There are described novel yellow to red azo compounds of the formula I ##STR1## wherein each D independently of the other is the radical of an aromatic or heterocyclic diazo component, each Z independently of the other is hydrogen or a C.sub.1 -C.sub.4 -alkyl group or an acylamino group, Y is hydrogen or an unsubstituted or substituted C.sub.1 -C.sub.6 -alkyl group, X is either the direct bond or C.sub.1 -C.sub.6 -alkylene, ##STR2## and n is a number from 2 to 6, preferably 2; and the substituent Y, in the case of an unsubstituted or substituted C.sub.1 -C.sub.6 -alkyl group, can also be bonded to the o-position relative to the N atom of the phenylene group to form a six-membered ring, or both Y substituents can be linked together to form a C.sub.1 -C.sub.6 -alkylene bridge; described also are processes for producing the novel compounds, and their use as dyes for dyeing and printing natural and synthetic textile materials, particularly polyamide and wool materials, and also cotton, whereby there are obtained dyeings which are distinguished by good general fastness properties, especially by a good dye build-up, very good fastness to wet processing, good fastness to light, and good resistance to formaldehyde and good stability to hydrolysis.

The invention relates to novel azo compounds, to processes for producing 
them, and to their use as dyes for dyeing and printing natural and 
synthetic textile materials, particularly polyamide and wool materials. 
The novel azo compounds correspond to the formula I 
##STR3## 
wherein each D independently of the other is the radical of an aromatic or 
heterocyclic diazo component, each Z independently of the other is 
hydrogen or a C.sub.1 -C.sub.4 -alkyl group or an acylamino group, Y is 
hydrogen or an unsubstituted or substituted C.sub.1 -C.sub.6 -alkyl group, 
X is either the direct bond or C.sub.1 -C.sub.6 -alkylene, 
##STR4## 
and n is a number from 2 to 6, preferably 2; and the substituent Y, in the 
case of an unsubstituted or substituted C.sub.1 -C.sub.6 -alkyl group, can 
be bonded to the o-position relative to the N atom of the phenylene group 
to form a six-membered ring, or both Y substituents can be linked together 
to form a C.sub.1 -C.sub.6 -alkylene bridge. 
As a radical of an aromatic or heterocyclic diazo component, D is for 
example a phenyl or naphthyl radical, or a radical of the thiazole, 
thiophene, imidazole, pyridine, indazole, pyrazole, triazole, 
brenzotriazole, thiadiazole, isothiazole, benzothiazole and phthalic acid 
imide series. These radicals can be identically or differently mono- or 
polysubstituted. Substituents are for example: CN; straight-chain or 
branched-chain C.sub.1 -C.sub.4 -alkyl and C.sub.1 -C.sub.4 -alkoxy 
groups; halogen, such as fluorine, chlorine or bromine; the CF.sub.3 
group; the SO.sub.2 -alkyl group, such as the methylsulfonyl, 
ethylsulfonyl, n- and iso-propylsulfonyl and n-, sec- and 
tert-butylsulfonyl groups; the SO.sub.2 -aryl group, such as the 
phenylsulfonyl group or naphthylsulfonyl group, which groups can be 
further substituted in the phenyl or naphthyl radical, for example by 
alkyl, especially methyl; the SO.sub.2 NH.sub.2 group; the SO.sub.2 
N-alkyl-N-cyclohexyl group, wherein the alkyl group has 1 to 4 carbon 
atoms, for example the SO.sub.2 N-methyl-N-cyclohexyl group or the 
SO.sub.2 -N-propyl-N-cyclohexyl group, the SO.sub.2 N(alkyl).sub.2 group, 
wherein the alkyl groups can have 1 to 4 carbon atoms, can be 
straight-chain or branched-chain and unsubstituted or substituted, for 
example the diethylaminosulfonyl group or the 
N-methyl-N-ethyl-aminosulfonyl group; it can also be the SO.sub.2 NH--R 
group, wherein R is an alkyl group having 1 to 8 carbon atoms which is 
unsubstituted or substituted, for example by phenyl, for example it is the 
monoethylaminosulfonyl group, n- and iso-monobutylaminosulfonyl group, 
monooctylaminosulfonyl group and benzylaminosulfonyl group; R can also be 
an aryl group, such as the phenyl or naphthyl group, or the cyclohexyl 
group or the group alkyl-(C.sub.1 -C.sub.4)--O--SO.sub.3 H. Further 
substituents in the radical D can be; the unsubstituted phenyl group or a 
phenyl group substituted by alkyl-(C.sub.1 -C.sub.4), particularly 
CH.sub.3, or the group alkyl (C.sub.1 -C.sub.4)--O--SO.sub.3 H; finally, 
the radical D can be substituted also by a fibre-reactive group, 
especially by an acyl group of a carboxylic acid, which contains at least 
one halogen atom which can be split off under dyeing conditions; the 
groups concerned are for example chloroacetylamino groups or 
.alpha.,.beta.-dibromopropionylamino groups or 
.alpha.,.beta.-dichloropropionylamino groups. 
Besides being able to be substituted by these stated substituents, the 
aromatic and heterocyclic radicals D can also be substituted by SO.sub.3 H 
groups, these groups either being bonded directly on the aromatic or 
heterocyclic ring or being located on one of the substituents. 
