Dyestuffs of the formula ##STR1## where the substituents are defined as in the descriptive part are highly suitable for dyeing and printing hydroxyl- or amide-containing materials. They produce bright dyeings and prints having good fastness properties.

The present invention relates to new triphendioxazine dyestuffs which 
contain reactive groups and have the general formula 
##STR2## 
where T.sub.1 and T.sub.2 are each H, Cl, Br, F, C.sub.1 -C.sub.4 -alkoxy, 
C.sub.1 -C.sub.4 -alkyl, optionally substituted phenyl or phenoxy, 
preferably Cl, 
and wherein 
the benzene rings D and the naphthalene rings can be further substituted, 
and wherein 
B is SO.sub.2 CH.dbd.CH.sub.2 or SO.sub.2 CH.sub.2 CH.sub.2 Z 
wherein 
Z is a detachable group such as 
##STR3## 
preferably OSO.sub.3 H, E is SO.sub.3 H, COOH or an optionally 
substituted sulphonamide group, 
W.sub.1 is a direct bond or a bridge member which is free of heterocyclic 
groups and is bonded to an aromatically carbocyclic C atom in T, SO.sub.2 
B being bonded to a C atom in W.sub.1 or, if W.sub.1 is a direct bond, to 
an aromatically carbocyclic C atom in T, X is O, NR or S 
where 
R is H or optionally substituted C.sub.1 -C.sub.4 -alkyl, 
W.sub.2 is an aliphatic, araliphatic or aromatically carbocyclic bridge 
member, 
a is 0 to 2, 
b is 0 to 2, a+b being 0 or 2, wherein if a+b=0 W.sub.1 has at least one 
anionic group conferring water-solubility, in particular a sulpho group or 
2 SO.sub.2 B groups are bonded to W.sub.1, 
and wherein, if E is SO.sub.3 H and a is 2, W.sub.1 represents W.sub.3, 
W.sub.3 being 
##STR4## 
wherein X is as defined above, 
Y is a direct bond or C.sub.1 -C.sub.6 -alkylene which is optionally 
substituted and/or optionally interrupted by hetero atoms, 
X.sub.1 is a direct bond, O or NR, preferably NH, and 
the benzene or naphthalene nucleus A can be substituted or 
EQU --X--Y.sub.1 -- (1d) 
wherein 
X is as defined above and 
Y.sub.1 is C.sub.2 -C.sub.6 -alkylene which is optionally interrupted by 
hetero atoms. 
Suitable W.sub.1 radicals, in addition to those mentioned for W.sub.3, are 
for example as follows: 
EQU --X--aralkylene-- (1f) 
wherein 
X is as defined above and 
aralkylene represents optionally further-substituted C.sub.1 -C.sub.6 
-alkylenephenylene, phenylene-C.sub.1 -C.sub.6 -alkylene, C.sub.1 -C.sub.6 
-alkylenenaphthylene or naphthylene-C.sub.1 -C.sub.6 -alkylene, or 
##STR5## 
wherein R is as defined above and 
the benzene or naphthalene nucleus G can be substituted. 
Preferred radicals W.sub.3 are 
##STR6## 
radicals. 
The optionally substituted sulphonamide radical E in the formula (1) 
preferably contains water-solubilising groups such as SO.sub.3 H or COOH. 
E represents in particular the following groupings E.sub.1 : 
(a) A radical of the formula 
##STR7## 
where R' is C.sub.2 -C.sub.6 -alkylene(O).sub.0 or .sub.1 --SO.sub.3 H and 
R is as defined above. 
(b) A radical of the formula SO.sub.2 --NH--SO.sub.2 R.sub.1 where 
R.sub.1 represents optionally substituted alkyl (preferably CH.sub.3) or 
optionally substituted aryl (in particular phenyl), 
(c) A radical of the formula 
##STR8## 
where R'.sub.1 is an aromatic radical having at least one SO.sub.3 H 
group, preferably a phenyl radical having 1 or 2 SO.sub.3 H groups. 
