Amino-fluoro-S-triazine disazo dyes of the H-acid series

Reactive dyes useful for dyeing natural and synthetic fibers of the formula ##STR1## in which D.sub.1 is a benzene or naphthalene radical, which can be substituted, D.sub.2 is a benzene radical, which can be substituted, R.sub.1 is hydrogen or C.sub.1-4 -alkyl, the bridge member --N(R.sub.1)-- is bonded to a ring carbon atom of D.sub.2, R.sub.2 is hydrogen or C.sub.1-4 -alkyl, which can be substituted, and R.sub.3 is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl.

The invention relates to reactive dyes of the formula 
##STR2## 
in which D.sub.1 is a benzene or naphthalene radical, which can be 
substituted, D.sub.2 is a benzene radical, which can be substituted, 
R.sub.1 is hydrogen or C.sub.1-4 -alkyl, the bridge member --N(R.sub.1)-- 
is bonded to a ring carbon atom of D.sub.2, R.sub.2 is hydrogen or 
C.sub.1-4 -alkyl, which can be substituted, and R.sub.3 is hydrogen or 
substituted or unsubstituted alkyl, cycloalkyl, aralkyl or aryl. 
The radicals D.sub.1 and D.sub.2 can contain the substituents customary in 
azo dyes. Examples of suitable further substituents are the following: 
alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 
isopropyl and butyl, alkoxy groups having 1 to 4 carbon atoms, such as 
methoxy, ethoxy, propoxy, isopropoxy and butoxy, acylamino groups having 1 
to 6 carbon atoms, such as acetylamino, propionylamino and benzoylamino, 
carbamoyl, sulfamoyl, amino groups, such as --NH.sub.2, methylamino and 
ethylamino, the ureido, hydroxyl and carboxyl group, halogen, such as 
fluorine, chlorine and bromine, and the sulfonic acid group. 
The radicals D.sub.1 and D.sub.2 contain in particular one or more sulfonic 
acid groups as further substituents. C.sub.1-4 -alkyl R.sub.1 can be: 
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl and 
tert.-butyl. An alkyl radical R.sub.2 can be substituted, for example by 
chlorine, hydroxyl, cyano, methoxy, carboxyl and sulfo. Examples of 
R.sub.2 are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 
sec.-butyl, tert.-butyl, .beta.-hydroxyethyl, .beta.-chloroethyl, 
.beta.-cyanoethyl, cyanomethyl, .gamma.-cyanopropyl, .beta.-methoxyethyl, 
.beta.-carboxyethyl, sulfomethyl and .beta.-sulfoethyl. Examples of 
R.sub.3 are: hydrogen, the same substituted and unsubstituted alkyl 
radicals which have been mentioned above for R.sub.2, methoxypropyl, 
ethoxyethyl, ethyoxypropyl and methoxybutyl, cyclohexyl, benzyl, 
4-sulfobenzyl, 4-methylbenzyl, phenethyl and in particular phenyl, which 
can be substituted by C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, acetylamino, 
ureido, carboxyl, halogen, sulfo, sulfomethyl, trifluoromethyl, sulfamoyl 
and carbamoyl, or naphthyl, which can be substituted by sulfo; R.sub.2 and 
R.sub.3 can also be closed to form a six-membered N-heterocyclic ring, 
which can contain a further hetero-atom, such as nitrogen, oxygen and 
sulfur. Examples of the amino radical --NR.sub.2 R.sub.3 in formula (1) 
are: --NH.sub.2, methylamino, ethylamino, propylamino, isopropylamino, 
butylamino, .beta.-methoxyethylamino, .gamma.-methoxypropylamino, 
N,N-dimethylamino, N,N-diethylamino, N-methyl-N-phenylamino, 
N-ethyl-N-phenylamino, .beta.-chloroethylamino, .beta.-hydroxyethylamino, 
.gamma.-hydroxypropylamino, benzylamino, cyclohexylamino, morpholino, 
piperidino, piperazino and, in particular, aromatic amino groups, such as 
phenylamino, toluidino, chloroanilino, anisidino, phenetidino, 2-, 3-and 
4-sulfoanilino, 2,5-disulfoanilino, sulfomethylanilino, 
N-sulfomethylanilino, 3- and 4-carboxyphenylamino, 
2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 
4-sulfonaphth-1-yl-amino, 3,6-disulfonaphth-1-yl-amino, 
3,6,8-trisulfonaphth-1-yl-amino and 4,6,8-trisulfonaphth-1-yl-amino. 
