Water-soluble disazo compounds containing 3-carboxy or 3-carbamoylpyridium-s-triazinyl groups and fiber-reactive groups of the vinyl sulfone series suitable as dyestuffs

Water-soluble disazo compounds having useful fiber-reactive dye properties, which conform to the general formula (1) defined hereinafter and dye carboxamido- and/or hydroxy-containing materials in fast shades. Fast dyeings on cellulose fiber materials can also be obtained in a weakly acid to neutral pH range, for example together with disperse dyes for dyeing a polyester fiber portion. ##STR1## in which: A is phenylene which may be substituted by methyl, ethyl, methoxy, chlorine or sulfo, or is a radical of the formula ##STR2## in which G is a direct bond or a group of the formula --CH.dbd.CH-- or --NH--CO--NH-- and R.sup.1 and R.sup.2 are each independently of the other hydrogen, sulfo, methyl, ethyl, methoxy or ethoxy; PA0 D is phenylene which may be substituted by methyl, ethyl, methoxy, ethoxy, sulfo, carboxy, chlorine or bromine, or is naphthalene which may be substituted by sulfo or is a group of the formula ##STR3## and K, as a radical of a coupling component, is a radical of the formula ##STR4## in which M is hydrogen or an alkali metal and R.sup.o is hydrogen or sulfo and the free azo-bond in the amino-naphthol radical is ortho to the hydroxy group, R* is hydrogen, methyl or ethyl and the benzene nucleus a can be substituted by methyl, ethyl, methoxy, ethoxy lower alkanoylamino, benzoylamino, ureido or chlorine; PA0 X is vinyl, .beta.-sulfatoethyl or .beta.-chloroethyl; PA0 R is carboxy or carbamoyl.

DESCRIPTION 
The present invention relates to the technical field of textile dyes. 
At present, cellulose fibers and polyester fibers cannot be dyed with one 
and the same dye in a uniform and level manner owing to their different 
chemical natures. One is forced to dye mixed materials of these two types 
of fiber, such as, for example, blend fabrics, in a two-stage process, 
namely first dye one of the fibers with the dye suitable for that purpose 
then the other fiber with the dye suitable for that type of fiber, in each 
case under different process conditions. Such a procedure is necessarily 
laborious and in need of replacement. It has therefore been attempted to 
dye such blend fiber materials using a dye mixture comprising a 
fiber-reactive dye for dyeing the cellulose fiber portion and a disperse 
dye for dyeing the polyester fiber portion. However, this procedure has 
appreciable disadvantages. The reason is that fiber-reactive dyes are 
customarily fixed on the cellulose fiber in an alkaline medium and 
disperse dyes, like to a certain extent the polyester fiber also, are 
customarily sensitive to alkali. The consequence is accordingly that, in 
fixing the fiber-reactive dyes in an alkaline medium, the disperse dyes 
which are present at the same time and in certain circumstances the 
polyester fibers also can be damaged. 
It was thus an object to reduce or even to remedy these previously 
disclosed disadvantages, in particular since the dyeing of blend fabrics, 
such as, for example, those of cellulose and polyester fibers, is becoming 
increasingly important. There thus also exists an increased interest in 
dyes which facilitate the dyeing of such blend fabrics, in particular in 
fiber-reactive dyes which are capable of becoming fixed on the cellulose 
fiber in the nonalkaline range and, in addition, can be employed at very 
low dyeing temperatures. 
For instance, German Offenlegungsschrift No. 2,634,308 and U.S. Pat. No. 
4,300,902 propose that such blend fiber materials be dyed with dyes which 
contain one or more s-triazinyl groups having a quaternary nitrogen 
substituent, such as a pyridinium radical, for example nicotinic acid, and 
later, according to U.S. Pat. No. 4,453,945, dyes of the same type having 
specifically a nicotinic acid radical as quaternary nitrogen substituent 
have been used for dyeing cellulose fibers and cellulose/polyester blend 
fibers. However, these dyes and the dyeing methods used therefor have 
disadvantages. While the dyes of German Offenlegunsschrift No. 2,634,308 
and U.S. Pat. No. 4,300,902 require dyeing temperatures of over 
150.degree. C., and by contrast the dyeing method of U.S. Pat. No. 
4,453,945, according to its own statements, is feasible at dyeing 
temperatures below 150.degree. C., the dyes mentioned in these three 
publications nonetheless have the serious disadvantage that their color 
yield, when used to dye cellulose fiber materials, such as cotton, by the 
exhaust method, is highly dependent on the pH value of the dye bath. 
Consequently, the depth of shade of dyeings with these known dyes on 
cotton fibers at pH values between 4 and 8 varies greatly, the general 
maxim being that the depth of shade increases with increasing pH and the 
maximum depth of shade, as with all conventional fiber-reactive dyes, is 
obtained in the strongly alkaline range, i.e. above a pH of 9 or even 10. 
In addition, the buildup of dyeings with these dyes, i.e. the relation 
between amount of dye used and color yield obtained on the cellulose fiber 
(color strength or depth of a shade), is inadequate, since beyond certain 
concentrations of dye in the dye bath the color yield on the fiber does 
not increase further as the amount of dye is increased to obtain deeper 
shades. These defects are also found with the dyes described in European 
Patent Application Publication No. 0,167,219A, which, in addition to a 
pyridinium-substituted s-triazinyl radical, contain a fiber-reactive group 
of vinylsulfonyl type. The same applies to the dyes described in U.S. Pat. 
No. 4,323,497. 
