US2003191293A1PendingUtilityA1

Reactive dyes containing a halobenzene nucleus

Assignee: BASF AGPriority: Nov 12, 1997Filed: Apr 8, 2002Published: Oct 9, 2003
Est. expiryNov 12, 2017(expired)· nominal 20-yr term from priority
C09B 62/443C09B 62/4401C09B 62/78
39
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Claims

Abstract

The invention relates to reactive dyes containing a halobenzene nucleus and, in particular, reactive dyes containing a halobenzene nucleus and two or more reactive components.

Claims

exact text as granted — not AI-modified
1 . A dye containing 
 at least one chromophore D;    at least a first, halobenzene, reactive group Z 1 , of the formula (I)                          in which:    n is 1 or 2    X, or each X independently, is an electron withdrawing group; and    Y is a halogen atom;    at least a second reactive group Z 2  selected from 
 (1) a group of the formula (I), given and defined above, but selected independently thereof;  
 (2) a group of the formula (II)  
                     
 wherein  
   m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0;    Y 1 , or each Y 1  independently, is a halogen atom or an optionally substituted pyridinium group; and    T is C 1-4 alkoxy, C 1-4 thioalkoxy or N(R 1 ) (R 2 ), in which each of R 1  and R 2  independently is hydrogen, optionally substituted C 1-4 alkyl or optionally substituted aryl; 
 (3) a group of the formula (III)  
                     
 wherein:  
   x is 1, 2 or 3; y is zero, 1 or 2; and    x+y≦3;    Y 2 , or each Y 2  independently, is a halogen atom or an optionally substituted pyridinium group; and    U or each U independently, is C 1-4 alkyl or C 1-4 alkylsulphonyl; 
 (4) a group of the formula (IV) 
 —SO 2 CH 2 CH 2 X 1   (IV) 
 wherein  
   X 1  is an eliminatable group; 
 (5) a group of the formula (V) 
 —SO 2 (CH 2 ) z CH═CH 2   (V) 
 wherein  
   z is zero or 1; and 
 (6) a group of formula (VI) 
 —W—C(R 10 )═CH 2   (VI) 
 wherein:  
   R 10  is hydrogen, C 1-4 alkyl or halogen; and    W is —OC(═O)— or —N(R 11 )C(═O)— in which R 11  is hydrogen or C 1-4  alkyl;    at least a first linking group L 1 , linking the said first, halobenzene, reactive group Z 1  to one of components (i) the or a chromophore D and (ii) the second reactive group Z 2 , which said first linking group L 1  presents an amino nitrogen to the reactive group Z 1  and to the component (i) or (ii) or, when component (i) contains a heterocyclic nitrogen atom, is linked directly to the nitrogen atom and which said first linking group L 1  optionally includes a hydrocarbon bridging group, which hydrocarbon bridging group B has at least two carbon atoms, is optionally substituted, optionally includes at least one hetero atom and is optionally a chromophore; and    when Z 2  is selected from the said groups (I)-(III), at least a second linking group L 2  linking the second reactive group Z 2  to one of (i) the or a chromophore D and (ii) the said first reactive group Z 1 , which said linking group L 2  is selected from 
 (1) a linking group L 1 , but selected independently thereof; or  
 (2) an amide linkage; and  
 (3) a sulphonamide linkage; and optionally at least one aromatic group Ar which, when Z 2  is selected from the said groups (IV)-(VI), may carry the said reactive group Z 2 .  
   
     
     
         2 . A dye according to  claim 1 , wherein the linking group L 1  has the formula (VII) 1   
       N(R)  (VII) 1   wherein R is hydrogen or optionally substituted C 1-4 alkyl, such that the same amino group presents itself to each of the reactive group Z 1  and the component (i) or (ii), as defined in  claim 1 .    
     
