CH678186A5 - - Google Patents

Abstract

Fibre-reactive compounds of the formula <IMAGE> in which Fc is the radical of a water-soluble azo, formazan, phthalo-cyanine, azomethine, oxazine, thiazine, phenazine or tri-phenylmethane dye which is in metal-free or metal complex form, which radical may contain a further fibre-reactive group each a is 0 or 1; b is 1 or 2; each X is a direct bond, -CO- or -SO2-; each R1 is hydrogen, unsubstituted C1-4 alkyl or C1-4 alkyl which is monosubstituted by hydroxy, halogen, -SO3H, -OSO3H or -COOH; and each Alk is C2-4alkylene; and each W is a divalent radical with N at each end; which compounds are in free acid or salt form, and mixtures thereof, are useful for dyeing or printing hydroxy group- or nitrogen-containing organic substrates, for example leather and fibre materials comprising natural or synthetic polyamides or natural or regenerated cellulose, especially cotton. The dyeings and prints obtained show good wet and light fastness and resistance to oxidative influences.

Description

       

  
 



  The present invention relates to chromophoric compounds containing a heterocyclic reactive group and processes for their preparation. These reactive dyes are used in dyeing and printing processes.



  The invention relates to compounds of the formula I.
EMI1.1
 



  correspond, as free acid or in salt form, wherein
 Fc for the remainder of a metal-free or metal-containing water-soluble chromophore from the azo, formazane, phthalocyanine, azomethine, oxazine, thiazine, phenazine or triphenylmethane series, which may contain an additional fiber-reactive group,
 each a, independently of one another, for 0 or 1 and
 b represents 1 or 2;
 each X, independently of one another, the direct bond, -CO- or -SO2-,
 each R1, independently of one another, is hydrogen, unsubstituted C1-4alkyl or C1-4alkyl which is substituted by hydroxy, halogen, cyano, -SO3H, -OSO3H or -COOH, and
 each alk, independently of one another, is C2-4alkylene,
 each W, independently of one another, for -NR1-B1-NR1-,
EMI1.2
 
EMI2.1
 



  where m is 0 or 1, and
 B1 for C2-6alkylene, for a C2-6alkylene chain which is interrupted by -O- or -NR1-, for C3-6alkylene substituted by one or two hydroxyl groups or by a carboxy group, for
EMI2.2
 



  stand in what
 n 0, 1, 2, 3 or 4 and
 R2 is hydrogen, C1-4alkyl, C1-4alkoxy, -COOH or -SO3H.



  The invention also relates to the mixtures of compounds of the formula I.



  Unless otherwise stated, any alkyl, alkenyl, alkynyl or alkylene group in the present specification may be linear or branched. In a hydroxy substituted alkyl or alkylene group attached to a nitrogen atom, the hydroxy group is preferably on a carbon atom that is not attached directly to the nitrogen atom. In a corresponding dihydroxy-substituted alkylene group, the hydroxyl groups are bonded to different carbon atoms, which are preferably not adjacent to one another.



  In an alkylene chain interrupted by -O- or -NR1- which is bonded to nitrogen, the -O- or -NR1 bridge is preferably not linked to carbon atoms which are bonded directly to the nitrogen atom.



  Halogen generally stands for fluorine, chlorine or bromine; preferred for chlorine or bromine and especially for chlorine.



  Fc preferably represents the remainder of a metal-free or metal-containing water-soluble chromophore from the mono- or disazo series, which, when metallized, is preferably in the form of a 1: 1 copper complex or 1: 2 chromium or 1: 2 cobalt complex, from the formazan, Copper or nickel phthalocyanine or the triphendioxazine series.
 X is preferably the direct bond or -SO2-.
 Alk preferably represents a C2-3 alkylene group.



  R1 as alkyl preferably contains 1 or 2 carbon atoms. As substituted alkyl it is preferably C1-3alkyl and preferably contains a substituent from the series hydroxy, -SO3H, -OSO3H and -COOH, of which hydroxy is particularly preferred.



  Each R1 preferably represents R1a, where each R1a independently of one another denotes hydrogen, methyl, ethyl, 2-hydroxyethyl, - (CH2) r-SO3H, - (CH2) r-OSO3H or - (CH2) q-COOH and r denotes 1 or 2 and q stand for 1, 2 or 3.



  R1 is more preferably R1b, each R1b independently of one another denoting hydrogen, methyl, ethyl or 2-hydroxyethyl. Each R1 particularly preferably represents hydrogen.



  R2 is preferably R2a, each R2a, independently of one another, being hydrogen, methyl, methoxy, -COOH or -SO3H; in particular R2 stands for R2b, where each R2b, independently of one another, denotes hydrogen or -SO3H.



  B1 preferably means B1a as -C2-4alkylene,
 -C2-3alkylene-O-C2-3alkylene-,
EMI3.1
 monohydroxy-substituted -C3-4alkylene-,
EMI3.2
 



  with n1 for 0, 1, 2 or 3.



  B1 is more preferably B1b as -C2-3alkylene, monohydroxy-substituted -C3-4alkylene-,
EMI4.1
 



  with n2 for 0, 1 or 2.



  B1 particularly preferably represents B1c as -C2-3alkylene or monohydroxy-substituted -C3-4alkylene.



  W preferably stands for W1, each W1, independently of one another,
EMI4.2
 



  means.



  W more preferably stands for W2, each W2, independently of one another,
EMI4.3
 



  means.



  W is particularly preferably W3, each W3, independently of one another, meaning -NH-B1c-NH-.



  Preferred metal-free or metal-containing compounds of the formula I correspond to the following types of compounds (1) to (7):



  Connections (1)
EMI4.4
 



  wherein
 DK the rest of a diazo component from the benzene or naphthalene series and
 KK is the remainder of a coupling component of the benzene or naphthalene series, the remainder of a heterocyclic coupling component or a CH-acidic enolizable compound,
 Z for
EMI5.1
 



  and b represents 1 or 2,
 wherein the 1 or 2 groups Z are bonded to the diazo component and / or coupling component via -NR1-.



  B is preferably 1.



  In a compound (1) means
 DK preferably one of the radicals (a) to (h), in which the labeled bond leads to the azo bridge,
EMI5.2
 
EMI6.1
 



  wherein
 R1 and R2 are as defined above,
 R3 is hydrogen, halogen, C1-4alkyl, C1-4alkoxy, acetylamino, benzoylamino, -SO3H or -COR13,
 R4 is hydrogen, halogen, C1-4alkyl, C1-4alkoxy or -COR13,
 R13 -OH, -OC1-4 alkyl or -NH2,
 Alk1 -C2-3alkylene-,
 R5 is hydrogen, -SO3H, C1-4alkyl or C2-4hydroxyalkyl,
 R50 is hydrogen or -SO3H, and
 R51
EMI6.2
 



  mean,
 n for 0, 1, 2, 3 or 4,
 p for 0, 1 or 2,
 q for 1, 2 or 3, and
 r represents 1 or 2;
 KK preferably one of the radicals (K1) to (K7), in which the labeled C atom indicates the coupling point,
EMI7.1
 



  wherein
 R1 is as defined above
 R6 is hydrogen, C1-4alkyl or C1-4alkoxy, and
 R7 represents hydrogen, halogen, C1-4alkyl, C1-4alkoxy, -NHCOC1-4alkyl or -NHCONH2;
EMI7.2
 



  wherein
 R1 is as defined above
 R8 is hydrogen, halogen, C1-4alkyl or C1-4alkoxy,
 R9 is hydrogen, halogen, C1-4alkyl, C1-4alkoxy, -COOH or -SO3H, and
 R10 is hydrogen, -SO3H or -NR1- (Z);
EMI7.3
 



   wherein
 R11 for -OH or -NH2, and
 R12 represents C1-4alkyl or -COR13,
 R13 is as defined above,
 Q1 for hydrogen, C1-4alkyl or
EMI8.1
 



   stands,
 R8 and R9 are as defined above, and
 R14 for hydrogen, halogen, C1-4alkyl,
EMI8.2
 



