US 4,294,755 AGrant
Pigments Containing Pyrazolo Quinazolone Radicals
Issue Date:1981-10-13
•6 Claims
Abstract
Azo compounds of the general formula ##STR1## where D is the radical of a diazo component of the aminoanthraquinone or aminophthalimide series, or the radical of a tetraazo component H.sub.2 N--D--NH.sub.2 having the formula: ##STR2## where Z is a direct bond, SO.sub.2, NH, CO, SO.sub.2 NH, CONH, NHCONH or NHCOCONH and the rings B are unsubstituted or substituted by Cl, Br, CH.sub.3, NO.sub.2 or OCH.sub.3 ; wherein said radical D is free from complex-forming hydroxyl and carboxyl groups and from ionic groups, n is 1 or 2, R is hydrogen or an aromatic radical, X is hydroxyl, alkyl, a carboxylic acid ester group, unsubstituted or substituted aryl or acylamino, and the ring A may be substituted but is free from SO.sub.3 H groups, are exceptionally suitable for use as pigments, for example for coloring surface coatings, printing inks or plastics.
Metadata
Assignee
- BASF Aktiengesellschaft
Inventor
- Hartmut Kanter
Application Information
Application Number:US 0833274
Filing Date:1979-10-10
Priority Date:1979-10-10
Art Unit:117
Classifications
IPC:
C09B 2901C09B 2952C09B 35233C09B 3526
Field of Search:
260106154288 Q
Patent Drawings
This patent does not have any drawings.
Description
BACKGROUND OF THE INVENTION
SUMMARY OF THE INVENTION
The present invention provides compounds of the general formula I ##STR3## where D is the radical of a diazo component of the aminoanthraquinone or aminophthalimide series, or the radical of a tetraazo component H.sub.2 N--D--NH.sub.2 having the formulae: ##STR4## wherein Z is a direct bond, SO.sub.2, N.sub.H, CO, SO.sub.2 NH, CONH, NHCONH or NHCOCONH and the rings B are unsubstituted or substituted by Cl, Br, CH.sub.3, NO.sub.2 or OCH.sub.3 ; wherein said radical D is free from complex-forming hydroxyl and carboxyl groups and from ionic groups, n is 1 or 2, R is hydrogen or an aromatic radical, X is hydroxyl, alkyl, a carboxylic acid ester group, unsubstituted or substituted aryl or acylamino, and the ring A may be substituted but is free from SO.sub.3 H groups.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred compounds according to the invention have the general formula Ia ##STR5## where D, n and R have the stated meanings, R.sup.1 is hydrogen, fluorine, chlorine, bromine, nitro, C.sub.1 -C.sub.4 -alkyl, trifluoromethyl, methoxy, ethoxy, aryloxy, carboxyl, a carboxylic acid ester group, unsubstituted or substituted carbamyl or sulfamyl, a sulfonic acid aryl ester group, arylsulfonyl, cyano, acylamino or phenyl, R.sup.2 is hydrogen, chlorine or bromine, R.sup.3 and R.sup.4 are hydrogen, chlorine or bromine or together are a fused ring and X is hydroxyl, methyl, a carboxylic acid ester group, unsubstituted or substituted aryl or acylamino.
The radicals D are in the main derived from the aniline, aminoanthraquinone or aminophthalimide series or from tetraazo components. D--NH.sub.2 may for example correspond to any of the following general formulae: ##STR6## where the radicals Y independently of one another are hydrogen, chlorine, bromine or acylamino, Y.sup.1 is hydrogen, chlorine, bromine, nitro, cyano, a carboxylic acid ester group, trifluoromethyl, alkoxy, methylsulfonyl, unsubstituted or substituted carbamyl or sulfamyl, unsubstituted or substituted arylcarbonyl, oxdiazolyl, quinazolonyl, phthalazinonyl or arylazo, Y.sup.2 is hydrogen, chlorine, bromine, nitro, cyano, a carboxylic acid ester group or unsubstituted or substituted oxdiazolyl, Y.sup.3 is hydrogen, chlorine or bromine, Y.sup.4 is hydrogen, chlorine, bromine or methyl, Y.sup.5 is hydrogen, chlorine, bromine, methyl or cyano and Y.sup.6 is hydrogen or unsubstituted or substituted phenyl or benzylamino.