The disazo dyes of the formula (1) are fibre-reactive since they contain a 
detachable fluorine atom in the s-triazine radical. 
Fibre-reactive compounds are to be understood as meaning those which are 
able to react with the hydroxyl groups of cellulose or with the amino 
groups of natural or synthetic polyamides with the formation of covalent 
chemical bonds. 
The radical D.sub.1 does not contain a reactive radical. 
Preferred reactive dyes are those of the formula 
##STR3## 
in which one Y is hydrogen and the other Y is sulfo and D.sub.1, R.sub.2 
and R.sub.3 are as defined under formula (1). 
Preferred reactive dyes are especially those of the formula (2) in which 
D.sub.1 is a benzene radical, which can be substituted by sulfo, methoxy 
and chlorine, or a naphthalene radical, which can be substituted by sulfo 
and nitro, R.sub.2 is hydrogen, methyl or ethyl and R.sub.3 is hydrogen, 
ethyl, .beta.-hydroxyethyl, butyl, phenyl, which can be substituted by 
methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, carboxyl and 
sulfo, or naphthyl, which can be substituted by sulfo, or in which the 
amino group --NR.sub.2 R.sub.3 is the morpholino radical. 
Particularly preferred reactive dyes are those of the formula 
##STR4## 
in which R.sub.2 is hydrogen, methyl or ethyl and R.sub.3 is hydrogen or 
phenyl, which can be substituted by methyl, methoxy, chlorine and sulfo. 
A valuable reactive dye of the category defined by formula (3) is the 
reactive dye of the formula 
##STR5## 
The preparation of the reactive dyes of the formula (1) comprises 
diazotisation, coupling and condensation reactions using a coupling 
component of the formula 
##STR6## 
a diazo component of the formula 
EQU D.sub.1 --NH.sub.2 ( 6), 
a further diazo component of the formula 
##STR7## 
2,4,6-trifluoro-s-triazine of the formula 
##STR8## 
and an amino compound of the formula 
##STR9## 
the said reactions being carried out in any order. 
In a preferred embodiment the coupling component of the formula (5) which 
is used is a compound of the formula 
##STR10## 
in which one Y is hydrogen and the other Y is sulfo, and the diazo 
component of the formula (7) which is used is a compound of the formula 
##STR11## 
The starting materials used are in particular compounds of the formulae (6) 
and (9) in which D.sub.1 is a benzene radical, which can be substituted by 
sulfo, methoxy and chlorine, or a naphthalene radical, which can be 
substituted by sulfo and nitro, R.sub.2 is hydrogen, methyl or ethyl and 
R.sub.3 is hydrogen, ethyl, .beta.-hydroxyethyl, butyl, phenyl, which can 
be substituted by methyl, methoxy, ethoxy, chlorine, acetylamino, ureido, 
carboxyl and sulfo, or naphthyl, which can be substituted by sulfo, or in 
which the amino group --NR.sub.2 R.sub.3 is the morpholino radical. 
The preferred reactive dyes of the formula (3) are obtained by 
diazotisation, coupling and condensation reactions using a diazo component 
of the formula 
##STR12## 
1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 
1,3-diaminobenzene-4-sulfonic acid, cyanuric fluoride and an amino 
compound of the formula (9), in which R.sub.2 and R.sub.3 are as defined 
under formula (3), the said reactions being carried out in any order. 
Since the individual process steps indicated above, i.e. diazotisation, 
coupling and condensation, can be carried out in different orders, and, if 
desired, some process steps can also be carried out at the same time, 
various process variants are possible. The starting materials to be used 
for each partial reaction can be seen from formula (1). In general, the 
reaction is carried out in successive steps and the order in which the 
simple reactions between the individual reactants of the formulae (5) to 
(9) are carried out can be freely chosen. 
Important process variants comprise 1. reacting a coupling component of the 
formula (5) with diazotised diazo components of the formulae (6) and (7) 
to give a disazo compound, subjecting the latter to a condensation 
reaction with 2,4,6-trifluoro-s-triazine of the formula (8) and subjecting 
the primary condensation product to a condensation reaction with an amino 
compound of the formula (9). 
