Disazo compounds conforming to the general formula (1) below and suitable for use as fiber-reactive dyes for the dyeing of carboxamido-containing and/or hydroxy-containing materials such as wool and, in particular, cellulose fiber materials, in navy hues having good fastness properties ##STR1## in which M is a hydrogen atom or an alkali metal or alkaline earth metal, PA1 D.sup.1 is a phenyl radical which can be substituted by substituents from the group consisting of chlorine, bromine, sulfo, alkyl and alkoxy and additionally by a vinylsulfonyl or .beta.-sulfatoethylsulfonyl group or by a group of the general formula (3) ##STR2## where X is a vinyl or .beta.-sulfatoethyl group; D.sup.2 is a radical of the general formula (4) ##STR3## in which M and X have one of the abovementioned meanings and the amino group --NH-- is bound to the benzene ring in the para-position with respect to the sulfo group --SO.sub.3 M or in the paara-position with respect to the free bond.

The invention is in the technical field of fiber-reactive disazo dyes. 
Example 50 of German Patent No. 965,902 and furthermore U.S. Pat. Nos. 
2,657,205, 4,257,770 and 4,492,654, British Patent No. 1,183,661, German 
Offenlegungsschrift No. 3,113,989 and European Patent No. 0,063,276B have 
disclosed disazo compounds which have fiber-reactive dye properties and 
are synthesized from 1-amino-8-naphthol-3,6-disulfonic acid as bivalent 
coupling component and having a diazo component coupled under acidic 
conditions and one coupled under neutral conditions, at least one of which 
contains a fiber-reactive group from the vinylsulfone series. 
Novel, useful disazo compounds have now been found, which have improved 
properties and conform to the general formula (1) 
##STR4## 
in which M is a hydrogen atom or an alkali metal such as sodium, potassium 
or lithium, or is the equivalent of an alkaline earth metal such as of 
calcium, alkali metal; 
D.sup.1 is a radical of the general formula (2) 
##STR5## 
in which R.sup.1 is a hydrogen, chlorine or bromine atom or is a sulfo 
group, an alkyl group of 1 to 4 carbon atoms such as the ethyl group and 
in particular methyl group, or is an alkoxy group of 1 to 4 carbon atoms 
such as the ethoxy and the methoxy group, 
R.sub.2 is a hydrogen, chlorine or bromine atom or is a sulfo group, an 
alkyl group of 1 to 4 carbon atoms such as the ethyl group and in 
particular methyl group, or is a n alkoxy group of 1 to 4 carbon atoms 
such as the ethoxy group and the methoxy group, and 
Z is a group of the general formula X--SO.sub.2 --in which X denotes the 
vinyl group or a .beta.-sulfatoethyl group, or 
Z is a hydrogen atom or a sulfo group or a group of the general formula (3) 
##STR6## 
in which X has one of the above meanings; D.sup.2 is a radical of the 
general formula (4) 
##STR7## 
in which M and X have one of the abovementioned meanings and the amino 
group --NH--is bound to the benzene ring in the para-position with respect 
to the sulfo group --SO.sub.3 M or in the para-position with respect to 
the free bond; the formula members D.sup.1 and D.sup.2 and also the 
formula members and R.sup.1 and R.sup.2 also the two X can each have 
meanings identical to one another or different from one another. 
Preferably D.sup.1 is a radical of the general formula (2) in which Z 
stands for the group of the formula X--SO.sub.2 --. Preferably X denotes a 
.beta.-sulfatoethyl group. If Z in the radical of the general formula (2) 
is a group of the general formula (3), the radical of the general formula 
(2) is preferably a radical of the general formula (2a) 
##STR8## 
in which M and X have one of the abovementioned meanings and the amino 
group --NH--is bound to the benzene ring in the para-position with respect 
to the sulfo group --SO.sub.3 M or in the para-position with respect to 
the free bond. 
If Z in the radical of the general formula (2) is a group conforming to the 
general formula X--SO.sub.2 --, R.sup.1 is preferably a hydrogen atom or a 
methoxy group and R.sup.2 is preferably a hydrogen atom or a chlorine atom 
or a methyl group or methoxy group. 
In particular, a disazo compound according to the invention which can be 
mentioned is one in which D.sup.1 is the 
4-(.beta.-sulfatoethylsulfonyl)phenyl group and D.sup.2 is the 
2-sulfo-5-[2'-nitro-4'-(.beta.-sulfatoethylsulfonyl)phenylamino]phenyl 
group. 