The present invention now provides new water-soluble compounds which 
conform to the general formula (1) mentioned and defined hereinafter, have 
fiber-reactive properties and not only can be used with advantage for 
dyeing cellulose fibers in the alkaline range but, surprisingly, are 
capable of becoming fixed on cellulose fibers even in the weakly acid and 
neutral range, namely under conditions of the so-called high-temperature 
neutral dyeing method (HTN method) at temperatures between 100.degree. and 
150.degree. C. and at a pH value between 4 and 8 in an aqueous medium, 
i.e. under the conditions of dyeing polyester fibers. By providing the new 
dyes of the general formula (1) it has become possible to use the hitherto 
usual and customary disperse dyes together with these new dyes in 
one-stage dyeing processes for dyeing cellulose/polyester fiber blends in 
which the two fiber components are dyed uniformly and fast by the 
respective type of dye and it is possible to obtain tone-on-tone dyeings 
if the disperse dye used has the same shade as the fiber-reactive dye. 
The fiber-reactive compounds according to the invention conform to the 
general formula (1) 
##STR5## 
where the symbols appearing in the formula have the following meanings: A 
is a phenylene radical, preferably a para-phenylene radical, which can be 
substituted by 1 or 2 substituents from the group consisting of methyl, 
ethyl, methoxy, chlorine and sulfo, preferably by a sulfo group, or is a 
radical of the general formula (2a) 
##STR6## 
in which G is a direct bond or a vinylidene radical of the formula 
--CH.dbd.CH-- or a bivalent urea radical of the formula --NH--CO--NH--, 
R.sup.1 denotes a hydrogen atom or a sulfo, methyl, ethyl, methoxy or 
ethoxy group, preferably a sulfo group, and 
R.sup.2 has one of the meanings of R.sup.1 and is identical to R.sup.1 or 
different from R.sup.1 ; 
D is a benzene ring which can be substituted by 1 or 2 substituents which 
are selected from the set consisting of 2 methyl groups, 2 ethyl groups, 2 
methoxy groups, 2 ethoxy groups, 1 sulfo groups, 1 carboxy group, 1 
chlorine atom and 1 bromine atom, or 
D is a naphthalene ring which can be substituted by a sulfo group, or 
D is a radical of the formula (2b) 
##STR7## 
K, as a radical of a coupling component, is an aminonaphtholsulfonic acid 
radical of the general formula (3) 
##STR8## 
of which preferably a radical of the general formula (3a), (3b) or (3c) 
##STR9## 
K is a radical of the general formula (4) 
##STR10## 
in which M stands for a hydrogen atom or an alkali metal, such as sodium, 
potassium or lithium, 
R.sup.o is a hydrogen atom or a sulfo group, the free azo bond in the 
formula (3) is ortho to the hydroxy group, 
R.sup.* is an ethyl group, or preferably a hydrogen atom or a methyl group, 
and 
the --SO.sub.3 M group in the formula (3a) is meta or para to the NH group 
and 
the benzene nucleus a can be substituted by 1 or 2 substituents from the 
group consisting of methyl, ethyl, methoxy, ethoxy, alkanoylamino of 2 to 
5 carbon atoms, such as acetylamino, benzoylamino, ureido and chlorine; 
X is a vinyl group, a .beta.-sulfatoethyl or a .beta.-chloroethyl group; 
R is a carboxy group or a carbamoyl group; 
the sulfo, sulfato and carboxy groups form anions equivalent to the 
pyridinium cation. 
of the radicals of the general formula (4), preference is given to a 
radical of the general formula (3d) 
##STR11## 
in which R.sup.3 is a hydrogen atom or a methyl or methoxy group and 
R.sup.4 is a methyl, methoxy, acetylamino or ureido group. 
Those symbols which each appear twice in the formula, namely D, K, X and R, 
can each have the same meaning in both cases or a different meaning in 
each case; preferably they have the same meaning. Preference is thus given 
to those of the disazo compounds according to the invention of the general 
formula (1) which are symmetrically constructed compounds. 
In the disazo compounds of the general formula (1), X is preferably a vinyl 
group and particularly preferably a .beta.-sulfatoethyl group. A is 
preferably an unsubstituted or sulfo-substituted p-phenylene radical, a 
2,2'- or 3,3'-disulfodiphen-4,4'-ylene radical or a radical of the formula 
(2c) or (2d) 
##STR12## 
where M has the abovementioned meaning. D is preferably a benzene ring 
which can be substituted by 1 or 2 substituents which are selected from 
the set consisting of 2 methoxy groups, 1 methyl group, 1 chlorine atom 
and 1 bromine atom, or preferably is a naphthalene ring which can be 
substituted by a sulfo group. of the disazo compounds according to the 
invention, in particular the disazo compounds according to the invention 
described in Working Example 7 and in Table Examples 8, 9, 20, 22, 35, 39 
and 47 can be singled out. 
The compounds according to the invention can be present in the form of 
their free acids and in the form of their salts, in particular the neutral 
salts. They are preferably in the form of their salts, in particular their 
alkali metal salts. They are preferably used in the form of these salts 
for dyeing and printing hydroxy and/or carboxamido-containing fiber 
materials. 
The present invention further relates to processes for preparing the 
compounds according to the invention. The compounds according to the 
invention can be prepared by reacting a compound of the general formula 
(5) 
##STR13## 
in which A, D, K and X have the meanings indicated for the formula (1), 
with nicotinic acid or nicotinamide. This reaction is carried out in a 
manner similar to the process measures customary for this type of 
reaction, as mentioned, for example, in previously cited European Patent 
Application Publication No. 0,167,219. Preferably, the reaction according 
to the invention takes place in an aqueous medium at a pH value between 4 
and 6, in particular between 4 and 5, and preferably at a temperature 
between 60.degree. and 100.degree. C., preferably between 80.degree. and 
90.degree. C. 
