Metal complex reactive dyestuffs

1:1 and 1:2 metal complex reactive dyestuffs based on at least one metallizable dyestuff of the formula ##STR1## wherein D=the radical of a metallizable diazo component with an OH group or COOH group in the o-position relative to the azo bridge, PA1 K=the radical of a coupling component which couples in the o-position relative to a phenolic or enolic OH group, PA1 W= ##STR2## R, R.sub.1 and R.sub.2 =H or a substituent Y=a group which can be split off, in particular halogen and PA1 Z=a divalent organic radical, and wherein PA1 the group ##STR3## is bonded, directly or via a bridge member, to an aromatic ring C atom of D or K, and their use for dyeing and printing materials containing hydroxyl groups and N-containing materials, such as cotton, wool and the like.

The invention relates to 1:1 and 1:2 metal complex reactive dyestuffs based 
on at least one metallisable dyestuff of the formula 
##STR4## 
wherein D=the radical of a metallisable diazo component with an OH group 
or COOH group in the o-position relative to the azo bridge, 
K=the radical of a coupling component which couples in the o-position 
relative to a phenolic or enolic OH group, 
W= 
##STR5## 
R, R.sub.1 and R.sub.2 =H or a substituent Y=a group which can be split 
off, in particular halogen and 
Z=a divalent organic radical, 
and wherein 
the group 
##STR6## 
is bonded, directly or via a bridge member, to an aromatic ring C atom of 
D or K. 
Possible metals are, in particular, Cu, Cr and Co. In the case of Cu 
complexes, the 1:1 complexes are of particular importance. In the case of 
1:2 complexes, the 2nd dyestuff radical can also be a radical of a 
dyestuff of the formula (I), in which case both radicals can be identical 
or different, or can be the radical of any desired metallisable dyestuff. 
A large number of suitable metallisable dyestuffs are described in the 
literature. 
Those radicals of dyestuffs of the formula (I) are, of course, also 
particularly suitable as the 2nd dyestuff radical, it being possible for 
the dyestuffs to be symmetric or unsymmetric. Dyestuffs of this type 
contain two radicals 
##STR7## 
in the molecule. 
Particularly valuable dyestuffs are 1:2 Cr complex dyestuffs and 1:2 Co 
complex dyestuffs based on identical dyestuffs (I), and in particular 
mixtures of the 1:2 Cr complexes and 1:2 Co complexes of identical 
dyestuffs. 
Symmetric or unsymmetric 1:2 Cr complexes and 1:2 Co complexes based on 
dyestuffs of the formula (I) and mixtures thereof are also preferred. 
Those 1:2 Cr complexes and Co complexes based on identical or different azo 
dyestuffs which contain only one reactive group are also particularly 
valuable. 
Quite generally, preferred dyestuffs are the 1:2 Cr complexes and 1:2 Co 
complexes of dyestuffs of the formula 
##STR8## 
wherein D.sub.1 is an optionally substituted o-hydroxy-phenyl, 
o-carboxyphenyl radical or o-hydroxynaphthyl radical and 
##STR9## 
is the radical of an aminohydroxynaphthalene, aminophenol or pyrazolone 
containing amino groups, which couples in the o-position relative to the 
phenolic or enolic OH group. 
In the case where 
##STR10## 
is bonded to K or K.sub.1, examples of suitable radicals D or D.sub.1 are 
o-hydroxyphenyl and o-carboxyphenyl as well as o-hydroxynaphthyl, which 
can contain substituents, such as sulpho, halogen, in particular Cl and 
Br, nitro, alkyl, in particular C.sub.1 -C.sub.4 -alkyl, and alkoxy, in 
particular C.sub.1 -C.sub.4 -alkoxy. 
Examples of preferred radicals D or D.sub.1 are 2-hydroxyphenyl, 
2-hydroxy-5-nitro-phenyl, 2-hydroxy-3-sulpho-5-nitro-phenyl, 
2-hydroxy-3-nitro-5-sulphophenyl, 2-hydroxy-5-sulphophenyl, 
2-hydroxy-4-sulphophenyl, 2-hydroxy-3-chloro-5-sulpho-phenyl, 
2-hydroxy-5-chlorophenyl, 2-hydroxy-3-sulpho-5-chlorophenyl, 
2-hydroxy-3-nitro-5-chlorophenyl, 2-hydroxy-3-chloro-5-nitrophenyl, 
2-hydroxy-3,5-dinitro-phenyl, 2-hydroxy-3,5-dichlorophenyl, 
2-hydroxy-4-nitro-phenyl, 2-hydroxy-5-methyl-phenyl, 
2-hydroxy-4-methyl-phenyl, 2-carboxy-phenyl, 2-hydroxy-4-sulpho-naphthyl 
and 2-hydroxy-4-sulpho-6-nitronaphthyl. 