  -SO3H or - (B3) aNR1- (Z), in which R1, Z and a are as defined above and B3 is a divalent bridge member;
EMI8.3
 



  wherein
 Q2 is hydrogen, C1-4alkyl, C5-6cycloalkyl, phenyl or phenyl- (C1-4alkyl), the phenyl ring of which is in each case unsubstituted or substituted by 1-3 substituents from the series C1-4alkyl, C1-4alkoxy, halogen, -COOH and - SO3H; -COR13 or C1-4alkyl monosubstituted by -SO3H, -OSO3H or -COR13,
 Q3 is hydrogen, -CN, -SO3H, -COR13, C1-4alkyl, by -OH, halogen,
EMI8.4
 



  -SO3H, -OSO3H or -NH2 monosubstituted C1-4alkyl, -SO2NH2,
EMI8.5
 



  wherein
 R15 represents hydrogen, C1-4alkyl or C2-4hydroxyalkyl and
 An (-) stands for a non-chromophoric anion,
 Q4 hydrogen,
EMI9.1
 C1-6alkyl, C2-4alkenyl, C2-4alkynyl, C5-6cycloalkyl, phenyl or phenyl (C1-4alkyl), the phenyl ring of which is in each case unsubstituted or substituted by 1-3 substituents from the series halogen, C1-4alkyl, C1-4alkoxy, -SO3H,
EMI9.2
  or -C1-6alkylene-Y, wherein
 Y is -COOH, -COOC1-4alkyl, -SO3H, -OSO3H, -OH, -CN, C1-4alkoxy, -NH2 or a protonatable aliphatic, cycloaliphatic, aromatic or heterocyclic amino group or quaternary ammonium group, and
 B2 for -C2-6alkylene, monohydroxy-substituted -C3-6alkylene, a C2-6alkylene chain which is interrupted by -O- or -NR1-,
EMI9.3
 



  or
 -B2- NR1- (Z) for
EMI9.4
 stand, mean and
 R1, R9, R10 and R13 are as defined above;
EMI9.5
 
EMI10.1
 



  wherein
 R16 is C1-4alkyl, phenyl or phenyl substituted by 1-3 substituents from the series halogen, C1-4alkyl and C1-4alkoxy and
 R1, a and m are as defined above.


 Connections (2)
 
EMI10.2
 



  wherein
 R6, R7, R1 and Z are as defined above,
 t represents 2 or 3, and
 R6x has one of the meanings of R6 and R7x has one of the meanings of R7, but is in each case independent of R6 and R7.



  Preferred compounds (2) are those in which each R6, R6x and R7x is hydrogen.



  Metal complexes, preferably 1: 1 copper complexes and 1: 2 metal complexes of cobalt or chromium, which are based on the following metallizable compounds (3a) or (3b), are provided as connection type (3),
EMI11.1
 



  wherein
 R1, Z and m are as defined above,
 A for
EMI11.2
 



  where m and q are as defined above,
 R17 for hydrogen, halogen, nitro, C1-4alkyl, C1-4alkoxy, -COR13, -SO3H or -NHCOCH3,
 R22 stands for OH, OCH3 or NH2, and
 R13 is as defined above.



  1: 2 chromium or 1: 2 cobalt complexes can be built from two identical or different azo compounds, i.e. they can be symmetrical or asymmetrical.



  1: 1 copper complexes based on compounds of type (3a), in which
 A stands for the benzene diazo component and the naphthalene coupling component the substituents in the arrangement
EMI12.1
 



  contains.



  Furthermore, 1: 1 copper complexes of the following formulas (3c) to (3e) are also provided as connection type (3):
EMI12.2
 



  wherein
 R50 represents hydrogen or SO3H, and
 R1, Z and r are as defined above;
EMI12.3
 



  wherein
 R52 for hydrogen, C1-4alkyl or C1-4alkoxy,
 m for 0 or 1, r for 1 or 2 and
 m + r stand for 2 or 3, and
 R1, R2, R50 and Z are as defined above;
EMI12.4
 



  R29 for hydrogen, COOH or SO3H, and
 R30 is hydrogen, C1-4alkyl, C1-4alkoxy or -O-Alk1-OR5, wherein
 t, R5 and Alk1 are as defined above, and
 R1, R52 and Z are as defined above.


 Connections (4)
 
EMI13.1
 



  wherein
 D1 and D2 independently of one another represent the residue of a diazo component of the aminobenzene or aminonaphthalene series, which contains at least one sulfo, sulfonamide or carboxy group, and
 each m is independently 0 or 1, but at least once m is 1, and
 R1, Z and n are as defined above.



  D1 preferably denotes D1a as the radical of the formula (ax) or (cx),
EMI13.2
 



  wherein
 R18 is a sulfo, sulfonamide or -COR13 group and
 R19 is hydrogen, halogen, C1-4alkyl, C1-4alkoxy, -NHCOCH3 or -SO3H,
 R13, m and p are as defined above and
 m + p stand for 1 or 2.



  D2 preferably denotes D2a as the radical of the formula (dx),
EMI14.1
 



  wherein the labeled bond leads to the azo group and the other free bond carries the reactive radical.



  The radical (dx) R18 is more preferably in the 2-position (based on the azo group in position 1) and the free bond to the reactive radical in the 4- or 5-position.


 Connections (5)
 
EMI14.2
 



  wherein
 one of X1 and X2 is -O- and the other is carboxy,
 R20 and R21, independently of one another, are hydrogen, halogen, C1-4alkyl, C1-4alkoxy, -COR13 or
 -NHCOC1-4 alkyl,
 R1, R13, Z and m are as defined above,
 each p independently represents 0, 1 or 2, where m + 2p is at least 2.


 Connections (6)
 
EMI15.1
 



  wherein
 Q stands for -O- or -S-,
 each R23, independently of one another, is hydrogen or -SO2CH2CH2OSO3H,
 every m, independently of one another, 0 or 1,
 each X3, independently of one another, -SO2-, -NR1-, - * CONR1-, or - * SO2NR1-, in which the labeled atom is bound to a C atom of the ring system, and
 each Alk2, independently of one another, is C2-4alkylene, and
 each R1 and Z, independently of one another, as defined above, and mixtures of the compounds (6).



  The groups Z contained in a compound (6) are preferably identical.


 Connections (7)
 
EMI15.2
 



  wherein
 c for 1, 2 or 3 and
 d stands for 0, 1 or 2 and
 c + d is a maximum of 3;
 Pc for the phthalocyanine residue,
 Me for Cu, Ni, Co, Fe or Al,
 each R24 and R25, independently of one another, represent hydrogen or C1-6alkyl or
 -NR24R25 is a saturated 5- or 6-membered heterocyclic ring, possibly with another
EMI16.1
 means in which R31 represents hydrogen, C1-4alkyl, 2-hydroxyethyl or 2-aminoethyl,
 R26 hydrogen, halogen, hydroxy, C1-4alkyl, C1-4alkoxy, -COOH or -SO3H,
 a 0 or 1,
 X4 a divalent, if necessary
EMI16.2
 including aliphatic, araliphatic or heterocyclic bridge member or the azo grouping -N = N-KK2, where KK2 for
EMI 16.3
 



   stands,
 R9, R11, R12, Q2 -B2-, -B3- and a are as defined above and the labeled C atom indicates the coupling point,
 Q3a is hydrogen, -CN, -SO3H, -COR13, C1-4alkyl, by -OH, halogen, -CN, C1-4alkoxy,
EMI 16.4
 



  -SO3H, -OSO3H or -NH2 monosubstituted C1-4alkyl, -SO2NH2,
EMI 16.5
 



  means, wherein R9, R13, R15 and An <THETA> are as defined above; also mixtures of the compounds (7).



  The group Z preferably represents Za of the formula
EMI17.1
 



  More preferably Z is Zb as group Za, where W1 is W2; particularly preferred for Zc as group Za, where W1 is W3.