The starting compounds of the general formula (5) are substantially known 
from previously cited U.S. Pat. No. 4,323,497 or can be synthesized 
similarly to the directions given therein. 
Furthermore, the compounds according to the invention can be prepared in a 
manner according to the invention by coupling a compound of the general 
formula (6) 
##STR14## 
in which A, B and K have the abovementioned meanings, with the diazonium 
compound of an aromatic amine of the general formula (7) 
EQU X--SO.sub.2 --D--NH.sub.2 ( 7) 
in which D and X have the abovementioned meanings. Here too the coupling 
reaction is carried out similarly to procedures well known for this 
purpose, for example in an aqueous solution at a pH value between 4 and 7 
and at a temperature between 0.degree. and 30.degree. C. 
The starting compounds of the general formula (6) can be prepared by 
reacting cyanuric chloride in any desired order with the amino compounds 
of the general formulae H--K--H and H.sub.2 N--A--NH.sub.2, where K and A 
have the abovementioned meaning, similarly to the known procedures to give 
a compound of the general formula (8) 
##STR15## 
in which A and K have the abovementioned meanings. The starting compounds 
(8) are substantially known from previously cited U.S. Pat. No. 4,323,497 
or can be synthesized similarly to the directions given therein. 
Subsequently, the compounds (8) are converted by reaction with nicotinic 
acid or nicotinamide in a manner similar to the above directions for the 
reaction of the compounds of the general formula (5) with nicotinic acid 
or nicotinamide into the starting compounds of the general formula (6). 
The precipitation and isolation of the compounds of the general formula (1) 
prepared according to the invention from the synthesis solutions is 
carried out in a conventional manner, for example by precipitating from 
the reaction medium by means of electrolytes or by evaporating the 
reaction solution, for example by spray drying, if desired after buffer 
substances have been added to the synthesis solution. 
The compounds according to the invention have dye properties. As a 
consequence of the fiber-reactive groups they possess, they can also be 
used as fiber-reactive dyes. They can be employed in customary and known 
methods of applying and fixing fiber-reactive dyes on hydroxy-containing 
and/or carboxamido-containing materials, in particular fiber materials, 
for dyeing (including printing), for example wool, synthetic polyamide 
fibers, but in particular cellulose fiber materials, such as cotton. These 
methods have been described in large numbers in the trade literature, 
including the patent literature, for example in German Offenlegungsschrift 
No. 3,440,265. 
The present invention thus also relates to the use of the compounds 
according to the invention for dyeing (including printing) 
hydroxy-containing and/or carboxamido-containing materials, in particular 
fiber material, specifically to a process for dyeing (including printing) 
such materials where a compound according to the invention is applied to 
the material, preferably from an aqueous solution, and fixed on the 
material by means of heat and/or by means of an acid-binding agent--in the 
case of dyeing of hydroxy-containing materials preferably at a pH value 
between 8 and 11 and at a temperature between 15.degree. and 120.degree. 
C., preferably between 20.degree. and 80.degree. C. 
The compounds according to the invention in addition have the great 
advantage, mentioned at the beginning, that they are capable of dyeing 
hydroxy-containing fiber materials, such as cellulose fiber materials, 
from an aqueous liquor, preferably in an aqueous dye bath, by an exhaust 
method, even in the weakly acid pH range of 5 and greater than 5, that is 
at a pH value between 5 and 7, i.e. surprisingly in the absence of 
alkaline substances, but if desired in the presence of a customary 
acid-binding buffer mixture for setting and maintaining the pH range and 
if desired in the presence of customary dyeing assistants, at a 
temperature between 100.degree. and 150.degree. C., preferably at a 
temperature of 120.degree. to 135.degree. C., and become fixed on these 
materials with fast results. Such buffers are for example aqueous 
solutions of phosphoric acid/sodium phosphate and acetic acid/sodium 
acetate. 
Under these dyeing conditions of the high-temperature neutral dyeing 
process, which are known per se (see German Auslegeschrift No. 2,835,035) 
and which essentially correspond to the dyeing conditions of dyeing 
polyester fibers or other synthetic fibers, such as cellulose triacetate 
fibers, with disperse dyes, it is possible to dye advantageously cellulose 
blend fiber materials, such as cellulose/cellulose triacetate fiber and 
cellulose/polyacrylonitrile fiber and in particular cellulose/polyester 
blend fiber materials, with a customary disperse dye at the same time and 
together with a fiber-reactive dye, namely an azo compound according to 
the invention, from a common aqueous dye liquor without the otherwise 
existing danger of damaging the disperse dye or the synthetic fiber, such 
as polyester fiber, in a one-stage process, and if desired tone-on-tone, 
to give uniform and fast results. 
The present invention also relates to a process for dyeing blend fiber 
materials of cellulose and synthetic fibers, preferably 
cellulose/polyester fiber blends, with one or more disperse dyes and one 
or more dyes according to the invention by action of these dyes on the 
fiber material from an aqueous dyeing liquor, preferably from an aqueous 
dye bath, at a temperature between 100.degree. and 150.degree. C., 
preferably at a temperature of 120.degree. to 135.degree. C., and at a pH 
value between 4 and 8, if necessary between 5 and 7.5 , preferably between 
5 and 7. 