Examples of optionally substituted R are CH.sub.3, C.sub.2 H.sub.5, 
n-C.sub.3 H.sub.7 and n-C.sub.4 H.sub.9, all of which can be substituted 
by OH, OCH.sub.3, COOH and SO.sub.3 H. 
Substituents of the optionally substituted phenyl and phenoxy radicals 
T.sub.1 and T.sub.2 are for example, Cl, CH.sub.3, C.sub.2 H.sub.5, 
OCH.sub.3 and OC.sub.2 H.sub.5. 
Examples of substituents of benzene rings D and the naphthalalene rings in 
formulae (1a) and (1b) respectively are Cl, Br, CH.sub.3, C.sub.2 H.sub.5, 
CH.sub.3 O, C.sub.2 H.sub.5 O and COOH. 
Examples of substituents of the benzene and naphthalene rings A and G 
respectively are Cl, Br, CH.sub.3, OCH.sub.3, COOH, SO.sub.3 H, SO.sub.2 
NHCH.sub.3, SO.sub.2 NH.sub.2, OC.sub.2 H.sub.5 and C.sub.2 H.sub.5. 
In formula (1a) the substituent --W.sub.1 --(SO.sub.2 B).sub.1-2 is 
preferably in the o-position relative to one of the two substituents E or 
--X--W.sub.2 --SO.sub.3 H. 
Preferred dyestuffs (1) have the formulae (2) to (5b): 
##STR9## 
wherein X, Y, X.sub.1, T.sub.1, T.sub.2, A, B and E.sub.1 are as defined 
above 
and wherein 
the sulpho group in the formula (2) and the radical E.sub.1 in the formula 
(2a) are in the o-position relative to the substituent 
##STR10## 
and wherein the nucleus D can be substituted by Cl, CH.sub.3, OCH.sub.3 or 
COOH and 
n is 1 or 2; 
##STR11## 
wherein X, B, T.sub.1, T.sub.2, D and E.sub.1 are as defined above and 
Y.sub.1 is C.sub.2 -C.sub.6 -alkylene which is optionally interrupted by 
hetero atoms 
and wherein 
the sulpho group in the formula (3) and the radical E.sub.1 in the formula 
(3a) are in the o-position relative to the substituent --X--Y.sub.1 
--SO.sub.2 B; 
##STR12## 
wherein n, B, T.sub.1 and T.sub.2 are as defined above; 
##STR13## 
wherein X.sub.2 is a direct bond, an arylene radical (preferably 
phenylene) which is substituted for example by SO.sub.3 H, Cl, OCH.sub.3, 
CH.sub.3, C.sub.2 H.sub.5, COOH or NH.sub.2, or an araliphatic radical, 
the SO.sub.2 B group is in the o-position relative to the substituent 
--X--Y--X.sub.2 --SO.sub.3 H and 
X, Y, B, T.sub.1, T.sub.2 and D are as defined above; 
##STR14## 
wherein n, B, T.sub.1, T.sub.2, X, Y, X.sub.2, D and G are as defined 
above 
and wherein 
the radical 
##STR15## 
in the formula (5a) and the radical 
##STR16## 
in the formula (5b) are in the o-position relative to the substituent 
--X--Y--X.sub.2 --SO.sub.3 H. 
Examples of suitable araliphatic radicals are phenylalkylene radicals whose 
alkylene chain can be interrupted by hetero atoms or by groups containing 
hetero atoms, such as 
##STR17## 
C.sub.1 -C.sub.6 -Alkylene Y is preferably substituted by COOH, SO.sub.3 H, 
halogen or optionally SO.sub.3 H-substituted phenyl. Interrupting hetero 
atoms are preferably O, S and N. 
##STR18## 
The invention also provides dyestuffs of the formula 
##STR19## 
wherein X, W.sub.2, T.sub.1, T.sub.2 and B are as defined above and 
K is COOH or --SO.sub.2 NH--SO.sub.2 R.sub.1, wherein R.sub.1 is as defined 
above, 
and wherein 
the group --SO.sub.2 B is in the o-position relative to the group 
--X--W.sub.2 --K. 
