Dyes having a diazo component and an isoquinoline coupling component

A compound having the formula (I): ##STR1## wherein D is a radical of a heterocyclic or aromatic component selected from the group of aniline, anthraquinone, phthalimide or aminobenzene radicals, wherein the radical is unsubstituted or is substituted by fluorine, chlorine, bromine, nitro, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, trifluoromethyl, cyano, C.sub.1 -C.sub.4 -alkylsulfonyl, carboxylic acid ester groups, carbamyl, sulfamyl, 1,3,4- or 1,2,4-oxadiazolyl or acylamino groups; X is CO-- or --SO.sub.2 --; and R is an aliphatic, aromatic or heterocyclic radical selected from the group of C.sub.1 -C.sub.20 alkyl which is unsubstituted or is substituted by chlorine, bromine, cyano or dialkylamino groups; or phenyl or methyl groups unsubstituted or substituted by fluorine, bromine, methyl, ethyl, methoxy, ethoxy, cyano, carbamyl, sulfamyl or acylamino groups; or amino group; or a radical of the formula: ##STR2## wherein ring a is unsubstituted or is substituted by nitro, fluro, bromine or methoxy groups; and ring b is unsubstituted or is substituted by chlorine, bromine or nitro groups. The majority of the compounds of the formula (I) have yellow hues and are used as pigments in printing inks and finishes, and as disperse dyes for synthetic fibers.

The present invention relates to compounds of the general formula I 
##STR3## 
where D is a radical of a diazo component, X is CO or SO.sub.2 and R is an 
aliphatic, aromatic or heterocyclic radical, an unsubstituted or 
substituted amino group, or a radical of the formula 
##STR4## 
and the rings a and b may furthermore be substituted. 
The radicals D are derived from heterocyclic or, in the main, aromatic 
diazo components, for example those of the aniline, anthraquinone, 
phthalimide or aminoazobenzene series. The diazo components may carry the 
substituents usually present in water-insoluble dyes, eg. fluorine, 
chlorine, bromine, nitro, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 
-alkoxy, trifluoromethyl, cyano, C.sub.1 -C.sub.4 -alkylsulfonyl, 
carboxylic acid ester groups, unsubstituted or substituted carbamyl or 
sulfamyl, unsubstituted or substituted 1,3,4- or 1,2,4-oxadiazolyl or 
acylamino. 
Specific examples of substituents, in addition to those stated above, are 
##STR5## 
Specific examples of important diazo components are o-nitroaniline, 
p-chloro-o-nitroaniline, p-methoxy-o-nitroaniline, p-aminoazobenzene, 
2,5-dichloroaniline, methyl anthranilate and 1-aminoanthraquinone. 
R is, for example, C.sub.1 -C.sub.20 -alkyl which may furthermore be 
substituted by chlorine, bromine, cyano or dialkylamino, but is preferably 
naphthyl or phenyl which is substituted by fluorine, chlorine, bromine, 
methyl, ethyl, methoxy, ethoxy, cyano, unsubstituted or substituted 
carbamyl, sulfamyl or acylamino. 
Typical examples of heterocyclic radicals R are: 
##STR6## 
Specific examples of radicals R are methyl, ethyl, p-chlorophenyl, benzyl, 
m-nitrophenyl, 
##STR7## 
The ring a may, for example, furthermore be substituted by nitro, chlorine, 
bromine or methoxy, and the ring b may be substituted by chlorine, bromine 
or nitro. 
To prepare the compounds of the formula I, a diazonium compound of an amine 
of the formula 
EQU D--NH.sub.2 
is reacted with a coupling component of the formula II 
##STR8## 
The diazotization and coupling are carried out in a conventional manner.