Using this dyeing method according to the invention, the synthetic fibers, 
such as polyester fibers, are dyed by the disperse dye and the cellulose 
fibers by the fiber-reactive azo compound according to the invention in 
the desired high quality (without the synthetic fiber, such as a cellulose 
triacetate or polyester fiber, being stained by the azo compounds 
according to the invention). The quality of the dyeing on the synthetic 
fibers is contingent upon the disperse dye and corresponds to the state of 
the art. Surprisingly, the cellulose fiber materials which are dyed with 
the azo compounds according to the invention under these conditions of 
dyeing with disperse dyes not only have a bright shade but considerable 
fastness properties (these fastness properties are present in any case 
when the azo compounds according to the invention are applied to the 
cellulose fiber materials in the alkaline range by the customary methods 
of applying and fixing fiber-reactive dyes). Of the good end-use and 
manufacturing fastness properties, in particular the good light fastness 
properties not only of the dry but also of the moist cellulose dye which 
has been impregnated with tap water or an alkaline perspiration solution, 
and also of the wet fastness properties, in particular the good wash, 
water, seawater, cross-dyeing and perspiration fastness properties and the 
good acid fading resistance and likewise good pleating, hot press, crock 
and sublimation fastness properties have to be singled out of dyes of 
cellulose fiber materials which are obtained with the azo compounds 
according to the invention, not only by applying methods for 
fiber-reactive dyes in the alkaline range, but also by applying dyeing 
methods for disperse dyes. 
The Examples which follow serve to illustrate the invention. The parts and 
percentages are by weight, unless otherwise stated. Parts by weight relate 
to parts by volume as the kilogram relates to liter. 
The compounds written in the Examples in the form of formulae have been 
written in the form of free acids; in general, they are prepared and 
isolated in the form of their alkali metal salts and used for dyeing in 
the form of these salts. In the same way, the starting compounds and 
components mentioned in the Examples, in particular Table Examples, in the 
form of the free acid can be used in the synthesis as such or in the form 
of their salts, preferably alkali metal salts, such as sodium or potassium 
salts. 
The absorption maxima (.lambda..sub.max values) mentioned in the Examples 
for the azo compounds according to the invention in the visible range were 
determined on their alkali metal salts in aqueous solution.

EXAMPLES 
Example 1 
40.4 parts of the disazo compound described in Example 1 of U.S. Pat. No. 
4,323,497 are dissolved in 500 parts of water, and 9.2 parts of 
nicotinamide and 30 parts of sodium acid are added; a pH value of 4.3 is 
set by means of glacial acetic acid, and the reaction batch is stirred at 
the boil for three hours. The batch is then cooled down, and the compound 
formed is salted out with potassium chloride, isolated, and dried at 
60.degree. to 80.degree. C. under reduced pressure. 
The result obtained is an electrolyte-containing dark red powder of the 
alkali metal salt (predominantly the potassium salt) of the compound of 
the formula 
##STR16## 
This compound has very good fiber-reactive dye properties and dyes for 
example wool or cellulose fiber materials by the application and fixing 
methods customary in the art for fiber-reactive dyes. On cotton, for 
example, deep bluish red dyeings and prints having good fastness 
properties are obtained (see Application Example 2). 
The compounds according to the invention can also be used with advantage 
for dyeing cellulose fiber materials under the conditions of dyeing 
polyester fibers with disperse dyes, i.e. from an aqueous solution at a pH 
value between 5 and 8 and at a temperature between 110.degree. and 
130.degree. C. (see Application Example 1). 
EXAMPLE 2 
187.5 parts of the disazo compound described in Example 4 of the U.S. Pat. 
No. 4,323,497 are reacted in an aqueous solution at a pH value of 5 to 7 
under reflux with 36 parts of nicotinic acid for some hours. The resulting 
disazo compound according to the invention is isolated in a conventional 
manner, for example by salting out with potassium chloride or by 
evaporating the solution. Written in the form of free acid, the disazo 
compound according to the invention has the formula 
##STR17## 
and exhibits very good fiber-reactive dye properties. Under alkaline 
fixing conditions as encountered in the customary dyeing and printing 
methods for fiber-reactive dyes, it produces, in particular on cotton, 
deep reddish violet dyes and prints having good fastness properties. 
Similarly, the so-called HTN process produces at a pH value between 6 and 7 
and at a temperature between 120.degree. and 140.degree. C., for example 
analogously to Application Example 1 or 4, deep violet dyes on cellulose 
fiber materials, which have the same good fastness properties. 
EXAMPLE 3 
168.5 parts of the disazo compound described in Example 54 of U.S. Pat. No. 
4,323,497 are reacted in aqueous solution at a pH value of 4 to 5 under 
reflux with 36 parts of nicotinic acid for several hours. The resulting 
disazo compound according to the invention is isolated in a conventional 
manner. When in the form of the free acid, it has the formula 
##STR18## 
and exhibits good fiber-reactive dye properties. On cellulose fiber 
materials, in particular, it produces on application of the customary 
application and fixing methods for fiber-reactive dyes in the alkaline 
range at dyeing temperatures of preferably up to 90.degree. C. as well as 
in a neutral to weakly acid dye bath at dyeing temperatures between 
100.degree. and 140.degree. C. deep orange dyeings having good wet and 
light fastness properties. 
