ,5-a]-pyrimidines (p. 2, 1. 48 - p. 4, 1. 1 ) are disclosed; dyeing formulations p. 47,

I. 25 to p. 50, 1. 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, 1. 16 to p. 3, 1. 16; dyeing formulations on p. 53, 1. 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, 1. 65 to p. 5, 1. 59;

(DC-10): EP 850 638, wherein developer compounds and oxidizing agents are disclosed; especially p. 2, I. 27 to p. 7, I. 46 and preferably p. 7, 1. 20 to p. 9, I. 26; dyeing formulations p. 2, 1. 3-12 and I. 30 to p. 14, and p. 28, 1. 35 - p. 30, 1. 20; preferably p. 30, I. 25 - p. 32, 1. 30;

(DC-1 1 ): 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, 1. 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, 1. 65; dyeing formulations in col. 2, I. 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, 1. 9, and p. 39, I. 1 to p. 40 I. 1 1 , preferably p. 8, I. 12 to p. 25 I. 6, p. 26, I. 7 to p. 30, I. 15; p. 1 , I. 25 to p. 8, I. 5, p. 30, I. 17 to p. 34 I. 25, p. 8, I. 12 to p. 25 I. 6, p. 35, I. 21 to 27, especially on p. 36, 1. 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, 1. 19 to p. 26, 1. 4, and autooxidisable dyes as dislosed especially on p. 26, 1. 10 to p. 28, I. 15; dyeing formulations especially on p. 34, 1.

5 to p. 35, Ii 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, 1. 41 to p. 7, 1. 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, 1. 50 to p. 8, 1. 44 are discloseded; dyeing formulations p. 21 , 1. 30 - p. 22, I. 57;

(DC-17): WO 99/48856, wherein oxidation dyeing compositions comprising cationic couplers are disclosed, especially p. 9, 1. 16 - p. 13, I. 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, 1. 42 - p. 5 I. 25; dyeing formulations p. 8, 1. 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 comprise 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 may be applied on the keratin-containing fiber, preferably the human hair in different 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 10O 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, I. 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, 1. 51 to p. 4, 1. 25, and p. 4, 1. 41 to p. 5 1. 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 permanent 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/O, O/W, 0/W/O, W/O/W 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, 1. 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 aminopropyl dimethicone; 0.3 % b.w. of hydroxypropyl guar hydroxypropytrimonium 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 water ad 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 comprise 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 Merquat^® 280 and the use thereof in hair dyeing as described, for example, in DE-A-4 421 031 , especially p. 2, I. 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 polymers, 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. bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol; structuring agents, such as glucose and maleic acid; hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin, 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, 1. 18 - p. 3, 1.

2, or EP-A-312 343, especially p. 2, 1. 59 - p. 3, 1. 1 1 ; protein hydrolysates, especially elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolysates, condensation products thereof with fatty acids and also quaternised protein hydrolysates; perfume oils, dimethyl isosorbitol and cyclodextrins, solubilisers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, anti-dandruff active ingredients, such as piroctones, olamines and zinc Omadine, substances for adjusting the pH value; panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extracts and vitamins; cholesterol; light stabilisers and UV absorbers as listed in Table below:

Table 1 : UV absorbers which may be use in the dyeing compositions of the present invention

No. Chemical Name CAS No.

33 Benzeneacetic acid, 3,4-dimethoxy-a-oxo- 4732-70-1

34 2-Propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester 5232-99-5

35 Anthralinic acid, p-menth-3-yl ester 134-09-8

36 1 ,3,5-Triazine-2,4,6-triamine, N,N'-bis[4-[5-(1 ,1-dimethylpropyl)-2- 288254-16-0 benzoxazolyl]phenyl]-N"-(2-ethylhexyl)- or Uvasorb K2A

37 2-Hydroxy-4-methoxy benzophenone-5-sulfonic acid 4065-45-6 38^" Alpha-(2-oxoborn-3-ylidene)toluene-4-sulphonic acid and its salts 56039-58-8

39 Methyl N,N,N-trimethyl-4-[(4,7,7-trimethyl-3-oxobicyclo[2,2,1]hept-2- 52793-97-2 ylidene)methyl]anilinium sulphate;

40 4- aminobenzoic acid 150-13-0

4Ϊ^~ 2- phenyl- 1 H- benzimidazole- 5- sulphonic acid 27503-81-7

42^~ 3,3'-(1 ,4-phenylenedimethylene)bis[7,7-dimethyl-2-oxo-bicyclo- 90457-82-2 [2.2.1]heptane-1-methanesulfonic acid]

43 1 H-Benzimidazole-4,6-disulfonic acid, 2,2'-(1 ,4-phenylene)bis-, 180898-37-7 disodium salt

44 Benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1- 92484-48-5 methylpropyl)-, monosodium salt

45 1-Dodecanaminium, N-[3-[[4-(dimethylamino)benzoyl]amino]propyl]- 156679-41-3 N,N-dimethyl-, salt with 4-methylbenzenesulfonic acid (1 :1 )

46 1-Propanaminium, N,N,N-trimethyl-3-[(1-oxo-3-phenyl-2-propenyl)- 177190-98-6 amino]-, chloride

47 1 H-Benzimidazole-4,6-disulfonic acid, 2,2'-(1 ,4-phenylene)bis- 170864-82-1 48^" 1-Propanaminium, 3-[[3-[3-(2H-benzotriazol-2-yl)-5-(1 ,1-dimethyl- 340964-15-0 ethyl)-4-hydroxyphenyl]-1-oxopropyl]amino]-N,N-diethyl-N-methyl-, methyl sulfate (salt)

49 2,2'-bis(1 ,4-phenylene)-1 H-benzimidazole-4,6-disulphonic acid mo349580-12-7, no sodium salt or Disodium phenyl dibenzimidazole tetrasulfonate or Neoheliopan AP

The use of UV absorbers can effectively protect natural and dyed hair from the damaging rays of the sun and increase the wash fastness of dyed hair. 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 described in WO 01/36396 especially on p. 1 , 1. 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. 1 1 , 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, 1. 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 described in WO 01/36396, especially on p. 1 1 , 1. 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, 1. 1 1 to p. 3, 1. 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 having a molecular weight from 150 to

50 000, for example such as those described in EP-A-801 942, 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, 1. 18 to 38, for example glycerol, propylene glycol, propylene glycol monoethyl ether, butyl glycol, benzyl alcohol, carbonates, hydrogen carbonates, guanidines, ureas and also primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole; opacifiers, such as latex; pearlising agents, such as ethylene glycol mono- and di-stearate; propellants, such as propane-butane mixtures, N₂O, dimethyl ether, CO₂ and air; antioxidants; preferably the phenolic antioxidants and hindered nitroxyl 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 substances are characterised by an anionic group that imparts water solubility, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having approximately 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-O-(CH₂-CH₂-O)_X-CH₂-COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = 0 or from 1 to 16, acyl sarcosides having 10 to 18 carbon atoms in the acyl group, acyl taurides having 10 to 18 carbon atoms in the acyl group, acyl 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 α-olefin sulfonates having 12 to 18 carbon atoms, α-sulfo fatty acid methyl esters of fatty acids having12 to 18 carbon atoms, - alkyl sulfates and alkyl polyglycol ether sulfates of formula R^O(CH₂-CH₂-O)_x-SO₃H, in which R' is a preferably linearar alkyl group having 10 to 18 carbon atoms and x' = 0 or from 1 to 12, mixtures of surface-active hydroxysulfonates according to DE-A-3 725 030; sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropylene glycol ethers according to DE-A-3 723 354, especially p. 4, 1. 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, I. 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 molecule, and also especially salts of saturated and especially unsaturated C₈-C₂₂carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Surface-active compounds that carry at least one quaternary ammonium group and at least one -COO^" or -SO3^" group in the molecule are terminated zwitterionic surfactants. Preference is given the so-called betaines, such as the N-alkylN,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 zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name cocoamidopropyl betaine.