     
         3 . A dye according to  claim 1 , wherein the linking group L 1  is a piperazinoalkylamino group of the formula (VII) 2   
       
         
           
           
               
               
           
         
         wherein each R, independently, is as defined in  claim 2 , such that respective amino nitrogens, one of the piperazine group and the other of the alkylamino group, present themselves respectively, to the reactive group Z 1  and to the component (i) or (ii), as defined in  claim 1 .  
       
     
     
         4 . A dye according to  claim 1 , wherein the linking group L 1  has the formula (VII) 3   
       —N(R)BN(R)—  (VII) 3   wherein B is a hydrocarbon bridging group as defined in  claim 1 , each R, independently , is as defined in  claim 1  and B is optionally linked additionally to at least one additional group —N(R).    
     
     
         5 . A dye according to  claim 4 , wherein the hydrocarbon bridging group B is an optionally substituted aryl group.  
     
     
         6 . A dye according to any preceding claim, of the formula (VIII) 
       Z 1 -L 1 -D-(L 2 ) a -Z 2   (VIII) 
       wherein: 
 D is a chromophore;  
 each of L 1  and L 2  is an amine or piperazine linkage of the formula 
 —N(R)—  (VII) 1 ; 
                   —N(R)BN(R)—  (VII) 3   
 wherein:  
 R, or each R independently, is hydrogen or C 1-4  alkyl;  
 B is a hydrocarbon bridging group which has at least two carbon atoms, is optionally substituted, optionally includes at least one hetero atom and is optionally a chromophore; 
 a is zero or 1; and  
 b is from 2 to 6 inclusive;  
 Z 1  is a group  
                     
 in which:  
 
 n is 1 or 2;  
 X, or each X independently, is an electron withdrawing group; and  
 Y is a halogen atom; and  
 when a is 1, Z 2  is:  
 a group of the formula (I), given and defined above but selected independently thereof; or  
 a group of the formula (II)  
                     
 wherein:  
 m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0;  
 Y 1 , or each Y 1  independently, is a halogen atom or an optionally substituted pyridinium group; and  
 T is C 1-4  alkoxy, thioalkoxy or N(R 1 ) (R 2 ) in which R 1  is hydrogen, optionally substituted C 1-4  alkyl or optionally substituted aryl and  
 R 2  is hydrogen or optionally substituted C 1-4  alkyl; or  
 a group of the formula (III)  
                     
 wherein: x is 1, 2 or 3; y is zero, 1 or 2; and x+y≦3;  
 Y 2 , or each Y 2  independently, is a halogen atom; and  
 U, or each U independently, is C 1-4  alkyl or C 1-4  alkylsulphonyl; and  
 when a is zero, Z 2  is: 
 —SO 2 CH 2 CH 2 X 1   (IV) 
 in which  
 X 1  is an eliminatable group; or 
 —SO 2 (CH 2 ) z CH═CH 2   (V) 
 wherein  
 z is zero or 1; or  
 a group of formula (VI) 
 —W—C(R 10 )═CH 2   (VI) 
 wherein:  
 R 10  is hydrogen, C 1-4 alkyl or halogen; and  
 W is —OC(═O)— or —N(R 11 )C(═O)— in which R is hydrogen or C 1-4  alkyl.  
 
     
     
         7 . A dye according to any preceding claim , wherein, in formula (I), X, or each X independently, is selected from nitro, cyano, alkylsulphonyl, dialkylaminosulphonyl and sulphonic acid or a salt thereof.  
     
     
         8 . A dye according to any preceding claim, wherein a group of the formula (II) is present, in which Y 1 , or each Y independently, is fluorine, chlorine or optionally substituted pyridinium.  
     
     
         9 . A dye according to any one of  claims 2  to  8 , wherein R, or each R independently, is hydrogen.  
     
     
         10 . A dye according to any preceding claim, wherein each of Z 1  and Z 2 , independently, is a group:  
       
         
           
           
               
               
           
         
       
       wherein each of X, n and Y is as defined in  claim 1 .  
     