EXAMPLE 4 
23.9 parts of 2-amino-5-naphthol-7-sulfonic acid are reacted in aqueous 
solution at a temperature between 0.degree. and 5.degree. C. and at a pH 
value of about 2 with 15.3 parts of cyanuric chloride; 5.5 parts of 
1,4-diaminobenzene are then added to the reaction batch, and the next 
condensation reaction is carried out 40.degree. to 60.degree. C. and at a 
pH value of 4 to 6. After the reaction has ended (no detectable free 
amine), 18.3 parts of nicotinamide are added, and the third condensation 
reaction is carried out by refluxing for three hours at a pH value between 
4.5 and 5. The compound thus obtained, which conforms to the general 
formula (6) mentioned in the description, now serves as a coupling 
component for preparing the disazo compound according to the invention, 
when it is reacted directly in its synthesis solution with the aqueous 
suspension of the diazonium salt of 31.1 parts of 
2-methoxy-5-(.beta.-sulfatoethylsulfonyl)-aniline. After the coupling 
reaction is ended, the disazo compound according to the invention is 
isolated in a conventional manner. 
The result obtained is an electrolyte-containing orange-red powder of the 
alkali metal salt of the compound of the formula 
##STR19## 
This compound has very good fiber-reactive dye properties and dyes for 
example wool or cellulose fiber materials by the application and fixing 
techniques customary in the art for fiber-reactive dyes. For instance, 
applied analogously to Application Example 2, it produces on cotton deep 
reddish orange dyeing and prints having good fastness properties. 
The compound according to the invention can also be used with advantage for 
dyeing cellulose fiber materials under the conditions of dyeing polyester 
fibers with disperse dyes, i.e. from an aqueous solution at a pH value 
between 5 and 8 and at a temperature between 120.degree. and 150.degree. 
C. (analogously to Application Example 1). 
EXAMPLE 5 
72.2 parts of 4-(.beta.-sulfatoethylsulfonyl)-2-sulfoaniline are 
conventionally diazotized and coupled to 31 parts of 3-aminophenylurea. 
After the coupling has ended, the azo compound is salted out of the 
reaction mixture by means of sodium chloride, filtered off, dissolved in 
1,000 parts of water and reacted with 39 parts of cyanuric chloride at a 
temperature below 10.degree. C. and at a pH value between 4 and 5. 
After the monocondensation product has been formed, an aqueous solution of 
10.8 parts of 1,4-diaminobenzene in 100 parts of water is added to the 
reaction mixture, the pH value is brought to 5 to 5.5, and the second 
condensation reaction is completed at 40.degree. to 50.degree. C. within 
the pH range of 5 to 5.5 by stirring for several hours. The reaction 
product is salted out by means of sodium chloride and filtered off, and 
suspended in 1,000 parts of water, and 36 parts of nicotinamide are added. 
This reaction batch is stirred at a temperature between 90.degree. and 
100.degree. C. and at a pH value between 4 and 5 for several hours, and 
the resulting disazo compound according to the invention is then salted 
out of the reaction mixture by means of potassium chloride. 
Filtration and drying give the alkali metal salt (predominantly the 
potassium salt) of the compound of the formula 
##STR20## 
in the form of an electrolyte-containing (predominantly potassium 
chloride-containing) brown powder. 
This compound has very good fiber-reactive dye properties and dyes for 
example wool or cellulose fiber materials by the application and fixing 
techniques customary in the art for fiber-reactive dyes. For example, 
applied analogously to Application Example 2, it produces on cotton deep 
dyeing and prints having a yellowish brown shade and good fastness 
properties. 
The compound according to the invention can also be used with advantage for 
dyeing cellulose fiber materials from an aqueous solution at a pH value 
between 5 and 8 and at a temperature between 110.degree. and 130.degree. 
C. under the conditions of the HTN process (for example analogously to 
Application Example 1). 
EXAMPLE 6 
18.5 parts of cyanuric chloride are reacted with 31.9 parts of 
1-amino-8-napthol-3,6-disulfonic acid and 20.7 parts of the disodium salt 
of 4,4'-diaminostilbene-2,2'-disulfonic acid in accordance with the 
directions of Example 1 of U.S. Pat. No. 4,323,497. To synthesize the 
disazo compound according to the invention, the condensation product thus 
prepared serves as a coupling component which is then reacted with the 
diazonium salt of 36 parts of 
2-bromo-4-(.beta.-sulfatoethylsulfonyl)-aniline. 
The disazo compound thus obtained is then reacted in its synthesis solution 
with 18.5 parts of nicotinic acid at a pH value of 4.5 to 5.0 and at a 
temperature of about 95.degree. C. for 3 hours to give the disazo compound 
according to the invention, which is then salted out by adding potassium 
chloride or isolated by evaporating or spray drying the reaction solution. 
Written in the form of the free acid, the disazo compound according to the 
invention has the formula 
##STR21## 
and exhibits very good fiber-reactive dye properties. For example, under 
the alkaline fixing conditions of the customary dyeing and printing 
methods for fiber-reactive dyes, it produces on cotton deep bluish red 
dyeings and prints having good fastness properties. 
Similarly, the so-called HTN process produces at a pH value between 6 and 7 
and at a temperature between 120.degree. and 140.degree. C., for example 
analogously to Application Example 1 or 4, deep violet dyeings on 
cellulose fiber materials which have the same good fastness properties. 
EXAMPLE 7 
Example 4 is repeated, except that 15.3 parts of cyanuric chloride are 
reacted with 23.9 parts of 2-amino-5-naphthol-7-sulfonic acid and then 
with 5.5 parts of 1,4-diaminobenzene and subsequently, in place of the 
nicotinamide of Working Example 4, with 18 parts of nicotinic acid. The 
coupling component thus obtained is then treated in its aqueous synthesis 
solution with an aqueous suspension of the diazonium salt of 41.1 parts of 
1-sulfo-6-(.beta.-sulfatoethylsulfonyl)-2-aminonaphthalene, and the 
coupling reaction is carried out at a pH value between 5 and 6. 