In preferred azo compounds of the formula I, D is the radical of an 
aromatic diazo component, particularly a phenyl group, which is mono- or 
polysubstituted by halogen, especially by chlorine, and optionally by 
SO.sub.3 H. 
As a C.sub.1 -C.sub.4 -alkyl group, Z is a straight-chain or branched-chain 
alkyl group, for example the methyl, ethyl, n-propyl, iso-propyl, n-, sec- 
or tert-butyl group; as an acylamino group, Z is in particular the 
acetylamino group. In preferred azo compounds, Z is the CH.sub.3 radical. 
The bridge member X can be the direct bond, which at the same time is the 
preferred meaning; or, as a C.sub.1 -C.sub.6 -alkylene bridge, it is one 
which can be either straight-chain or branched-chain. 
When the symbol Y denotes an unsubstituted C.sub.1 -C.sub.6 -alkyl group, 
this can be straight-chain or branched-chain; examples of such Y groups 
are: the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl or 
tert-butyl group, as well as the n- and iso-pentyl group and n- and 
iso-hexyl group. Apart from being substituted by the SO.sub.3 H group, all 
these alkyl groups Y can be further substituted for example by an OH, CN, 
--OSO.sub.3 H or phenyl group. In preferred azo compounds of the formula 
I, Y is an unsubstituted alkyl group, especially the C.sub.2 H.sub.5 
group. 
The azo compounds of the formula I can be of symmetrical nature 
(preferred), that is to say, the two symbols D and Z are each identical or 
are of asymmetrical nature. If they are asymmetrical compounds, it is 
possible for example for the two diazo components D and/or the two 
substituents Z to be of a different nature, for example in such a manner 
that the two radicals D are identical and one Z is hydrogen and the other 
Z methyl. 
A particularly valuable azo compound, especially on account of its good 
fastness to wet processing and to light on polyamide materials, 
corresponds to the formula 
##STR5## 
Mention may also be made of the azo compounds of the following formulae, 
which likewise yield dyeings having good wet fastness properties on 
polyamide materials: 
##STR6## 
The azo compounds of the formula I are yellow to red compounds which can be 
produced for example by coupling 2 mols of a diazo component of the 
formula II D--NH.sub.2 with 1 mol of a coupling component of the formula 
III 
##STR7## 
in which formulae II and III, the symbols D, Z, Y and X have the meanings 
defined under the formula I, the procedure being such that starting 
compounds II and III are used which yield azo compounds of the formula I 
containing 2 to 6 SO.sub.3 H groups, and/or that starting compounds II and 
III are used which have no SO.sub.3 H groups, in which case the coupling 
product is sulfonated after the coupling reaction. 
The diazo components of the formula II are known: they are for example the 
following compounds: 
##STR8## 
There are preferably used those diazo components D which are derived from 
an aromatic diazo component, particularly from a phenyl group which is 
mono- or polysubstituted by halogen, and optionally by SO.sub.3 H. 
The coupling components of the formula III, both those with and those 
without an SO.sub.3 H group, are for the most part novel. The following 
are given as examples of coupling components of this type: 
##STR9## 
Coupling components of the formula III preferably used are those wherein Z 
is a C.sub.1 -C.sub.4 -alkyl group, especially the CH.sub.3 group, X is 
the direct bond, and Y an unsubstituted C.sub.1 -C.sub.6 -alkyl group, 
particularly the C.sub.2 H.sub.5 group. 
The compounds of the formula III can be obtained by various process 
variants, for example by condensing in a known manner 2 mols of an amine 
of the formula 
##STR10## 
with one mol of a dihalogen compound of the formula 
EQU Hal--CH.sub.2 --X--CH.sub.2 --Hal 
wherein Z, Y and X have the meanings defined under the formula I, and "Hal" 
is a halogen atom. 
Another possibility for producing in particular compounds of the formula 
III wherein Y is unsubstituted or substituted alkyl is to alkylate or 
condense, in a known manner, a compound of the formula 
##STR11## 
with a compound introducing the group Y. 
When the compounds of the formula III are asymmetrical compounds on the 
basis of the substituents Z, these compounds can be produced for example 
by condensing a mixture of amines of the formulae 
##STR12## 
wherein Z, Y and X have the meanings defined under the formula I, and 
"Hal" is a halogen atom. 
In the case where in the formula III the two Y substituents are linked 
together to form an alkylene bridge, the compounds in question can be 
produced by the procedure described in J. Amer. Chem. Soc., 40, 1429 
(1918). 
The compounds of the formula III obtained in the described manner can be 
sulfonated for example by means of oleum or chlorosulfonic acid. 
The coupling reaction of the compound II with the compound III is performed 
in a known manner. 
The invention hence relates also to the novel intermediates of the formula 
IV 
##STR13## 
wherein each Z independently of the other is hydrogen or a C.sub.1 
-C.sub.4 -alkyl group or an acylamino group, Y.sub.1 is hydrogen or an 
unsubstituted or substituted C.sub.1 -C.sub.6 -alkyl group, X is either 
the direct bond or C.sub.1 -C.sub.6 -alkylene, 
##STR14## 
m is a number from 0-2, and the substituent Y.sub.1, in the case of an 
unsubstituted or substituted C.sub.1 -C.sub.6 -alkyl group, can also be 
bonded to the o-position relative to the N atom of the phenyl group to 
form a six-membered ring. 