     
         11 . A dye according to  claim 10 , wherein each of Z 1  and Z 2  is the same as the other.  
     
     
         12 . A dye according to any one of  claims 1  to  9 , wherein a is 1 and Z 2  is  
       
         
           
           
               
               
           
         
         wherein Y 1 , m, T and p are as defined in  claim 1 .  
       
     
     
         13 . A dye according to any one of  claims 1  to  9 , wherein a is 1 and Z 2  is  
       
         
           
           
               
               
           
         
       
       where Y 2 , x, U and y are as defined in  claim 1 .  
     
     
         14 . A dye according to any one of  claims 1  to  9 , wherein a is zero and Z 2  is 
       —SO 2 CH 2 CH 2 X 1   (IV) 
       where X 1  is as defined in  claim 1;  or 
       —SO 2 (CH 2 ) z CH═CH 2   (V) 
       wherein z is as defined in  claim 1 .  
     
     
         15 . A dye according to any preceding claim, wherein D is an azo chromophore.  
     
     
         16 . A dye according to  claim 15 , wherein D is a monoazo chromophore.  
     
     
         17 . A dye according to  claim 16 , which has the formula (XVII)  
       
         
           
           
               
               
           
         
         wherein:  
         each R independently and a is as defined in  claim 1;   
         one of Z 3  and Z 4  is a group Z 1  and the other is is a group Z 2 ;  
         the group Z 4  is selected from the groups of the formulae (I)-(III), given and defined in  claim 1;   
         Ar is a benzene or naphthalene nucleus;  
         R 3 , or each R 3  independently, is C 1-4  alkyl, nitro, halo or sulphonic acid or salt thereof;  
         c is zero or 1-4;  
         R 4 , or each R 4  independently, is a sulphonic acid or a salt thereof; and  
         d is 1 or 2.  
       
     
     
         18 . A dye according to  claim 15 , wherein D is a disazo chromophore.  
     
     
         19 . A dye according to  claim 18 , which has the formula (XVIII)  
       
         
           
           
               
               
           
         
       
       wherein:  
       one of Z 5  and Z 6  is a group Z 1  and the other is a group Z 2 ; 
 each of f and g independently is zero or 1;  
 when Z 5  or Z 6  is any of the groups of the formulae (I)-(III), given and defined in  claim 1 , f or g respectively is 1 and when Z 5  or Z 6  is any of the groups of the formulae (IV)-(VI), given and defined in  claim 1 , f or g respectively is zero;  
 each of c and e, independently, is zero or 1-4;  
 d is 1 or 2;  
 each R independently is as defined in  claim 1;   
 each of Ar 1  and Ar 2  is an optionally substituted aryl group; and  
 each of R 3  and R 4  is as defined in  claim 17 .  
 
     
     
         20 . A dye according to  claim 19 , wherein each of Z 5  and Z 6  is the same group  
       
         
           
           
               
               
           
         
       
       wherein X, Y and n are as defined in  claim 1 .  
     
     
         21 . A dye according to  claim 19 , wherein one of Z 5  and Z 6  is a group of the formula (I), given and defined in  claim 1 , and the other of Z 5  and  6  Z is selected from groups of the formulae (II) and (III), given and defined in  claim 1 .  
     
     
         22 . A dye according to  claim 18 , which dye has the formula  
       
         
           
           
               
               
           
         
       
       wherein: 
 B is a hydrocarbon bridging group as defined in  claim 1;   
 one of G 1  and G 2  is ODH and the other is NH 2 ;  
 each of X, Y, Y 1  and n is as defined in  claim 1;   
 each of Ar 1 , Ar 2 , R3, R 4 , c and d is as defined in  claim 19;  and  
 each of R 5  and e is as defined in  claim 19 .  
 
     
     
         23 . A dye according to  claim 22 , wherein B is an optionally substituted aryl group.  
     