Tetraazo components correspond to the general formula
where D is, for example, ##STR7## and Z is a direct bond, SO.sub.2, NH, CO, SO.sub.2 NH, CONH NHCONH or NHCOCNH. The rings B may in addition be substituted by chlorine, bromine, methyl, nitro or methoxy.
Examples of carboxylic acid esters groups R.sup.1, Y.sup.1 and Y.sup.2 are COOCH.sub.3, COOC.sub.2 H.sub.5, COOC.sub.3 H.sub.7, COOC.sub.4 H.sub.9, ##STR8## COOC.sub.6 H.sub.5, COOC.sub.2 H.sub.4 OCH.sub.3 or COOCH.sub.2 C.sub.6 H.sub.5 and examples of carboxylic acid ester groups X are COOCH.sub.3 and COOC.sub.2 H.sub.5.
Examples of amine radicals which may be present in unsubstituted or substituted carbamyl and sulfamyl radicals R.sup.1 and Y.sup.1 are: NH.sub.2, NHCH.sub.3, NHC.sub.2 H.sub.5, NHC.sub.3 H.sub.7, NHC.sub.4 H.sub.9, ##STR9## NHCH.sub.2 C.sub.6 H.sub.5, NHC.sub.6 H.sub.4 Cl, NHC.sub.6 H.sub.3 Cl.sub.2, NHC.sub.6 H.sub.2 Cl.sub.3, NHC.sub.6 H.sub.4 Br, NHC.sub.6 H.sub.4 OCH.sub.3, NHC.sub.6 H.sub.4 OC.sub.2 H.sub.5, NHC.sub.6 H.sub.3 ClOCH.sub.3, NHC.sub.6 H.sub.4 NHCOCH.sub.3, NHC.sub.6 H.sub.4 NHCOC.sub.6 H.sub.5, NHNHCOC.sub.6 H.sub.5, NHNHCOC.sub.6 H.sub.4 Cl, NHNHCOC.sub.6 H.sub.4 CH.sub.3, NHC.sub.6 H.sub.3 ClCH.sub.3, NHC.sub.6 H.sub.2 Cl.sub.2 OCH.sub.3 and NHC.sub.6 H.sub.2 Cl.sub.2 CH.sub.3.
Examples of sulfonic acid aryl ester groups R.sup.1 are: SO.sub.2 OC.sub.6 H.sub.5, SO.sub.2 OC.sub.6 H.sub.4 CH.sub.3, SO.sub.2 OC.sub.6 H.sub.4 Cl, SO.sub.2 OC.sub.6 H.sub.4 Br, SO.sub.2 OC.sub.6 H.sub.4 OCH.sub.3, SO.sub.2 OC.sub.6 H.sub.4 NHCOCH.sub.3 and SO.sub.2 OC.sub.6 H.sub.3 Cl.sub.2.
Within the scope of the general definition, examples of heterocyclic radicals Y.sup.1 and Y.sup.2 are: ##STR10## where T is an unsubstituted or substituted aromatic radical.
Examples of acylamino radicals R.sup.1, X and Y.sup.1 are: NHCOCH.sub.3, NHCOC.sub.2 H.sub.5, NHCOC.sub.3 H.sub.7, NHCOC.sub.6 H.sub.5, NHCOC.sub.6 H.sub.4 Cl, NHCOC.sub.6 H.sub.3 Cl.sub.2, NHCOC.sub.6 H.sub.4 Br, NHCOC.sub.6 H.sub.4 OCH.sub.3, NHCOC.sub.10 H.sub.7, NHCONH.sub.2, NHCONHC.sub.6 H.sub.5, NHCOCONH.sub.6 H.sub.5, ##STR11## and examples of acylamino radicals Y and NHCOCH.sub.3, NHCOC.sub.6 H.sub.5 and NHCOC.sub.6 H.sub.4 Cl.