The last two reaction steps can also be carried out in a different order, 
by first subjecting the 2,4,6-trifluoro-s-triazine to a condensation 
reaction with an amino compound of the formula (9) and subjecting the 
resulting primary condensation product to a condensation reaction with the 
abovementioned disazo compound. 
The procedure employed for the preparation of the abovementioned disazo 
compound is advantageously first to couple a diazotised diazo component of 
the formula (6) with a coupling component of the formula (5) and then to 
couple the resulting monoazo compound with a diazotised diazo component of 
the formula (7). 2. diazotising a diazo component of the formula (6) and 
coupling the resulting compound with a coupling component of the formula 
(5) and also subjecting 2,4,6-trifluoro-s-triazine of the formula (8) to a 
condensation reaction with an amino compound of the formula (9), 
subjecting the primary condensation product to a condensation reaction 
with a diazo component of the formula (7) and diazotising the resulting 
secondary condensation product and coupling the resulting product with the 
monoazo compound prepared initially. 
The preferred procedure for the preparation of the reactive dye of the 
formula (4) comprises diazotising sulfanilic acid and 
1,3-phenylenediamine-4-sulfonic acid and coupling the reaction product 
with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, subjecting the 
resulting intermediate of the formula 
##STR13## 
to a condensation reaction with cyanuric fluoride and subjecting the 
primary condensation product to a condensation reaction with 
m-chloroaniline. 
The diazotisation of the diazo components is as a rule effected by the 
action of nitrous acid in aqueous-mineral acid solution at low 
temperature. 
The coupling of the diazo component of the formula (6) with the coupling 
component of the formula (5) in the ortho-position relative to the H.sub.2 
N group is effected in strongly acid solution, at pH values of 1 to 2; the 
coupling of the diazo component of the formula (7) with the coupling 
component of the formula (5) in the orthoposition relative to the HO group 
is effected in the weakly acid or neutral to weakly alkaline range, at pH 
values between 6.5 and 8. 
In general, it is necessary first to carry out the coupling reaction in 
acid solution. In some cases, for the coupling reactions in which a 
diaminobenzenesulfonic acid is used as the diazo component of the formula 
(7), it is advantageous not to use this as itself, but, instead of this, 
to use an amino-acylamino-benzenesulfonic acid, for example 
5-acetylaminoaniline-2-sulfonic acid, from which the acetyl group is 
detached by saponification after the coupling reaction has gone to 
completion, before carrying out the further condensation reaction. 
Furthermore, it is also possible to use a nitro-amino compound, for 
example 5-nitroaniline-2-sulfonic acid, as the diazo component of the 
formula (7) and, after the coupling reaction has taken place, to reduce 
the nitro group to the amino group with sodium sulfide or sodium 
hydrosulfide. 
The condensation reactions of 2,4,6-trifluoro-s-triazine of the formula (8) 
with the diazo components of the formula (7) and the amino compounds of 
the formula (9) are preferably effected in aqueous solution or suspension, 
at low temperature and at a weakly acid or neutral to weakly alkaline pH 
value, so that at least one fluorine atom still remains as a detachable 
radical in the finished reactive dye of the formula (1). Advantageously, 
the hydrogen fluoride liberated during the condensation reaction is 
neutralised continuously by adding aqueous alkali metal hydroxides, alkali 
metal carbonates or alkali metal bicarbonates. 
The preparation of the diazo intermediates is not described in all cases in 
the illustrative examples which follow, but is obvious from what has been 
stated above. 
Examples of starting compounds for the preparation of the reactive dyes of 
the formula (1) are: 
(a) Coupling components of the formula (5) 
1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H-acid), 
1-amino-8-hydroxynaphthalene-4,6-disulfonic acid (K-acid) and 
1-amino-8-hydroxynaphthalene-4-sulfonic acid. 