The resulting diazo compound according to the invention is isolated in a 
conventional manner. Written in the form of the free acid, it has the 
formula 
##STR22## 
and exhibits very good fiber-reactive dye properties. On cellulose fiber 
material, in particular, it produces by the customary application and 
fixing techniques for fiber-reactive dyes in the alkaline range at dyeing 
temperatures of preferably up to 90.degree. C. as well as in a neutral or 
weakly acid dye bath at dyeing temperatures between 100.degree. and 
140.degree. C., deep orange dyeings having good wet and light fastness 
properties. 
EXAMPLES 8 to 18 
The Table Examples which follow describe further disazo compounds according 
to the invention in terms of the symbols appearing in a general formula 
(A) 
##STR23## 
The compounds according to the invention can be prepared in a manner 
according to the invention, for example analogously to one of the above 
Working Examples, using the components evident from the Table Examples, 
and cyanuric chloride. They have good fiber-reactive dye properties and, 
not only in the presence of alkaline agents at dyeing temperatures (fixing 
temperatures) of up to 100.degree. C. but also in the weakly acid to 
neutral or weakly alkaline range at temperatures between 100.degree. and 
140.degree. C., produce on cellulose fiber materials deep, fast dyeings 
and prints in the hue indicated in the particular Table Example. 
__________________________________________________________________________ 
Substituent 
Substituent 
Hue 
Example 
Radical A 
Group R 
Group X--SO.sub.2 --D- 
R.sup.4 
R.sup.3 
R* (.lambda..sub.max = . . . 
__________________________________________________________________________ 
nm) 
8 1,4-Phenylene 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
Methoxy 
Methyl 
H orange (360) 
sulfonyl)-phenyl 
9 1,4-Phenylene 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
Acetylamino 
Hydrogen 
H orange (386) 
sulfonyl)-phenyl 
10 1,4-Phenylene 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
Hydrogen 
Hydrogen 
CH.sub.3 
orange (365) 
sulfonyl)-phenyl 
11 2-Bromo-4-(.beta.-sulfato- 
Methyl Hydrogen 
CH.sub.3 
orange 
ethylsulfonyl)- 
phenyl 
12 1,4-Phenylene 
Carboxy 
4-(.beta.-Sulfatoethyl-) 
Ureido Hydrogen 
CH.sub.3 
orange (375) 
sulfonyl)-phenyl 
13 1,4-Phenylene 
Carboxy 
1-Sulfo-6-(.beta.-sulfato- 
Ureido Hydrogen 
H orange (388) 
ethylsulfonyl)- 
naphth-2-yl 
14 2,2'-Disulfo- 
Carboxy 
4-(.beta.-Sulfatoethyl- 
Ureido Hydrogen 
H orange (342) 
stilben-4,4'- 
sulfonyl)-phenyl 
ylene 
15 2,2'-Disulfo- 
Carboxy 
2-Methoxy-5-(.beta.-sul- 
Ureido Hydrogen 
H orange (365) 
stilben-4,4'- 
fatoethylsulfonyl)- 
ylene phenyl 
16 2,2'-Disulfo- 
Carbamoyl 
2-Methoxy-5-(.beta.-sul- 
Ureido Hydrogen 
H orange (394) 
stilben-4,4'- 
fatoethylsulfonyl)- 
ylene phenyl 
17 3,3'-Disulfo- 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
Ureido Hydrogen 
H orange 
diphenyl-4,4'- 
sulfonyl)-phenyl 
ylene 
18 3,3'-Disulfo- 
Carboxy 
4-(.beta.-Sulfatoethyl- 
Ureido Hydrogen 
H orange 
diphenyl-4,4'- 
sulfonyl)-phenyl 
ylene 
__________________________________________________________________________ 
EXAMPLES 19 to 37 
The Table Examples below describe further disazo compounds according to the 
invention in terms of the symbols appearing in a general formula (B) 
##STR24## 
the 6- and 7-positions marked therein are intended to indicate whether the 
bond of the triazinylamino radical is bonded to the naphthol radical in 
the 6- or in the 7-position. The compounds according to the invention can 
be prepared in a manner according to the invention, for example 
analogously to one of the above Working Examples, using the components 
evident from the Table Examples, and cyanuric chloride. They have good 
fiber-reactive dye properties and, not only in the presence of alkaline 
agents at dyeing temperatures (fixing temperatures) of up to 100.degree. 
C., but also in the weakly acid to neutral or weakly alkaline range at 
temperatures between 100.degree. and 140.degree. C., produce on cellulose 
fiber materials deep, fast dyeings and prints in the hue indicated in the 
particular Table Example. 
__________________________________________________________________________ 
6- or 7- 
Hue 
Example 
Radical A Group R 
Group XSO.sub.2D 
R* position 
(.lambda..sub.max = . . . 
__________________________________________________________________________ 
nm) 
19 1,4-Phenylene 
Carboxy 
2-Methoxy-4-(.beta.-sul- 
H 7- red 
fatoethylsulfonyl)- 
phenyl 
20 1,4-Phenylene 
Carboxy 
4-(.beta.-Sulfatoethyl- 
H 6- orange (476) 
sulfonyl)-phenyl 
21 1,4-Phenylene 
Carboxy 
4-(.beta.-Sulfatoethyl- 
CH.sub.3 
6- orange (472) 
sulfonyl)-phenyl 
22 2-Sulfo-1,4- 
Carboxy 
2-Methoxy-5-(.beta.-sul- 
CH.sub.3 
6- red (492) 
phenylen fatoethylsulfonyl)- 
phenyl 
23 2-Sulfo-1,4- 
Carboxy 
2,5-Dimethoxy-4-(.beta. 