The novel intermediates of the formula IV are used as coupling components 
for producing in particular azo compounds of the formula I, which for 
their part can be applied as dyes for dyeing and printing textile 
materials dyeable with anionic dyes, especially polyamide materials and 
wool, but also cellulose materials, such as cotton. Dyeing can be 
performed by any continuous or discontinuous methods suitable for the 
substrate concerned (for example exhaust, padding or printing processes). 
There are obtained with the azo dyes according to the invention dyeings 
which have good general fastness properties, particularly on polyamide and 
wool materials, such as above all a good dye build-up, very good wet 
fastness properties (fastness to perspiration, to washing and to hot 
water), good fastness to light, good resistance to formaldehyde and good 
stability to hydrolysis; finally, the novel azo dyes have a high degree of 
exhaustion, independently of the addition of auxiliaries. 
The textile materials can be in the most varied stages of processing: they 
can be in the form of knitted goods, fabrics, yarns and fibres, as well as 
in the form of finished articles, such as shirts.

Unless otherwise stated in the following Examples, which serve to further 
illustrate the invention, `parts` are parts by weight, percentages are 
percent by weight, and the temperatures are given in degrees Centigrade. 
The cationic dyes can be either in the free acid form --SO.sub.3 H or in 
the form of their salts --SO.sub.3.sup..crclbar. M.sup..sym., wherein M is 
for example an alkali metal, lithium, sodium, potassium, ammonium, mono-, 
di- and tri(C.sub.2 -C.sub.3 -alkanolammonium or mono-, di-, tri- or 
tetra-(C.sub.1 -C.sub.4 -alkyl)-ammonium. 
EXAMPLE 1 
A mixture consisting of 321 g of m-toluidine, 94 g of 1,2-dibromoethane and 
40 g of magnesium oxide is stirred for 12 hours at a temperature of 
100.degree.-102.degree., and then for 2 hours at 123.degree.-125.degree., 
whereupon 300 ml of isopropanol and 10 g of a filtering auxiliary 
(diatomaceous earth) are added, and the mixture is clarified through a 
suction filter. The filter residue is subsequently washed with 200 ml of 
hot isopropanol; the filtrates are combined, and the isopropanol and the 
excess of m-toluidine are afterwards removed in vacuo to leave as residue 
the product of the formula 
##STR15## 
in the form of viscous oil. 
By using, in place of dibromoethane, the dihalogen compounds listed in 
column I of the following Table 1, with otherwise the same procedure, 
there are obtained the products shown in column II. 
TABLE 1 
__________________________________________________________________________ 
II 
I 
##STR16## 
No. 
Dihalogen compound X 
__________________________________________________________________________ 
2 BrCH.sub.2CH.sub.2CH.sub.2Br 
CH.sub.2 
3 BrCH.sub.2CH.sub.2CH.sub.2CH.sub.2Br 
CH.sub.2CH.sub.2 
4 Br[CH.sub.2 ].sub.6Br 
[CH.sub.2].sub.4 
##STR17## 
##STR18## 
6 
##STR19## 
##STR20## 
7 BrCH.sub.2CHCHCH.sub.2Br 
CHCH 
8 
##STR21## 
##STR22## 
9 
##STR23## 
##STR24## 
10 BrCH.sub.2CH.sub.2OCH.sub.2CH.sub.2Br 
CH.sub.2OCH.sub.2 
__________________________________________________________________________ 
EXAMPLE 11 
A mixture consisting of 120 g of the compound of the formula 
##STR25## 
170 g of diethyl sulfate, 44 g of magnesium oxide and 500 ml of ethylene 
glycol monoethyl ether is stirred for 6 hours at a temperature of 
100.degree., whereupon 10 g of a filtering auxiliary are added and the 
mixture is clarified through a suction filter. The filter residue is 
washed with a total amount of 100 ml of hot ethylene glycol monoethyl 
ether, and the solvent is then removed in vacuo from the combined 
filtrates. The residue is taken up in 400 ml of toluene, and extraction is 
performed by shaking in a separating funnel three times with 80 ml of 0.5N 
sodium hydroxide solution each time, the resulting product being then 
washed neutral with water. The organic phase is dried over magnesium 
sulfate, the toluene is removed in vacuo, and the residue is subjected to 
fractional distillation under high vacuum to yield the product of the 
formula 
__________________________________________________________________________ 
Elementary analysis: 
__________________________________________________________________________ 
##STR26## calculated: found: 
C 81.03, H 9.52, N 9.45; C 81.22, H 
9.54, N 9.34. 
__________________________________________________________________________ 
in the form of viscous oil: b.p. 0.4 mm Hg/158.degree.-169.degree.. 
By using, in place of the above-given starting materials, equivalent 
amounts of the compounds 2-7 and 10 listed in column II of Table 1, with 
otherwise the same procedure, there are obtained the corresponding 
compounds of the formulae 
__________________________________________________________________________ 
##STR27## b.p. 0.1 mm Hg/73.degree., 
##STR28## b.p. 0.1 mm Hg/105.degree., 
##STR29## b.p. 0.1 mm Hg/165-167.degree. 