Examples of suitable radicals 
##STR11## 
Examples of suitable radicals 
##STR12## 
are o-hydroxy-amino-sulpho-naphthyl radicals and aminophenylpyrazolonyl 
and aminonaphthylpyrazolonyl radicals. 
Examples of radicals of this type are 
##STR13## 
R.sub.3 =C.sub.1 -C.sub.4 -alkyl, COOH, CONH.sub.2 or CN. 
The ring A can contain further substituents, in particular Cl, Br, C.sub.1 
-C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or sulpho. 
Particularly suitable radicals of this type are 
##STR14## 
examples of radicals K and K.sub.1 which are free from reactive groups are 
o-hydroxyphenyl radicals, o-hydroxynaphthyl radicals, 
o-hydroxy-sulphonaphthyl radicals, phenyl-pyrazolyl radicals and the 
radical of an acetoacetanilide. 
Examples of radicals of this type are: 
##STR15## 
R.sub.3 =C.sub.1 -C.sub.4 -alkyl, CN, COOH or CONH.sub.2 ; it being 
possible for the ring A to contain further substituents, in particular Cl, 
Br, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or sulpho. 
Particularly suitable radicals of this type are 
##STR16## 
The ring B can contain further substituents, such as Cl, Br, C.sub.1 
-C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or sulpho. 
Particularly suitable radicals of this type are 
##STR17## 
Examples of suitable radicals R-R.sub.2 are H, alkyl, in particular C.sub.1 
-C.sub.4 -alkyl, and aralkyl. 
Suitable radicals Y are, in particular, halogen, such as F, Cl and Br. 
Suitable bridge members Z are, in particular, optionally substituted 
phenylene, naphthylene and alkylene. Substituents which may be mentioned 
here are: sulpho, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy and 
halogen. The following bridge members may be mentioned as examples: 
##STR18## 
Preferred dyestuffs are the 1:2 Cr complexes and 1:2 Co complexes of 
dyestuffs of the formulae: 
##STR19## 
The dyestuffs IV-VIII which contain H, NH.sub.2, acetylamino or 
benzoylamino instead of --NH--W are particularly suitable as the second 
component for metal complex dyestuffs with only one reactive group, in 
particular for those with the particular dyestuffs IV to VIII. 
##STR20## 
R.sub.4 =NO.sub.2, SO.sub.3 H or Cl, R.sub.5 =SO.sub.3 H, halogen, in 
particular Cl, or C.sub.1 -C.sub.4 -alkyl and 
R.sub.3 =C.sub.1 -C.sub.4 -alkyl, CN, COOH or CONH.sub.2. 
Furthermore, those dyestuffs of the formulae indicated above, in which 
##STR21## 
are preferred. 
Amongst the dyestuffs (III)-(VIII), those symmetric or asymmetric 1:2 Cr 
complexes or 1:2 Co complexes in which the 2nd dyestuff is also a dyestuff 
of the general formula (III)-(VIII), or mixtures of these Cr and Co 
complexes, are preferred. 
The following are examples of dyestuffs which are preferred as the second 
component in the 1:2 Cr mixed complexes and 1:2 Co mixed complexes 
##STR22## 
Further suitable dyestuffs are described, for example, in Belgian Pat. No. 
664,682. 
The cobalt mixed complexes which are obtained by forming the mixed cobalt 
complex of a dyestuff of the formula (IV) and of a dyestuff of the formula 
(VIII) are also particularly suitable dyestuffs. The ratio of (IV) to 
(VIII) can vary within wide limits and is appropriately 0.1:1 to 0.1, 
preferably 0.5:1 to 1:0.5. 
The dyestuffs are prepared in a manner which is in itself known: 
(A) 1:1 or 1:2 metal complexes based on at least one metallisable dyestuff 
of the formula 
##STR23## 
are reacted with a compound of the formula 
##STR24## 
wherein Y.sub.1 =a radical which can be split off, in particular halogen, 
such as Cl, 
preferably with 1 mol of (XI) per --NH--R group. 
The 1:2 complexes are prepared in a known manner by metallising the 
corresponding azo dyestuffs. 