Examples of radicals R and T are phenyl, naphthyl or pyridyl which may or may not be substituted by chlorine, bromine, nitro, methyl, methoxy or ethoxy; R, but not T, may furthermore be hydrogen. Specific examples are: 2-, 3- and 4-chlorophenyl, 2,4-, 2,5- and 3,5-dichlorophenyl, 2,4,5-trichlorophenyl, 2-, 3- and 4-bromophenyl, 2,5-dibromophenyl, 2- and 4-methoxyphenyl, 2- and 4-tolyl, 2,3-, 2,4- and 3,4-dimethylphenyl, 1- and 2-naphthyl, 4-chloro-1-naphthyl and 3-pyridyl.
A compound of the formula I may be prepared by reacting a diazonium compound of an amine of the formula DNH.sub.2 or H.sub.2 N--D--NH.sub.2 with a coupling component of the formula ##STR12## where X is preferably hydroxyl or acylamino, if R is not hydrogen.
The coupling components are known from the literature of may be prepared by methods similar to those described in the literature. Details of suitable methods of performing the reactions may be found in the Examples, where parts and percentages are by weight. Temperatures are given in degrees centigrade.
The compounds of the formula I range from yellow to red and may be used as disperse dyes or as pigments, depending on the substituents. The pigments are frequently distinguished by great brilliance, high scattering power and excellent lightfastness and fastness to weathering, and may be used for coloring surface coatings, printing inks, plastics and plastic dispersions.
The pigments are not always obtained in the optimum physical form for a particular use. However, they can be converted to the most appropriate form by conventional methods, such as milling with salt, reprecipitation from sulfuric acid and/or heating in water or a solvent, in the presence or absence of wetting agents, dispersants and/or a grinding medium.
Compounds of the formula I particularly suitable for use as pigments are those which carry electron-attracting groups, such as NO.sub.2, CN, COOR, --COAryl or heterocyclic radicals in the diazo component in the o-position to the azo bridge, or have an arylazo group in the p-position in the diazo component.
Compounds of particular importance are those of the formula Ib ##STR13## where D is the radical of a diazo component which is free from complex-forming hydroxyl and carboxyl groups and from ionic groups, and R.sup.1 to R.sup.4 and X have the stated meanings. Preferably, X is methyl, or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, nitro or methoxy.
Preferably, D is substituted phenyl or anthraquinonyl and R.sup.1 to R.sup.4 are hydrogen, chlorine, bromine, a carboxylic acid ester group or unsubstituted or substituted carbamyl or sulfamyl.
The preferred pigments, in the appropriate physical form, very frequently have very good fastness to weathering and combine high scattering power with a brilliant pure shade. They are therefore particularly suitable as an equivalent substitute for, eg., chromate pigments or molybdate pigments, for which purpose they may also be used as a mixture with inorganic pigments of the spinel type.
EXAMPLE 1
8.6 parts of 2-nitro-4-chloroaniline are dissolved in 10 parts of dimethylformamide, the solution is poured into a mixture of 20 of concentrated hydrochloric acid, 50 parts of water and 50 parts of ice, and diazotization is carried out by dropwise addition of a solution of 3.5 parts of sodium nitrite in 10 parts of water at 0.degree.-5.degree. C. After 1 hour, excess nitrite is destroyed with amidosulfonic acid, the solution is clarified by filtration, the pH is brought to 5 by adding sodium acetate and a suspension of 10 parts of 2-methylpyrazolo[5,1b]quinazolone, 100 parts of isobutanol and 8 parts of 50% strength aqueous sodium hydroxide solution is added dropwise in the course of one hour. The mixture is stirred for 1 hour at 0.degree.-5.degree. C. and 1 hour at 50.degree. C. The colorant is then filtered off, washed with hot water and then with methanol, dried, stirred for 2 hours with 80 parts of dimethylformamide at 80.degree. C., again filtered, washed with methanol, dried and milled. 15 parts of an orange crystalline powder of the formula ##STR14## are obtained.
The colorants identified in Table 1 by their diazo components and coupling components are obtained similarly.