Elementary analysis: calculated: C 
81.76, H 10.29, N 7.95, found: C 
81.79, H 10.18, N 8.10. 
##STR30## 
##STR31## 
##STR32## b.p. 0.7 mm Hg/184-188.degree., 
Elementary analysis: calculated: C 
81.34, H 9.38, N 8.63, found: C 
82.01, H 9.64, N 8.71 
##STR33## 
__________________________________________________________________________ 
EXAMPLE 12 
A mixture of 270 g of N-ethyl-m-toluidine, 94 g of 1,2-dibromoethane and 40 
g of magnesium oxide is stirred for 12 hours at 100.degree.-105.degree. 
and subsequently for 2 hours at 123.degree.-125.degree., whereupon the 
mixture is diluted with 300 ml of isopropanol and, after the addition of 
10 g of a filtering auxiliary, clarified through a suction filter. The 
filter residue is washed with 200 ml of hot isopropanol; the filtrates are 
then combined, and the isopropanol is removed in vacuo. The residue is 
subjected to fractional distillation under high vacuum, whereby the 
product of the formula 
##STR34## 
which is identical to that of Example 11, can be isolated as a viscous 
oil. 
By using, in place of dibromoethane, equivalent amounts of the dihalogen 
compounds shown in column I of the following Table 2, the procedure 
otherwise being the same, there are obtained the compounds listed in 
column II. 
TABLE 2 
__________________________________________________________________________ 
II 
I 
##STR35## 
No. Dihalogen compound X 
__________________________________________________________________________ 
13 BrCH.sub.2CH.sub.2CH.sub.2Br 
CH.sub.2 
14 BrCH.sub.2CH.sub.2CH.sub.2CH.sub.2Br 
CH.sub.2CH.sub.2 
15 Br[CH.sub.2].sub.6Br [CH.sub.2].sub.4 
16 
##STR36## 
##STR37## 
17 
##STR38## 
##STR39## 
18 ClCH.sub.2CH CHCH.sub.2Cl CHCH 
19 
##STR40## 
##STR41## 
20 
##STR42## 
##STR43## 
21 ClCH.sub.2CH.sub.2OCH.sub.2CH.sub.2Cl 
CH.sub.2OCH.sub.2 
__________________________________________________________________________ 
EXAMPLE 22 
A mixture of 120 g of the compound of the formula 
##STR44## 
138 g of 2-bromoethanol and 40 g of magnesium oxide is stirred for 12 
hours at 120.degree.-122.degree., whereupon 300 ml of isopropanol and 10 g 
of a filtering auxiliary are added, and the mixture is clarified through a 
suction filter. The filter residue is washed with a total of 200 ml of hot 
isopropanol, and from the combined filtrates the isopropanol is distilled 
off in vacuo. The residue is subjected to fractional distillation under 
high vacuum, and the product of the formula 
##STR45## 
is separated in the form of viscous oil. 
If there are used, instead of the above stated starting material, 
equivalent amounts of the compound of the formula 
##STR46## 
with otherwise the same procedure, there is obtained the product of the 
formula 
##STR47## 
By using, instead of bromoethanol, equivalent amounts of benzyl chloride, 
the procedure otherwise being the same, there are obtained the compounds 
of the formulae 
##STR48## 
EXAMPLE 23 
A mixture consisting of 120 g of the compound of the formula 
##STR49## 
60 g of acrylonitrile, 4 g of copper(1) chloride and 150 ml of glacial 
acetic acid is stirred under reflux for 24 hours. The acetic acid is 
thereupon removed in vacuo, and the residue is treated with a 3% solution 
of ethylenediamine in water; the residue is afterwards treated firstly 
with water, then with 2% hydrochloric acid, and finally again with water 
until a neutral reaction is indicated. Drying in vacuo at 70.degree. 
yields the product of the formula 
##STR50## 
EXAMPLE 24 
A mixture consisting of 120 g of the compound of the formula 
##STR51## 
125 g of propanesultone-1,3, 40 g of magnesium oxide and 600 ml of 
ethylene glycol monoethyl ether is stirred for 12 hours at 
110.degree.-115.degree., whereupon the solvent is removed as completely as 
possible in vacuo. To the residue is added 1 liter of water and then 
hydrochloric acid is added in order to dissolve residues of magnesium 
salts; the pH value is subsequently adjusted to about 5 by the addition of 
potassium hydroxide solution, and the product of the formula 
##STR52## 
is precipitated as potassium salt, which dissolves in water to give a 
colourless solution. 
EXAMPLE 25 
44.8 g of the compound of the formula 
##STR53## 
are introduced into a mixture of 23.5 g of 20% oleum and 53 g of 98% 
sulfuric acid at 15.degree., whereupon the mixture is cooled to 
10.degree., and 42 g of 65% oleum are added at this temperature. The 
temperature is raised to 20.degree.-22.degree., and the mixture is stirred 
for a further 2 hours at this temperature, and is then poured into a 
mixture of 180 g of ice and 75 ml of water. The solution obtained is 
heated to 80.degree., and about 170 g of calcium carbonate are added until 
the solution is neutral; it is then diluted with 350 ml of water; 50 g of 
a filtering auxiliary (diatomaceous earth) are added and the mixture is 
filtered through a suction filter, whereupon the filter residue is washed 
with hot water. Sodium carbonate is added to the brown solution at 
80.degree. until the pH value is 7-8, and the precipitated calcium 
carbonate is separated through a suction filter. The filtrate is 
evaporated in vacuo to dryness, and the residue is subsequently dried in a 
vacuum chamber at 70.degree. to yield the product of the formula 
##STR54## 
in the form of its sodium salt, as a light-beige coloured powder, which 
readily dissolves in water. 