The compound (XI) and its preparation are described in DT-OS (German 
Published Specification) No. 2,607,028. 
(B) 1:1 or 1:2 metal complexes of dyestuffs of the formula (X) are first 
reacted with 1 mol, per --NH--R group, of a compound (XII) 
##STR25## 
wherein Y, Y.sub.1 and Y.sub.2 =a radical which can be split off, in 
particular halogen, such as Cl, 
and the products are then reacted with the equivalent amount 
##STR26## 
wherein R.sub.1, Z and R.sub.2 have the meaning indicated above. 
The calculated amount of a solution of cyanuric chloride in an organic 
solvent, such as acetone, or of an aqueous suspension is introduced, for 
example, into the solution or suspension, adjusted to 0.degree. C., of the 
metal complex dyestuff, the pH we kept at 4-7 with an alkali, for example 
dilute sodium carbonate solution. The mixture is stirred at 0.degree. 
until the starting dyestuff has disappeared, and the calculated amount of 
an aqueous solution or aqueous paste of 
##STR27## 
is then introduced. The pH of the reaction solution is kept at 4-6.5 by 
adding an alkali, such as dilute sodium carbonate solution, the reaction 
solution being warmed to 40.degree.-50.degree.. The reaction has ended 
after 2-5 hours. 
(C) Dyestuffs of the formula 
##STR28## 
are first reacted according to one of the processes described in A and B 
to give a reactive dyestuff of the formula 
##STR29## 
and the product is then converted into the 1:1 or 1:2 metal complex 
dyestuff in a known manner. 
(D) Alternatively, a suitable coupling component is first reacted with the 
reactive component according to one of the processes described in A or B, 
a diazo component is coupled to the product and the coupling product is 
metallised. 
(E) Chromium mixed complex reactive dyestuffs of the formula 
##STR30## 
are prepared by a process in which the 1:1 Cr complex, free from reactive 
groups, of one of the two monoazo dyestuffs is prepared by customary 
processes, this complex is reacted with the 2nd monoazo dyestuff, free 
from reactive groups, to give the chromium mixed complex and finally this 
complex is converted into the reactive dyestuff by one of the processes 
described in A and B. 
The new dyestuffs are suitable for dyeing and printing materials containing 
Hydroxyl groups and N-containing materials, such as cotton, wool and the 
like, by the customary processes. 
The formulae indicated in the description are those of the free acids, 
unless otherwise indicated. In general, the salts, in particular the 
alkali metal salts, and preferably the sodium salts, potassium salts or 
lithium salts, are obtained in the preparation and dyeing is also 
generally carried out with these salts.

EXAMPLE 1 
A solution of 18.5 parts by weight of cyanuric chloride in 140 parts by 
volume of acetone is added dropwise, at 0.degree. C. in the course of 30 
minutes, to a solution of the 1:2 Co complex obtained from 0.1 mol of the 
monoazo dyestuff of the formula 
##STR31## 
in 600 parts by volume of water. The pH is kept at 4-5.5 with about 28 
parts by volume of 20% strength by volume sodium carbonate solution and 
the mixture is stirred at 0.degree. C. for 2 hours. 0.1 Mol of the 
reactive component of the formula 
##STR32## 
(prepared by reacting 2,4,6-trifluoro-5-chloropyrimidine with 
2,4-diamino-benzene-1-sulphonic acid) is then introduced and the mixture 
is stirred, warmed to 40.degree.-50.degree. C. and stirred at 
40.degree.-50.degree. for 6 hours, the pH being kept at 5-6 with 20% 
strength by volume sodium carbonate solution. The mixture is then 
clarified and the filtrate is evaporated in a rotary evaporator at 
70.degree.-80.degree.. 
When pulverised, the dyestuff is a black powder which gives a fast reactive 
print in corinth shades on cotton and viscose staple. 
EXAMPLE 2 
1,000 parts by volume of an aqueous solution of 0.1 mol of the reactive 
component 
##STR33## 
are added dropwise, at 40.degree.-50.degree. C. and at pH 6.5, to a 
solution of the 1:2 Cr complex obtained from 0.1 mol of the monoazo 
dyestuff of the formula 
##STR34## 
in 600 parts by volume of water. The pH is kept at 5.5-6.5 with 20% 
strength by volume sodium carbonate solution and the mixture is stirred at 
40.degree.-50.degree. for 5 hours. After clarifying, the filtrate is 
evaporated to dryness in a rotary evaporator at 70.degree. C. When 
pulverised, the dyestuff is a black powder which gives, under printing 
conditions for reactive dyestuffs, a greenish-tinged grey with good 
fastness properties on cotton and viscose staple. 