EXAMPLE 27
22.4 parts of 1-aminoanthraquinone are introduced into a mixture of 46 parts of 96% strength sulfuric acid and 34 parts of 40% strength nitrosylsulfuric acid at a rate such that the temperature does not exceed 40.degree. C., and the mixture is then stirred for two hours at 40.degree. C. Thereafter the solution is stirred into 300 parts of ice and water, and the diazonium sulfate which has crystallized out is filtered off, washed with ice water and stirred into 400 parts of water. The pH is brought to 4-5 with sodium acetate and after having added 10 parts of glacial acetic acid a suspension prepared by stirring 27 parts of 5,7-dichloro-2-methyl-pyrazolo[5,1b]quinazolone and 10 parts of 50% strength aqueous sodium hydroxide solution with 300 parts of isobutanol at 90.degree. C. is added dropwise at 40.degree. C. To complete the coupling, the mixture is stirred for 2 hours at 95.degree. C., after which it is filtered hot, the filter residue is washed with water and then with methanol and the colorant thus obtained is dried and milled. 44 parts of a red powder are obtained; this is stirred with 300 parts of dimethylformamide for 2 hours at 80.degree. C., filtered off hot, washed with dimethylformamide and then with methanol, dried and milled. A red crystalline powder of the formula ##STR46## is obtained.
The colorants identified in Table 2 by their diazo components and coupling components are obtained similarly.
EXAMPLE 153
19.6 parts of 3-chloro-6-amino-phthalimide, in a mixture of 150 parts of glacial acetic acid, 50 parts of propionic acid and 30 parts of concentrated hydrochloric acid, are diazotized, at 5.degree. C., with 7 parts of sodium nitrite. After 2 hours, the excess nitrite is destroyed with amidosulfonic acid and the pH is brought to 4-5 by adding solid sodium acetate. 20 parts of 2-methylpyrazolo[5,1b]quinazolone are stirred with 200 parts of isobutanol and 10 parts of 50% strength aqueous sodium hydroxide solution for 2 hours at 90.degree. C., and the mixture is cooled to 20.degree. C. and then added dropwise in the course of 1 hour to the diazo solution. The mixture is stirred for 1 hour at 20.degree. C. and 2 hours at 60.degree. C. and is then filtered, and the filter residue is washed with glacial acetic acid, then with water and thereafter with methanol, and is dried. 36 parts of crude product are obtained; this is stirred with 360 parts of dimethylformamide for 2 hours at 100.degree. C., filtered off, washed with methanol, dried and milled. 35 parts of a yellow crystalline powder of the formula ##STR183## are obtained.
The colorants identified in Table 3 by their diazo components and coupling components are obtained similarly.
EXAMPLE 184
35.4 parts of 7-(N-phenylsulfamyl)-2-methyl-pyrazolo[5,1-b]-quinazolone, 20 parts of sodium hydroxide and 6 parts of an alkylnaphthalenesulfonate are stirred into 300 parts of water, a suspension of 1-anthraquinone-diazonium sulfate, as described in Example 27, is added and the mixture is stirred for 1 hour. After adding 30 parts of glacial acetic acid, the batch is stirred for 1 hour at room temperature, 1 hour at 40.degree. C., 1 hour at 60.degree. C. and 2 hours under reflux, and the product is filtered off hot and washed with water. The moist filter cake is introduced into 310 parts of molten phenol and this mixture is stirred for 4 hours at 140.degree. C. during which water distils off. After having added 400 parts of methanol at 50.degree. C., the mixture is filtered and the filter residue is washed with methanol until the filtrate is clear, and is then dried and milled. 57.5 parts of a brilliant red pigment powder, of the same formula as in Example 48, but having improved technological properties, are obtained.
The pigments which have the general formula shown below and are characterized in Table 4 by the meanings of D, X and R.sup.1 are obtained similarly.