When there is used, instead of the above-mentioned starting material, an 
equivalent amount of the compound of the formula 
##STR55## 
the procedure otherwise being the same, there is obtained the compound of 
the formula 
##STR56## 
EXAMPLE 26 
A mixture consisting of 190 g of the compound of the formula 
##STR57## 
108 g of 1,4-dibromobutane and 40 g of magnesium oxide is stirred for 12 
hours at 120.degree.-125.degree., whereupon the mixture is diluted with 
300 ml of toluene and, after the addition of 10 g of a filtering 
auxiliary, it is clarified through a suction filter. The filter residue is 
washed with hot toluene, the filtrates are combined, and the toluene is 
then distilled off in vacuo. The residue is subjected to fractional 
distillation under high vacuum to thus obtain the product of the formula 
##STR58## 
EXAMPLE 27 
5.10 g of 2,5-dichloroaniline-4-sulfonic acid are dissolved in 60 ml of 
water to form a neutral solution; 5.25 ml of 4N nitrite solution are 
added, and the whole is poured, with thorough stirring, onto a mixture of 
60 g of fine ice and 6 ml of 36% hydrochloric acid. After completed 
diazotisation, the nitrite excess is decomposed with sulfamic acid. The pH 
value of the diazo suspension is adjusted to 3 by the careful addition of 
solid sodium carbonate at 0.degree.-2.degree.. There is then added 
dropwise at 0.degree.-2.degree. a solution of 3 g of the compound of the 
formula 
##STR59## 
in 15 ml of acetic acid, the pH value being maintained at 3-4 by the 
addition of ammonium acetate. After completed coupling, the pH value is 
adjusted to 5.5 with sodium hydroxide solution, the temperature is raised 
to 55.degree., and 2 vol.% of sodium chloride is added, whereupon the dye 
precipitates after a short time as sodium salt. The resulting dye of the 
formula 
##STR60## 
readily dissolves in water to give a red shade. The dyeings produced with 
this dye at pH 6 on polyamide have very good fastness to wet processing 
and good fastness to light. The degree of exhaustion at pH 6 and the 
build-up are excellent. 
By using, in place of 2,5-dichloroaniline-4-sulfonic acid, equivalent 
amounts of the diazo components D--NH.sub.2 listed in Table 3 under I, 
with otherwise the same procedure, there are obtained, after diazotisation 
and coupling thereof to the coupling component given in the above Example, 
the dyes of the formula 
##STR61## 
which likewise produce at pH 6 on polyamide dyeings having fastness to wet 
processing and to light. 
TABLE 3 
______________________________________ 
II 
I Shade on 
No. Diazo component (D)NH.sub.2 
polyamide 
______________________________________ 
28 
##STR62## bluish-red 
29 
##STR63## " 
30 
##STR64## " 
31 
##STR65## " 
32 
##STR66## " 
33 
##STR67## red 
34 
##STR68## " 
35 
##STR69## " 
36 
##STR70## " 
37 
##STR71## " 
38 
##STR72## " 
39 
##STR73## " 
40 
##STR74## bluish-red 
______________________________________ 
EXAMPLE 40a 
When there is used as coupling component the compound of the formula 
##STR75## 
and the diazo component given in Example 34, with otherwise the same 
procedure, there is obtained the dye of the formula 
##STR76## 
which dyes polyamide at pH 6 in a red shade which is fast to wet 
processing and to light. 
By using as diazo component 2,5-dichloroaniline-4-sulfonic acid and as 
coupling component any one of those listed in the following Table 4, the 
procedure otherwise being the same, there are obtained dyes of the formula 
##STR77## 
which produce on polyamide at pH 6 dyeings which are fast to wet 
processing and to light. 
TABLE 4 
______________________________________ 
No. 
##STR78## amidepoly-onShade 
______________________________________ 
41 CH.sub.2 red 
42 CH.sub.2CH.sub.2 " 
43 
##STR79## " 
44 
##STR80## " 
45 CH.sub.2CH.sub.2CH.sub.2CH.sub.2 
" 
46 CHCH " 
47 CH.sub.2OCH.sub.2 " 
48 
##STR81## " 
49 
##STR82## " 
______________________________________ 
By using as coupling component an equivalent amount of the compound of the 
formula 
##STR83## 
with otherwise the same procedure, there is obtained the dye of the 
formula 
##STR84## 
which produces at pH 6 on polyamide scarlet dyes having fastness to wet 
processing and to light. 
EXAMPLE 50 
10.3 g of 5-chloroaniline-2,4-disulfonamide are dissolved at 50.degree. in 
40 ml of sulfolane; the solution is diluted with 50 ml of hot water, and 
10 ml of 36% hydrochloric acid are then added. After cooling to 2.degree., 
the mixture is diazotised with 20 ml of 4N nitrite; it is stirred for a 
further 30 minutes at 0.degree.-2.degree., and a nitrite excess is 
decomposed with sulfamic acid. 