(b) Diazo components of the formula (6) 
aniline, o-, m- and p-toluidines, o-, m- and p-anisidines, o-, m- and 
p-chloroanilines, 2,5-dichloroaniline, .alpha.- and .beta.-naphthylamine, 
2,5-dimethylaniline, 5-nitro-2-aminoanisole, 4-amino-diphenyl, aniline-2-, 
-3- and -4-carboxylic acids, 2-aminodiphenyl ether, 2-, 3- or 
4-aminobenzenesulfonamide or 2-, 3- or 4-aminobenzenesulfonic acid 
mono-methyl-or -ethyl-amides or 2-, 3- or 4-aminobenzenesulfonic acid 
dimethyl- or diethyl-amides, aniline-2-, -3- and -4-sulfonic acid, 
aniline-2,5-disulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 
4-chloro-5-methylaniline-2-sulfonic acid, aniline-2,4-disulfonic acid, 
aniline-3,5-disulfonic acid, 2-amino-4- or -5-sulfobenzoic acid, 
2-methylaniline-3,5-disulfonic acid, 2-methylaniline-5-sulfonic acid, 
2-methoxyaniline-3,5-disulfonic acid, 2-chloroaniline-4-sulfonic acid, 
2,3-dimethylaniline-4,6-disulfonic acid, 
2,5-dimethylaniline-4,6-disulfonic acid, 
5-chloro-4-methylaniline-2-sulfonic acid, 3-acetylaminoaniline-6-sulfonic 
acid, 4-acetylaminoaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic 
acid, 3,4-dichloroaniline-6 -sulfonic acid, 4-methylaniline-2-sulfonic 
acid, 3-methylaniline-6-sulfonic acid, 2,4-dimethoxyaniline-6-sulfonic 
acid, 4-methoxyaniline-2-sulfonic acid, 5-methoxyaniline-2-sulfonic acid, 
2,5-dichloroaniline-4-sulfonic acid, 2,4-dimethylaniline-5-sulfonic acid, 
2-methoxyaniline-5-sulfonic acid, 2-methylaniline-4-sulfonic acid, 
4-nitroaniline-2-sulfonic acid, 4-ethoxyaniline-2-sulfonic acid, 
4-ethylaniline-2-sulfonic acid, 4-acetylaminoaniline, 
4-ethoxyaniline-3-sulfonic acid, 3,4-dichloroaniline, o-, m- and 
p-nitroaniline, m- and p-aminoacetanilide, 
4-amino-2-acetylaminotoluene-5-sulfonic acid, 4-methoxyaniline-3-sulfonic 
acid, 1-aminonaphthalene-2-, -4-, -5-, -6-, -7- or -8-sulfonic acid, 
2-aminonaphthalene-1-, -5- or -6-sulfonic acid, 1-aminonaphthalene-3,6-or 
-5,7-disulfonic acid, 2-aminonaphthalene-1,5-, -1,7-, -3,6-, -5,7-, -4,8- 
or -6,8-disulfonic acid, 1-aminonaphthalene-2,5,7-trisulfonic acid, 
2-aminonaphthalene-1,5,7-, -3,6,8- or -4,6,8-trisulfonic acid, 
1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid, 
2-amino-1-hydroxynaphthalene-4,8-disulfonic acid, 
1-amino-3-acetylaminobenzene (saponified), 
1-amino-3-acetylaminobenzene-5-or -6-sulfonic acid (saponified), 
1-amino-4-acetylaminobenzene-2-sulfonic acid (saponified), 
1-amino-3-(N-acetyl-N-methylamino)-benzene (saponified), 3- or 
4-nitroaniline (reduced), 2-methoxy-4- or -5-nitroaniline (reduced), 
2-methoxy-3-nitro-5-methylaniline (reduced) and 
2-methoxy-3-nitro-5-chloroaniline. 
(c) Diazo components of the formula ( 7) 
1,3- and 1,4-diaminobenzene, 1,3- and 1,4-diaminoanisole, 1,3- and 
1,4-diaminotoluene, 1,3-diamino-4-chlorobenzene, 
1,3-diamino-4-ethylbenzene, 1,3-diamino-4-ethoxybenzene, 
1,3-diaminobenzene-4-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, 
1,4-diaminobenzene-2,5-disulfonic acid, 1,4-diaminobenzene-2,6-disulfonic 
acid and 1,3-diaminobenzene-4,6-disulfonic acid. 