  Preferred compounds (1) are those of the formulas (1a) to (1d): compounds of the formula (1a),
EMI17.2
 



  where Za is as defined above and is bound either to DK1 or to KK1,
 DK1 means one of the residues (a1) to (f1) and (h1), in which the labeled bond leads to the azo group:
EMI17.3
 



  wherein p is 0 or 1, or 2 and each R3a and R4a, independently of one another, is hydrogen, chlorine, methyl, methoxy, ethoxy or -COOH;
EMI17.4
 



  wherein m is 0 or 1, t is 2 or 3, and R5a is hydrogen, methyl, ethyl, -SO3H or 2-hydroxyethyl;
EMI18.1
 



  wherein m is 0 or 1, r is 1 or 2, and m + r is 2 or 3;
EMI18.2
 



  wherein R1b, R4a and p are as defined above;
EMI18.3
 



  wherein R1b and r are as defined above;
EMI18.4
 



  where R51a for
EMI18.5
 



  or
EMI19.1
 



  stands and
 R50, R1b, a and r are as defined above;
 and KK1 is one of the radicals (K2a), (K4a) and (K5a) as defined below or (K3) as defined above,
EMI19.2
 



  where R8a is hydrogen, chlorine, methyl or methoxy,
 R9a is hydrogen, chlorine, methyl, methoxy, -SO3H or -COOH, and
 R10a for hydrogen, SO3H or
EMI 19.3
 stand;
EMI 19.4
 



  wherein R11, R8a and R9a are as defined above,
 R12a is methyl, -COOH or -CONH2, and
 R14a for hydrogen, chlorine, methyl, ethyl, -SO3H or
EMI19.5
 stand;
EMI19.6
 



  wherein Q2a for hydrogen, methyl, ethyl, phenyl, -COR13, -CH2SO3H or -CH2OSO3H, Q3b for hydrogen, -CN, -SO3H, -COR13, methyl, ethyl, -CH2SO3H or -CH2NH2,
 Q4a for hydrogen,
EMI19.7
 Methyl, ethyl, cyclohexyl, phenyl or phenyl (C1-2alkyl), the phenyl ring of which is substituted by 1 or 2 substituents from the series chlorine, methyl, methoxy, -SO3H, -COOH,
 -NH2 and
EMI19.8
  may be substituted, or -C1-4alkylene-Y2,
 B2a for -C2-4alkylene, monohydroxy-substituted -C3-4alkylene-,
EMI20.1
 



  or B2a together with
EMI20.2
  to which it is bound for
EMI20.3
 



  stand;



  Y2 for -COOH, -SO3H, -OSO3H, -OH, -CN, methoxy or -NR27R28, each R27 and R28, independently of one another, for hydrogen, unsubstituted C1-4alkyl, by hydroxy, C1-4alkoxy, -COOH, -SO3H , -NH (C1-4alkyl) or -N (C1-4alkyl) 2 monosubstituted C1-4alkyl, unsubstituted cyclohexyl, cyclohexyl, phenyl or phenyl (C1-4alkyl) substituted by 1 to 3 methyl groups, the phenyl ring of which is in each case unsubstituted or substituted by one or two groups from the series halogen, preferably chlorine, C1-4alkyl, C1-4alkoxy, -SO3H and -COOH, or -NR27R28 for a piperidine, morpholine or piperazine ring, each of which is unsubstituted or up to three methyl groups may contain stand;


 Compounds of the formula (1b),
 
EMI20.4
 



  wherein
 m + r for 2 or 3,
 R6a for hydrogen, methyl or methoxy and
 R7a represents hydrogen, chlorine, methyl, methoxy, -NHCOCH3 or -NHCONH2;


 Compounds of the formula (1c),
 
EMI21.1
 



  wherein
 DK2 represents a radical of formula (a1), (b1) or (c1) as defined above;


 Compounds of formula (1d)
 
EMI21.2
 



  wherein the sulfo group is in the 3- or 4-position of the naphthyl radical and
 DK3 represents a radical of the formula (a2) or (c2),
EMI21.3
 



  wherein R3a and R4a are as defined above,
EMI21.4
 



  where m + p is 1 or 2.



  Preferred compounds (2) correspond to the formula (2a),
EMI22.1
 



  wherein R7a is as defined above and m + r is 2 or 3.



  Preferred compounds (3) are 1: 1 copper complexes based on the metal-free compounds (3a1) or (3b1),
EMI22.2
 



  R17a for hydrogen, chlorine, bromine, nitro, methyl, methoxy, -SO3H or -COOH,
 R22a for OH or OCH3, and
 m + r represent 2 or 3;
EMI22.3
 



  where R22a is as defined above. Furthermore, 1: 1 copper complexes of the following formulas (3c1), (3d1) and (3e1) are preferred as compounds (3),
EMI23.1
 



  wherein
 R50 and R2a are as defined above,
 R52a for hydrogen, methyl or methoxy, and
 D3a for
EMI23.2
 



  stand in which R30a is hydrogen, methyl or methoxy.



  Preferred compounds (4) correspond to the formula (4a),
EMI23.3
 



  wherein D1a, R4 and R18 are as defined above; more preferred are compounds of formula (4a) in which R4 is hydrogen and R18 in position 2 and
EMI24.1
  are bound in position 4 or 5 of the phenyl radical.



  Preferred compounds (5) are those in which -NR1-Z is
EMI24.2
  R20 and R21 stand for R20a and R21a, which independently of one another denote hydrogen, chlorine, methyl, methoxy, -COOH or -NHCOCH3.



  Preferred compounds (6) are those in which
 
 Q for -O-
 each X3, independently, for
EMI24.3
 
 each R1, independently of one another, for R1b,
 each Alk2, independently of one another, for -C2-3alkylene-, and
 each Z, independently of one another, stands for Za.



  In a compound (6), the two groups bearing Za are more preferably identical.



  Preferred compounds (7) are those in which
 Me for Cu or Ni, and
 R24 and R25 both represent hydrogen.



  More preferred are those compounds (7) in which
 Me for Cu or Ni,
 c for 2 or 3 and d for 0,
 each R1, independently of one another, for R1b,
 Z for Za,
 R26 for hydrogen, -COOH or -SO3H, and either
 a for 0 or
 a stands for 1 and X4 for -N = NKK2, with KK2 the rest
EMI25.1
 



  means and Q2a, Q3b and -B2a- are as defined above.



  The compounds listed as preferred above are each still more preferred
 
 (1) Za for Zb;
 (2) Za for Zc;
 (3) Za for Zc and each R1b for hydrogen.
 



   The nature of the cation of the sulfo groups and any additional carboxy groups present in compounds of the formula I, if these are in salt form, is not a critical factor, but can be any non-chromophoric cation which is customary in the chemistry of reactive dyes. However, the prerequisite is that the corresponding salts meet the condition of water solubility.



  Examples of suitable cations are alkali metal ions or unsubstituted or substituted ammonium ions, such as, for example, lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium and mono-, di- and triethanolammonium.



  Preferred cations are the alkali metal ions and ammonium, of which sodium is particularly preferred.



  In general, in a compound of formula I the cations of the sulfo groups and optionally carboxy groups may be the same or different and represent a mixture of the above cations, i.e. the compound can also be in mixed salt form.



  The present invention further comprises a process for the preparation of the compounds of the formula I, which is characterized in that a compound of the formula II,
EMI26.1
 



  where Y3 is -W-H or chlorine and Fc, X, R1, Alk, a, b and W are as defined above,
 in the case of Y3 = -W-H with 5-cyano-2,4,6-trichloropyrimidine, or in the case of Y3 = chlorine with the amount of a compound of the formula III corresponding to the exchange of a chlorine atom on the triazine ring,
EMI26.2
 



  where W is as defined above.



  In a compound of the formula II, Y3 is preferably -W-H. The reaction of a compound of formula II, wherein Y3 is -W-H, with 5-cyano-2,4,6-trichloropyrimidine is advantageously carried out at 0 ° -40 ° C. and pH 7-9; Water is normally used as the reaction medium, but 5-cyano-2,4,6-trichloropyrimidine can also be added in solution in an organic solvent, for example acetone.



  Disazo compounds of formula (4) can also be obtained by using a compound of formula IV
EMI26.3
 



  wherein D2, R1, Z, m and n are as defined above, diazotized and alkaline to a compound of formula V.
EMI27.1
 



  where D1, R1, Z, m and n are as defined above.