5 g of the compound of the formula 
##STR85## 
are then dissolved at 50.degree. in 50 ml of water with the addition of 4 
ml of 36% hydrochloric acid, and this solution is added dropwise to the 
diazo solution, the temperature being maintained at 8.degree.. The mixture 
is subsequently stirred for 17 hours at room temperature, the temperature 
is then raised to 50.degree., and the dye which has precipitated is 
filtered off and washed with 200 ml of water. The filter material is 
suspended in 200 ml of water, the temperature is raised to 45.degree., and 
the pH value of the mixture is adjusted with conc. sodium hydroxide 
solution to 7.4. 2.5 vol.% of sodium chloride and 70 ml of 95% alcohol are 
added, whereupon the dye which has precipitated is filtered off, washed 
with 150 ml of 5% sodium chloride solution, and subsequently dried at 
70.degree. in vacuo. 
The resulting dye of the formula 
##STR86## 
dissolves in water to give a red shade. The red dyeings produced using 
this dye at pH 6 on polyamide have good fastness to light and to wet 
processing. 
By using, in place of the above-stated coupling component, equivalent 
amounts of the coupling components shown in the following Table 5, with 
otherwise the same procedure, there are obtained the dyes of the formula 
##STR87## 
having similar properties. 
TABLE 5 
______________________________________ 
No. 
##STR88## amidepoly-onShade 
______________________________________ 
51 CH.sub.2 red 
52 CH.sub.2CH.sub.2 " 
53 
##STR89## " 
54 
##STR90## " 
55 CH.sub.2CH.sub.2CH.sub.2CH.sub.2 
" 
56 CHCH " 
57 CH.sub.2OCH.sub.2 " 
58 
##STR91## " 
59 
##STR92## " 
______________________________________ 
If there are used, in place of the initially stated coupling component, 
equivalent amounts of the coupling component of the formula 
##STR93## 
with otherwise the same procedure, there is obtained, with use of 
5-chloroaniline-2,4-disulfonamide as the diazo component, the dye of the 
formula 
##STR94## 
which produces at pH 6 on polyamide bluish-red dyeings having fastness to 
wet processing and to light. 
If there are used in the last Example, instead of 
2,4-disulfonamido-5-chloro-aniline as the diazo component, an equivalent 
amount of 2,5-dichloroaniline-4-sulfonic acid, the procedure otherwise 
being the same, there is obtained the dye of the formula 
##STR95## 
which dyes polyamide from an aqueous bath at pH 6 in bluish-red shades 
having fastness to wet processing and to light. 
EXAMPLE 60 
2/100 ml of the diazo compound of 2,5-dichloroaniline-4-sulfaethylamine as 
an aqueous suspension, the pH value of which has been adjusted to 3 with 
sodium carbonate, is added at 0.degree.-5.degree. to a solution of 1/100 
mol of the compound of the formula 
##STR96## 
in the form of its sodium salt dissolved in 100 ml of water. Coupling is 
performed at 0.degree.-5.degree., the pH value being kept at 3-4; the pH 
value is subsequently adjusted to 7 with sodium hydroxide solution, and 
the dye is isolated in the customary manner by salting out with sodium 
chloride. The resulting dye of the formula 
##STR97## 
dyes polyamide at pH 6 in bluish-red shades having fastness to wet 
processing and to light. 
By using, instead of the above-given coupling component, equivalent amounts 
of the coupling component of the formula 
##STR98## 
the procedure being otherwise the same, there is obtained the dye of the 
formula 
##STR99## 
which has similar properties. 
With use of an equivalent amount of the coupling component of the formula 
##STR100## 
the procedure otherwise being the same, there is obtained the dye of the 
formula 
##STR101## 
which dyes polyamide at pH 6 from an aqueous bath in bluish-red shades 
fast to wet processing and to light. 
By using, instead of 2,5-dichloroaniline-4-sulfethylamide, an equivalent 
amount of the diazonium compound of 2-amino-benzothiazole, with otherwise 
the same procedure, there are obtained the corresponding dyes of the 
formula 
##STR102## 
which dye polyamide at pH 6 in fast bluish-red shades. 
EXAMPLE 61 
1/100 mol of the compound of the formula 
##STR103## 
obtained by diazotisation of 2,5-dichloroaniline-4-sulfethylamine and 
coupling to the compound of the formula 
##STR104## 
is dissolved in 40 ml of pyridine; 4 g of chlorosulfonic acid are then 
added, and the mixture is stirred for 8 hours at a temperature of 
68.degree.-70.degree.. After cooling of the mixture, a small amount of 
water is added, 6 g of sodium bicarbonate are subsequently added, and the 
pyridine is distilled off in vacuo at 40.degree.-50.degree. bath 
temperature. To the residue are added 30 ml of water; the pH value is 
adjusted to 7, and the dye is precipitated at 60.degree. with sodium 
chloride; the dye is in the form of oil, which is isolated and 
subsequently freed in vacuo at 70.degree. from adhering water. The 
resulting dye of the formula 
##STR105## 
readily dissolves in water to give a red shade. The red dyeings produced 
with the use of this dye at pH 6 on polyamide have good fastness to wet 
processing and to light. 