     
         24 . A dye according to  claim 19 , wherein one of Z 5  and Z 6  is a group  
       
         
           
           
               
               
           
         
       
       wherein: X, Y and n are as defined in  claim 1  and the other of Z 5  and Z 6  is the group —SO 2 CH 2 CH 2 OSO 3 H or —SO 2 CH═CH 2 .  
     
     
         25 . A dye according to  claim 24 , which has the formula  
       
         
           
           
               
               
           
         
       
       wherein 
 G 3  is C 2 H 4 OSO 3 H or a salt thereof or —CH═CH 2 ;  
 G 1  and G 2  are as defined in  claim 22;   
 R 4  and d are as defined in  claim 17;  and  
 each of n and 1, independently, is zero, 1 or 2.  
 
     
     
         26 . A dye according to  claim 25 , which has the formula  
       
         
           
           
               
               
           
         
       
       where each of G 1  and G 2  is as defined in  claim 22  and G 3  is as defined in  claim 25 .  
     
     
         27 . A dye according to  claim 1 , of the formula 
       Z 1 -L 1 -D [L 3 ] q -[Z 3 -L 4   r [J 1 ] s [L 2 ] a Z 2 [L 5 -J 2 ] t   
       wherein: 
 Z 3  is a third reactive group selected from the groups of the formulae (I)-(III), given and defined in  claim 1;   
 each of J 1  and J 2 , independently, is an optionally substituted aryl group or a chromophore;  
 L 3  is a linking group linking Z 3  and D;  
 L 4  is a linking group linking Z 3  and J 1 ;  
 L 5  is a linking group linking Z 2  and J 2 ;  
 each of q, r, s and t independently, is zero or 1;  
 each of Z 1 , Z 2 , L 1 , L 2  and a is as defined in  claim 1;  and  
 when at least one of a and t is 1, Z 2  is selected from the groups of the formulae (I)-(III), given and defined in  claim 1 .  
 
     
     
         28 . A dye according to  claim 27 , wherein q is 1, r is 1, s is 1, each of a and t is zero and Z 2  is selected from the groups of the formulae (IV)-(VI), given and defined in  claim 1 .  
     
     
         29 . A dye according to  claim 27 , wherein q is 1, r is 1, s is zero, a is zero and t is 1.  
     
     
         30 . A dye according to any one of  claims 27  to  29 , wherein each of L 3  and L 4 , independently, is selected from one of the groups of the formulae (VII) 1 , (VII) 2  and (VII) 3 , given and defined in  claim 6 .  
     
     
         31 . A dye according to  claim 30 , wherein each of L 3  and L 4  is a group of the formulae (VII) 1 , given and defined in  claim 6 .  
     
     
         32 . A dye according to  claim 27 , wherein q is 1, r is zero, s is 1, a is zero and t is zero.  
     
     
         33 . A dye according to  claim 32 , wherein L 3  is a group of the formula (VII) 3    
       —N(R)BN(R)—  (VII) 3   wherein B is a triazine group substituted by a non-reactive group.    
     
     
         34 . A dye according to any one of  claims 27  to  33 , wherein the chromophore D is an azo chromophore derived from 1-hydroxy-8-aminonaphthalene substituted by at least one sulphonic acid group.  
     
     
         35 . A dye according to  claim 1  of the formula 
       Z 1 -L 1 -D 1 [L 3 -Z 3 (L 4 -Z 4 ) 1 L 5 -D 2 ] k [L 2 ] a Z 2   
       wherein: 
 D 1  is a first chromophore;  
 D 2  is a second chromophore;  
 Z 3 , when present, is a third reactive group selected from the groups of the formulae (I)-(III), given and defined in  claim 1;   
 Z 4 , when present, is a fourth reactive group selected from the groups of the formulae (I)-(III), given and defined in  claim 1;   
 L 3  is a linking group linking Z 3  to D 1 ;  
 L 4  is a linking group linking Z 3  to Z 4 ;  
 L 5  is a linking group linking D 2  to one of Z 3  and Z 4 ;  
 each of k and l, independently, is zero or 1; and  
 each of Z 1 , Z 2 , L 1 , L 2  and a is as defined in  claim 1 .  
 