  The compounds of the formula I can be isolated in a manner known per se; e.g. the compounds can be separated from the reaction mixture by conventional salting out with alkali metal salts, filtered off and dried (in vacuo) at a slightly elevated temperature.



  Depending on the reaction and isolation conditions, a compound of the formula I is obtained as a free acid or preferably in salt form or as a mixed salt and then contains, for example, one or more of the cations mentioned above. Salts or mixed salts can, however, also be prepared starting from the free acid in a conventional manner and vice versa, or a conventional salting-out process can also be carried out.



  The starting compounds of the formula II, III, IV and V are either known or can be obtained from known starting materials analogously to methods known per se.



  The compounds of formula I and mixtures thereof are reactive dyes; they are suitable for dyeing or printing hydroxyl-containing or nitrogen-containing organic substrates. Preferred substrates are leather and fiber materials which consist of or contain natural or synthetic polyamides and in particular natural or regenerated cellulose, such as cotton, viscose or cellulose. The most preferred substrate is textile material that consists of or contains cotton.



  The compounds of the formula I can be used in dyeing liquors or in printing pastes by all dyeing or printing processes customary for reactive dyes. It is preferred to dye in the temperature range of 30-80 ° C. using the exhaust process.



  The compounds according to the invention can be used as a single dye or because of their good combinability as a combination element with other reactive dyes of the same class, which have comparable dyeing properties e.g. regarding general fastness properties, pull-out value, etc. can be used. The combination dyeings obtained show just as good fastness properties as the dyeings with individual dye.



  With the compounds of the formula I, good extraction and fixing values are obtained. The unfixed dye can be easily washed out. The dyeings and prints obtained show good lightfastness. They also have good wet fastness properties, e.g. in terms of fastness to washing, water, sea water and sweat and have good resistance to oxidative influences such as chlorine-containing water, hypochlorite bleach, peroxide bleach and perborate-containing detergents.



  The following examples serve to illustrate the invention. In the examples, parts mean parts by weight or volume and percentages mean percent by weight or volume; the temperatures are given in degrees Celsius.


 example 1
 



  18.3 parts (= 0.025 mol) of compound (B)
EMI29.1
 



  are placed in 500 parts of water. At 25 °, an acetone solution of 6.1 parts (20% excess) of 5-cyano-2,4,6-trichloropyrimidine is added. The reaction mixture shows a spontaneous drop in pH, which is kept at 7-7.5 by the continuous addition of 20% sodium carbonate solution. At the same time, the reaction temperature is raised to a final value of 35 °. The reaction is complete after 3-4 hours, which is checked by thin layer chromatography.



  To isolate the reaction product, the cloudy orange-red solution obtained is heated to 40 ° and stirred with filter earth for about 10 minutes. Then it is clarified and sprinkled into the filtrate with stirring sodium chloride (approx. 10%). The fine precipitate is filtered off and dried in vacuo at about 50 °. The result is the dye of the formula
EMI29.2
 



   which gives orange colors on cotton. The dyeings and prints on cotton obtained by customary methods show good wet fastness and very good light fastness and are resistant to oxidative influences.


 Preparation of the starting compound (B)
 



  a) 9.6 parts of 2-aminonaphthalene-3,6,8-trisulfonic acid are dissolved in 60 parts of water with 4.3 parts of 30% sodium hydroxide solution at pH 12. By dropwise addition of 11 parts of 30% hydrochloric acid, a readily stirrable suspension is obtained, which is diazotized with 6.5 parts of 4N sodium nitrite solution after the addition of 25 parts of ice at 0-5 °. The diazonium salt solution obtained is added at 3-7 ° for 30 minutes to a suspension consisting of 3.9 parts of 3-aminophenylurea in 25 parts of ice water, the pH being kept at 5.0 by adding 22 parts of 20% sodium carbonate solution. A red solution is formed, which contains the aminoazo compound (A)
EMI30.1
 



  contains.



  b) 5.1 parts of cyanuric chloride are stirred in 30 parts of ice water for 30 minutes. The dye solution formed in stage a) is then added in 5 minutes. The condensation takes place at pH 6.0 in the presence of 8 parts of 20% sodium carbonate solution. The resulting red-orange solution is mixed with a solution consisting of 3.3 parts of 1,2-diaminopropane in 50 parts of ice water, the pH of which was adjusted to 6.0 with 8 parts of 30% hydrochloric acid. The temperature of the reaction mixture is slowly raised to 48-50 ° within one hour, the pH of 6.0 being maintained by adding 20 parts of 20% sodium carbonate solution. Before the orange dye formed is separated off, its precipitation is completed with 100 parts of sodium chloride. The result is compound (B).


 Examples 2-200
 



  Analogously to the method described in Example 1, additional metal-free compounds of the formula I can be prepared using appropriate starting materials to form the desired chromophoric part Fc, which are listed in the following Tables 1-11, for which the appropriate formula is given at the beginning.



  With the compounds of Examples 2-200 substrates, which consist of or contain cellulose fibers, and in particular textile materials made of cotton, can be dyed or printed in the specified shades by customary drawing and printing processes. The dyeings and prints obtained on cotton are good lightfast and wetfast and resistant to oxidative influences.



  The divalent group listed under column - W - of Table 1 and all of these tables below can represent an asymmetric diamino group. Normally the linkage with the triazine ring on the one hand and the pyrimidine ring on the other hand takes place in the given order; however, the linkage can also take place in the reverse order, that is to say pyrimidine / triazine ring, namely if the reaction product of pyrimidine compound and diamine is used as the starting material for the preparation.
EMI31.1
 
EMI32.1
 
EMI33.1
 



  With the dyes of Examples 2-19 greenish yellow dyeings are obtained on cotton.
EMI34.1
 



  With the dyes of Examples 20-25 greenish yellow dyeings are obtained on cotton.
EMI35.1
 



  With the dyes of Examples 26-29 greenish yellow dyeings are obtained on cotton.
EMI36.1
 
EMI37.1
 
EMI38.1
 
EMI39.1
 
EMI40.1
 
EMI41.1
 
EMI42.1
 



  With the dyes of Examples 72-86 greenish yellow cotton dyeings are obtained.
EMI42.2
 
EMI43.1
 



  With the dyes of Examples 87-99 greenish yellow cotton dyeings are obtained.
EMI43.2
 
EMI44.1
 
EMI45.1
 
EMI46.1
 
EMI47.1
 
EMI48.1
 
EMI49.1
 
EMI50.1
 
EMI51.1
 
EMI52.1
 
EMI53.1
 
EMI54.1
 



  Cotton dyes in orange tones are obtained with the dyes of Examples 176-200.


 Example 201
 



  15.6 parts (0.02 mol) of the dye of the formula
EMI54.2
 



  are dissolved in 300 parts of water at pH 8.5-9 and adjusted to pH 6.0 with a little hydrochloric acid. 3.9 parts (0.02 mol + 5%) of cyanuric chloride are added and the pH is kept at 5.5-6.5 with sodium hydroxide solution while stirring at 10-15 °. The implementation is completed after about an hour. 1.6 parts (0.02 mol + 10%) of 1,2-diaminopropane are added to the resulting reaction mixture (0.02 mol). The reaction takes place at 40-50 °, the pH being kept at 5.5-6.5 with sodium hydroxide solution. The reaction is complete after about two hours.



  4.6 parts (0.02 mol + 10%) of 5-cyano-2,4,6-trichloropyrimidine are then added to the fine dye suspension obtained (0.02 mol). The reaction is carried out at 15-20 ° and pH 8.5-9.0. The dye is obtained by the usual salting out, filtering off and drying in accordance with the formula
EMI55.1
 



  of cotton in blue tones. The dyeings have high light fastness, they are good wet fast and resistant to oxidative influences.


 Examples 202-291
 



  Analogously to the method described in Example 201, further metal-containing compounds of the formula I can be prepared using appropriate starting materials to form the desired chromophoric part Fc, which are listed in the following tables 12-17, for which the appropriate formula is given at the beginning.