H 6- bluish red (500) 
phenylen sulfatoethylsulfonyl)- 
phenyl 
24 1,4-Phenylene 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
H 7- orange (480) 
sulfonyl)-phenyl 
25 1,4-Phenylene 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
H 6- orange (470) 
sulfonyl)-phenyl 
26 1,4-Phenylene 
Carbamoyl 
1-Sulfo-6-(.beta.-sul- 
H 6- orange 
fatoethylsulfonyl)- 
naphth-2-yl 
27 2,2'-Disulfo- 
Carbamoyl 
1-Sulfo-6-(.beta.-sul- 
H 6- red (492) 
stilben-4,4'- fatoethylsulfonyl)- 
ylene naphth-2-yl 
28 2,2'-Disulfo- 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
CH.sub.3 
6- orange 
stilben-4,4'- sulfonyl)-phenyl 
ylene 
29 2,2'-Disulfo- 
Carbamoyl 
2-Methoxy-5-(.beta.-sul- 
CH.sub.3 
6- red 
stilben-4,4'- fatoethylsulfonyl)- 
ylene phenyl 
30 2,2'-Disulfo- 
Carbamoyl 
2,5-Dimethoxy-4-(.beta.- 
H 6- red 
stilben-4,4'- sulfatoethylsulfonyl)- 
ylene phenyl 
31 2,2'-Disulfo- 
Carbamoyl 
2-Bromo-4-(.beta.-sulfato- 
H 6- orange 
stilben-4,4'- ethylsulfonyl)-phenyl 
ylene 
32 3,3'-Disulfo- 
Carbamoyl 
2-Bromo-4-(.beta.-sulfato- 
H 6- red 
stilben-4,4'- ethylsulfonyl)-phenyl 
ylene 
33 3,3'-Disulfo- 
Carboxy 
4-(.beta.-Sulfatoethyl- 
H 6- red 
stilben-4,4'- sulfonyl)-phenyl 
ylene 
34 3,3'-Disulfo- 
Carboxy 
2-Methyl-5-methoxy- 
H 6- red 
stilben-4,4'- 4-(.beta.-sulfatoethyl- 
ylene sulfonyl)-phenyl 
35 2,2'-Disulfo- 
Carboxy 
4-(.beta.-Sulfatoethyl- 
H 6- orange 
diphenyl- sulfonyl)-phenyl 
4,4'-ylene 
36 
##STR25## 
Carboxy 
4-(.beta.-Sulfatoethyl- sulfonyl)-phenyl 
H 6- orange 
37 
##STR26## 
Carbamoyl 
4-(.beta.-Sulfatoethyl- sulfonyl)-phenyl 
H 6- orange 
__________________________________________________________________________ 
EXAMPLES 38 to 56 
The Table Examples which follow describe further disazo compounds according 
to the invention in terms of the symbols appearing in a general formula 
(C) 
##STR27## 
The compounds according to the invention can be prepared in a manner 
according to the invention, for example analogously to one of the above 
Working Examples, using the components evident from the Table Examples, 
and cyanuric chloride. They have good fiber-reactive dye properties and, 
not only in the presence of alkaline agents at dyeing temperatures (fixing 
temperatures) of up to 100.degree. C. but also in the weakly acid to 
neutral or weakly alkaline range at temperatures between 100.degree. and 
140.degree. C., produce on cellulose fiber materials deep, fast dyeings 
and prints in the hue indicated in the particular Table Example. 
__________________________________________________________________________ 
Position of 
SO.sub.3 H rela- 
Hue 
Example 
Radical A Group R 
Group XSO.sub.2D 
tive to NH 
(.lambda..sub.max = . . . 
__________________________________________________________________________ 
nm) 
38 1,4-Phenylene 
Carboxy 
4-(.beta.-Sulfatoethylsul- 
meta- bluish red (510) 
fonyl)-phenyl 
39 1,4-Phenylene 
Carboxy 
4-Vinylsulfonyl-phenyl 
meta- bluish red 
40 1,4-Phenylene 
Carboxy 
2-Bromo-4-(.beta.-sulfato- 
meta- bluish red (512) 
ethylsulfonyl)-phenyl 
41 2-Sulfo-1,4- 
Carboxy 
4-(.beta.-Sulfatoethyl- 
meta- bluish red (510) 
phenylene sulfonyl)-phenyl 
42 1,4-Phenylene 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
meta- bluish red 
sulfonyl)-phenyl 
43 1,4-Phenylene 
Carbamoyl 
2-Methoxy-5-(.beta.-sul- 
meta- reddish violet 
fatoethylsulfonyl)- 
phenyl 
44 1,4-Phenylene 
Carbamoyl 
2-Methoxy-5-(.beta.-sul- 
para- red 
fatoethylsulfonyl)- 
phenyl 
45 1,4-Phenylene 
Carbamoyl 
2-Methoxy-5-vinyl- 
para- red 
sulfonyl-phenyl 
46 1,4-Phenylene 
Carboxy 
4-(.beta.-Sulfatoethyl- 
para- red (490) 
sulfonyl)-phenyl 
47 2,2'-Disulfo- 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
para- bluish red 
stilben-4,4'- sulfonyl)-phenyl 
ylene 
48 2,2'-Disulfo- 
Carboxy 
4-(.beta.-Sulfatoethyl- 
meta- reddish violet 
stilben-4,4'- sulfonyl)-phenyl 
ylene 
49 2,2'-Disulfo- 
Carboxy 
2-chloro-5-methoxy- 
meta- reddish violet (525) 
stilben-4,4'- 4-(.beta.-sulfatoethylsul- 
ylene fonyl)-phenyl 
50 
##STR28## 
Carboxy 
4-(.beta.-Sulfatoethyl- sulfonyl)-phenyl 
meta- bluish red (508) 
51 
##STR29## 
Carbamoyl 
4-(.beta.-Sulfatoethyl- sulfonyl)-phenyl 
meta- bluish red (508) 
52 
##STR30## 
Carbamoyl 
6-(.beta.-Sulfatoethyl- sulfonyl)-naphth-2-yl 
meta- reddish violet 
53 3,3'-Disulfo- 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
meta- reddish violet 
diphenyl-4,4'- sulfonyl)-phenyl 
ylene 
54 3,3'-Disulfo- 
Carboxy 