The substituents "sulfo", "carboxy" and "sulfato" include not only their 
acid form but also their salt form. Accordingly sulfo groups denote groups 
conforming to the general formula --SO.sub.3 M, carboxy groups, groups 
conforming to the general formula --COOM and sulfato groups, conforming to 
the general formula --OSO.sub.3 M in which M has one of the abovementioned 
meanings. 
The novel azo compounds can be present in an acid form and in the form of 
their salts. Preferably they are in the form of their salts and are used 
preferably in the form of these salts for dyeing (here and hereinafter 
understood in its general meaning and including printing) hydroxy- and/or 
carboxamido-containing materials, in particular fiber materials. 
The present invention furthermore relates to a process for the preparation 
of disazo compounds of the general formula (1), which comprises coupling a 
monoazo compound of the general formula (5) 
##STR9## 
in which D.sup.1 and M have one of the abovementioned meanings with a 
diazonium salt of an aromatic amine of the general formula D.sup.2 
--NH.sub.2, where D.sup.2 has one of the abovementioned meanings, at a pH 
between 4 and 7.5, preferably between 5 and 6.5, in an aqueous or 
aqueous-organic medium, but preferably aqueous medium. As a rule, the 
coupling reaction is carried out at a temperature between 0 and 30.degree. 
C. 
Disazo compounds of the general formula (1) in which the formula radical(s) 
X each stand for a vinyl group can be prepared according to the invention 
also by reacting a disazo compound of the general formula (1) in which one 
or both formula radicals X denote a .beta.-sulfatoethyl group in an 
aqueous solution at a pH between 10 and 12, preferably between 10.5 and 
11.5,with an alkali such as sodium hydroxide. The reaction is carried out 
at a temperature between 15 and 50.degree. C, preferably between 20 and 
40.degree. C, the reaction time usually being 5 to 20 minutes; at the 
higher temperatures within the temperature range given, a shorter reaction 
time within the time range given must be maintained to avoid the 
disadvantageous formation of .beta.-hydroxyethylsulfonyl groups. 
The starting compounds of the general formula (5) are synthesized by 
generally known methods by the coupling reaction of 
1-amino-3,6-disulfo-8-naphthol with a diazonium salt of an aromatic amine 
of the general formula D.sup.1 --NH.sub.2, where D.sup.1 has the 
abovementioned meaning, in a strongly acidic aqueous medium. The starting 
compounds conforming to the general formula D.sup.1 --NH.sub.2 have been 
described numerous times in the literature, for example in U.S. Pat. No. 
4,701,523. Likewise the aminodiphenylamine compounds conforming to the 
general formulae D.sup.2 --NH.sub.2 and D.sup.1 --NH.sub.2, where Z is 
identical to a radical of the general formula (3), have been described in 
this U.S. Patent in columns 5 and 6 or can be synthesized analogously to 
instructions given there. 
The disazo compounds of the general formula (1) prepared according to the 
invention can be precipitated and isolated from the synthesis solutions by 
generally known methods, thus, for example, either by precipitation from 
the reaction medium by means of electrolytes such as, for example, sodium 
chloride or potassium chloride, or by evaporation of the reaction 
solution, for example spray-drying, it being possible to add a buffer 
substance to the synthesis solution. 
The disazo compounds according to the invention of the general formula (1) 
--hereinafter designated as compounds (1) --have, as already mentioned, 
fiber-reactive dye properties. They can therefore be used for dyeing 
hydroxy.TM..TM.and/or carboxamido-containing materials, in particular 
fiber materials. It is also possible to add the solutions which are formed 
during the synthesis of compounds (1), if necessary after the addition of 
a buffer substance and if necessary even after concentration, directly as 
liquid formulations for dyeing. 
The present invention therefore also relates to the use of compounds (1) 
for dyeing hydroxy and/or carboxamido-containing materials or to processes 
to apply them on these substrates. Preferably the materials are used in 
the form of fiber materials, in particular in the form of textile fibers 
such as yarns, wound packages and fabrics. This can be done analogously to 
known procedures. 
Hydroxy containing materials are those of natural or synthetic origin such 
as, for example cellulose fiber materials or regeneration products thereof 
and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, 
but also other plant fibers such as linen, hemp, jute and ramiefiber; 
regenerated cellulose fibers are, for example, staple viscose and filament 
viscose. 