  The metal complexes of Examples 202-291 can be used to dye or print substrates which consist of or contain cellulose fibers and, in particular, textile materials made of cotton in the specified shades of color by the customary drawing and printing process. The dyeings and prints obtained on cotton are highly lightfast, wetfast and resistant to oxidative influences.
EMI56.1
 
EMI57.1
 



  With the dyes of Examples 202-214 blue dyeings are obtained on cotton.
EMI57.2
 
EMI58.1
 



  The dyes of Examples 215-226 give blue dyeings on cotton.
EMI58.2
 
EMI59.1
 



  The dyes of Examples 227-250 give ruby-red dyeings on cotton.
EMI60.1
 



  With the dyes of Examples 251-256, dark blue dyeings are obtained on cotton.
EMI60.2
 
EMI61.1
 
EMI61.2
 
EMI62.1
 
EMI63.1
 



   Blue dyes are obtained with the dyes of Examples 269-291.


 Example 292
 



  45.3 parts of the monoazo dye of the formula prepared in the customary manner
EMI64.1
 



  are dissolved with 700 parts of water. 18.5 parts of cyanuric chloride are sprinkled in at 20-25 ° C. for 30 minutes. At pH 6.0-6.5, stirring is continued until no free amino group can be detected. Then 11.1 parts of 1,2-diaminopropane are added and the mixture is stirred at 40-50 ° for two hours, a pH of 7.0 being maintained by adding dilute sodium carbonate solution. The condensation product is salted out with sodium chloride and filtered off; the paste is redissolved in 900 parts of water. 24.9 parts of 5-cyano-2,4,6-trichloropyrimidine are added, and the mixture is then stirred at 0-5 ° for 2 hours. In the course of the reaction, a pH of 8-9 is maintained by adding dilute soda solution. The resulting dye is separated and isolated by adding sodium chloride. It corresponds to the formula
EMI64.2
 



  and when dried it is a dark red powder that dissolves in water with a red color. The dyeings obtained on cotton are scarlet red, they show good light and wet fastness and are resistant to oxidative influences.


 Examples 293-319
 



  Analogously to the method described in Example 292, further compounds of the formula I can be prepared using the appropriate starting materials. They correspond to the formula (T18)
EMI65.1
 



  for which the variables are listed in Table 18 below. The dyeings obtained with the dyes of Examples 293-319 on cotton show good light and wet fastness properties and are resistant to oxidative influences.



  The color of the cotton dyeing is given in the last column I;
 it means d = orange
 and k = scarlet
EMI65.2
 
EMI66.1
 


 Example 320
 



  5 parts of cyanuric chloride are stirred in a mixture of 10 parts of water and 20 parts of ice to give a homogeneous suspension. A neutral solution of 30 parts of the tetrasodium salt of the dye of the formula is added
EMI67.1
 



  in 160 parts of water and stirred at 5 ° and pH 5.5-6.0 until no free amino group can be detected. At pH 6.5-7.0, the mixture is slowly warmed to 15 ° and 3.25 parts of 1,2-diaminopropane are added. The pH is kept at 6.0 using hydrochloric acid. The mixture is heated at 50 ° for 3 hours until no more educt can be detected, 70 parts of sodium chloride are added and the red suspension is filtered off. The filter cake is washed with 500 parts of 20% sodium chloride solution. The resulting paste is introduced into 500 parts of water and 4.5 parts of 5-cyano-2,4,6-trichloropyrimidine are added. At 20 ° C., the mixture is stirred for 12 hours until the reaction is complete, 80 parts of sodium chloride are added and the dye which has separated out is filtered off. It corresponds to the formula
EMI67.2
 



  and when dried it is a dark red powder that dissolves in water with a red color. The dye dyes cotton in bluish red tones, the dyeings obtained have very good general fastness properties.


 Examples 321-416
 



  Analogously to the method described in Example 320, further compounds of the formula I can be prepared using the appropriate starting materials, which are listed in the following tables 19-22, for which the relevant formula is given at the beginning. With the dyes of Examples 321-416, cellulose fibers and in particular cotton can be dyed using the customary exhaust method. The dyeings obtained are all bluish red and show good fastness properties.
EMI68.1
 
EMI69.1
 
EMI70.1
 
EMI70.2
 
EMI71.1
 
EMI71.2
 
EMI72.1
 
EMI73.1
 
EMI74.1
 


 Example 417
 



  212 parts of cyanuric chloride are stirred in a mixture of 560 parts of ice and 200 parts of water for 45 minutes. A solution of 190 parts of 2,4-diaminobenzene-1-sulfonic acid in 920 parts of water and 112 parts of 30% sodium hydroxide solution is then added and the mixture is stirred on an ice bath for 6 hours. The white suspension is indirectly diazotized.



  In the meantime, 140 parts of 4-aminobenzoic acid are diazotized in the usual way and acidically coupled to 320 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid. The red suspension is then mixed with the above diazo solution and coupled alkaline.



  120 parts of 1,2-diaminopropane are added to the resulting blue solution and left to react for 2 hours. The reaction mixture is then salted out with sodium chloride (25% of the volume) and filtered. The blue filter cake is dissolved in 10 times the amount of water.



  A suspension of 175 parts of 5-cyano-2,4,6-trichloropyrimidine in 350 parts of water and 150 parts of ice, which was stirred for 45 minutes, is added within 2 hours. The reaction mixture is kept at pH 9 for three hours, then it is salted out with sodium chloride (10% of the volume) and filtered. The filter cake is dried at 40 ° in a vacuum. The isolated dye has the formula
EMI75.1
 



  and dyes cellulose material, especially cotton in navy blue tones. These dyeings have good fastness properties such as good light and wet fastness and resistance to oxidative influences.


 Examples 418-456
 



  Analogously to the method described in Example 417, further compounds of the formula I can be prepared using the appropriate starting materials. They have the formula (T23)
EMI75.2
 



  for which the variables are listed in Table 23 below. With the dyes of Examples 418-456, cellulose fibers and in particular cotton can be dyed by the customary exhaust method. The dyeings obtained are navy blue and show very good general fastness properties.
EMI76.1
 
EMI77.1
 


 Example 457
 



  65.9 parts of the dye of the formula prepared by known methods
EMI77.2
 



  are dissolved in 1200 parts of water. 37 parts of cyanuric chloride are sprinkled in at 20-25 ° C. for 30 minutes. The mixture is stirred for one hour at pH 6.0-6.5, which is maintained by continuously adding dilute sodium carbonate solution. Then 22.2 parts of 1,2-diaminopropane are added and the mixture is stirred at 40-50 ° for 2 hours, a pH of 7.0 being maintained by adding dilute sodium carbonate solution. The condensation product is salted out with sodium chloride and filtered off. The paste obtained is redissolved in 1400 parts of water. 49.5 parts of 5-cyano-2,4,6-trichloropyrimidine are then added and the mixture is stirred at a temperature of 5-10 ° for 2 hours. During the reaction, the pH is kept at 8-9 by adding dilute sodium carbonate solution. The resulting dye is separated and isolated by adding sodium chloride. He has the formula
EMI78.1
 



   and, when dried, is a black powder that dissolves in water with a deep blue color and dyes cotton in deep blue tones. The dyeings show very good light and wet fastness properties.


 Examples 458-472
 



  Analogously to the method described in Example 457, further compounds of the formula I can be prepared. They correspond to the formula (T24),
EMI78.2
 



  for which the variables are listed in Table 24 below. The dyes of Examples 458-472 dye cotton in deep blue tones, the dyeings show very good light and wet fastness properties.
EMI79.1
 


 Example 473
 



  25.7 parts (0.025 mol) of the dye base, prepared by methods known per se by sulfochlorination of copper phthalocyanine and subsequent reaction with 1,3-diaminobenzene-4-sulfonic acid, which contains about 2.5 sulfonic acid groups and 1 sulfamide group per molecule dissolved with 200 parts of water at pH 6.5-7.0. After the addition of 150 parts of ice, 4.6 parts of cyanuric chloride are added at 0-5 ° and the mixture is stirred at pH 6.0-6.5 for two hours. 2.8 parts of 1,2-diaminopropane are then added, and the mixture is then stirred at 0-5 ° for one hour before the temperature is raised to 30-35 ° in the course of two hours and the pH to 7.5 with 20% sodium carbonate solution -8.0 can be set. The reaction product is salted out with 70 parts of sodium chloride and filtered off.