Ampholytic surfactants are surface-active compounds that, in addition to a C₈-Ci₈-alkyl 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-alkylpropionic 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-Cieacylsarcosine.

Suitable non-ionic surfactants are described in WO 00/10519, especially p. 45, 1. 1 1 to p. 50, I. 12. Non-ionic surfactants contain as hydrophilic group, for example, a polyol group, a poly- alkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds 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 example, hydrotalcites, alkali metal salts of ether carboxylic acids, alkali metal oxides, hydroxides or alcoholates are used as catalysts.

The use of products having restricted homologue distribution may be preferred.

Examples of 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, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethy-lammonium chloride, lau- ryldimethylammonium 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 products Q2-7224 (manufacturer: Dow Corning; a stabilised trimethylsilylamodimethicone), Dow Corning 929 emulsion (comprising a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and also Abil^®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80), 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 alkyl-group-containing compounds used as surfactants may be single substances, but the use of natural raw materials of vegetable or animal origin is generally preferred in the preparation of such substances, with the result that the substance mixtures obtained have different alkyl chain lengths according to the particular starting material used.

The 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 comprises 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- rine, sodium sulfite, dithionithe, ammonium sulfite, sodium bisulfite, sodium metabisulfite, hydroquinone, phosphines, borhydride, cyanoborohydride, triacetoxy 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 comprises 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 naturally 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 20Og.

Oxidizing agents are for example persulfate or diluted hydrogen peroxide solutions, hydrogen peroxide emulsions or hydrogen peroxide gels, alkaline earth metal peroxides, organic peroxides, 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, I. 52 to 55, and I. 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 triethanolamine, alkali metal (sodium) hydroxides, earth metal hydroxides or compounds of the formula R₃ FL

\ / ⁵

N-R-N , wherein

R₆

R is a propylene residue, which may be substituted with OH or Ci-C₄alkyl, R₃, R₄, R₅ and R₆ are independently or dependently from each other hydrogen, d-C₄alkyl or hydroxy-(CrC₄)alkyl.

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, 1. 19 to I. 27.

The first compartment contains for examle 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 at 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 1 1 , 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 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, 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.

Aw 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 preferably does not exceed approximately 3% b.w. relative to the total weight of composition (A'). These binders are preferably selected from oils and liquid fatty substances of inorganic, synthetic, animal or plant origin.

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 with 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 citric acid, a citric acid gel, a suitable buffer solution with 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.

Examples

A. Preparation Examples: Example AZO-01

12.4 g 4-fluoroanilin 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 2Og of the compound of formula

(AZO-101 a)

are obtained

6.9 g of cisteamine dihydrochloride are added at 293 K under nitrogen atmosphere to 20 g of the compound of formula (101 a) in 12Og isopropanol 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 ).

¹H-NMR Data in deuterated methanol (128 scans)/ 360MHz:

Example AZO-02

12.4 g 2-fluoroanilin 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 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 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 50 ml 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

is obtained

The product s characterized by H-NMR Data in deuterated methanol (128 scans)/ 360MHz:

8.002 ddd J = 7.6;J=7.5; j =1 .4 1.029

7.893 S 2.00 imidazol

7.812 m J = 8.6, J = 6.7, 0.99 J = 1.4

7.505 ddd J = 8.6 1.06

7.436 t 0.949

4.21 1 S 5.78 dimethyl of imidazol

3.69 S 4.01 methy of monomethylsulfate

1 1g cisteamin chlorohydrate are added to 27g of compound of formula (102a) in 20 g triethylamine and 12Og isopropanol under nitrogen atmosphere at 293 K, .The temperature is raised to 333 K. The reaction mixture is stirred for 28 hours at this temperature. 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 washed with 45 ml isopropanol and dried in vacuum to obtain 17.6 g of product f formula (102).

The product is characterized by ¹H-NMR Data in deuterated methanol (128 scans)/ 360MHz:

Example AZO-03

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 ml 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 ml 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

Is obtained.

38.8 g of the product of formula (103a) are added to a stirred mixture of 10.6 g of cisteamin chlorohydrate in 15 g triethylamine and 7Og acetonitrile under nitrogen atmosphere at 293 K. The temperature is maintained at 273 K. The reaction mixture is stirred for 20 hours at this temperature. The reaction mass is filtered off and the filter residue washed with 45 ml of acetonitrile and dried in vacuum to obtain 42 g of product of formula (103). The product is characterized by ¹H-NMR Data in deuterated methanol (128 scans)/ 360MHz:

Example AZO-04

10O g 4-fluoro-3nitro-anilin is added to a stirred mass of 80 g methanol, heated to 333 K, 0.1 ml sulfuric acid added, and then 90 ml of propionic anhydride during 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 1 10 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 during 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 1 1 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 suspension 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 14O g dryed product of formula

38.8 g of the product of formula (104a) are added under nitrogen atmosphere at 293 K to a stirred mixture of 10.6 g of cisteamin chlorohydrate in 15 g triethylamine and 7Og acetonitrile. The temperature is maintained at 273 K. The reaction mixture is stirred for 20 hours at this temperature. The reaction mass is filtered off and the filter residue is washed with 45 ml of acetonitrile and dried in vacuum to obtain 32.6 g of product of formula (104). Characterization by ¹H-NMR Data in deuterated methanol (128 scans)/ 360MHz

Example AZO-05

10O 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 pH 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 Then the filtercake from the 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

is obtained

Characterizeation by ¹H-NMR Data in deuterated methanol (128 scans)/ 360MHz

48 g of the compound of formula (105a) are added to a stirred mixture of 1 1.6 g of cisteamin chlorohydrate in 15 g triethylamin and 7Og acetonitrile under nitrogen atmosphere at 293 K. Then the temperature is maintained at 273 K. The reaction mixture is stirred for 20 hours at this temperature. The reaction mass is filtered off and the filter residue is washed with 45 ml acetonitrile and dried in vacuum to obtain 42.6 g of the compound of formula (105).

Characterization by ¹H-NMR Data in deuterated methanol (128 scans)/ 360MHz:

Example AZO-06

1.Formation of the Hydrazone: 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 stirring 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. Stirring 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 15.4 g 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/hydrochloric acid/ice slurry. The phases are separated, washed with water and dried. The obtained solution of toluenesulfonate diester is used in the 3. step.

3.Alkylation: 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.

Characterization by ¹H-NMR data in deuterated methanol (32 scans)/ 360MHz:

Example AZO-07

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 amidosulfuric 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 toluenesulfonate diester is used in the following step

3.Alkylation: 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.

Characterization by ¹H-NMR Data in deuterated methanol (128 scans)/ 360MHz:

Residues of the compound

8.095 d J = 8.6; 2.07

7.867 d J=4.2 2.00 thiazol

7.696 d overlaid 6 phenylene

7.470 d J = 4.3 1.968 thiazol

7.217 d J = 8.6 4.00 tosyl

7.083 d J = 8.6 3.97 phenylene

4.856 t 5.6 4.08 methylene

3.419 S 12 methyl

3.139 t 5.6 4.01 methylen

2.309 S 6.00 Methyl

Example AZO-08:

Monoazo synthesis

90.0 g 2-amino-6-methoxy-benzothiazol are added to a stirred solution of 135 ml 60% sulfuric acid at 293 K. 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 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 dimethylaniline 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.Alkylation: 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 by ¹H-NMR in deuterated methanol (128 scans)/ 360MHz:

Example AZO-09

Same preparation process as described in example A8, but with the difference that 2-amino- benzothiazol instead of 2-amino-6-methoxy-benzothiazol is used. Example AZO-10:

19.9 g of N,N'-dimethyl-ethylendiamine are added with stirring to 12Og acetonitrile and compound of the formula of formula (101 a) 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. 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 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.Alkylation: 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 of a dark solid product. The product is recristallized twice from methanol.