The reactive component is prepared by stirring 0.1 mol of the compound 
##STR35## 
in 520 parts by volume of water and cooling the mixture to 0.degree. C. 
with 140 parts by weight of ice. A solution of 18.5 parts by weight of 
cyanuric chloride in 140 parts by volume of acetone is added dropwise to 
the solution in the course of 45 minutes, the pH being kept at 5.5-6.5 
with 20% strength by volume sodium carbonate solution. The mixture is 
subsequently stirred at 0.degree.-2.degree. C. and pH 5.5-6.5 for 2 hours 
and is clarified. 
EXAMPLE 3 
A solution of the 1:2 Cr complex obtained from 0.2 mol of the monoazo 
dyestuff of the formula 
##STR36## 
and 1:2 Co complex obtained from 0.1 mol of the same monoazo dyestuff in 
1,150 parts by volume of water is cooled to 0.degree. by external cooling. 
The pH of the solution is 6. A suspension of 55.6 parts by weight of 
cyanuric chloride in 100 parts by volume of water, 200 parts by weight of 
ice and 4.15 parts by weight of a commercially available nonionic 
emulsifier based on fatty alcohol polyglycol ether is then introduced. The 
mixture is stirred at 0.degree. C. for 2 hours; the pH is kept at 5-6 with 
20% strength by volume sodium carbonate solution. Thereafter, 0.3 mol of 
the reactive component 
##STR37## 
is added in the form of an aqueous paste and the mixture is warmed to 
40.degree.-50.degree. C. and stirred at 40.degree.-50.degree. C. for 4 
hours, the pH of the reaction solution being kept at 5-6 with 20% strength 
by volume sodium carbonate solution. The reaction solution is clarified 
with a little active charcoal and the solution is evaporated in a rotary 
evaporator at 70.degree. C. After pulverising, a black powder is obtained 
which gives neutral black reactive prints with good fastness properties on 
cotton and viscose staple. 
In a manner analogous to that described in Examples 1-3, using the 
corresponding starting compounds gives the dyestuffs described in the 
table which follows, which dye cellulose materials in the colour shades 
indicated. 
__________________________________________________________________________ 
Metal 
Dyestuff complex Colour 
__________________________________________________________________________ 
##STR38## 1:2 Cr greenish-tinged black 
##STR39## 1:2 Cr brown 
##STR40## 1:2 Co brown 
##STR41## 1:2 Co brown 
##STR42## 1:2 Co brown 
##STR43## 1:2 Co brownish-tinged yellow 
##STR44## 1:2 Co brownish-tinged orange 
##STR45## 1:2 Co reddish-tinged brown 
##STR46## 1:2 Co reddish-tinged brown 
##STR47## 1:2 Co black 
##STR48## 1:2 Cr black 
##STR49## 1:2 Co corinth 
##STR50## Mixture of 1:2 Cr and 1:2 Co, 
molar ratio 2:1 
black 
##STR51## Mixture of 1:2 Cr and 1:2 Co, 
molar ratio 2:1 
black 
##STR52## 1:2 Cr blue 
##STR53## 1:2 Co reddish-tinged navy 
blue 
##STR54## 1:2 Cr navy blue 
##STR55## 1:2 Co corinth 
##STR56## 1:2 Cr greenish-tinged grey 
##STR57## 1:2 Co corinth 
##STR58## 1:2 Cr grey 
##STR59## 1:2 Cr grey 
##STR60## 1:2 Cr grey 
##STR61## 1:2 Cr grey 
Formation of the mixed cobalt complex, Metal 
Molar ratio 1:1 complex Colour 
__________________________________________________________________________ 
##STR62## 1:2 Co brown 
Mixture of the 1:2 Co complexes, 
Molar ratio 1:1 Colour 
__________________________________________________________________________ 
##STR63## brown 
##STR64## 
##STR65## brown 
##STR66## brown 
##STR67## 
Metal 
Dyestuff complex Colour 
__________________________________________________________________________ 
##STR68## 1:2 Cr black 
##STR69## 1:2 Co black 
##STR70## 1:2 Co brown 
##STR71## Mixture of 1:2 Cr and 1:2 Co, 
molar ratio 2:1 
black 
##STR72## Mixture of 1:2 Cr and 1:2 Co, 
molar ratio 2:1 
black 
##STR73## Mixture of 1:2 Cr and 1:2 Co, 
molar ratio 2:1 
black 
__________________________________________________________________________ 
EXAMPLE 4 
0.1 mol of the 1:1 Cr complex of the monoazo dyestuff of the formula 
##STR74## 
and 0.1 mol of the monoazo dyestuff of the formula 
##STR75## 
are stirred in 700 parts by volume of water, the mixture is warmed to 
70.degree. and the dyestuffs are converted into the chromium mixed complex 
at pH 6-7 in the course of 2 hours. The mixture is clarified with a little 
active charcoal, 1,000 parts by volume of an aqueous solution of 0.1 mol 
of 
##STR76## 
(preparation described in Example 2) are added and the mixture is stirred 
at 40.degree.-50.degree. C. for 5 hours, the pH being kept at 5-6 with 20% 
strength by volume sodium carbonate solution. 