     
     
         36 . A dye according to  claim 35  wherein a is 1, Z 2  is a group of the formula (I), given and defined in  claim 1 , k is zero and D 1  is a tetrakisazo chromophore containing two residues of H-acid linked together by a group forming part of the chromophore.  
     
     
         37 . A dye according to  claim 35 , wherein a is 1, each of Z 1  and Z 2  is a group of the formula (I), given and defined in  claim 1 , each of k and l is 1; 
 each of D 1  and D 2  is a disazo chromophore containing a respective residue of H-acid,    each of Z 3  and Z 4  is a group of the formula (II), given and defined in  claim 1 , and    L 4  is a linking group of the formula (VII) 2  or (VII) 3 , given and defined in  claim 6 .    
     
     
         38 . A dye according to  claim 35 , wherein a is 1, Z 2  is a group of the formula (I), given and defined in  claim 1 , k is 1 and l is 1.  
     
     
         39 . A dye according to  claim 35 , wherein a is 1, Z 2  is a group of the formula (I), given and defined in  claim 1 , k is 1 and l is zero.  
     
     
         40 . A dye according to  claim 1 , of the formula 
       Z 1 -L 1 -Z 3 -L 3 -D-Z 2   
       wherein: 
 Z 3  is a third reactive group selected from the groups (I)-(III), given and defined in  claim 1;  and  
 L 3  is a third linking group selected from the groups (VII) 1 , (VII) 2  and (VII) 3 , given and defined in  claim 6;   
 Z 2  is a second reactive group selected from the groups (IV)-(VI), given and defined in  claim 1;  and  
 each of Z 1  and L 1  is as defined in  claim 1 .  
 
     
     
         41 . A dye according to  claim 40 , wherein L 1  is a linking group of the formula (VII) 2  or (VII) 3 , given and defined in  claim 6 .  
     
     
         42 . A dye according to  claim 40  or  claim 41 , wherein Z 3  is a group of the formula (II), given and defined in  claim 1 .  
     
     
         43 . A dye according to  claim 1 , of the formula 
       D-L 2 -Z 2 -L 1 -Z 1   
       wherein: 
 Z 2  is selected from groups of the formulae I-(III), given and defined in  claim 1;  and  
 each of D, Z 1 , L 1  and L 2  is as defined in  claim 1 .  
 
     
     
         44 . A dye according to  claim 43 , wherein Z 4  is a group of the formula (II), given and defined in  claim 1 .  
     
     
         45 . A dye according to  claim 43  or  claim 44 , wherein L 2  is a linking group selected from the groups (VII) 1 , (VII)  2  and (VII) 3   1 , given and defined in  claim 6 .  
     
     
         46 . A dye according to  claim 43 , wherein L 2  is a linking group of the formula (VII) 2  or (VII) 3 , given and defined in  claim 6 .  
     
     
         47 . A dye according to any one of  claims 43  to  46 , wherein L 1  is a group of the formula (VII 3 ) , given and defined in  claim 6 , in which B is an optionally substituted aryl group.  
     
     
         48 . A dye according to any one of  claims 43  to  46 , wherein L 1  is a group of the formula (VII 3 ) , given and defined in  claim 6 , in which B is a chromophoric bridging group.  
     
     
         49 . A dye according to any one of  claims 40  to  48 , wherein the chromophore D is a disazo dye containing a residue derived from H-acid and having azo groups at the 2- and 7-positions.  
     