Example AZO-11

Same preparation process as described in example A10, but with the difference that ethylendiamine is used instead of N,N'-dimethyl-ethylendiamine.

Example AZO-12

1. 16.9 g of ethylenediamine are added to the compound of the formula (101a) (prepared in Example A1 ) and 12Og 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. Acylating agent: A mixture of 15.4 g 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.Alcylation: 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.

¹H-NMR Data in deuterated methanol (128 scans)/ 360MHz

Example AZO-13

1.Formation of the Hvdrazone: 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 during 15 minutes and stirring 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 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 cisteamine 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. Alkylation: The foregoing hydrazone is dissolved in methanol by stirring with the dibromide solution. The temperature is raised to 60°C and maintained at 60°C 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.

Characterization by ¹H-NMR data in deuterated methanol (32 scans)/ 360MHz:

Example AZO-14:

1. 9.9 g of N,N-dimethyl-ethylendiamine are added to 12Og acetonitrile and to the compound of the formula (101 a) (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 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 acetonitrile. Then the material is dried in vacuum to obtain 16 g of product.

2. Alkylating agentA 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/chlorhidric 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.Alkylation: 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 recristallized twice from methanol.

Example AZO-15:

The compound of formula (102a) (prepared in example 2) is reacted with N,N-dimethyl-ethy- lenediamine according to the procedure as described in Example A14. The same alkylating agent is used to give the compound of formula (1 15).

Example AZO-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'-dimethyl-ethylendiamin is added at 293 K, under nitrogen atmosphere, with stirring to 12Og isopropanol and the foregoing compound of the formula (AZO-101 a).

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 material is dried in vacuum to obtain 16 g of the product:

2. Alkylating agent

A solution of 22.5 g of cysteamine dichlorohydrate in water and 31.4 g Bromoacetic chloride were cooled with stirring to 273K and then pH was hold through NaOH solution added in small amounts, maintaining the temperature. After completion of the addition the mixture was left over night in the refrigerator. The mixture has two phases, which are separated, washed with water and dried. The compound is used in the following step

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 (1 17a). 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 (1 17b) 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 material is dried in vacuum to obtain 57.5 g of the product (AZO-1 17). MS (ES+): m/z 403 (M²⁺). Example AZO-18:

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 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 276K by cooling. After the addition the mixture is stirred for four hours. The solution is dropped to a well-stirred water ice mixture (40Og) 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 10Og monoazo dye of formula (1 18a) is obtained.

2. Alkylation

14.7g of the monoazo dye of formula (1 18a), 9.9g of the alkylating agent of formula (AZO-1 17b) and 0.1 g Kl are stirred for 2Oh in 100ml tetramethylurea at 100°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). Example AZO-19:

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 (60Og) 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 1 h 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 (1 19a) are obtained.

2. Alkylation

39.1g of the monoazo dye of the formula (1 19a) and 13.8g of the alkylating agent (1 17b) and 0.1 g Kl are stirred for 2Oh 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. Example AZO-20:

1. Monoazo 10Og of 2-amino-thiazol are added to a well-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 (70Og) 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) 18Og 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) are obtained.

2. 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 2Oh at 100°C. The solvent is destilled off under reduced pressure and the residue is extracted with tetrahydrofurane (5x500 ml) and vacuum-dried. 21g of the dye of formula (120) arere obtained as a deep blue powder.

Example STY-01 : Preparation of the compound of formula

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 O⁰C and then 41.0 g of tosyl chloride are added in small amounts, maintaining the temperature at O⁰C 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 2^nd reaction step.

2. Alkylation

The alkylation agent obtained in the 1^st 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 isopropanol 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 - 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

Example STY-02: Preparation of the compound of formula

O

_/S-O O

1. Alkylating agent

A mixture of 15.4g 2,2-dithiodiethanol in 100 ml chloroform and 24.1g pyridine are cooled with stirring to O⁰C 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 2 ->nd reaction step. 2. Alkylation

Two equivalents (18.8 g) of 4-methyl-pyridine are dissolved in the foregoing alkylation 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 2^nd 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 recristallized twice from methanol.

The product is characterized by the following data: - The HPLC-MS gave a main component of a dication of the mass 512 - 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

Example STY-03: Preparation of the compound of formula

1. Alkylating agent

A mixture of 25.4 g of cisteamine as dichlorohydrate in 100 ml water is cooled with stirring to O⁰C and 41.0 g of bromoacetic acid bromide are added in small amounts, maintaining the temperature at O⁰C by external cooling. The pH is adjusted with sodium hydroxide to 8.0. After completion of the addition the mixture 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 2 reaction step.

2. Alkylation

The alkylation agent obtained in the 1^st reaction step is added to 50 ml isopropaol and dissolved in two equivalent amounts (18.8 g) of 4-methyl-pyridine. 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 2^nd 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.

The product is characterized by the following data:

- The HPLC-MS gives a main component of a dication of the mass 682

- 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

Example STY-04: Preparation of the compound of formula

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^nd 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 to 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 3^rd reaction step and 200 ml water are cooled with stirring to O⁰C and then 41.0 g of the acid chloride obtained in reaction step 1 dissolved in tetrahydrofurane are added in 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. The product may beused as such for dyeing applications.

The product is characterized by the following data:

- 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

Example STY-05: Preparation of the compound of formula

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 O⁰C 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 2^nd reaction step.

2.Alkylation The alkylation agent obtained in the 1^st reaction step is delivered from the solvent and dissolved in two equivalents (18.8 g) 2-methyl-pyridine. The temperature is raised to 80°C and maintained at 60°C during the following 16 hours. 3. Condensation

50 ml of isopropanol are added to the reaction mixture obtained in the 2 ->nⁿd^α 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.

The product is characterized by the following data: - The HPLC-MS gave a main component of a dication of the mass 682. - 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

Example STY-06: Preparation of the compound of formula

1. Acylating agent

24.0 g of thionyl chloride are added to a mixture of 21.4 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. Alkylation

The dimethylsulfate as alkylation agent is used without solvent, with two equivalent amounts (18.8 g) of 4-methyl-pyridine. 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 2^nd reaction step.

Then 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 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. Acylation A mixture of 55 g of the styrene compound obtained in the 3^rd reaction step and 200 ml water is cooled with stirring to O⁰C and then 45.0 g of the acid chloride obtained in the 1^st reaction step, dissolved in tetrahydrofurane, are added in small amounts, maintaining the temperature at O⁰C 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.

The product is characterized by the following data:

- 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

Example STY-07: Preparation of the compound of formula

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^th 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 2 ->nⁿd^α 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 to 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 3^rd reaction step in 200 ml water are cooled with stirring to O⁰C and then 35.0 g of the acid chloride obtained in the 1^st reaction step, diluted with 30 ml tetrahydrofurane are added in small amounts, maintaining the temperature at O⁰C 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.

The product is characterized by the following data:

- 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz

Example STY-08: Preparatin of the compound of formula

1. Acylating agent

A mixture of 18.4 g 2,2-dithioglycolic acid in 100 ml chloroform and 24.0 g thionyl chloride are added in small amounts, maintaining the temperature at 2O⁰C by external cooling.