EXAMPLE 257
22.4 parts of 1-aminoanthraquinone and 30 parts of concentrated hydrochloric acid are stirred with 300 parts of glacial acetic acid for 1 hour at room temperature. 7.5 parts of sodium nitrite are then added in portions over 1 hour, and the mixture is stirred for a further 2 hours. To remove excess nitrite, urea is added, the mixture is buffered with 35 parts of anhydrous sodium acetate, and a suspension, prepared at 40.degree. C., of 42 parts of 2-methyl-pyrazolo[5,1-b]-quinazolone-7-sulfonic acid 2',4'-dichlorophenyl ester and 10 parts of 50% strength aqueous sodium hydroxide solution in 400 parts of isobutanol is added dropwise over 1 hour. The mixture is stirred for 3 hours at 40.degree. C., 1 hour at 60.degree. C. and 2 hours at the reflux temperature and is filtered, and the product is washed with hot water and dried. The crude product is then stirred with 500 parts of dimethylformamide at 80.degree. C. for 2 hours, filtered off, washed with methanol, dried and milled. 58 parts of a brilliant red powder of the formula ##STR304## are obtained.
The pigments of the general formula ##STR305## listed in Table 5 are obtained by a similar method.
USE EXAMPLE 1
10% strength full-shade baking finish on paper
(a) 30% strength full-shade paste
3 parts of the colorant of Example 27 and 7 parts of a varnish-like binder (for example Grinding Base 100S from Lawter Chemicals Inc., Chicago) are passed 6 times through a triple-roll mill under 10 bar pressure, to give a full-shade paste.
(b) 10% strength full-shade coating paste used for coloring
2 parts of the full-shade paste obtained in (a) are mixed with 4 parts of a binder mixture, comprising 1 part of an alkyd resin modified with soybean oil, 2 parts of an alkyd resin modified with synthetic fatty acid and 3 parts of a solvent-free melamine resin.
(c) Coloration process
Using a film coater, a 100 .mu.m thick layer of the surface-coating paste obtained as described in (b) is applied to cardboard printed with a black bar and is baked for 45 minutes at 120.degree. C. in a drying oven. A high-hiding and brilliant red coloration having excellent lightfastness and fastness to weathering is obtained.
USE EXAMPLE 2
1:20 reduction baking finish
(a) 30% strength white paste
42 parts of a binder, obtained by mixing 1 part of an alkyd resin modified with soybean oil and 2 parts of an alkyd resin modified with synthetic fatty acid are milled with 30 parts of titanium dioxide (rutile grade), 22 parts of a solvent-free melamine resin and 6 parts of a colloidal silica by passing 6 times through a triple-roll mill under 10 bar pressure, to give a 30% strength white paste.
(b) Surface-coating paste used for coloring
0.5 part of the 30% strength full-shade paste obtained as described in 1(a) and 10 parts of the 30% strength white paste obtained as described in 2(a) are mixed, and milled, on a millstone mill.
(c) Coloration process
Using a film coater, a 100 .mu.m thick layer of the surface-coating paste (b) is applied to cardboard and baked for 45 minutes at 120.degree. C. in a drying oven. A yellowish red coloration having excellent lightfastness and fastness to weathering is obtained.
USE EXAMPLE 3
Plasticized PVC (0.1% strength coloration)
0.05 part of the colorant obtained as described in Example 27 and 50 parts of a mixture itself prepared from 65 parts of PVC powder, 36 parts of di-ethylhexyl phthalate and 2 parts of dibutyl-tin bis-(hexyl thioglycolate), are homogenized for about 8 minutes on a mixing mill at 150.degree.-160.degree. C., and then converted to hides which are polished on a calender. Brilliant red hides having excellent lightfastness are obtained. If titanium dioxide is added during the compounding operation, yellowish red reductions having excellent light-fastness are obtained.
USE EXAMPLE 4
Rigid PVC (0.1% strength coloration)
0.1 part of colorant obtained as described in Example 27, 100 parts of PVC powder (suspension polymer or emulsion polymer) and 2 parts of dibutyl-tin bis-(hexyl thioglycolate) are homogenized in about 8 minutes at 150.degree.-160.degree. C. on a mixing mill. The hides obtained are pressed to form sheets on a platen press at 140.degree. C. under about 0.4 kg/cm.sup.2. Brilliant red pressed sheets having excellent lightfastness are obtained. If titanium dioxide is added during the compounding operation, yellowish red reductions having excellent lightfastness are obtained.