In order to isolate the reactive dyestuff, the mixture is evaporated in a 
rotary evaporator at a water bath temperature of 70.degree.. A black 
dyestuff powder is obtained which, under printing conditions for reactive 
dyestuffs, gives a black with good fastness properties on cotton. 
In an analogous manner, using the corresponding starting compounds gives 
the dyestuffs described in the table which follows, which dye cellulose 
materials in the colour shades indicated. 
__________________________________________________________________________ 
Chromium mixed complex Colour 
__________________________________________________________________________ 
##STR77## brown 
##STR78## olive 
##STR79## olive 
##STR80## green 
##STR81## brown 
##STR82## brown 
##STR83## brown 
##STR84## brown 
##STR85## brown 
##STR86## brown 
##STR87## brown 
##STR88## brown 
##STR89## black 
##STR90## black 
__________________________________________________________________________ 
##STR91## 
EXAMPLE 5 
Cellulose fabric is printed with a printing paste consisting of 80 g of the 
dyestuff from Example 3, 150 g of urea, 20 g of sodium bicarbonate, 10 g 
of the sodium salt of m-nitrobenzenesulphonic acid, 240 g of water and 500 
g of 4% strength alginate thickener, dried, steamed at 100.degree. C. for 
2 minutes and rinsed with hot water. A neutral black print with good 
fastness to washing and light is obtained. 
EXAMPLE 6 
0.1 mol of the copper complex of the aminoazo dyestuff of the formula 
##STR92## 
prepared in a known manner by coupling diazotised 
2-amino-naphthalene-4,8-disulphonic acid with 
1-acetylamino-8-hydroxynaphthalene-3,6-disulphonic acid, oxidative 
coppering of the coupling product and alkaline saponification of the 
N-acetyl group, are dissolved in 750 ml of water under neutral conditions. 
A solution of 0.1 mol of 
4-(2,4-difluoro-5-chloropyrimidyl)-amino-2-aminobenzenesulphonic acid in 
about 1,000 ml of water is added dropwise to 0.1 mol of a cyanuric 
chloride suspension in ice-water at 0.degree. and the pH of the mixture is 
kept at 5.5 by adding 20% strength sodium carbonate solution dropwise, 
until the reaction has ended. The mixture is then combined with the 
dyestuff solution described above. A pH value of 5-6 is maintained, at 
40.degree., by adding 20% strength sodium carbonate solution dropwise, 
until the condensation reaction has ended. The product is isolated in the 
customary manner, for example by salting out with sodium chloride. The 
dried dyestuff is a dark powder which dissolves in water giving a 
blue-coloured solution and dyes cotton by the known dyeing and printing 
processes for reactive dyestuffs in dark blue shades with a good degree of 
fixing. 
If instead of 
4-(2,4-difluoro-5-chloropyrimidyl)-amino-2-aminobenzenesulphonic acid, the 
equivalent amount of 
5-(2,4-difluoro-5-chloropyrimidyl)-amino-2-aminobenzenesulphonic acid is 
used for the preparation of the reactive component, a similar dark blue 
reactive dyestuff is obtained. 
If the copper complex compounds of the formulae 
##STR93## 
prepared in the customary manner are used as the dyestuff component, after 
reaction with the reactive components described, reactive dyestuffs are 
obtained which dye cotton in violet shades. 
If the copper complex of the disazo dyestuff of the formula 
##STR94## 
is used as the dyestuff component and the reaction is carried out with the 
reactive components described above, dark blue reactive dyestuffs are 
obtained.