4-(.beta.-Sulfatoethyl- 
meta- reddish violet 
diphenyl-4,4'- sulfonyl)-phenyl 
ylene 
55 2,2'-Disulfo- 
Carboxy 
4-(.beta.-Sulfatoethyl- 
meta- reddish violet 
diphenyl-4,4'- sulfonyl)-phenyl 
ylene 
56 2,2'-Disulfo- 
Carbamoyl 
4-(.beta.-Sulfatoethyl- 
meta- reddish violet 
diphenyl-4,4'- sulfonyl)-phenyl 
ylene 
__________________________________________________________________________ 
APPLICATION EXAMPLE 1 
50 parts of a cotton fabric are introduced into a dye bath composed of 1 
part of the disazo compound according to the invention of Example 1 (in 
the form of a neutral salt), 50 parts of anhydrous sodium sulfate, 800 
parts of water and 200 parts of an aqueous buffer solution prepared from 
200 parts of water and 20 parts of 85% strength phosphoric acid and 
brought to pH 6 with sodium hydroxide solution. The fabric is treated in 
the bath at a temperature of 130.degree. C. with constant agitation for 90 
minutes. The dyeing obtained is then aftertreated by rinsing with warm and 
with hot water, by washing in an aqueous bath composed of 1,500 parts of 
water and 1.5 parts of a non-ionic agent at the boil for 15 minutes, and 
rinsing again with warm water, and dried. 
The result obtained is a deep blueish-red dyeing which has a good light 
fastness on dry and moist fabric, including a good perspiration light 
fastness, and good wet fastness properties, such as a good water, 
60.degree. C. and 95.degree. C. wash, perspiration and chlorinated water 
fastness, and also a good crock fastness. In addition the compound 
according to the invention exhibits a good color buildup in this dyeing 
process. 
If the dyeing process is carried out not at pH 6 but at pH 5, pH 7 or pH 8, 
similar blueish-red dyeings having virtually the same depth of shade as 
the dye prepared at pH 6 are obtained. 
APPLICATION EXAMPLE 2 
If the disazo compound according to the invention of Example 1 is used for 
dyeing cellulose fiber material, such as cotton fabric, in a dyeing method 
customary for fiber-reactive dyes, for example in an exhaust method at a 
temperature of 60.degree. C. or 80.degree. C. in the presence of an 
alkaline agent, such as sodium carbonate and sodium hydroxide solution, 
and of an electrolyte salt such as sodium sulfate, this likewise produces 
very deep blueish-red dyes having good fastness properties, of which in 
particular the good light fastness on dry and moist fabric, including a 
good perspiration light fastness, and also the good crock fastness and the 
good water, wash, perspiration and chlorinated water fastness properties 
can be singled out. 
APPLICATION EXAMPLE 3 
A dye bath is prepared from 80 parts of water, 0.05 part of the disazo 
compound according to the invention of Example 4, 5 parts of anhydrous 
sodium sulfate and 20 parts of an aqueous buffer solution which is capable 
of maintaining a pH value of 6, and 0.1 part of a predispersed disperse 
dye of Colour Index No. 11,227 (C.I. Disperse Orange 25) and 0.1 part of a 
commercially available dispersant customary for use with disperse dyes, 
such as ligninsulfonic acid, are then added. 
This dyeing liquor is used to dye 5 parts of a polyester/cotton blend 
fabric (50:50) at a temperature of 130.degree. C. and at a pH value of 6 
for 90 minutes. The dyed fabric is then taken out of the dyeing liquor and 
aftertreated and finished (for example as described in Application Example 
1). The result obtained is a uniformly dyed orange fabric where both the 
fiber portions are fully penetrated. The dyeing has the good fastness 
properties of the cotton dyeings of Example 4 and of the polyester dyeings 
of the known disperse dye. 
APPLICATION EXAMPLE 4 
A dye bath is prepared from 59 parts of water, 1 part of the disazo 
compound according to the invention of Example 3, 50 parts of anhydrous 
sodium sulfate and 5 parts of phosphoric acid, and the bath is brought to 
pH 4.5 with sodium carbonate. 50 parts of a cotton fabric are then 
introduced, and the dyeing is carried out in a sealed apparatus at a 
dyeing temperature of 140.degree. C. by constantly agitating for 30 
minutes. The dyed fabric is then removed and finished by rinsing with hot 
and cold water, by treatment at the boil for 15 minutes in an aqueous bath 
containing a small amount of a nonionic detergent, by rinsing again with 
water and drying. 
The result obtained is a deep orange cotton fabric having very good 
fastness properties.