(d) 2,4,6-Trifluoro-s-triazine of the formula (8) (cyanuric fluoride) 
(e) Amino compounds of the formula (9) 
ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, 
isopropylamine, butylamine, dibutylamine, isobutylamine, sec.-butylamine, 
tert.-butylamine, hexylamine, methoxyethylamine, ethoxyethylamine, 
methoxypropylamine, chloroethylamine, hydroxyethylamine, 
dihydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, 
.beta.-sulfatoethylamine, benzylamine, cyclohexylamine, aniline, o-, m- 
and p-toluidine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dimethylaniline, o-, 
m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 3- or 
4-acetylaminoaniline, o-, m- and p-nitroaniline, o-, m- and p-aminophenol, 
2-methyl-4-nitroaniline, 2-methyl-5-nitroaniline, 2,5-dimethoxyaniline, 
3-methyl-4-nitroaniline, 2-nitro-4-methylaniline, 3-nitro-4-methylaniline, 
o-, m- and p-anisidine, o-, m- and p-phenetidine, 
2-methoxy-5-methylaniline, 2-ethoxy-5-methoxyaniline, 4-bromoaniline, 
3-aminobenzamid, 4-aminophenylsulfamide, 3-trifluoromethylaniline, 3- and 
4-aminophenylurea, 1-naphthylamine, 2-naphthylamine, 
2-amino-1-hydroxy-naphthalene, 1-amino-4-hydroxy-naphthalene, 
1-amino-8-hydroxy-naphthalene, 1-amino-2-hydroxy-naphthalene, 
1-amino-7-hydroxy-naphthalene, orthanilic acid, metanilic acid, sulfanilic 
acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 
aniline-3,5-disulfonic acid, anthranilic acid, m- and p-aminobenzoic acid, 
4-aminophenylmethanesulfonic acid, aniline-N-methanesulfonic acid, 
2-aminotoluene-4-sulfonic acid, 2-aminotoluene-5-sulfonic acid, 
p-aminosalicylic acid, 1-amino-4-carboxy-benzene-3-sulfonic acid, 
1-amino-2-carboxybenzene-5-sulfonic acid, 
1-amino-5-carboxy-benzene-2-sulfonic acid, 1-naphthylamine-2-, -3 -, -4-, 
-5-, -6-, -7- and -8-sulfonic acid, 2-naphthylamine-1-, -3-, -4-, -5-, 
-6-, -7- and -8-sulfonic acid, 1-naphthylamine-2,4-, -2,5-, -2,7-, -2,8-, 
-3,5-, -3,6-, -3,7-, -3,8-, -4,6-, -4,7-, -4,8- and -5,8-disulfonic acid, 
2-naphthylamine-1,5-, -1,6-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7- and 
-6,8-disulfonic acid, 1-naphthylamine-2,4,6-, -2,4,7-, -2,5,7-, -3,5,7-, 
-3,6,8- and -4,6,8-trisulfonic acid, 2-naphthylamine-1,3,7-, -1,5,7-, 
-3,5,7-, -3,6,7-, -3,6,8-and -4,6,8-trisulfonic acid, 2-, 3- and 
4-aminopyridine, 2-aminobenzthiazole, 5-, 6- and 8-aminoquinoline, 
2-aminopyrimidine, morpholine, piperidine and piperazine. 
The reactive dyes of the formula (1) can be isolated and processed to 
usable, dry dye preparations. Isolation is preferably effected at 
temperatures which are as low as possible, by salting out and filtering. 
If desired, the dyes filtered off can be dried after adding diluents 
and/or buffers, for example after adding a mixture of equal parts of 
monosodium phosphate and disodium phosphate; preferably, drying is carried 
out at temperatures which are not too high and under reduced pressure. In 
certain cases the dry preparations according to the invention can be 
prepared direct, i.e. without intermediate isolation of the dyes, by 
spray-drying the entire mixture in which they were prepared. 
The reactive dyes of the formula (1) are novel. They are distinguished by 
high reactivity and give dyeings which have good wet fastness properties 
and good fastness to light. Particular mention should be made of the fact 
that the dyes have good solubility and electrolyte solubility coupled with 
good uptake characteristics and good fixing of the dye, and that the 
portions not fixed can be removed easily. The dyeings are dischargeable. 