After completion of the addition the mixture is heated to remove the formed gases and to complete the reaction.

The solvent is removed by distillation under low pressure and the acid chloride is used as such in the following step 2. Alkylation

The dimethylsulfate as alkylation 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 2^nα 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 recristallized twice from isopropanol.

4. Acylation A mixture of 49 g of thestyrene compound obtained in the 3^rd reaction step and 200 ml water are cooled with stirring to O⁰C and then 41.0 g of acid chloride obtained in the 1st reaction step are added in small amounts, maintaining the temperature at by O⁰C 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.

The product is characterized by the following data:

- 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

Example STY-09: Preparation of the compound of formula

1. Alkylating agent

A mixture of 21.5 g 2-hydroxyethyl-methylamine are neutralized with hydrochloric acid and evaporated to dryness. The salt is suspended in chloroform and cooled under stirring to O⁰C and then 41.0 g of thionyl chloride are added in small amounts, maintaining the temperature at by O⁰C 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 2^nd reaction step.

2. Alkylation

The alkylation agent obtained in the 1^st 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 2^nd 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

is confirmed by 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

4. 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 O⁰C and then 22.0 g of mesyl chloride are added in small amounts, maintaining the temperature at O⁰C 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 such in the 5^th reaction step.

5. Alkylation

Two equivalents (18.8g) of the intermediate dye molecule obtained in the 3^rd reaction step are dissolved in alkylation agent obtained in the 4^th 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.

The product is characterized by the following data:

- 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz

Example STY-10: Preparation of the compound of formula

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 70°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 1^st 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

is confirmed by 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

3. 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 O⁰C and then 41.Og of tosyl chloride are added in small amounts, maintaining the temperature at O⁰C 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 4^th reaction step.

4. Alkylation

Two equivalents (56g) of the intermediate dye molecule are dissolved in the foregoing alkylation agent obtained in the 4^th 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.

The product is characterized by the following data:

- 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

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

MS (ES+): m/z 440 (M²⁺). UVA/IS [nm] (water): Xi = 567, X₂ = 616.

Example ANT-02:

2.06 g of the compound of formula (101 ) are dissolved in 30 ml NMP and 530 μl 4-bromo- butyryl chloride are added under stirring. 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

UVA/IS [nm] (water): λ_max 564. Example ANT-03:

Stepi: 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 1072-1 1-3) 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 40°C. 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

¹³C NMR (DMSOd₆) [ppm]: δ 181.68, 181.23, 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-amino-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

MS (ES+): m/z 383 (IVT). UVA/IS [nm] (water): λi 567, λ₂ 615.

Example ANT-05:

Step 1: To a solution of 61.32 g 1-(3-aminopropyl)-imidazole, 5.92 g lithium hydroxide and 1.48 g Cu(I)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 1 h. 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

MS (ES-): m/z 425 (M^"). UVA/IS [nm] (water): λi = 591 , λ₂ = 633.

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/z 347 (M+1 ). UVA/IS [nm] (water/acetonitrile 1 :1 ): λi 569, λ₂ 612.

Step 3: 1.28 g of the compound of formula (105b) and 0.73 g of bis(2-(2-bromoacetamido)- ethyl)-disulfide (RN 697755-79-6) are dissolved in 20 ml DMF and stirred for 3 days 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 0.935 g of the compound of formula

MS (ES+): m/z 463 (M^⁺). UVA/IS [nm] (water/acetonitrile 1 :1 ): λi 571 , λ₂ 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-ethanolamine 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 ml of water for 30 min, then filtered off and dried under vacuum at 60°C to obtain 1.69 g of the compound of formula

MS (ES+): m/z 402 (M+1 ). UVA/IS [nm] (water/acetonitrile 1 :1 ):

= 554, λ₂ = 591. Step 2: 0.50 g of the compound of formula (106a) and 0.29 g of the bis(toluolsulfonate) 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 50°C. 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 461 (M²⁺). UVA/IS [nm] (water/acetonitrile 1 :1 ): λ_λ 556, λ₂ 593.

Example ANT-07:

Step 1: 1.43 g of 1-(2-chloroacetamido)-anthraquinone (RN 20149-91-1 ) and 6.46 g imidazole are mixed in 10 ml o-dichlorobenzene and stirred at 1 10°C for 1 h. The reaction mixture is cooled to room temperature and poured into 1 L water under stirring. The precipitate is filtered, washed with water and dried under vacuum at 60°C to yield 1.30 g of the compound of formula

MS (ES+): m/z 332 (M+1 ). UVA/IS [nm] (water/acetonitrile 1 :1 ): λ_max 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 filtered and washed twice with 100 ml acetone. The filter cake is dried under vacuum at 50°C to yield 1.72 g of the compound of formula

MS (ES+): m/z 448 (IvT). UVA/IS [nm] (water): λ_max = 395.

Example NIT-01 : Preparation of the compound of formula

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 resulting 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. Example NIT-02: Preparation of the compound of formula

5.66g (25.2 mmol) cystamin dihydrochloride are furnished in 40ml dimethylsulfoxide.

8.46g (100.8mmol) sodium hydrogen carbonate are added stepwise.

Then 10.Og (50.4mmol) 4-fluoro-3-nitrophenylacetamide, dissolved in 100ml dimethylsulfoxide are added dropwise at 45°C.

The reaction mixture is stirred for 7h at 80°C 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: 199-201⁰C.

Example NIT-03: Preparation of the compound of formula

5.00 g (9.8 mmol) of di 2-[4-acetamino-2-nitrophenyl]ethyl disulfide are furnished in 50ml of

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 precipitate is filtered off and washed with 10% sodium hydrogen carbonate solution and then neutral with water.

3.5g (84%) of a violet dye are obtained.

Mp.: 193-195°C Example NIT-04: Preparation of the compound of formula

a. 20 g of 4-fluoro-3-nitrophenylacetamid, 8.48 g of potassium carbonate and 9.07 g of N₁N- dimethyl-ethylenediamine are dissolved in 50 ml dimethyl sulfoxide. The reaction mixture is stirred for 3 days at 80°C and then cooled to room temperature. The resulting suspension is poured into 300 ml of ice and filtered. The collected solid is dried in vacuo over night at 60°C to yield 23.79 g of a red powder.

MS (ES-): m/z 265 (M-1 ). UV/VIS [nm] (water): λ_max 458

b. 34 g of the compound of formula (104a) and 30 g of the bis(toluolsulfonate) of (2-hydroxy- ethyl)-disulfide (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 resulting 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⁺), UV/VIS [nm] (water): λ_max 466. Example XAN-01 : Preparation of the compound of formula

(XAISM 01 )

(aij 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-dithiodiethanol, 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.