  It is redissolved in 250 parts of water, 6.3 parts of 5-cyano-2,4,6-trichloropyrimidine are added at 0-5 ° C. and the mixture is stirred at this temperature for three hours. At the same time, the pH is kept at 8-8.5 by adding soda. After the condensation has ended, the mixture is salted out with 45 parts of sodium chloride, the dye precipitate is suctioned off sharply and dried at 35 °. The dye obtained has the formula
EMI80.1
 



  it dyes cellulose material and especially cotton in brilliant turquoise tones. The dyeings show good light fastness and perfect wet fastness.


 Example 474
 



  If, instead of the 25.7 parts of copper phthalocyanine dye base mentioned in Example 473, the equivalent amount of nickel phthalocyanine dye base, namely 25.5 parts (= 0.025 mol), is obtained, Example 473 analogous [NiPc] dye, the cotton in tints blue-green with good fastness properties.


 Examples 475-480
 



  Analogous to the method described in Examples 473 and 474, further phthalocyanine dyes can be prepared. They correspond to the formula (T25),
EMI81.1
 



  for which the variables are listed in Table 25 below. In the last column I the color of the dyeing on cotton is given; it means e = brilliant turquoise and f = blue-green. The dyeings show good fastness properties.
EMI81.2
 


 Example 481
 



  25.5 parts of the dye base, prepared by methods known per se by sulfochlorination of nickel phthalocyanine and subsequent reaction with 1,3-diaminobenzene-4-sulfonic acid, which contains about 2.5 sulfonic acid groups and 1 sulfamide group per molecule, are in 150 parts of water stirred with 1.8 parts of sodium nitrite. The solution, cooled to 0-2 °, is added dropwise to 100 parts of ice / water and 12 parts of 30% hydrochloric acid. The diazonium salt suspension obtained is allowed to flow into a solution consisting of 300 parts of ice / water and 5.9 parts of 1- (3 min -methylaminopropyl) -6-hydroxy-4-methylpyridone- (2) while maintaining a temperature of 0-5 ° . During the coupling reaction, the pH is kept at 9-9.5 by adding 20% sodium hydroxide solution.

  The resulting green solution is cyanuric chloride, then with 1,2-diaminopropane and then with 5-cyano-2,4,6-trichloropyrimidine according to the information in Example 473 to the dye of the formula
EMI82.1
 



  implemented, which is isolated in an analogous manner. It dyes cellulose material and especially cotton in brilliant green tones. These colors show valuable properties such as high light fastness and perfect wet fastness.


 Examples 482-519
 



  Analogous to the method described in Example 481, further phthalocyanine dyes can be prepared. They correspond to the formulas (T26) and (T27),
EMI83.1
 



  for which the variables are listed in the following tables 26 and 27.



  With the dyes of Examples 482-519, green dyeings are obtained on cotton, which are additionally brilliant in the case of nickel phthalocyanine. These dyeings show valuable fastness properties such as good light and wet fastness properties.
EMI84.1
 
EMI85.1
 


 Example 520
 



  Analogously to the method described in Example 481, using the corresponding starting compounds, the dye of the formula
EMI86.1
 



  be made and isolated. This dye gives brilliant green cotton dyeings that have good light and wet fastness properties.



  According to the methods described above, the dyes of Examples 1 to 520 are obtained as sodium salts. Depending on the reaction and isolation conditions chosen or by subsequent measures, they can be prepared in a manner known per se in the form of the free acid or in another salt form or else mixed salt form and then, for example, one or more of the cations listed further in the description contain.



  Possible uses of the dyes described are illustrated below.


 Instructions for use A
 



  10 parts of cotton fabric (bleached) are introduced at 40 ° C. into a dyebath which contains 0.3 part of the dye from Example 1 and 15 parts of Glauber's salt (calcined) in 300 parts of demineralized water. After 30 minutes at 40 ° C., a total of 6 parts of soda (calcined) are added at intervals of 10 minutes, in portions of 0.2; 0.6; 1,2 and finally 4 parts, the temperature being kept at 40 °. The dyeing is then continued at 40 ° for one hour. The dyed material is then rinsed in running cold water for 3 minutes, then in running hot water for 3 minutes. The dyeing is boiled for 15 minutes in 500 parts of demineralized water in the presence of 0.25 part of a commercially available anionic surfactant.

   After rinsing in running water (hot for 3 minutes), centrifugation is carried out and the color is dried in a drying cabinet at approx. 70 °. An orange-colored cotton dyeing of good fastness properties is obtained, which in particular shows good light and wet fastness properties and is stable against oxidative influences.


 Application regulation B
 



  10 parts of cotton material (bleached) are added to a dyebath containing 10 parts of Glauber's salt (calcined) in 300 parts of demineralized water. The bath is heated to 40 ° within 10 minutes, then 0.5 part of the dye from Example 1 is added. After a further 30 minutes at 40 ° C., 3 parts of soda (calcined) are added, and then the dyeing is continued for a further 45 minutes at 40 ° C.



  The dyed material is rinsed with running cold water, then with hot water and washed boiling analogously to that described for regulation A. After rinsing and drying, an orange cotton dyeing is obtained which has the properties listed for regulation A.


 Instructions for use C
 



  In a modification of dyeing instruction A, 0.3 part of the dye from Example 481 is used and instead of the portionwise addition of a total of 6 parts of soda, only 2 parts of soda (calcined) are added in one portion; the initial temperature of 40 ° is then increased to 60 ° and dyeing is continued for an hour at 60 °. Otherwise the procedure is the same as specified in regulation A. A brilliant green cotton dyeing with a particularly good lightfastness is obtained.


 Instructions for use D
 



  2.5 parts of the dye from Example 473 are dissolved in 2000 parts of water. 100 parts of cotton fabric are added to the dyebath, and the temperature is set to 80 ° within 10 minutes. 30 minutes after the addition of 100 parts of Glauber's salt (calcined), 20 parts of soda (calcined) are added to the dyebath. The dyeing is continued at 80 ° for one hour. The dyed material is then removed from the dyebath, cold under running water first, then rinsed hot and washed boiling analogously to that described for regulation A. After rinsing and drying you get a brilliant turquoise color with good fastness properties.



  The dyes according to the other examples or dye mixtures thereof can be used for dyeing in an analogous manner to that described in the regulations A-D. The dyeings obtained have good fastness properties.


 Application instruction E
 
 <tb> <TABLE> Columns = 2
 <tb> Title: A printing paste with the ingredients
 <tb> <SEP> 40 <SEP> parts of the dye from Example 1
 <tb> <SEP> 100 <SEP> parts of urea
 <tb> <SEP> 350 <SEP> parts of water
 <tb> <SEP> 500 <SEP> parts of a 4% sodium alginate thickener
 <tb> <SEP> 10 <SEP> parts of sodium bicarbonate
 <tb> <SEP> 1000 <SEP> parts in total
 <tb> </TABLE>



   is applied to cotton material using the usual printing processes.



  The printed material is steamed for 4-8 minutes at 102-104 DEG and then rinsed cold and hot. The fixed cotton material is then washed at the boil (analogous to regulation A) and dried. The orange print obtained shows good general fastness properties.



  Analogously to regulation E, the dyes of the other examples or dye mixtures from examples 1-520 can also be used for printing on cotton. In all cases, prints with good fastness properties are obtained.