If there is used, in place of the aforementioned disazo dye, the same dye 
but one containing no methyl group in the benzene nuclei of the coupling 
component, the procedure otherwise being the same, there is obtained by 
reaction with chlorosulfonic acid the dye of the formula 
##STR106## 
which dyes polyamide at pH 6 in a red shade which is fast to light and to 
wet processing. 
EXAMPLE 62 
A mixture consisting of 55 g of N-ethyl-N-chloroethylaniline, 162 g of 
N-ethyl-m-toluidine and 6 g of magnesium oxide is stirred for 2 hours at a 
temperature of 148.degree.-150.degree., in the course of which formed 
water is distilled off at reduced pressure into a receiver. The mixture is 
allowed to cool, the magnesium salts are filtered off, and the filtrate is 
subjected to distillation under high vacuum, whereupon the formed product 
of the formula 
##STR107## 
is obtained as viscous oil. 
If there is used, instead of N-ethyl-m-toluidine, an equivalent amount of 
N-ethyl-aniline, the procedure otherwise being the same, there is obtained 
the product of the formula 
##STR108## 
EXAMPLES 63-72 
If the diazo components D--NH.sub.2 listed in the following Table 6 are 
coupled (at the position .fwdarw.) in the customary manner in the acid pH 
range to the coupling component of the formula 
##STR109## 
there are obtained disazo dyes which dye polyamide at pH 6 with a very 
good degree of exhaustion. The dyeings obtained have a high fastness to 
wet processing. 
TABLE 6 
______________________________________ 
Shade 
on 
poly- 
No. Diazo component DNH.sub.2 amide 
______________________________________ 
63 
##STR110## red 
64 
65 ##STR111## "- 
##STR112## " 
66 
##STR113## " 
67 
##STR114## " 
68 
##STR115## " 
69 
##STR116## " 
70 
##STR117## yellow 
70a 
##STR118## " 
71 
##STR119## " 
72 
##STR120## red- dish- yellow 
______________________________________ 
EXAMPLES 73-84 
By employing the coupling component of the formula 
##STR121## 
the procedure otherwise being analogous to that in Examples 63-72, there 
are obtained, with use of the diazo components given in Table 7, disazo 
dyes which have similar properties. 
TABLE 7 
______________________________________ 
Shade 
on 
poly- 
No. Diazo components amide 
______________________________________ 
73 
##STR122## red 
74 
##STR123## " 
75 
##STR124## " 
76 
##STR125## " 
77 
##STR126## " 
78 
##STR127## yel- low- ish- red 
79 
##STR128## red 
80 
##STR129## yellow 
81 
##STR130## " 
82 
##STR131## " 
83 
##STR132## " 
84 
##STR133## red- dish- yellow 
______________________________________ 
EXAMPLE 85 
2/100 mol of the diazonium compound of 2,5-dichloroaniline-4-sulfonic acid 
is coupled, at a temperature of 0.degree.-2.degree. and a pH value of 3-4, 
with 1/100 mol of the compound of the formula 
##STR134## 
(produced according to J. Amer. Chem. Soc. 40, 1429 (1918) or Ber. 22, 
1778), and the formed dye of the formula 
##STR135## 
is subsequently isolated as sodium salt, which forms a red powder which 
dissolves in water to give a red shade. 
Dyed on polyamide at pH 6, the dye has a very high degree of exhaustion. 
The red dyeings obtained have good fastness to wet processing and to 
light. 
When there are used, in place of 2,5-dichloroaniline-4-sulfonic acid, 
equivalent amounts of the diazo components, D--NH.sub.2, given in the 
following Table 8, there are obtained disazo dyes of the formula 
##STR136## 
which produce on polyamide at pH 6 dyeings likewise having very good wet 
fastness properties. 
TABLE 8 
______________________________________ 
Shade on 
No. Diazo components DNH.sub.2 
polyamide 
______________________________________ 
86 
##STR137## red 
87 
##STR138## " 
88 
##STR139## " 
89 
##STR140## " 
______________________________________ 
EXAMPLE 89a 
If the coupling component of the formula 
##STR141## 
is used, and to this are coupled 2 equivalents of diazotised 
2,5-dichloroaniline-4-sulfonic acid, there is obtained the dye of the 
formula 
##STR142## 
which dyes polyamide at pH 6 in a red shade having very good fastness to 
wet processing. 
When there are used, in place of the coupling component given above, 
equivalent amounts of the coupling component of the formula 
______________________________________ 
##STR143## 
Elementary analysis: 
______________________________________ 
calculated: 
C 81.16, H 8.33, N 16.52 
found: C 80.83, H 8.63, N 10.89 
______________________________________ 
(prepared according to J. Amer. Chem. Soc. 40, 1429 (1918) or Ber. 22, 1778 
with use of m-toluidine instead of aniline), there are obtained, with the 
use of the diazo components, D--NH.sub.2, given in the following Table 9, 
disazo dyes of the formula 
##STR144## 
which produce on polyamide at pH 6 likewise dyeings having a high degree 
of exhaustion and good fastness to wet processing. 