     
         50 . A dye according to any one of  claims 43  to  48 , wherein D is a group of the formula  
       
         
           
           
               
               
           
         
       
     
     
         51 . A dye according to  claim 1 , of the formula 
       D 2 -L 2 -Z 2 -L 3 -D 1 -L 1 -Z 1   
       wherein: 
 each of D 1  and D 2 , independently, is a chromophore;  
 L 3  is a linking group selected from groups of the formula (I)-(III), given and defined in  claim 1;  and  
 each of Z 1 , Z 2 , L 1  and L 2  is as defined in  claim 1 .  
 
     
     
         52 . A dye according to  claim 1 , of the formula  
       
         
           
           
               
               
           
         
       
       wherein: 
 each of D 1  and D 2 , independently, is a chromophore;  
 L 3  is a linking group selected from the groups of the formulae (I)-(III), given and defined in  claim 1;  and  
 each of Z 1 , Z 2 , L 1  and L 2  is as defined in  claim 1 .  
 
     
     
         53 . A dye according to  claim 1 , of the formula.  
       
         
           
           
               
               
           
         
       
       wherein: 
 one of Z 3  and Z 4  is a reactive group Z 2 ;  
 each of Z 3  and Z 4 , independently, is a reactive group selected from the formulae (IV)-(VI), given and defined in  claim 1;   
 each of t and u, independently, is zero or 1 and at least one of t and u is 1;  
 D is a chromophore;  
 Ar is an optionally substituted aryl group;  
 L 1  is a group of the formula  
                     
 wherein each R, independently, is as defined in claim; and  
 Z 1  is as defined in  claim 1 .  
 
     
     
         54 . A dye according to  claim 53 , wherein D is a disazo dye containing a residue derived from H-acid.  
     
     
         55 . A dye according to  claim 1 , wherein the or a chromophore D contains a heterocyclic nitrogen atom and the linking group has the formula  
       
         
           
           
               
               
           
         
         wherein each of B,R and b is as defined in  claim 6  and the bond {circle over (1)} is linked to the heterocyclic nitrogen atom of the chromophore.  
       
     
     
         56 . A dye according to  claim 55 , of the formula 
       Z 1 -L 1 -D N L 2  a Z 2 L 5 —Ar] t   
       wherein: 
 D N  is a chromophore containing a heterocyclic group including a nitrogen atom;  
 L 1  is a group of the formula (VII) 4  or (VII) 5 , given and defined in  claim 55 , directly attached via the bond {circle over (1)}, to the nitrogen atom of the said chromophore D N ;  
 Ar is an optionally substituted aryl group;  
 and each of Z 1 , Z 2 , L 2 , L 5 , a and t is as defined in  claim 27 .  
 
     
     
         57 . A dye according to  claim 56 , wherein the chromophore D has the formula  
       
         
           
           
               
               
           
         
       
     
     
         58 . A dye according to any one of  claims 27  to  56 , which is an azo dye having at least two azo groups therein.  
     
     
         59 . A dye according to  claim 15 , wherein D is a trisazo or tetrakisazo chromophore.  
     
     
         60 . A dye according to  claim 1 , wherein the chromophore D is an anthraquinone.  
     
     
         61 . A dye according to  claim 60 , which is of the formula 
       D A -L 3 -Ar-L 2 -Z 2 -L 1 -Z 1   
       wherein: 
 D A  is an anthraquinone chromophore;  
 L 3  is a linking of the formula (VII) 1 , given and defined in  claim 6;   
 Ar is an optionally substituted aryl group; and  
 each of Z 1 , Z 2 , L 1  and L 2  is as defined in  claim 1 .  
 
     
     
         62 . A dye according to  claim 61 , wherein each of L 1  and L 2 , independently, is a linking group of the formula (VII) 1 , (VII) 2  or (VII) 3 , given and defined in  claim 6 .  
     
     
         63 . A dye according to  claim 62 , wherein each of L 1  and L 2 , independently is a group of the formula (VII) 3 , given and defined in  claim 6 , in which B is an optionally substituted aryl group.  
     