The product is characterized by ¹H-NMR data in deuterated methanol (128 scans)/360MHz:

8,350 d 6,7 1 ,98 phe

7,831 d ϋberlagert 6,7 2,02 Phe

7,831 d ϋberlagert 6,6 2,03 phe

7,425 d 6,1 2,04 phe

7,153 d 8,8 4,02 xanten

7,102 d 9,1 4,05 xanten

6,984 S 4,0 xanten

4,21 t 6 4,00 Ethylen

3,70 t 7 16,10 ethyl

2,57 t 6 4,08 Ethylen

1 ,319 t 7 24,3 Ethyl

Examples XAN-02 - XAISMO:

The following compounds (XAN-102 - XAN-110) can be prepared according to the method desribed in Example XAN-01 :

Example XAN-1 1 : Preparation of the compound of formula

(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.Og 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 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 methanol (128 scans)/ 360MHz

7,970 d 9,7 1 ,98 phe

7,571 d (overlaid) 9,5 2,02 phe

7,571 d (overlaid) 9,6 2,03 phe

7,436 d 2,6 2,04 xanthene

7,215 d 6,8 4,02 xanthene

7,102 d 6,5 2,025 phe

6,528 S 4,05 xanten

4,19 t 7 4,00 ethylene

3,29 t 7 16,10 methyle

2,57 t 7 4,08 ethylene

Example XAN-12: Preparation of the compound of formula

(XAISM 12)

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.Og 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.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/ 360MHz

8,350 d 6,7 1 ,98 phe

7,831 d overlaid 6,7 2,02 phe

7,831 d overlaid 6,6 2,03 phe

7,425 d 6,1 2,04 phe

7,153 d 8,8 4,02 xanthene

7,102 d 9,5 4,025 xanthene

6,984 S 4,05 xanthene

4,21 t 6 4,00 ethylene

3,70 t 7 16,10 ethylene 2,57 6 4,08 ethylene 2,319 7 16,3 ethylene

Example XAN-13: Preparation of the compound of formula

(a) Alkylating agent

A mixture of 15.4g 2,2-dithiodiethanol in 100 ml chloroform and 241g pyridine are cooled with stirring to O⁰C.

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.Og) 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.

The 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 9Og of an orange solid product.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz 7,970 d 6,7 1 ,98 phe

7,571 d overlaid 6,5 2,02 phe

7,571 d overlaid 6,6 2,03 phe

7,436 d 2,6 2,04 xanthene

7,215 d 8,8 4,02 xanthene

7,102 d 9,5 2,025 phe

6,528 S 4,05 xanthene

4,19 t 7 4,00 ethylene

3,29 t 7 16,10 ethyl

2,57 t 7 4,08 ethylene

1 ,319 t 7 24,3 ethyl

Example XAN-14: Preparation of the compound of formula

(XAISM 14)

(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.Og 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% 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.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz

7,970 d 9,7 1 ,98 phe

7,571 d overlaid 9,5 2,02 phe

7,571 d overlaid 9,6 2,03 phe

7,436 d 2,6 2,04 xanthene

7,215 d 6,8 4,02 xanthene

7,102 d 6,5 2,025 phe

6,528 S 4,05 xanthene 4,19 7 4,00 ethylene 3,29 7 16,10 ethyl 2,57 7 4,08 ethylene 1 ,319 7 24,3 ethyl

Example ARY-01 :

A solution of 10.00 g Pergascript I-6B (RN 50292-95-0), 1.259 g dithiodiethanol and 3.95 g of toluene sulfonic acid monohydrate in 100 ml chloroform is refluxed for 4 days with a water separator.

After that time no separation of water is observed any more.

The solvent is removed in vacuo and the crude product was purified by column chromatography (silica, toluene/acetone gradient).

Yield: 1.78 g of the compound of formula

MS (ES+): m/z = 677 (IVT); UV/VIS: λ_max = 531 nm.

Example OXA-01 (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.

Finally 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 NaHCθ₃ 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

MS (ES+): m/z 617 (M+1 ).

Step 2: 0.88g HBr (33%) are added drop wise to a suspension of 0.5g of the compound of formula (1 o1 a) 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 1 h.

The resulting blue solution is stirred for an additional hour, then cooled to room temperature and poured into 200 ml of acetone.

The precipitate is collected by filtration and dried in vacuo to obtain 0.43g of the compound of

formula (OXA-101 )

as a dark blue powder, which can be used for the dyeing of hair.

MS (ES+): m/z 453 (M²⁺); UV/VIS ( water): λ_maxi 642nm, λ_max2 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 1 h, during which time the temperature is rising 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 10g 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

as a dark blue powder, which is used for step 3.

MS (ES+): m/z 337 (M⁺-I ); UV/VIS ( water): λ_maxi 634nm, λ_max2 590nm.

Step 3: A solution of 0.5g of the compound of formula (102a), 0.24g of bis(2-(2-bromo- acetamide)ethyl)-disulfide (RN 697755-79-6) and 0.08 g of potassium carbonate in 50ml 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.

MS (ES+): m/z 453 (IVT); UV/VIS ( water): λ_maxi 642nm, λ_max2 588nm.

Preparation of the compound of formula (PRO-101a)

(a) Condensation

35.7g 1 ,3,3 trimethyl-2-methylene-indoline are added to 6Og 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

4Og 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.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz:

is obtained.

(b) Alkylation

One equivalent (10.0g) sodium thiosulfate is dissolved in 3Og of the alkylating dye (101c) with 75 ml ethanol as solvent. The temperature is raised to reflux andmaintained at 80°C during the following 4 hours.

The product of formula (PRO-101 b)

is obtained.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz

(c) Hydrolysis

One equivalent (4,Og) sodium hydroxide is dissolved with absolute ethanol as solvent in the compound (101 b) 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.

The compound of formula (PRO-101 d)

is obtained.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz

Example PRO-02: Preparation of the compound of Formula

(a) Alkylation

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.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz

8,335 d 6,7 1 ,00 vinyl

7,997 d 6,7 2,01 Phe

7,669 d 16,6 2,03 lnd

7,58 m 6,1 1 ,04 lnd

7,532 m 6,5 1 ,025 ind

7,32 d 16,9 1 ,01 vinyl

6,996 d 6,4 2,00 Phe

4,016 S 3,00 methyl

3,952 t 6 2,03 ethylene

3,548 t 6 2,05 ethylene

3,235 S 3,087 methyl(amine)

1 ,826 S 6,04 Di Me-ind Example PRO-03: Preparation of the compound of formula

One equivalent (14.Og) 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.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz

Example PRO-04: Preparation of the compound of formula

(a) Alkylation

68.8g 4-methyl-pyridine are dissolved in 80ml absolute ethanol as solvent. The temperature is raised to 333 K. 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.Og) 2-chloroethyl-methylamino-benzaldehyde, 250ml 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 at ,

The reaction product is precipitated by cooling, then separated by filtration and dried in vacuum to obtain 24Og of an orange solid product.

The product is recristallized twice from methanol.

The product of formula (PRO-104a)

is obtained.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz

(C):

One equivalent (6.Og) thiourea is dissolved with 75 ml absolute ethanol as solvent in 2Og 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. The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz

Example 5: Preparatin of the compound of formula (PRO-105)

One equivalent (8.Og) of potasium thioacetate is dissolved with absolute ethanol as solvent to 2Og of the alkylating dye of formula (PRO-104a).

The temperature is raised to reflux and 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

Example 6: Preparation of the compound of formula (PRO-106)

One equivalent (6.Og) thiourea is dissolved in absolute ethanol+ft the compound of formula

(PRO-104a).

The temperature is raised to reflux and maintained at 80°C 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

Example PRO-07: Preparation of the compound of formula (PRO-107)

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 product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/ 360MHz

Example PRO-8: Preparation of the compound of formula

One equivalent (9.Og) of potassium thiocyanate is dissolved with 100 ml absolute ethanol in 2Og of the compound of formula (PRO-104a). 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.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz

Example PRO-9: Preparation of the compound of formula (PRO-109)

(a) Alkylation 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.

(b) Condensation the equivalent amount (15Og) 2-chloroethyl-methylamino-benzaldehyde, 250 ml ethanol 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 22Og of an orange solid product of formula

The product is recristallized twice from methanol.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/ 360MHz

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) Hydrolysis

One equivalent (4.Og) 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

Example PRO-10: Preparation of the compound of formula

(a) Alkylation

25Og 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 (150Og) 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 34Og of an orange solid product of formula

The product is recristallized twice from methanol.

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.

(C]

One equivalent (6.Og) thiourea is dissolved in 30 g of the the compound of formula (108a) with absolute ethanol.