USE EXAMPLE 5
Printing ink
5 parts of the colorant obtained as described in Example 153, 30-40 parts of resin (for example rosin modified with a phenol-formaldehyde resin) and 65 parts of toluene are thoroughly mixed in a disperser. This gives a toluene-based gravure printing ink having good lightfastness and good tinctorial strength.
USE EXAMPLE 6
Plasticized PVC; 1:10 reduction
0.25 part of colorant, obtained as described in Example 184, 2.5 parts of titanium dioxide (rutile grade) and 50 parts of a mixture itself obtained from 65 parts of polyvinyl chloride powder, 36 parts of di-ethylhexyl phthalate and 2 parts of dibutyl-tin bis-(hexyl thioglycolate), are homogenized in about 8 minutes on a mixing mill at 150.degree.-160.degree. C., and then converted to hides which are polished on a calender. Brilliant red hides having excellent lightfastness and fastness to migration are obtained.
USE EXAMPLE 7
Polyethylene (0.05% strength coloration)
0.05 part of colorant obtained as described in Example 189 and 100 parts of high-pressure polyethylene powder are dry-blended in a drum mixer. The mixture is melted, and homogenized, on an extruder at a barrel temperature of 160.degree.-200.degree. C. The colored material is granulated by die-face cutting or by drawing strands which are cooled and granulated. The granules obtained are then injection-molded at 200.degree. C. or compression-molded to various shapes on presses. Brilliant orange moldings having excellent lightfastness and heat stability are obtained.
Claims
We claim:
1. An azo compound of the formula: ##STR343## wherein D is an unsubstituted anthraquinone radical or an anthraquinone radical substituted by one or more substituents selected form the group consisting of chlorine, bromine, NHCOCH.sub.3, CH.sub.3, NHCOC.sub.6 H.sub.5 or NHCOC.sub.6 H.sub.4 Cl; or D is a amino phthalimide radical of the formula: ##STR344## or D is the radical of a tetraazo component H.sub.2 N--D--NH.sub.2 having the formulae: ##STR345## Y.sup.5 is hydrogen, chlorine, bromine, methyl or cyano; and Y.sup.6 is hydrogen, phenyl, benzoylamino, or phenyl or benzoylamino which are substituted by nitro; wherein Z is a direct bond, SO.sub.2, NH, CO, SO.sub.2 NH, CONH, NHCONH, or NHCOCONH and the rings B are unsubstituted or substituted by chlorine, bromine, methyl, nitro, or methoxy; wherein said radical D is free from complex-forming hydroxyl and carboxyl groups; n is one or two; R is hydrogen or a phenyl, naphthyl or pyridyl radical which may be substituted by chlorine, bromine, nitro, methyl, methoxy or ethoxy; X is hydroxyl, alkyl or a carboxylic acid alkyl ester having an alkyl ester radical selected from the group consisting of C.sub.1 -C.sub.6 alkyl or alkoxyalkyl, phenyl and benzyl; or X is phenyl, naphthyl or pyridyl which is unsubstituted or substituted by chlorine, bromine, nitro, methyl, methoxy or ethoxy; or X is acylamino selected from the group consisting of NHCOCH.sub.3, NHCOC.sub.2 H.sub.5, NHCOC.sub.3 H.sub.7, NHCOC.sub.6 H.sub.5, NHCOC.sub.6 H.sub.4 Cl, NHCOC.sub.6 H.sub.3 Cl.sub.2, NHCOC.sub.6 H.sub.4 Br, NHCOC.sub.6 H.sub.4 OCH.sub.3, NHCOC.sub.10 H.sub.7, NHCONH.sub.2, NHCONHC.sub.6 H.sub.5, ##STR346## and the ring A is a substituted or unsubstituted, with a proviso that said ring A is free from SO.sub.3 H groups.