     
         64 . A dye according to  claim 1 , wherein the chromophore D is a metal phthalocyanine.  
     
     
         65 . A dye according to  claim 64 , of the formula  
       
         
           
           
               
               
           
         
       
       wherein: 
 Cu PC is a copper phthalocyanine chromophore;  
 X+Y+Z≦4;  
 each of R 21  and R 22 , independently, is hydrogen or optionally substituted C 1-4 alkyl;  
 B is a hydrocarbon bridging group; and  
 Z 1  is as defined in  claim 1 .  
 
     
     
         66 . A dye according to  claim 1 , wherein the chromophore D is a triphendioxazine chromophore.  
     
     
         67 . A dye according to  claim 66 , which is of the formula 
       Z 1 -L 1 -[Z 3 -L 3 ] q -D T -[Z 4 ] r -L 2 -Z 2   
       wherein: 
 D T  is a triphendioxazine chromophore;  
 each of L 2 , L 3  and L 4 , independently, is a linking group of the formula (VII) 1 , (VII) 2  or (VII) 3 , given and defined in  claim 6;   
 each of Z 2 , Z 3  and Z 4  is a reactive group selected from groups of the formulae (I)-(III), given and defined in  claim 1;   
 each of q and r is zero or 1; and  
 each of Z 1  and L 1  is as defined in  claim 1 .  
 
     
     
         68 . A dye according to  claim 67 , wherein Z 2  is a group of the formula (I), given and defined in  claim 1  and each of Z 3  and Z 4  is a group of the formula (II), given and defined in  claim 1 .  
     
     
         69 . A dye according to  claim 67  or  claim 68 , wherein each of L 1 , L 2 , L 3  and L 4  is a group of the formula (VII) 3 , given and defined in  claim 6 .  
     
     
         70 . A dye according to  claim 1 , wherein the chromophore D is a formazan chromophore.  
     
     
         71 . A dye according to  claim 70 , of the formula 
       [Z A ] a -D F -L-Z B -L 1 -Z 1   
       wherein: 
 D F  is a formazan chromophore;  
 one of Z A  and Z B  is a group Z 2 , given and defined in  claim 1;   
 L is a linking group of the formula (VII) 1 , (VII) 2  or (VII) 3 , given and defined in  claim 6;   
 each of Z 1  and L 1  is as defined in  claim 1 ,  
 a is zero or 1;  
 Z A  is selected from groups of the formulae (IV)-(VI), given and defined in  claim 1;  and  
 Z B  is selected from groups of the formulae (I)-(III),given and defined in  claim 1 .  
 
     
     
         72 . A dye of the formula  
       
         
           
           
               
               
           
         
       
     
     
         73 . A dye of the formula  
       
         
           
           
               
               
           
         
       
     
     
         74 . A dye of the formula  
       
         
           
           
               
               
           
         
       
     
     
         75 . A dye of the formula  
       
         
           
           
               
               
           
         
       
     
     
         76 . A dye of the formula  
       
         
           
           
               
               
           
         
       
     
     
         77 . A dye of the formula  
       
         
           
           
               
               
           
         
       
     
     
         78 . A process for preparing a dye of the formula (VIII) 1   
       Z 1 -L 1 -D-L 2 -Z 2   (VIII) 1   
       wherein: 
 D is a chromophore;  
 each of L 1  and L 2  independently, is N(R);  
 each R, independently, is hydrogen or C 1-4 alkyl;  
 each of Z 1  and Z 2  is a group  
                     
 in which:  
 n is 1 or 2  
 X, or each X independently, is an electron withdrawing group; and  
 Y is a halogen atom,  
 which process comprises reacting a chromophoric compound of the formula (XX) 
 H(R)N-D-N(R)H  (XX) 
 wherein each of D and R is as defined above, with at least two moles, per mole of the chromophoric compound of the formula (XX) , of a dihalobenzene component comprising at least one dihalobenzene compound of the formula (XXI)  
                     
 wherein each of X, Y and n is as defined above, to obtain the dye of the formula (VIII) 1 .  
 