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

Example PRO-1 1 : Preparation of the compound of formula

One equivalent (6.Og) of thiourea is dissolved in 3Og of the compound of formula (PRO-H Oa) with absolute, ethanol. The temperature is raised to reflux andmaintained at 80°C during the following 48 hours.

(b) Hydrolysis

One equivalent (4.Og) 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

Example PRO-12: Preparation of the compound of formula

(a) Alkylation

250 g 2-methyl-quinoline are dissolved in 80 ml absolute ethanol. The temperature is raised to 333 K.

94g dimethylsulfate 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.Og) 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 34Og of an orange solid product of formula compound of formula (PRO-1 10). The product is recristallized twice from methanol.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz Showing a complex spectrum. Throught HPLC/MS the identity was proofed, obtaining a single peak with the mass of 337/339 dalton

Example PRO-13: Preparation of the compound of formula

One equivalent (6.Og) thiourea is dissolved in 3Og 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 dalton

Br

Example PRO-14: Preparation of the compound of formula (PRO-1 14)

(a) Alkylating agent

A mixture of 15.4 g 2,2-dithiodiethanol in 100 ml chloroform and 24.1 g pyridine are cooled with stirring to O⁰C 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 toluenesulfonate 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 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, then separated by filtration and dried in vacuum to obtain 39g of an orange solid product. The product is recristallized twice from isopropanol.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz

Id]

One equivalent (5,0 g) of thiourea is dissolved in 2Og of the foregoing alkylating dye with 75 ml absolute ethanol .

The temperature is raised to reflux and maintained at 80°C during the following 48 hours. (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.

The product is characterized by ¹H-NMR data in deuterated chloroform (128 scans)/360MHz

Example PYR-01 : Preparation of the compound of formula

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 O⁰C.

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 dimethylamino-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.

- 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz:

Example PYR-02: Preparation of the compound of formula

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 O⁰C 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.

- 1 H-NMR data in deuterated methanol128 scans)/ 360MHz:

Example PYR-03: Preparation of the compound of formula

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 O⁰C 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-pyridine. The temperature is raised to 70°C and maintained during the following 24 hours.

c. Condensation 50 ml of tolurnr 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 41g 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 255.

- 1 H-NMR data in deuterated chloroform (128 scans)/ 360MHz.

Example PYR-04: Preparation of the compound of formula

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 O⁰C.

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 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 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.

The product is characterized by the following data:

- The HPLC-MS gives a main component of a monocation of the mass 258.

- 1 H-NMR data in deuterated methanol (128 scans)/ 360MHz:

Example PYR-05: Preparation of the compound of formula

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 O⁰C 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 recristallized 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.

- 1 H-NMR data in deuterated Methanole (128 scans)/ 360MHz:

Example PYR-06: Preparation of the compound of formula

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 O⁰C 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 dried.

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 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 44 g of a brown solid product.

The product is recristallized twice from isopropanol.

The product is characterized by the following data:

- The HPLC-MS gave a main component of a monocation of the mass 297.

- 1 H-NMR data in deuterated methanol (128 scans)/ 360MHz:

B - Application Examples

Sulfide dyes, which can be combined are shown in Table EX-1 , but are not limmited to these examples.

Table EX-1 : sulfide dyes USEFUL FOR HAIR DYEING MIXTURES

Comp.

Of_ Structure Color formula

(101 ) yellow

Table EX-1 : sulfide dyes USEFUL FOR HAIR DYEING MIXTURES

Comp.

Of_ Structure Color formula

(120) orange

(121 ) orange

(122) orange

(123) orange

For the treatment of hair the following compositions were used:

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 plate.The 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 dried 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.

υn C = = copper, B = brown, G = green, V = violet

1) B = brown, S = black

Claims

Claims:

1. Mixture of dyes selected from the compounds of formula (1 ) D₁ — (Z₁). — Y₁ — S — A , wherein

A is hydrogen; a radical of formula (1 a) * — S-Y₂ — (Z₂)- D₂ ; or a thio ester group of

formula (1b) wherein

-( ' ^■

E is O; S; or N-R₃; B₁ is -OR_b; -NR_bR_c, or -SR_b;

R₃, R_b and R_c, independently from each other are hydrogen; CrC₁₂alkyl; C₆-Ci₂aryl; or C₆- Ci₂aryl-Ci-Ci₂alkyl;

D₁ and D₂ independently from each other is a radical of formula (Ia₁) ;

An -

and formula

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; Ci-Ci₆alkyl, 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; CrCi6alkoxy, (poly)-hydroxy- C₂-C₄-alkoxy; halogen; SO₂NR₃₃R₃₄; SR₃₃; NR₃₃R₃₄; OR₃₃; SO₂; COOR₃₃; NR₃₃COR₃₄; or CONR₃₃;

Qi is a bivalent radical selected from -N=N-; -CR_d=N-; -N=CR_d-; -NR_d-N=CR_e-; and

T₁ is a bivalent radical of an aromatic or heteroaromatic substituted or unsubstituted compound;

Rd and R_e independently from each other are hydrogen; unsubstituted or substituted C₁- C₁₄alkyl; C₂-C₁₄alkenyl; C₅-C₁₀aryl; CrC^alkyl-Cs-C^aryl; or Cs-C^aryl-CrC^alkyl; R₃₃ and R₃₄ independently from each other are hydrogen; CrC₁₂alkyl, which may be substituted by one or more C-ι-C₅alkyl, C-ι-C₅-alkoxy, hydroxy or -(CO)-H; -(CO)-CrC₅alkyl; phenyl or phenyl-CrC₄alkyl, wherein the phenyl moiety may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, halogen, -NH₂, mono-Cr

C₅alkylamino, di-Ci-C₅alkylamino, -NO₂, carboxy or hydroxy; R₄, R₅ and Re independently from each other are hydrogen; Ci-C₂oalkyl or Ci-C₂oalkoxy, which may be substituted by one or more CrC₅alkoxy, halogen, -NH₂, mono-Ci-C₅alkylamino, di-Ci-C₅alkylamino, -NO₂ or hydroxy; C₃-C₆cycloalkyl; -C(O)H; -C(O)-C_rC₅alkyl; halogen;

NO₂; OH; phenyl, which may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, halogen, -NH₂, mono-Ci-C₅alkylamino, di-Ci-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

W₁, W₂, W₃ or W₄ is -N⁺; and the radical MZ₁^-Y₁-S-A is bonded to W₁ or W₂; R₃₅ and R₃₆ independently from each other are hydrogen; CrC₁₂alkyl, which may be substituted by one or more CrC₅alkyl, CrC₅-alkoxy, hydroxy or -(CO)-H;

-(CO)-C-ι-C₅alkyl; phenyl or phenyl-C-ι-C₄alkyl, wherein the phenyl moiety may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, halogen, -NH₂, mono-Cr

C₅alkylamino, di-CrC₅alkylamino, -NO₂, carboxy or hydroxy; R₇, R₈, Rg and R₁₀ independently from each other are hydrogen; CrC₂₀alkyl; CrC₂₀alkoxy; C₃-

Cβcycloalkyl; halogen; NO₂; OH; SH; or a radical of formula (I c₁) '

X₁ is CrC₁₈alkylene; -(CO)-CrC₁₈alkylene CrC₁₈arylene; C₆-C₁₈arylene-CrC₁₂alkylene; or -(OCH₂CH₂)_n2-O-;

O T₂ is a radical of formula (I c₂) * — N- -x,- ; or -0-(X₃)Si

Q₂ is a cationic biradical of a saturated, aromatic or heteroaromatic group; or a radical of

formula (I c₃)