2. An azo compound of the formula: ##STR347## where D is an aminoanthraquinone radical of the formula: ##STR348## or D is an aminophthalimide radical of the formula: ##STR349## or D is the radical of a tetrazo component H.sub.2 N-D-NH.sub.2 having the formula: ##STR350## wherein the radicals Y independently of one another are hydrogen, chlorine, bromine, NHCOCH.sub.3, NHCOC.sub.6 H.sub.5 or NHCOC.sub.6 H.sub.4 Cl; Y.sup.4 is hydrogen, chlorine, bromine, or methyl; Y.sup.5 is hydrogen, chlorine, bromine, methyl or cyano; and Y.sup.6 is hydrogen, phenyl or benzoylamino, or phenyl or benzoylamino which are substituted by nitro; wherein Z is a direct bond, SO.sub.2, NH, CO, SO.sub.2 NH, CONH, NHCONH or NHCOCOHN and the rings B are unsubstituted or substituted by Cl, Br, CH.sub.3, NO.sub.2 or OCH.sub.3 ; wherein said radical D is free from complex forming hydroxyl and carboxyl groups, n is one or two; R is hydrogen or a phenyl, naphthyl or pyridyl radical which may be substituted by chlorine, bromine, nitro, methyl, methoxy or ethoxy; R.sup.1 is hydrogen, fluorine, chlorine, bromine, nitro, C.sub.1 -C.sub.4 alkyl, trifluoromethyl, methoxy, ethoxy, aryloxy, carboxy, a carboxylic acid alkyl ester having an alkyl ester radical selected from the group consisting of C.sub.1 -C.sub.6 alkyl or alkoxyalkyl, phenyl and benzyl; unsubstituted or substituted carbamyl or sulfamyl, a sulfonic acid aryl ester group, arylsulfomyl, cyano, acylamino selected from the group consisting of NHCOCH.sub.3, NHCOC.sub.2 H.sub.5, NHCOC.sub.3 H.sub.7, NHCOC.sub.6 H.sub.5, NHCOC.sub.6 H.sub.4 Cl, NHCOC.sub.6 H.sub.3 Cl.sub.2, NHCOC.sub.6 H.sub.4 Br, NHCOC.sub.6 H.sub.4 OCH.sub.3, NHCOC.sub.10 H.sub.7, NHCONH.sub.2, NHCONHC.sub.6 H.sub.5, ##STR351## or R.sup.1 is phenyl; R.sup.2 is hydrogen, chlorine or bromine; R.sup.3 and R.sup.4 are hydrogen, chlorine or bromine; and X is hydroxy, methyl, a carboxylic acid alkyl ester having an alkyl ester radical selected from the group consisting of C.sub.1 -C.sub.6 alkyl or alkoxyalkyl, phenyl, and benzyl; or X is phenyl, naphthyl or pyridyl which is unsubstituted or substituted by chlorine, bromine, nitro, methyl, methoxy or ethoxy; or X is acylamino selected from the group consisting of NHCOCH.sub.3, NHCOC.sub.2 H.sub.5, NHCOC.sub.3 H.sub.7, NHCOC.sub.6 H.sub.5, NHCOC.sub.6 H.sub.4 Cl, NHCOC.sub.6 H.sub.3 Cl.sub.2, NHCOC.sub.6 H.sub.4 Br, NHCOC.sub.6 H.sub.4 OCH.sub.3, NHCOC.sub.10 H.sub.7, NHCONH.sub.2, NHCONHC.sub.6 H.sub.5, ##STR352##
3. An azo compound as claimed in claim 2, where R is hydrogen.
4. A compound as claimed in claim 2 or 3, where X is methyl, phenyl or phenyl substituted by chlorine, bromine, methyl, methoxy or nitro and D and R.sup.1 and R.sup.4 have the stated meanings.
5. A compound as claimed in claim 2 or 3, where D is an amino anthraquinone radical having the amino group at position 1-thereof.
6. A compound as claimed in claim 4, where D is an amino anthraquinone radical having the amino group at position 1-thereof.
Patent Citations (6)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US3167537 | 1965-01-01 | Menzel et al. | |
| US3316238 | 1967-04-01 | Hanke et al. | |
| US4053463 | 1977-10-01 | Junge | |
| DEX2245093 | 1974-03-01 | ||
| DEX2360986 | 1975-07-01 | ||
| GBX1399651 | 1975-07-01 |