    

Claims (10)

      1. Compounds of formula I. EMI90.1      as free acid or in salt form, wherein  Fc for the remainder of a metal-free or metal-containing water-soluble chromophore from the azo, formazane, phthalocyanine, azomethine, oxazine, thiazine, phenazine or triphenylmethane series, which may contain an additional fiber-reactive group,  each a, independently of one another, for 0 or 1 and  b represents 1 or 2; ;  each X, independently of one another, the direct bond, -CO or -SO2-,  each R1, independently of one another, is hydrogen, unsubstituted C1-4alkyl or C1-4alkyl which is substituted by hydroxy, halogen, cyano, -SO3H, -OSO3H or -COOH, and each alk, independently of one another, is C2-4alkylene,  each W, independently of one another, for -NR1-B1-NR1-, EMI90.2   EMI90.3      where m is 0 or 1, and  B1 for C2-6alkylene, for a C2-6alkylene chain which is interrupted by -O- or -NR1-, for C3-6alkylene substituted by one or two hydroxyl groups or by a carboxy group, for EMI91.1      stand in what  n 0, 1, 2, 3 or 4 and  R2 is hydrogen, C1-4alkyl, C1-4alkoxy, -COOH or -SO3H. 2nd Compounds according to claim 1, wherein each R1, independently of one another, for R1b as hydrogen, methyl, ethyl or 2-hydroxyethyl, and each W, independently of one another, for EMI91.2      stand in what  B1b C2-3 alkylene, monohydroxy-substituted C3-4 alkylene, EMI91.3      R2b is hydrogen or -SO3H, and  n2 is 0, 1 or 2. 3. Metal-free compounds (1) according to claim 1, which of the formula EMI91.4      correspond to what  DK the rest of a diazo component from the benzene or naphthalene series and  KK is the rest of a coupling component of the benzene or naphthalene series, the rest of a heterocyclic coupling component or a CH-acidic enolizable compound,  Z for EMI92.1      stands in what  W is as defined in claim 1, and  b stands for 1, with Z passing over the diazo or coupling component EMI92.2  wherein R1 is as defined in claim 1. 4th Compounds according to Claim 3, which correspond to the formula (1b) or (1d) and which are present as free acid or in salt form, EMI92.3      wherein EMI93.1      B1a for -C2-4alkylene, C2-3alkylene-0-C2-3alkylene-, EMI93.2   monohydroxy-substituted -C3-4alkylene-, EMI93.3      n1 for 0, 1, 2 or 3,  each R1b, independently of one another, is hydrogen, methyl, ethyl or 2-hydroxyethyl, and  R2a represents hydrogen, methyl, methoxy, -COOH or -SO3H; ;  m for 0 or 1,  r for 1 or 2, and  m + r stand for 2 or 3,  R6a is hydrogen, methyl or methoxy, and  R7a is hydrogen, chlorine, methyl, methoxy, -NHCOCH3 or -NHCONH2, EMI94.1      wherein  Za and each R1b, independently of one another, as defined above,  a represents 0 or 1,  the sulfo group is in the 3- or 4-position of the naphthyl ring, and  DK3 represents a group of the formula (a2) or (c2), EMI94.2      wherein  each R3a and R4a, independently of one another, are hydrogen, chlorine, methyl, methoxy, ethoxy or  -COOH stands, EMI94.3      wherein  m for 0 or 1,  p for 0, 1 or 2, and  m + p stand for 1 or 2. 5. Metal-free compounds according to claim 1, according to the formula EMI94.4      as free acid or in salt form, wherein  Z for EMI95.1      stands,  R1 and W are as defined in claim 1,  t for 2 or 3,  R6 is hydrogen, C1-4alkyl or C1-4alkoxy, and  R7 represents hydrogen, halogen, C1-4alkyl, C1-4alkoxy, -NHCOC1-4alkyl or -NHCONH2,  R6x, independently of one another, has one of the meanings of R6, and  R7x, independently of one another, have one of the meanings of R7. 6. Metal complexes according to claim 1, which are based on a metallizable compound (3a) or (3b), EMI95.2      stands,  R1 and W are as defined in claim 1,  A for EMI96.1      stands,  every m, independently of one another, for 0 or 1,  q for 1, 2 or 3,  R17 for hydrogen, halogen, nitro, C1-4alkyl, C1-4alkoxy, -COR13, -SO3H or -NHCOCH3,  R22 for OH, OCH3 or NH2, and  R13 represents OH, -OC1-4alkyl or NH2,  where the metal complexes, as free acid or in salt form, represent 1: 1 copper complexes or symmetrical or asymmetrical 1: 2 chromium or 1: 2 cobalt complexes. 7.1: 1: copper complexes according to claim 1, which correspond to one of the formulas (3c) to (3e), EMI96.2   EMI97.1      as free acid or in salt form, wherein  Z for EMI97.2      stands,  R1 and W are as defined in claim 1,  R50 means hydrogen or SO3H,  r for 1 or 2,  m for 0 or 1, and  m + r stand for 2 or 3,  R2 is as defined in claim 1, and  R52 denotes hydrogen, C1-4alkyl or C1-4alkoxy,  D3 for EMI97.3      t for 2 or 3,  R29 for hydrogen, COOH or SO3H,  R30 for hydrogen, C1-4alkyl, C1-4alkoxy or -O-Alk1-OR5,  Alk1 for C2-3alkylene, and  R5 represents hydrogen, SO3H, C1-4alkyl or C2-4hydroxyalkyl. 8th. Compounds according to claim 1, according to the formula EMI98.1      as free acid or in salt form, wherein  c for 1, 2 or 3, and  d stands for 0, 1 or 2, with the restriction that  that c + d is not greater than 3;  Z for EMI98.2      stands,  each R1, independently of one another, and W are as defined in claim 1,  Pc the phthalocyanine residue and  Me mean copper, nickel, cobalt, iron or aluminum,  each R24 and R25, independently of one another, represents hydrogen or C1-6alkyl, or  -NR24R25 is a saturated 5- or 6-membered heterocyclic ring which is another EMI98.3  can contain, in which R31 is hydrogen, C1-4alkyl, 2-hydroxyethyl or 2-aminoethyl,  R26 for hydrogen, halogen, hydroxy, C1-4alkyl, C1-4alkoxy, COOH or SO3H,  a for 0 or 1,  X4 for a divalent, if necessary EMI99.1   containing aliphatic,  araliphatic or heterocyclic bridge member or for -N = N-KK2,  KK2 for EMI99.2      where the labeled C atom indicates the coupling point,  R11 for OH or NH2,  R12 for C1-4alkyl or -COR13,  R13 for OH, -OC1-4alkyl or NH2,  R9 for hydrogen, halogen, C1-4alkyl, C1-4alkoxy, COOH or SO3H,  B3 stand for a divalent bridge member and  a is as defined above;  Q2 is hydrogen, C1-4alkyl, C5-6cycloalkyl, phenyl or phenyl (C1-4alkyl), the phenyl ring of which is unsubstituted or substituted by 1 to 3 substituents from the series C1-4alkyl, C1-4alkoxy, halogen, COOH and SO3H; -COR13 or C1-4alkyl monosubstituted by -SO3H, -OSO3H or -COR13,  Q3a hydrogen, CN, SO3H, -COR13, C1-4alkyl, through hydroxy, halogen, CN, C1-4alkoxy, EMI99.3      -SO3H, -OSO3H or  NH2 monosubstituted C1-4 alkyl;  SO2NH2, EMI99.4      R15 is hydrogen, C1-4 alkyl or C2-4 hydroxyalkyl, and  An <(-)> mean a non-chromophoric anion and  R9 and R13 are as defined above,  B2 for C2-6alkylene, monohydroxy-substituted -C3-6alkylene, a C2-6alkylene chain which is interrupted by -O- or -NR1-, EMI100.1      wherein R1 and m are as defined in claim 1, or EMI100.2      stand. 9. Mixtures of compounds of formula I according to claim 1. 10th  A process for the preparation of compounds of formula I according to claim 1, characterized in that a compound of formula II, EMI100.3      where Y3 is -W-H or chlorine and Fc, X, R1, Alk, a, b and W are as defined in claim 1,  in the case of Y3 the meaning of -W-H with 5-cyano-2,4,6-trichloropyrimidine,  or in the case of Y3, the meaning of chlorine, with the amount of a compound of the formula III corresponding to the replacement of a chlorine atom on the triazine ring, EMI101.1      where W is as defined above.       