The reactive dyes of the formula (1) are suitable for dyeing and printing 
very diverse materials, such as silk, leather, wool, high molecular weight 
polyamide fibres and high molecular weight polyurethanes, but especially 
cellulose-containing materials of fibrous structure, such as linen, 
cellulose, regenerated cellulose and in particular cotton. They are 
suitable both for the exhaustion process and for dyeing by the pad dyeing 
method, according to which the goods are impregnated with aqueous dye 
solutions, which can also contain salts, and the dyes are fixed after an 
alkali treatment or in the presence of alkali, if necessary with the 
action of heat. 
They are also suitable for printing, especially on cotton, but are likewise 
also suitable for printing nitrogen-containing fibres, for example wool, 
silk or mixed fabrics containing wool. 
It is advisable to subject the dyeings and prints to thorough rinsing with 
cold and hot water, if necessary with the addition of an agent which acts 
as a dispersing agent and promotes the diffusion of the non-fixed portions 
.

In the following examples parts are by weight and the temperatures are 
given in degrees Centigrade. 
EXAMPLE 1 
A neutral solution of 70.2 parts of the disazo dye of the formula 
##STR14## 
in 500 parts of water is cooled to 0.degree. to 5.degree. C. by adding 300 
parts of ice. 10 parts of cyanuric fluoride are allowed to run in the 
course of 5 to 10 minutes, with vigorous stirring, and at the same time 
the pH of the reaction mixture is kept between 6 and 7 by the dropwise 
addition of 2N sodium hydroxide solution. After the acylation has gone to 
completion, 10.7 parts of o-toluidine are added to the solution of the 
difluorotriazine dye and the reaction mixture is warmed to 30.degree. to 
35.degree. C. and the pH is kept between 7 and 8 by dropwise addition of 
2N sodium hydroxide solution. After the reaction has gone to completion, 5 
parts of disodium hydrogen phosphate are added to the solution of the 
monofluorotriazine dye and the solution is evaporated to dryness in a 
rotary evaporator at 40.degree. to 45.degree. C. 
The dye thus obtained dyes cotton in navy blue shades. 
Similar dyes, which also dye cotton in navy blue shades, are obtained when 
the above example is repeated using equivalent amounts of the amines 
listed below in place of o-toluidine. 
______________________________________ 
Example Amines 
______________________________________ 
2 m-Toluidine 
3 p-Toluidine 
4 2,4-Dimethylaniline 
5 2,5-Dimethylaniline 
6 2,6-Dimethylaniline 
7 Ethanolamine 
8 Aniline 
9 N-Methylaniline 
10 N-Ethylaniline 
11 m-Chloroaniline 
12 p-Chloroaniline 
13 Acetyl-m-phenylenediamine 
14 Acetyl-p-phenylenediamine 
15 o-Anisidine 
16 p-Anisidine 
17 4-Aminophenyl-urea 
18 3-Aminophenyl-urea 
19 p-Aminobenzoic acid 
20 Metanilic acid 
21 2-Aminonaphthalene-6-sulfonic acid 
22 Ammonia 
23 m-Anisidine 
24 4-Ethoxyaniline 
25 Morpholine 
26 Taurine 
______________________________________ 
Further dyes, which dye cotton in the shades listed in column III, are 
obtained when the amino group-containing disazo dyes listed in column I 
are reacted with cyanuric fluoride and the amines listed in column II. 
__________________________________________________________________________ 
I II III 
__________________________________________________________________________ 
##STR15## Aniline greenish-tinged blue 
##STR16## 3-Aminotoluene 
greenish-tinged blue 
##STR17## n-Butylamine 
greenish-tinged blue 
##STR18## Aniline-3-sul- fonic 
greenish-tinged blue 
##STR19## 4-Aminoanisole 
blue 
##STR20## 3-Chloroaniline 
strongly greenish- 
tinged blue 
##STR21## Ethylamine 
blue-green 
##STR22## N-Methylaniline 
strongly greenish- 
tinged blue 
##STR23## 3-Aminotoluene 
strongly greenish- 
tinged blue 
##STR24## Metanilic acid 
strongly greenish- 
tinged blue 
##STR25## Ammonia blue 
__________________________________________________________________________ 
EXAMPLE 2 
A neutral solution of 17.3 parts of orthanilic acid in 200 parts of water 
is cooled to 0.degree. C. by adding 250 parts of ice. 9 parts of cyanuric 
fluoride are allowed to run in the course of 10 minutes, with vigorous 
stirring, and the pH is kept between 6 and 7 by the dropwise addition of 
2N sodium hydroxide solution. When no further unchanged orthanilic acid is 
detectable, a neutral solution of 18.8 parts of m-phenylenediaminesulfonic 
acid in 50 parts of water is added to the solution of the primary 
condensation product, the temperature is allowed to rise to 20.degree. to 
25.degree. C. and the pH of the reaction mixture is kept between 6.5 and 
7.0. After the reaction has gone to completion, the secondary condensation 
product is salted out by adding 15% by volume of potassium chloride and 
filtered off. 