In the formulae (1) to (5c), the following groupings have a preferred 
meaning: 
(1), (2) to (5c): B=CH.sub.2 CH.sub.2 OSO.sub.3 H 
(2) to (5c): T.sub.1, T.sub.2 =Cl 
(2) to (3a), (5) to (5c): X=NH, D is unsubstituted 
(2) and (2a): X.sub.1 =direct bond Y=direct bond or --CH.sub.2 --, 
--CH.sub.2 --CH.sub.2 -- the radical 
##STR20## 
preferably represents 
##STR21## 
(3), (3a): Y.sub.1 =--CH.sub.2 --CH.sub.2 -- (5), (5a), (5b): X.sub.2 
=direct bond and Y=--CH.sub.2 --CH.sub.13 or Y=direct bond and 
##STR22## 
The invention also provides a process for preparing the dyestuffs of the 
formula (2), (2a), (3), (3a), (4), (5), (5a) and (5b) which is 
characterised in that the diarylides of the formulae 
##STR23## 
are treated with an acid condensing agent which, through elimination of 
hydrogen, causes ring closure to the triphendioxazine system. The acid 
condensing agent used is 10 to 50% strength oleum. The reaction 
temperature is of the order of 0.degree. to 80.degree. C., preferably 
20.degree. to 60.degree. C. For instance, the diarylides can be cyclised 
at temperatures of 10.degree. to 50.degree. C., preferably 20.degree. to 
40.degree. C., with 5 to 10 times the weight of 30-50% strength, 
preferably 35-40% strength, oleum. 
The diarylides can also be cyclised in accordance with British Patent 
Specification No. 1,589,915, where the reaction is carried out at 
0.degree. to 60.degree. C. in 5 to 30% strength oleum with 1-3 moles of 
persulphate per mole of diarylide. 
Examples of ring closures with oleum are found in German 
Offenlegungsschrift No. 2,503,611. 
It is particularly preferred to prepare compounds of the formula (2) to 
(5c) in which B is CH.sub.2 CH.sub.2 OSO.sub.3, the starting material 
being compounds of the formulae (6) to (9c) in which B is CH.sub.2 
CH.sub.2 OH. 
The ring closure in oleum is accompanied by a sulphation of the OH group to 
the sulphuric acid ester. 
Further aliphatic OH groups are sulphated under the conditions of the ring 
closure, and sulphations of aromatic rings can occur. 
The diarylides of the formulae (6) to (9c) can be prepared by known 
methods, as mentioned, for example, in German Offenlegungsschriften Nos. 
2,302,382, 2,344,781, 2,503,611 and 2,823,828 and in British Patent 
Specification No. 2,059,985. For instance, 1 mole of a p-benzoquinone, in 
particular 2,3,5,6-tetrachloro-1,4-benzoquinone, can be reacted with 2 
moles of a compound of the formula 
##STR24## 
wherein B.sub.1 is B or CH.sub.2 CH.sub.2 OH to give the diarylides of the 
formulae (6) to (9c). 