Carboxamido-containing materials are, for example, synthetic and natural 
polyamides and polyurethanes, in particular in the form of fibers, for 
example wool and other animal hair, silk, leather, nylon 6,6, nylon 6, 
nylon 11 and nylon 4. 
The compounds (1) can be, in accordance with the use according to the 
invention, be applied to and fixed on the substrates mentioned, in 
particular to and on the fiber materials mentioned, by the application 
procedures known for water-soluble dyes, in particular for fiber-reactive 
dyes, for example by applying a compound (1) in dissolved form to the 
substrate or incorporating it therein and fixing it on this or in this 
substrate by the action of heat and/or by the action of an agent having an 
alkaline action. Such dyeing and fixation methods have been described 
numerous times not only in the technical but also in the patent literature 
such as, for example in U.S. Pat. No. 4,492,654 already mentioned at the 
beginning. 
Using compounds (1), strong navy to bluish black or greenish black or 
purely black dyeings and prints having good fastness properties can be 
prepared not only on carboxamido-containing materials but also on 
hydroxyl-containing material, such as in particular cellulose fiber 
material. In addition to the good light fastness of the dry dyed material 
and of the dyed material which has been moistened by drinking water or an 
alkaline or acidic perspiration solution, the good wet fastness 
properties, in particular the good wash, chlorine water, water, seawater, 
acid and alkali fastness properties and also the good acid and alkaline 
cross-dyeing and acid and alkaline perspiration fastness properties should 
be mentioned in particular. Compounds (1) are distinguished by good color 
build-up and by high degrees of fixation. 
The Examples which follow serve to illustrate the invention. Parts and 
percentages are by weight, unless stated otherwise. Parts by weight relate 
to parts by volume such as the kilogram to the liter. 
The compounds described in these Examples by the formula are given in the 
form of the free acids; in general, they are prepared and isolated in the 
form of their sodium or potassium salts and are used for dyeing in the 
form of their salts. Likewise, the starting compounds and components 
mentioned in the Examples which follow, in particular in the 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) 
given for the visible region were determined at 20.degree. C. on the 
aqueous solution of the alkali metal salts.

EXAMPLE 1 
An aqueous solution [preparation described below]of the diazonium salt of 
102 parts of 
2-nitro-4-(.beta.-sulfatoethyl-sulfonyl)-4'-sulfo-3'-aminodiphenylamine is 
added to an aqueous suspension of 121 parts of a monoazo compound 
(obtainable by acid coupling reaction of equivalent amounts of 
1-amino-3,6-disulfo-8-naphthol and 4-.beta.-sulfatoethylsulfonylaniline) 
in about 800 parts of water at a pH of 1.5 to 2; the coupling reaction is 
carried out at a pH between 6 and 6.5 and a temperature between 5 and 
25.degree. C [the diazonium salt is prepared by dissolving 102 o 30 parts 
of 2-nitro-4-('-sulfatoethylsulfonyl)-3'-amino-diphenylamine-4'-sulfonic 
acid in 1000 parts of water at a pH between 6.0 and 6.5 with the addition 
of sodium bicarbonate, then adding 36.2 parts of a 40% strength aqueous 
sodium nitrite solution and 300 parts of ice and then rapidly adding 100 
parts of a 31% strength aqueous hydrochloric acid solution to this mixture 
with stirring; stirring is continued for another hour at 0 to 5.degree. C, 
and excess nitrous acid is destroyed in the usual manner with a small 
amount of sulfamic acid]. After the second coupling reaction has been 
completed, the reaction batch is set to a pH of 5 with phosphoric acid and 
evaporated to dryness under reduced pressure. This gives a black 
electrolyte-containing powder of the sodium salt of the compound of the 
formula 
##STR10## 
The disazo compound according to the invention shows very good 
fiber-reactive dye properties and produces, on the materials mentioned in 
the description such as, in particular cellulose fibre materials, for 
example cotton, with the application and fixation methods customary in the 
art, in particular the application conditions customary for fiber-reactive 
dyes, navy dyeings having good fastness properties, of which in particular 
the good light fastness properties of the dry dyed material and also of 
the dyed material which has been moistened with drinking water or a 
perspiration solution; and also the good wash and chlorine fastness 
properties should be mentioned in particular. 