1. Compounds of formula I. EMI90.1      as free acid or in salt form, wherein  Fc for the remainder of a metal-free or metal-containing water-soluble chromophore from the azo, formazane, phthalocyanine, azomethine, oxazine, thiazine, phenazine or triphenylmethane series, which may contain an additional fiber-reactive group,  each a, independently of one another, for 0 or 1 and  b represents 1 or 2; ;  each X, independently of one another, the direct bond, -CO or -SO2-,  each R1, independently of one another, is hydrogen, unsubstituted C1-4alkyl or C1-4alkyl which is substituted by hydroxy, halogen, cyano, -SO3H, -OSO3H or -COOH, and each alk, independently of one another, is C2-4alkylene,  each W, independently of one another, for -NR1-B1-NR1-, EMI90.2   EMI90.3      where m is 0 or 1, and  B1 for C2-6alkylene, for a C2-6alkylene chain which is interrupted by -O- or -NR1-, for C3-6alkylene substituted by one or two hydroxyl groups or by a carboxy group, for EMI91.1      stand in what  n 0, 1, 2, 3 or 4 and  R2 is hydrogen, C1-4alkyl, C1-4alkoxy, -COOH or -SO3H. 2nd Compounds according to claim 1, wherein each R1, independently of one another, for R1b as hydrogen, methyl, ethyl or 2-hydroxyethyl, and each W, independently of one another, for EMI91.2      stand in what  B1b C2-3 alkylene, monohydroxy-substituted C3-4 alkylene, EMI91.3      R2b is hydrogen or -SO3H, and  n2 is 0, 1 or 2. 3. Metal-free compounds (1) according to claim 1, which of the formula EMI91.4      correspond to what  DK the rest of a diazo component from the benzene or naphthalene series and  KK is the rest of a coupling component of the benzene or naphthalene series, the rest of a heterocyclic coupling component or a CH-acidic enolizable compound,  Z for EMI92.1      stands in what  W is as defined in claim 1, and  b stands for 1, with Z passing over the diazo or coupling component EMI92.2  wherein R1 is as defined in claim 1. 4th Compounds according to Claim 3, which correspond to the formula (1b) or (1d) and which are present as free acid or in salt form, EMI92.3      wherein EMI93.1      B1a for -C2-4alkylene, C2-3alkylene-0-C2-3alkylene-, EMI93.2   monohydroxy-substituted -C3-4alkylene-, EMI93.3      n1 for 0, 1, 2 or 3,  each R1b, independently of one another, is hydrogen, methyl, ethyl or 2-hydroxyethyl, and  R2a represents hydrogen, methyl, methoxy, -COOH or -SO3H; ;  m for 0 or 1,  r for 1 or 2, and  m + r stand for 2 or 3,  R6a is hydrogen, methyl or methoxy, and  R7a is hydrogen, chlorine, methyl, methoxy, -NHCOCH3 or -NHCONH2, EMI94.1      wherein  Za and each R1b, independently of one another, as defined above,  a represents 0 or 1,  the sulfo group is in the 3- or 4-position of the naphthyl ring, and  DK3 represents a group of the formula (a2) or (c2), EMI94.2      wherein  each R3a and R4a, independently of one another, are hydrogen, chlorine, methyl, methoxy, ethoxy or  -COOH stands, EMI94.3      wherein  m for 0 or 1,  p for 0, 1 or 2, and  m + p stand for 1 or 2. 5. Metal-free compounds according to claim 1, according to the formula EMI94.4      as free acid or in salt form, wherein  Z for EMI95.1      stands,  R1 and W are as defined in claim 1,  t for 2 or 3,  R6 is hydrogen, C1-4alkyl or C1-4alkoxy, and  R7 represents hydrogen, halogen, C1-4alkyl, C1-4alkoxy, -NHCOC1-4alkyl or -NHCONH2,  R6x, independently of one another, has one of the meanings of R6, and  R7x, independently of one another, have one of the meanings of R7. 6. Metal complexes according to claim 1, which are based on a metallizable compound (3a) or (3b), EMI95.2      stands,  R1 and W are as defined in claim 1,  A for EMI96.1      stands,  every m, independently of one another, for 0 or 1,  q for 1, 2 or 3,  R17 for hydrogen, halogen, nitro, C1-4alkyl, C1-4alkoxy, -COR13, -SO3H or -NHCOCH3,  R22 for OH, OCH3 or NH2, and  R13 represents OH, -OC1-4alkyl or NH2,  where the metal complexes, as free acid or in salt form, represent 1: 1 copper complexes or symmetrical or asymmetrical 1: 2 chromium or 1: 2 cobalt complexes. 7.1: 1: copper complexes according to claim 1, which correspond to one of the formulas (3c) to (3e), EMI96.2   EMI97.1      as free acid or in salt form, wherein  Z for EMI97.2      stands,  R1 and W are as defined in claim 1,  R50 means hydrogen or SO3H,  r for 1 or 2,  m for 0 or 1, and  m + r stand for 2 or 3,  R2 is as defined in claim 1, and  R52 denotes hydrogen, C1-4alkyl or C1-4alkoxy,  D3 for EMI97.3      t for 2 or 3,  R29 for hydrogen, COOH or SO3H,  R30 for hydrogen, C1-4alkyl, C1-4alkoxy or -O-Alk1-OR5,  Alk1 for C2-3alkylene, and  R5 represents hydrogen, SO3H, C1-4alkyl or C2-4hydroxyalkyl. 8th. Compounds according to claim 1, according to the formula EMI98.1      as free acid or in salt form, wherein  c for 1, 2 or 3, and  d stands for 0, 1 or 2, with the restriction that  that c + d is not greater than 3;  Z for EMI98.2      stands,  each R1, independently of one another, and W are as defined in claim 1,  Pc the phthalocyanine residue and  Me mean copper, nickel, cobalt, iron or aluminum,  each R24 and R25, independently of one another, represents hydrogen or C1-6alkyl, or  -NR24R25 is a saturated 5- or 6-membered heterocyclic ring which is another EMI98.3  can contain, in which R31 is hydrogen, C1-4alkyl, 2-hydroxyethyl or 2-aminoethyl,  R26 for hydrogen, halogen, hydroxy, C1-4alkyl, C1-4alkoxy, COOH or SO3H,  a for 0 or 1,  X4 for a divalent, if necessary EMI99.1   containing aliphatic,  araliphatic or heterocyclic bridge member or for -N = N-KK2,  KK2 for EMI99.2      where the labeled C atom indicates the coupling point,  R11 for OH or NH2,  R12 for C1-4alkyl or -COR13,  R13 for OH, -OC1-4alkyl or NH2,  R9 for hydrogen, halogen, C1-4alkyl, C1-4alkoxy, COOH or SO3H,  B3 stand for a divalent bridge member and  a is as defined above;  Q2 is hydrogen, C1-4alkyl, C5-6cycloalkyl, phenyl or phenyl (C1-4alkyl), the phenyl ring of which is unsubstituted or substituted by 1 to 3 substituents from the series C1-4alkyl, C1-4alkoxy, halogen, COOH and SO3H; -COR13 or C1-4alkyl monosubstituted by -SO3H, -OSO3H or -COR13,  Q3a hydrogen, CN, SO3H, -COR13, C1-4alkyl, through hydroxy, halogen, CN, C1-4alkoxy, EMI99.3      -SO3H, -OSO3H or  NH2 monosubstituted C1-4 alkyl;  SO2NH2, EMI99.4      R15 is hydrogen, C1-4 alkyl or C2-4 hydroxyalkyl, and  An <(-)> mean a non-chromophoric anion and  R9 and R13 are as defined above,  B2 for C2-6alkylene, monohydroxy-substituted -C3-6alkylene, a C2-6alkylene chain which is interrupted by -O- or -NR1-, EMI100.1      wherein R1 and m are as defined in claim 1, or EMI100.2      stand. 9. Mixtures of compounds of formula I according to claim 1. 10th  A process for the preparation of compounds of formula I according to claim 1, characterized in that a compound of formula II, EMI100.3      where Y3 is -W-H or chlorine and Fc, X, R1, Alk, a, b and W are as defined in claim 1,  in the case of Y3 the meaning of -W-H with 5-cyano-2,4,6-trichloropyrimidine,  or in the case of Y3, the meaning of chlorine, with the amount of a compound of the formula III corresponding to the replacement of a chlorine atom on the triazine ring, EMI101.1      where W is as defined above.