The following are examples of amines of the formulae (10) to (13c): 
##STR25## 
p-Benzoquinones suitable for the condensation with the amines of the 
formulae (10) to (13c), in addition to the 2,3,5,6-tetrachlorobenzoquinone 
already mentioned, are (reactions of this type are described in detail in 
German Offenlegungsschrift No. 2,823,828): 1,4-benzoquinone, 
2-methyl-1,4-benzoquinone, 2-ethyl-1,4-benzoquinone, 
2-n-propyl-1,4-benzoquinone, 2-isopropyl-1,4-benzoquinone, 
2,2'-ethoxyethyl-1,4-benzoquinone, 2-phenyl-1,4-benzoquinone, 
2-(4'-methylphenyl)-1,4-benzoquinone, 
2-(4'-methoxyphenyl)-1,4-benzoquinone, 
2-(3'-chlorophenyl-1,4-benzoquinone, 2-(4'-nitrophenyl)-1,4-benzoquinone, 
2,5-dimethyl-1,4-benzoquinone, 2-methyl-5-ethyl-1,4-benzoquinone, 
2-methyl-3-chloro-1,4-benzoquinone, 2-methyl-6-chloro-1,4-benzoquinone, 
2-methyl-3,5-dichloro-1,4-benzoquinone, 
2-methyl-3,5,6-tribromo-1,4-benzoquinone, 
2-(4'-methylphenoxy)-3,6-dibromo-1,4-benzoquinone, 
2-(3'-methylphenoxy)-3,6-dibromo-1,4-benzoquinone, 
2-methyl-3,5,6-trichloro-1,4-benzoquinone, 
2-methyl-3-chloro-5-bromo-1,4-benzoquinone, 
2-methyl-3,6-dichloro-1,4-benzoquinone, 2-methyl-3,6-dichloro-5-bromo- 
1,4-benzoquinone, 2-phenyl-3,6-dichloro-1,4-benzoquinone, 
2-(4'-methoxyphenyl)-3,6-dichloro-1,4-benzoquinone, 
2-(4'-chlorophenyl)-3,6-dichloro-1,4-benzoquinone, 
2-(4'-nitrophenyl)-3,6-dichloro-1,4-benzoquinone, 
2-(4'-nitrophenyl-3,5,6-trichloro-1,4-benzoquinone, 
2,5-dimethyl-3,6-dibromo-1,4-benzoquinone, 
2,5-dimethyl-3-chloro-1,4-benzoquinone, 
2-methyl-5-n-propyl-6-bromo-1,4-benzoquinone, 
2-methyl-5-isopropyl-3-chloro-1,4-benzoquinone, 
2-methyl-5-isopropyl-6-bromo-1,4-benzoquinone and 
2-(2'-chlorophenyl)-3,5,6-tribromo-1,4-benzoquinone, 
2-methyl-3-methoxy-1,4-benzoquinone, 
2,3,5,6-tetramethoxy-1,4-benzoquinone, 2,3,5,6-tetraphenoxy-1,4-benzoquino 
ne, 2,3,5,6-tetra-(4'-methylphenoxy)-1,4-benzoquinone, 
2,3,5,6-tetra-(4'-methoxyphenoxy)-1,4-benzoquinone, 
2,3,5,6-tetra-(4'-chlorophenoxy)-1,4-benzoquinone, 
2,3,5,6-tetra-4-(3'-methyl-4'-chlorophenoxy)-1,4-benzoquinone, 
2-ethyl-3,6-dimethoxy-1,4-benzoquinone, 
2-chloro-3,6-dimethoxy-1,4-benzoquinone, 
2,3,5-trimethoxy-1,4-benzoquinone, 2,5-dimethyl-3,6-dimethoxy-1,4-benzoqui 
none, 2,5-dimethyl-3,6-dimethoxy-1,4-benzoquinone, 
2-methyl-3,6-dimethoxy-1,4-benzoquinone, 2-methyl-5,6-dimethoxy-1,4 
-benzoquinone, 2-ethyl-3,6-dimethoxy-1,4-benzoquinone, 
2-chloro-3-n-propyl-5-methoxy-1,4-benzoquinone, 
2-chloro-3,5-dimethoxy-1,4-benzoquinone and 
2,3,5,6-tetrabromo-1,4-benzoquinone. 
The new dyestuffs of the formula (1) are suitable for dyeing and printing 
hydroxyl- or amide-containing materials, such as textile fibres, yarns and 
fabrics made of wool, silk, nylon and polyurethane fibres, and for the 
wash-fast dyeing and printing of natural or regenerated cellulose, 
cellulose materials being advantageously treated in the presence of 
acid-binding agents and, if desired, under heat, using the processes 
disclosed for reactive dyestuffs of the type according to the invention. 
The formulae shown are those of the corresponding free acids. The dyestuffs 
are generally isolated, and used in dyeing, in the form of the alkali 
metal salts, in particular the sodium salts. 
The weights referred to in the examples relate to the free acid. The colour 
codes shown in the examples are the indicator numbers given in the Colour 
Index hue indication chart. 
The formulae given in the following examples always refer to one of the 
isomeric reaction products formed in the reaction; as to the position of 
the substituents in the two outer aromatic rings of the triphendioxazine 
system of the isomeric reaction products, reference is made to what was 
said under formulae (2) to (5c).