EXAMPLE 2 
Starting from the disazo compound according to the invention of Example 1, 
100 parts of this disazo compound are dissolved in 500 parts of water at 
20 to 25.degree. C. By adding a 33% strength aqueous sodium hydroxide 
solution, a pH of 11 is set and maintained for 10 minutes at a temperature 
of 25.degree. C. Glacial acetic acid is then added to the batch to set a 
pH of 5, 120 parts of sodium chloride are added, and stirring of the batch 
is continued for two to three hours. The disazo compound salted out is 
filtered off, washed with a 20% strength aqueous sodium chloride solution 
and dried at about 60.degree. C under reduced pressure. This gives the 
disazo compound according to the invention of the formula 
##STR11## 
as an electrolyte containing (sodium chloride containing) black powder. 
This disazo compound according to the invention likewise has very good 
fiber-reactive dye properties and produces, by the application methods 
customary for fiber-reactive dyes, navy dyeings having the good properties 
mentioned for the disazo compound according to the invention of Example 1. 
EXAMPLE 3 
250 parts of ice and then 35 parts of a 40% strength aqueous sodium nitrite 
solution are added to a solution of 36.6 parts of 4-vinylsulfonylaniline 
in 500 parts of water and 65 parts of a 31% strength aqueous hydrochloric 
acid. After excess nitrous acid has been destroyed with sulfamic acid, 63 
parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are added to 
this diazonium salt suspension, and the coupling reaction is continued for 
another hour with stirring at a temperature between 3 and 8.degree. C; 
finally, the pH is brought to 1.5 to 1.8 with sodium bicarbonate, and 
stirring is continued for another three hours at 5 to 12.degree. C. 
The solution of the diazo component described in Example 1 is added to the 
suspension of the monoazo compound thus prepared, and the coupling 
reaction is carried out under the conditions mentioned in Example 1. 
The disazo compound according to the invention is isolated in the usual 
manner, for example by salting it out with sodium chloride or by 
evaporation, such as, for example, by spray-drying. This gives the disazo 
compound according to the invention of the formula (written in the form of 
the free acid) 
##STR12## 
as an electrolyte containing (such as, for example sodium chloride 
containing) black powder. This disazo compound according to the invention 
also has very good fiber-reactive dye properties and produces, for example 
on cotton, strong navy dyeings having the good properties mentioned for 
the disazo compound according to the invention of Example 1. 
EXAMPLES 4 TO 23 
In the Table Examples which follow, further disazo compounds according to 
the invention conforming to a general formula (A) 
##STR13## 
are described by means of their components (M having one of the meanings 
mentioned in the description and preferably being an alkali metal). They 
can be prepared in a manner according to the invention, such as, for 
example, by one of the procedures described in the previous Working 
Examples, from the components evident from formula (A). They have very 
good fiber-reactive dye properties and produce, on the materials mentioned 
in the description, such as, in particular, cellulose fiber materials, for 
example cotton, strong dyeings and prints having good fastness properties 
and the hue (in this case for a cotton dyeing) mentioned in the particular 
Table Example. The numbers in parentheses indicate the absorption maximum 
in nm. 