TABLE 9 
______________________________________ 
Shade on 
No. Diazo components DNH.sub.2 
polyamide 
______________________________________ 
90 
##STR145## red 
91 
##STR146## " 
92 
##STR147## " 
93 
##STR148## " 
94 
##STR149## " 
______________________________________ 
EXAMPLE 95 
(A) 1. Diazotisation 
1.73 g of orthanilic acid are dissolved in 25 ml of water with sodium 
hydroxide solution at pH 7, and 2.5 ml of 4N sodium nitrite are added. The 
solution is added dropwise to a mixture of 25 g of ice and 2.5 ml of 
concentrated hydrochloric acid. The diazo solution obtained is 
subsequently stirred, and any excess of nitrite present is decomposed with 
sulfamic acid. 
(B) Coupling to the monoazo dye 
2.82 g of the reaction product of N-ethyl-m-toluidine with 
N-ethyl-N-(2-chloroethyl)-aniline are dissolved in 25 ml of water with the 
addition of 3 ml of concentrated hydrochloric acid, and this solution is 
added dropwise to the diazo solution (A) produced above. The mixture is 
stirred cold for some time, and a constant pH value of 4 is then 
established with 4N sodium acetate. The monoazo dye which has precipitated 
is filtered off and washed with water. 
(C) 2. Diazotisation 
3.27 g of 2-amino-4'-methyl-diphenylsulfone-4-sulfonic acid are diazotised 
in the same manner as orthanilic acid under (A). 
(D) Coupling to the disazo dye 
The paste of the monoazo dye obtained under (B) is dissolved in 100 ml of 
water with sodium hydroxide solution at pH 7. The diazo suspension (C) is 
added in portions. To the reaction mixture are added 5 ml of pyridine, and 
stirring is continued overnight at room temperature. The dye is isolated 
by adjustment of the pH value to about 0.5 with conc. hydrochloric acid 
and filtered off; the paste is then taken into solution in 100 ml of water 
with sodium hydroxide solution at pH 7, and subsequently evaporated to 
dryness. 
There are obtained 6.26 g of a scarlet dye powder of the formula 
##STR150## 
The dye has an excellent build-up capacity on polyamide and has good 
general fastness properties. 
EXAMPLE 96 
(A) 1. Diazotisation 
1.73 g of orthanilic acid are diazotised as under Example 95(A). 
(B) Coupling to the monoazo dye 
2.68 g of N,N'-diethyl-N,N'-diphenyl-diaminoethane are dissolved in 30 ml 
of water with the addition of 3 ml of concentrated hydrochloric acid, and 
the solution is added to the diazo solution produced above. Stirring is 
maintained for 1 day at 40.degree.-45.degree., and the monoazo dye thus 
obtained is then filtered off. 
(C) 2. Diazotisation 
3.27 g of 2-amino-4'-methyl-diphenylsulfone-4-sulfonic acid are diazotised 
in the same manner as orthanilic acid in Example 95(A). 
(D) Coupling to the disazo dye 
The paste of the monoazo dye obtained under (B) is dissolved in 100 ml of 
water with sodium hydroxide solution at pH 9, and 10 ml of 4N sodium 
acetate solution are added. After the addition of the disazo suspension 
(C), stirring is continued for a time, and the pH value is then brought to 
7 with sodium hydroxide solution. To the solution which has been clarified 
by filtration are added 15 g of potassium chloride; and the product which 
precipitates is filtered off and dried. The yield is 4.95 g of a 
reddish-orange dye powder of the formula 
##STR151## 
EXAMPLE 97 
A dye bath is prepared from 4000 parts of water, 4 parts of ammonium 
acetate, 2 parts of the dye according to Example 27 and an amount of 
acetic acid to bring the pH value of the bath to 6. 100 parts of a 
synthetic polyamide tricot are introduced into the dye bath obtained; the 
bath is then heated within half an hour to boiling and the material is 
dyed for 45 minutes at 100.degree.. A red dyeing have good fastness to wet 
processing is obtained. 
EXAMPLE 98 
100 parts of wool knitting yarn are introduced at 50.degree. into a dye 
bath which contains, to 4000 parts of water, 2 parts of the dye of Example 
27, 4 parts of ammonium sulfate and 2 parts of a levelling auxiliary. The 
liquor is brought to boiling in the course of 45 minutes, and is held for 
a further 45 minutes at boiling temperature. The dyed material is then 
removed, thoroughly rinsed with cold water and dried. A red wool dyeing 
having good fastness properties is obtained. 
EXAMPLE 99 
2 g of the dye according to Example 70a are dissolved in 100 ml of hot 
water; the liquor is briefly boiled up and is then padded directly in a 
padding machine, with a liquor absorption of 70-80%, onto 10 g of 
mercerized bleached cotton satin. The cotton satin impregnated with dye is 
subsequently dried in a drying chamber at 70.degree.. To fix the dye, 200 
ml of water containing 6 g of calc. sodium sulfate are heated to 
95.degree., and in the aqueous sodium sulfate solution at 95.degree. the 
dried cotton satin impregnated with dye is treated for 30 minutes, with 
the temperature being maintained at 95.degree. and the fabric being kept 
in continual motion. The dyeing is subsequently rinsed in a standing bath 
with hot and cold water and is then ironed at 190.degree.. A yellow cotton 
dyeing having good fastness properties is thus obtained.