     
     
         79 . A process for preparing a dye of the formula (VIII) 1   
       Z 1 -L 1 -D-L 2 -Z 2   (VIII) 2   
       wherein: 
 D is a chromophore;  
 each of L 1  and L 2  independently, is N(R);  
 each R, independently, is hydrogen or C 1-4 alkyl;  
 Z 1  is a group  
                     
 in which:  
 n is 1 or 2  
 X, or each X independently, is an electron withdrawing group; and  
 Y is a halogen atom; and  
 Z 2  is selected from the groups (II) and (III) given and defined in  claim 1;   
 which process comprises reacting a chromophoric compound of the formula (XX) 
 H(R)N—D—N(R)H  (XX) 
 wherein each of D and R is as defined above, with one mole, per mole of the chromophoric compound of the formula (XX), of each of  
 (a) a dihalobenzene compound of the formula (XXI)  
                     
 wherein each of Z, X, Y and n is as defined above; and  
 (b) a compound selected from  
                     
 wherein:  
 m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0;  
 Y 1 , or each Y 1  independently, is a halogen atom or an optionally substituted pyridinium group; and  
 T is C 1-4 alkoxy, C 1-4 thioalkoxy or N(R 1 ) (R 2 ), in which each of R 1  and R 2  independently is hydrogen, optionally substituted C 1-4 alkyl or optionally substituted aryl;  
 x is 1, 2 or 3; y is zero, 1 or 2; and x+y≦3;  
 Y 2 , or each Y 2  independently, is a halogen atom or an optionally substituted pyridinium group;  
 U or each U independently, is C 1-4 alkyl or C 1-4 alkylsulphonyl; and  
 Y is as defined above;  
 the said reactions of the compound of the formula (XX) with each of the respective compounds of the formulae (XII) and (XIII) being carried out simultaneously or one before the other, in either order, to obtain a dye of the formula (VIII) 2 .  
 
     
     
         80 . A process for preparing a dye of the formula (VIII) 3   
       Z 1 -L 1 -D-Z 2   (VIII) 3   
       wherein: 
 D is a chromophore  
 L 1  is N(R), in which R is hydrogen or C 1-4 alkyl;  
 Z 1  is a group  
                     
 in which n is 1 or 2; X, or each X independently, is an electron withdrawing group; and Y is a hydrogen atom; and Z 2  is a group of the formula (IV) 
 —SO 2 CH 2 CH 2 X 1   (IV) 
 wherein X 1  is an eliminatable group;  
 a group of the formula (V) 
 —SO 2 (CH 2 ) z CH═CH 2   (V) 
 wherein z is zero or 1; and  
 a group of formula (VI) 
 —W—C(R 10 )═CH 2   (VI) 
 wherein:  
 R 10  is hydrogen, C 1-4 alkyl or halogen; and  
 W is —OC(═O)— or —N(R 11 )C(═O)— 
 in which R 11  is hydrogen or C 1-4 alkyl;  
 which process comprises reacting a chromophoric compound of the formula (XXIV) 
 H(R)N-D-Z 2   (XXIV) 
 wherein D and Z 2  are as defined above, with a dihalobenzene compound of the formula (XXI)  
                     
 wherein each of X, Y and n is as defined above, to obtain the dye of the formula (VIII) 3 .  
 
     
     
         81 . A process for the colouration of a substrate, which process comprises applying to the substrate a dye according to any one of  claims 1  to  77 .  
     
     
         82 . A process according to  claim 81 , wherein the dye is applied to the substrate by exhaust dyeing, padding or printing.  
     
     
         83 . A process according to  claim 82 , wherein the dye is applied by ink jet printing.

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