______________________________________ 
Disazo compound according to formula (A) 
Ex. Radical D.sup.3 - 
Radical D.sup.4 - 
Hue 
______________________________________ 
4 2-Sulfo-4-[2'-nitro- 
2-Sulfo-4'-[2'-nitro 
navy 
4'-(.beta.-sulfatoethyl- 
4'-(.beta.-sulfatoethyl- 
(623) 
sulfonyl)phenyl- 
sulfonyl)phenyl- 
amino]phenyl amino]phenyl 
5 2-Bromo-4-(.beta.-sulfato- 
2-Sulfo-5-[2'-nitro- 
navy 
ethylsulfonyl)phenyl 
4'-(.beta.-sulfatoethyl- 
(616) 
sulfonyl)phenyl- 
amino]phenyl 
6 2-Methoxy-4-(.beta.-sul- 
2-Sulfo-5-[2'-nitro- 
navy 
fatoethylsulfonyl)- 
4'-(.beta.-sulfatoethyl- 
(621) 
phenyl sulfonyl)phenyl- 
amino]phenyl 
7 4-Vinylsulfonyl- 
2-Sulfo-4-[2'-nitro- 
navy 
phenyl 4'-(.beta.-sulfatoethyl- 
(613) 
sulfonyl)phenyl- 
amino]phenyl 
8 2-Chloro-5-(.beta.-sulfato- 
2-Sulfo-5-[2'-nitro- 
navy 
ethylsulfonyl)phenyl 
4'-(.beta.-sulfatoethyl- 
(618) 
sulfonyl)phenyl- 
amino]phenyl 
9 2-Bromo-4-(.beta.-sulfato 
2-Sulfo-4-[2'-nitro- 
navy 
ethylsulfonyl)phenyl 
4'-(.beta.-sulfatoethyl- 
(624) 
sulfonyl)phenyl- 
amino]phenyl 
10 2-Sulfo-4-vinylsul- 
2-Sulfo-5-[2'-nitro- 
greenish 
fonylphenyl 4'-(.beta.-sulfatoethyl 
navy 
sulfonyl)phenyl- 
(622) 
amino]phenyl 
11 2-Sulfo-4-(.beta.-sulfato- 
2-Sulfo-4-[2'-nitro- 
greenish 
ethylsulfonyl)phenyl 
4'-(.beta.-sulfatoethyl 
navy 
sulfonyl)phenyl- 
(632) 
amino]-phenyl 
12 2-Sulfo-4-(.beta.-sulfato- 
2-Sulfo-5-[2'-nitro- 
navy 
ethylsulfonyl)-5- 
4'-(.beta.-sulfatoethyl- 
(625) 
methoxyphenyl sulfonyl)phenyl- 
amino]phenyl 
13 4-(.beta.-Sulfatoethyl- 
2-Sulfo-4-[2'-nitro- 
navy 
sulfonyl)-2-methoxy- 
4'-(.beta.-sulfatoethyl- 
(635) 
5-methylphenyl sulfonyl)phenyl- 
amino]phenyl 
14 4-Sulfophenyl 2-Sulfo-5-[2'-nitro- 
navy 
4'-(.beta.-sulfatoethyl- 
(593) 
sulfonyl)phenyl- 
amino]phenyl 
15 4-Sulfophenyl 2-Sulfo-4-[2'-nitro- 
navy 
4'-(.beta.-sulfatoethyl- 
(603) 
sulfonyl)phenyl- 
amino]phenyl 
16 2-Sulfo-4-chloro- 
2-Sulfo-5-[2'-nitro- 
navy 
phenyl 4'-(.beta.-sulfatoethyl 
(603) 
sulfonyl)phenyl- 
amino]phenyl 
17 2-Sulfophenyl 2-Sulfo-5-[2'-nitro- 
navy 
4'-(.beta.-sulfatoethyl 
(598) 
sulfonyl)phenyl- 
amino]phenyl 
18 2-Chloro-4-(.beta.-sul- 
2-Sulfo-5-[2'-nitro- 
navy 
fatoethylsulfonyl)- 
4'-(.beta.-sulfatoethyl 
(615) 
phenyl sulfonyl)phenyl- 
amino]phenyl 
19 2,6-Dibromo-4-(.beta.-sul- 
2-Sulfo-4-[2'-nitro- 
reddish 
fatoethylsulfonyl)- 
4'-(.beta.-sulfatoethyl- 
navy 
phenyl sulfonyl)phenyl- 
(582) 
amino]phenyl 
20 2,5-Disulfophenyl 
2-Sulfo-5-[2'-nitro- 
navy 
4'-(.beta.-sulfatoethyl- 
(606) 
sulfonyl)phenyl- 
amino]phenyl 
21 2,5-Disulfophenyl 
2-Sulfo-4-[2'-nitro- 
navy 
4'-(.beta.-sulfatoethyl- 
(617) 
sulfonyl)phenyl- 
amino]phenyl 
22 2-Sulfo-4-methyl- 
2-Sulfo-5-[2'-nitro- 
navy 
phenyl 4'-(.beta.-sulfatoethyl- 
(598) 
sulfonyl)phenyl- 
amino]phenyl 
23 2-Sulfo-5-[2'-nitro- 
2-Sulfo-5-[2'-nitro- 
navy 
4'-(.beta.-sulfatoethyl- 
4'-(.beta.-sulfatoethyl- 
(615) 
sulfonyl)phenyl- 
sulfonyl)phenyl- 
amino]phenyl amino]phenyl 
______________________________________