R_f, R_g and R_h independently from each other are hydrogen; CrC₁₄alkyl; C₂-C₁₄alkenyl; C₆-C₁₀aryl; Ce-C^aryl-CrC^alkyl; or Crdoalky^Cs-doaryl); X₂, X₃ and X₄ independently from each other are C-i-C-iβalkylene;

-(CO)-Ci-Ci₈alkylene-Ci-Ci₈arylene; C₆-Ci8arylene-Ci-Ci₂alkylene; or -(OCH₂CH₂)_n-O-; t is 0; or 1

R₃₇ is hydrogen; or CrC₂₀alkyl; R38, R39 and R₄0 independently from each other are hydrogen, Ci-C₂oalkyl, C₄-Ci₂cycloalkyl, C₆-Ci₃aralkyl; phenyl-CrC₅alkyl; or R₃₈ and R₃₉ together with the linking nitrogen atom form a C₄-Ci₂-membered heterocyclic ring which may be interrupted by one or more than one -O- or -NH- goups; n-[ is is 0 or 1 ; p is O; or 1 ; s is 0; or 1 ; t is O; or 1 ; u is O or i ;

R₁₁, R₁₂ and R-₁₃ independently from each other are hydrogen; C-ι-C₂oalkyl or CrC₂oalkoxy, which may be substituted by one or more CrC₅alkoxy, halogen, -NH₂, mono-d-

C₅alkylamino, di-CrC₅alkylamino, -NO₂ or hydroxy; C3-Cecycloalkyl; -C(O)H; -C(O)-C₁- C₅alkyl; -C(O)OH; -C(O)O-C_rC₅alkyl; halogen; NO₂; OH; SH; phenyl, which may be substituted by one or more C-ι-C₅alkyl, C-ι-C₅alkoxy, halogen, -NH₂, mono-Cr C₅alkylamino, di-CrC₅alkylamino, -NO₂ or hydroxy; or a radical -NR₄₁R₄₂; Q₃ is is -C(O)-; -C(O)O-; -OCO-; -N(R)-X₅-; -CON(R)-; -(R)NC(O)-; -0-; -S-; -S(O)-; or -S(O)₂-;

T₃ is the direct bond; *— N— * ; or a cationic biradical of a saturated, aromatic or

R, heteroaromatic group;

Ri, R_k, Ri independently from each other are CrC₁₄alkyl; C₂-C₁₄alkenyl; C₆-C₁₀aryl; C₆-C₁₀aryl- d-Cioalkyl; or Ci-Cioalkyl(C₅-Ci_Oaryl);

R₄₁ and R₄₂ independently from each other are hydrogen; CrC₁₂alkyl, which may be substituted by one or more C-ι-C₅alkyl, C-ι-C₅-alkoxy, hydroxy or -(CO)-H; -(CO)-C₁- C₅alkyl; phenyl or phenyl-CrC₄alkyl, wherein the phenyl moiety may be substituted by one or more C-ι-C₅alkyl, C-ι-C₅alkoxy, halogen, -NH₂, mono-CrC₅alkylamino, di-Cr C₅alkylamino, -NO₂, carboxy or hydroxy; or a radical of formula *— -X-N if-R₄₄ ; wherein

R₄₅ at least one of the radicals Rn, Ri₂ or R₁₃ is NO₂; R₄₃, R₄₄ and R₄₅ independently from each other are hydrogen; Ci-Ci₄alkyl; C₂-Ci₄alkenyl; C₆-

Cioaryl; C₆-Cioaryl-Ci-Ci_Oalkyl; or Ci-Cioalkyl(C₅-Cioaryl); X₅ and X₆ independently from each other are the direct bond; CrCioalkylene; C₅-

Ciocycloalkylene; C₅-Ci₀arylene; or C₅-Cioarylene-(Ci-Ci_Oalkylene); R₁₄ is N⁺R₄₆R₄₇;

R₄₆ and R₄₇ independently from each other are hydrogen; CrC₁₂alkyl; or phenyl-CrC₄alkyl; or R₄₆ and/or R₄₇ are a bivalent C3-C₆alkylene radical which is linked to the carbon atoms C¹ or C² in formula (1 e) respectively and, together with the linking nitrogen atom form a 6 to 16- membered carbocyclic ring; R₁₅ is is NR₄₈R₄Cj; or OR₄₈;

R₄₈ and R₄₉, independently from each other are hydrogen; CrC₁₂alkyl; or phenyl-CrC₄alkyl; or R₄₈ and R₄₉are a bivalent C₃-C₆alkylene radical which is linked to the carbon atoms C³ or C⁴ in formula (1e) respectively and, together with the linking nitrogen or oxygen atom form a 6 to 16-membered carbocyclic ring; or

R₄₈ and R₄₉ together with the linking nitrogen atom form a 4 to 8 membered carbocyclic ring; R₁₆, R₁₇, R₁₈, R₁₉ and R₂₀ independently form each other are hydrogen; CrC₁₂alkyl; halogen;

0-R₅₂

NR₅oR₅₁; or a radical of formula (I e₁) * — / ;

0 R₅o and R₅₁ independently from each other are hydrogen; CrC₁₂alkyl; phenyl-CrC₄alkyl; or a

radical of formula (I e₂)

V₁ is -O-; or -NR₅₃;

R₅₂ and R₅₃ independently from each other are hydrogen; or CrC₅alkyl;

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 C-ι-C₁₂alkyl, C-ι-C₁₂alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or by the radical -NR₅₄R₅₅ or -OR₅₆; B₄ is C6-Cioarylene, or a bivalent radical of a 5-7-membered heterocyclic compound, which may be substituted by CrC₁₂alkyl, CrCi₂alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or by the radical -NR₅₄R₅₅ or -OR₅6;

Rs₄ R55 and R₅₆ independently from each other are hydrogen; or CrC₁₂alkyl, which may be substituted by hydroxy or C₆-Ci₀aryl; or

R₅₄ and R₅₅ together with the linking nitrogen atom form a 5 to 7 membered heterocyclic ring; or

R₅₅ and R₅₆ together with the linking nitrogen atom form a piperidine ring of

formula (If₁) *— N , wherein

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; CrC₂oalkyl; CrC₂oalkoxy; C₃-

Cecycloalkyl; C₅-Cioaryl; 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 Ci-Ci₄alkyl, C₂-Ci₄alkenyl, C₆-Ci₀aryl, C₆-Cioaryl-Ci-Cioalkyl 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 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 -O-; or -N(R₂₄)-; or -S-; R₂₇ is hydrogen; or Ci-C₅alkyl;

R₂8 is a radical of formula (Ig₁) ; (ig₂) ; or

(Ig₃) or R₂₇ and R₂β together with the linking carbon atom ¹C form

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 R₅g independently from each other are hydrogen; or Ci-C₅alkyl; R₂g, R30, R3₁ and R₃₂ independently from each other are hydrogen; hydroxy; -S-H; -S-Cr Ci₂alkyl; halogen; d-C^alkyl or Ci-Ci₂alkoxy, which may be substituted by one or more

CrC₅alkyl, C_rC₅-alkoxy, hydroxy, -(CO)-H or -(CO)-C_rC₅alkyl; -NR₆₉R₇₀; -NO₂; -(CO)H or

(CO)-Ci-C₅alkyl; C₆-Ci₂aryl, C₆-Ci₂aryl-Ci-C₄alkyl or C₆-Ci₂aryl-Ci-C₄alkoxy, wherein the aryl moiety may be substituted by one or more CrC₅alkyl, Ci-C₅alkoxy, -(CO)-H or