The Examples which follow illustrate the preparation. Parts and percentages 
are by weight, unless stated otherwise. 
Some of the compounds of the formula II, and the preparation of these, have 
been disclosed in the literature, for example in Bull. Chem. Soc. Jap. 48 
(1975), 2915 and J. Heterocycl. Chem. 6 (1969), 9. 
Novel compounds of the formula II may be prepared by a similar method. 
The majority of the compounds of the formula I have yellow hues and, 
depending on their solubilities, are mainly used as pigments in printing 
inks and finishes, and as disperse dyes for synthetic fibers, such as 
polyesters. 
Compounds of the formula I a 
##STR9## 
where D.sup.1 is 1-anthraquinoyl or phenyl which is unsubstituted or 
substituted by chlorine, bromine, nitro or methoxy, R.sup.1 is methyl or 
is phenyl which is unsubstituted or substituted by chlorine, bromine or 
benzoylamino and X has the stated meanings, are particularly important. 
EXAMPLE 1 
13.8 parts of o-nitroaniline in 35 parts of water and 25 parts by volume of 
32% strength hydrochloric acid are stirred overnight at room temperature. 
The mixture is then made up to 270 parts by volume with ice-water, and 32 
parts of 23% strength sodium nitrite solution are added rapidly at 
0.degree. C. Stirring is continued for two hours, after which the excess 
nitrite is destroyed with amidosulfonic acid and the mixture is filtered. 
A mixture of 28 parts of the coupling component of the formula 
##STR10## 
1,500 parts of water and 50 parts of 50% strength NaOH is poured into the 
above diazonium salt solution at 0.degree. C., the pH of the mixture is 
brought to 4-5, and stirring is continued for 2 hours. The precipitate is 
filtered off under suction, washed with water and a little cold methanol, 
and dried, giving 36 parts of a yellow powder. 
Other pigments are obtained when the diazo components given in the Table 
below are reacted with the coupling components listed in the same Table, 
the reaction being carried out as described in Example 1. 
__________________________________________________________________________ 
Ex- 
ample 
Diazo component 
Coupling component Hue 
__________________________________________________________________________ 
##STR11## 
##STR12## reddish yellow 
3 
##STR13## " very greenish yellow 
4 
##STR14## " greenish yellow 
5 
##STR15## 
##STR16## yellow 
6 
##STR17## 
##STR18## yellow 
7 " 
##STR19## reddish yellow 
8 " 
##STR20## reddish yellow 
__________________________________________________________________________ 
EXAMPLE 9 
138 parts of o-nitroaniline are dissolved in a mixture of 850 parts by 
volume of formic acid and 150 parts by volume of propionic acid, and 160 
parts of nitrosylsulfuric acid are added dropwise in the course of about 
1.5 hours, at 0.degree.-5.degree. C. Excess nitrite is destroyed with 
amidosulfonic acid. 
The diazonium salt solution is then allowed to run into a filtered mixture 
of 316 parts of the coupling component of the formula 
##STR21## 
15,000 parts by volume of water and 500 parts by volume of 50% strength 
sodium hydroxide solution, at 0.degree. C. The pH of the mixture is 
brought to 5-6 with NaOH, and stirring is continued for about one hour. 
The precipitate is filtered off under suction, washed salt-free with cold 
water and dried under reduced pressure at 60.degree. C. 385 parts of a 
yellow powder are obtained in this manner. 
Other pigments are obtained when the diazo components and coupling 
components given below are reacted as described in Example 9. 
__________________________________________________________________________ 
Ex- 
ample 
Diazo component Coupling component Hue 
__________________________________________________________________________ 
10 
##STR22## 
##STR23## orange 
11 
##STR24## 
##STR25## greenish yellow 
12 
##STR26## 
##STR27## reddish yellow 
13 
##STR28## 
##STR29## very greenish yellow 
14 
##STR30## 
##STR31## yellow 
__________________________________________________________________________ 
EXAMPLE 15 
225 parts of 1-aminoanthraquinone are introduced into 1,250 parts of 
sulfonic acid monohydrate at about 30.degree.-35.degree. C., and the 
mixture is stirred for one hour (the suspension should no longer contain 
any crystalline aminoanthraquinone). Thereafter, the mixture is poured 
into 4,000 parts of ice and 1,000 parts of water, and 315 parts of 23% 
sodium nitrite solution are added dropwise at 0.degree.-5.degree. C. 
Stirring is continued for two hours, after which the mixture is filtered 
and excess nitrite is destroyed with amidosulfonic acid. 
The diazonium salt solution is run into a mixture of 241 parts of the 
coupling component of the formula 
##STR32## 
500 parts of 50% strength NaOH, 15,000 parts of water and 100 parts of 
sodium acetate, at 0.degree.-5.degree. C. The pH is kept at 6-7 by adding 
50% strength sodium hydroxide solution. After about 1 hour, the mixture is 
heated to 90.degree. C. by means of steam, and the product is filtered off 
under suction from the hot suspension, washed salt-free and dried. 365 
parts of a red powder are obtained. 
Other pigments are obtained when the diazo components given in the Table 
below are reacted with the coupling components given in the same Table, 
the reaction being carried out as described in Example 15. 
__________________________________________________________________________ 
Ex- 
ample 
Diazo component 
Coupling component Hue 
__________________________________________________________________________ 
16 
##STR33## 
##STR34## orange 
17 
" 
##STR35## orange 
18 
" 
##STR36## yellowish orange 
19 
" 
##STR37## very reddish yellow 
20 
##STR38## 
##STR39## reddish yellow 
21 
##STR40## 
##STR41## yellow 
22 
##STR42## 
##STR43## yellow 
23 
" 
##STR44## yellow 
24 
" 
##STR45## yellow 
__________________________________________________________________________ 
EXAMPLE 25 
Printing Ink 
5 parts of the dye obtained in Example 1, 30-40 parts of resin (for example 
colophonium resin modified with phenol-formaldehyde) and 65 parts of 
toluene are mixed thoroughly in a disperser. The toluene-based standard 
yellow gravure printing ink obtained has good lightfastness and color 
strength.