25 parts of 4N sodium nitrite solution are added to a neutral suspension of 
45.6 parts of the secondary condensation product described above in 150 
parts of water and the mixture is cooled to 0.degree. to 5.degree. C. with 
ice. 30 parts of 10N hydrochloric acid are added and after several hours 
the excess nitrite is destroyed with sulfamic acid. 
The yellow suspension of the diazo compound which is thus obtained is then 
poured into an ice-cold neutral solution of 50.3 parts of the dye 
##STR26## 
in 150 parts of water, to which 30 parts of sodium bicarbonate have also 
been added prior to the coupling reaction. 
A clear solution forms (volume about 750 parts) and the dye formed is 
salted out from this by adding 10% by volume of a mixture of sodium 
chloride and potassium chloride in a ratio of 1:1. After filtering, the 
dye paste is mixed with a concentrated aqueous solution of 5 parts of 
disodium hydrogen phosphate and dried in vacuo at 50.degree. C. 
The dye thus obtained dyes cotton in navy blue shades. 
EXAMPLE 3 
10 parts of cyanuric fluoride are added dropwise in the course of about 10 
minutes to an ice-cold, neutral solution of 17.3 parts of orthanilic acid 
in 400 parts of water, the pH value of the reaction mixture being kept 
between 6 and 7 by adding 1N sodium hydroxide solution at the same time. 
The primary condensation product thus obtained is then poured into a 
neutral solution of 70.2 parts of the disazo dye of the formula 
##STR27## 
in 500 parts of water and the reaction mixture is warmed to 30.degree. to 
35.degree. C. and the pH value is kept between 7 and 8 by the dropwise 
addition of 1N sodium hydroxide solution. 
After the acylation has gone to completion, 5 parts of disodium hydrogen 
phosphate are added to the solution of the monofluorotriazine dye and the 
solution is evaporated to dryness in a rotary evaporator at 40.degree. to 
45.degree. C. The dye thus obtained dyes cotton in navy blue shades. 
When the procedure of the above example is repeated except that 18.72 parts 
of 4-aminotoluene-3-sulfonic acid are used in place of orthanilic acid, a 
dye is obtained which also dyes cotton in navy blue shades. 
Dyeing instructions I 
2 parts of the dye obtained according to Example 1 are dissolved in 100 
parts of water with the addition of 0.5 part of sodium 
m-nitrobenzenesulfonate. A cotton fabric is impregnated with the resulting 
solution so that the liquor pick-up is 75% and is then dried. 
The fabric is then impregnated with a solution, at 20.degree., which 
contains, per litre, 5 grams of sodium hydroxide and 300 grams of sodium 
chloride, and squeezed off to a liquor pick-up of 75% and the dyeing is 
steamed for 30 seconds at 100.degree. to 101.degree., rinsed, soaped for a 
quarter of an hour in a 0.3% boiling solution of a non-ionic detergent, 
rinsed and dried. 
Dyeing instructions II 
2 parts of the dye obtained according to Example 1 are dissolved in 100 
parts of water. 
The solution is added to 1,900 parts of cold water, 60 parts of sodium 
chloride are added and 100 parts of a cotton fabric are put into this 
dyebath. 
The temperature is raised to 40.degree. and after 30 minutes 4 parts by 
volume of 30% sodium hydroxide solution, 10 parts of calcined sodium 
carbonate and a further 60 parts of sodium chloride are added. The 
temperature is maintained at 40.degree. for 30 minutes and the dyeing is 
then rinsed and soaped for 15 minutes in a 0.3% boiling solution of a 
non-ionic detergent, rinsed and dried.