-(CO)-Ci-C₅alkyl; -NR₆₉R₇₀; -NO₂; -(CO)-H; or -(CO)-C_rC₅alkyl; R₆₉ and R₇₀ independently from each other are hydrogen; hydroxy; CrCi₂alkyl; hydroxy-Cr

Ci₂alkyl; -(CO)-H; -(CO)-Ci-C₅alkyl; phenyl or phenyl-CrC₅alkyl, wherein the phenyl moiety may be substituted by one or more CrC₅alkyl, Ci-C₅alkoxy, halogen, -NH₂, mono-

Ci-C₅alkylamino, di-Ci-C₅alkylamino, -NO₂, carboxy or hydroxy;

Yi and Y₂ independently from each other are unsubstituted or substituted, straight-chain or branched, interrupted or uninterrupted CrCi_Oalkylene; C₅-Ci₀cycloalkylene;

C₅-Ci₀arylene; or-C₅-Ci₀arylene-(Ci-Ci₀alkylene);

Z₁ and Z₂ independently from each other are *-(CH₂)_q-C(O)-**; *-(CH₂CH₂-O)_w-**;

*-(CH₂)_q-C(O)O-**; *-(CH₂)_q-OCO-**; *-(CH₂)_q-N(R₆₀)-**;

*-(CH₂)_q-CON(R₆₀)-**; *-(CH₂)_q-(R₆₀)NC(O)-**; -0-; -S-; -S(O)-; -S(O)₂-; or a cationic biradical of a substituted or unsubstituted aromatic or heteroaromatic compound of the

formul

(1 d)

Gi and G₂ independently from each other are N; -0-; -S-; or a radical of CR₆₄; the asterix * indicates the linkage to D₁ and/or D₂; the asterix ** indicates the linkage to Yi and/or Y₂ ;

R₆O, Rβi_> Rβ2, Rβ3 and R₆₄ independently from each other are hydrogen; d-Ci₄alkyl; C₂-

Ci₄alkenyl; C₆-Ci₀aryl; C₅-Cioaryl-(Ci-Ci_Oalkyl) ; or -Ci-Ci₀alkyl(C₅-Ci₀aryl); R₂9, R30, R3₁ and Rβ₂ independently from each other are hydrogen; hydroxy; -S-H;

-S-Ci-C"i₂alkyl; halogen; Ci-Ci₂alkyl or Ci-Ci₂alkoxy, which may be substituted by one or more C_rC₅alkyl, C_rC₅-alkoxy, hydroxy, -(CO)-H or -(CO)-C_rC₅alkyl; -NR₆₅R₆₆; -NO₂; -(CO)H or (CO)-CrC₅alkyl; C₆-Ci₂aryl, C₆-Ci₂aryl-C_rC₄alkyl or C₆-Ci₂aryl-Ci-C₄alkoxy, wherein the aryl moiety may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, -(CO)-H or -(CO)-CrC₅alkyl; -NR₆₇R₆₈; -NO₂; -(CO)-H; or -(CO)-C_rC₅alkyl;

Res, R66.R67 and R₆₈ independently from each other are hydrogen; hydroxy; Ci-Ci₂alkyl; hydroxy-Ci-Ci₂alkyl; -(CO)-H; -(CO)-Ci-C₅alkyl; phenyl or phenyl-C_rC₅alkyl, wherein the phenyl moiety may be substituted by one or more CrC₅alkyl, CrC₅alkoxy, halogen, -NH₂, mono-Ci-C₅alkylamino, di-Ci-C₅alkylamino, -NO₂, carboxy or hydroxy; q is a number from O to 5; w is a number from one to 5; r is O; or 1 ; and

An is an anion.

2. Mixture according to claim 1 , wherein Yi and Y₂ are CrC₅alkylene.

3. Mixture according to claim 1 or 2, wherein

Z₁ and Z₂ independently from each are other -N(R₆₀)-; — N— ; -CON(R₆₀)-; -(CH₂)_qNC(O)-;

^R61 -O-; or -S-; and

R₆₀ R₆₁ and q are defined as in claim 1.

4. Mixture according to any of claims 1 to 3, wherein A is a radical of formula (1 a); and D₂ has the same meaning as D₁;

Y₂ has the same meaning as Y₁; and Z₂ has the same meaning as Z₁.

5. Mixture according to any of claims 1 to 4, wherein

Ri

\

An - IN

D₁ and D₂ independently from each other are a radical of formula (1 a₈) *— τ_r ^Qi — "

(Ia₉) _{1 i (1 aii)} or

-

(I a₁₂) ; wherein

R₁, R₂₁Q₁, T₁ and An^" independently from each other are defined as in claim 1.

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

(AZO-01) wherein

Reg, R70, R7₂ and R73 independently from each other are hydrogen; unsubstituted or substituted Ci-Ci₄alkyl; C₅-C_1ocycloalkyl; C₂-C₁₄alkenyl; C₅-Cioaryl-(Ci-Ci_Oalkyl); CrC₁₀alkyl-(C₅- C_1oaryl); C₅-C_1oaryl;

,0 R₇₁ is hydrogen; or a radical of formula (2a) ^~NR72

R₇₃

An is an anion; and Y₁ is defined as in claim 1.

7. Mixture according to claim 1 , wherein the dyes are selected from the compounds of formula (STY-01 ) , wherein

one of W₁ or W₂ is -N⁺- the other is -CH; and the biradical .-(Z₁J_n-Y₁-S-S-Y₂-(Z₁)-* j_s bonded to -N⁺; and

R₄, R₅, Re, Y-i, 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

(STY-03)

wherein

R₄, R₅, Re, Z₁, Y₁, Y₂, An and r are defined as in claim 1.

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

(ANT-01 ) ; wherein

FL O

T₂ is a radical of formula * N- -C- -XO ; or -O-(X₂)_S;

Re is hydrogen; CrC₂oalkyl; NH₂; or hydroxy; and R_f, Q₂, Z₁, Y₁, X₂, p, r and s are defined as in claim 1.

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

(ANT-01 ) , wherein

R₁₁, R₁₂ and R₁₃, independently from each other are hydrogen; Ci-C₅alkyl; -C(O)H;

-C(O)-C_rC₅alkyl; -C(O)OH; -C(O)O-C_rC₅alkyl; NO₂; Or -NH(CO)-CH₃; Y₁ is CrC₁₀alkylene; C₅-C₁₀cycloalkylene; C₅-C₁₀arylene; or Cs-doarylene-^rdoalkylene); Xe is the direct bond: or CrC₅alkylene;

T₃ is the direct bond; or

R₁ and R_k each independently from each other are hydrogen; d-Ci₄alkyl; C₂-Ci₄alkenyl; C₆- Cioaryl; C₆-Cioaryl-Ci-Ci_Oalkyl; or Ci-Cioalkyl(C₅-Cioaryl).

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

(XAN-01 ) , wherein

Ri₄, Ri5, Rr₁₆, Ri7, R₁S, R19, R20, Yi, Y2 and V₁ are defined as in claim 1.

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

(TRI-01 ) , wherein

R_m is CrC₁₂alkyl, CrC₁₂alkoxy, phenyl, hydroxy, halogen, sulfonic acid, carboxylate, or the radical -NR_nR₀ Or -OR_n; and R_n, R₀, B₁ and B₂ are defined as in claim 1.

13. Mixture according to claim 1 , wherein

14. Mixture according to claim 1 , wherein the dyes are selected form the compounds of formula

(PYR-02) , wherein

R₃₁ is hydrogen; C-ι-C₅-alkoxy; halogen; or -NR_pR_q, wherein

R_p and R_q, independently from each other are hydrogen; CrC₁₂alkyl; -(CO)-H; or

-(CO)-C_rC₅alkyl; 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.