Azo dyes having a 3-cyano- or 3-carbamoyl-2,6-diamino-pyridine coupling component

Abstract

Dye formulations for dyeing and printing cellulose and cellulosic textile material which in addition to conventional components contain a dye of the general formula (I): ##STR1## in which D is the radical of a diazo component;R is hydrogen, C.sub.1 to C.sub.7 alkyl, phenyl or phenyl bearing methyl as a substituent;X is cyano, carbamoyl or substituted carbamoyl;R.sup.1 is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical;R.sup.2 is hydrogen or an aliphatic, cycloaliphatic or araliphatic radical;R.sup.3 and R.sup.4 independently of one another have the same meanings as R.sup.1 and R.sup.2 ; andR.sup.1 --n--r.sup.2 and R.sup.3 --N--R.sup.4 independently of one another are saturated heterocyclic radicals.

Description

The invention relates to dye formulations for dyeing and printing cellulose or cellulosic textile material which in addition to conventional components contain a dye of the general formula (I): ##STR2## in which D is the radical of a diazo component;

R is hydrogen, C.sub.1 to C.sub.7 alkyl, phenyl or phenyl bearing methyl as a substituent; X is cyano, carbamoyl or substituted carbamoyl; R.sup.1 is hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic radical; R.sup.2 is hydrogen or an aliphatic, cycloaliphatic or araliphatic radical; R.sup.3 and R.sup.4 independently of one another have the same meanings as R.sup.1 and R.sup.2 ; and R.sup.1 --n--r.sup.2 and R.sup.3 --N--R.sup.4 independently of one another are saturated heterocyclic radicals.

The radical D may be derived particularly from an amine of the benzene, naphthalene, benzothiazole, benzoisothiazole, thiazole, thiadiazole, indazole, pyrazole, thiophene, azobenzene, phthalimide, naphthalimide or anthraquinone series.

Examples of substituents of the radical of the diazo component D are:

In the benzene series: fluoro, chloro, bromo, nitro, cyano, trifluoromethyl, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, carboxylic esters such as C.sub.1 to C.sub.8 alkoxycarbonyl, phenoxycarbonyl, phenoxyethoxycarbonyl or .beta.-C.sub.1 to .beta.-C.sub.4 alkoxyethoxycarbonyl, optionally N-monosubstituted or N,N-disubstituted carbamoyl or sulfamoyl, methyl, ethyl, butyl, octyl, hexyl, methoxy or ethoxy and also carboxy. N-substituents of carbamoyl or sulfamoyl are for example methyl, ethyl, phenyl, benzyl, phenylethyl, cyclohexyl, norbornyl, propyl, butyl, .beta.-hydroxyethyl, .gamma.-hydroxypropyl, .beta.-methoxyethyl, .gamma.-methoxypropyl, .gamma.-ethoxypropyl and also pyrrolidide, piperidide and morpholide.

In the azobenzene series: fluoro, chloro, bromo, nitro, cyano, trifluoromethyl, methyl, ethyl, carboxy, methoxy and ethoxy, the carboxylic esters, carbamoyl and sulfamoyl radicals referred to under the benzene series, and hydroxy.

In the heterocyclic series: chloro, bromo, nitro, cyano, methyl, ethyl, phenyl, methoxy, ethoxy, methylmercapto, .beta.-carbomethoxyethylmercapto, .beta.-carboethoxyethylmercapto, carbomethoxy, carboethoxy, acetyl, methylsulfonyl and ethylsulfonyl.

In the anthraquinone series: chloro, bromo, amino, acetyl, methyl, ethyl, phenylamino, tolylamino, hydroxy, methoxy, ethoxy, cyano and carboxy.

In the benzene and naphthalene series diazo components are preferred which have at least one substituent which decreases the basicity such as methylsulfonyl, phenylsulfonyl, ethylsulfonyl, carboxylic ester, optionally N-substituted carbamoyl, chloro, bromo, trifluoromethyl and particularly cyano.

Radicals R other than hydrogen are for example ethyl, n-propyl, isopropyl, butyl, pentyl, .alpha.-ethylpentyl, phenyl or methylphenyl and preferably methyl.

Examples of R.sup.1, other than hydrogen, are the following substituents: alkyl of one to eight carbon atoms, alkyl of two to eight carbon atoms, alkyl of two to eight carbon atoms bearing hydroxy, cyano, alkoxy or one to eight carbon atoms, phenoxy, phenoxyethoxy or benzyloxy as a substituent, cyclohexyl, norbornyl, benzyl, phenylethyl, phenylhydroxyethyl, phenylpropyl, phenylbutyl, phenyl, phenyl bearing chloro, methyl, trifluoromethyl, pyrrolidonyl, methoxy or ethoxy as a substituent,

C.sub.5 to C.sub.12 polyalkoxyalkyl, C.sub.4 to C.sub.9 hydroxypolyalkoxyalkyl, C.sub.1 to C.sub.8 alkanoyloxy C.sub.2 to C.sub.6 alkyl, C.sub.7 to C.sub.11 aroyloxy C.sub.2 to C.sub.6 alkyl, C.sub.1 to C.sub.8 alkylaminocarbonyloxy C.sub.2 to C.sub.6 alkyl, C.sub.6 to C.sub.10 arylaminocarbonyloxy C.sub.2 to C.sub.6 alkyl, C.sub.1 to C.sub.8 alkoxycarbonyl C.sub.2 to C.sub.7 alkyl and C.sub.1 to C.sub.18 alkanoyl, C.sub.8 to C.sub.10 aralkanoyl, C.sub.7 to C.sub.11 aroyl, C.sub.1 to C.sub.4 alkylsulfonyl and C.sub.6 to C.sub.10 arylsulfonyl.

In addition to those already specified, the following are specific examples of suitable radicals R.sup.1 :

1: unsubstituted or substituted alkyl: Ch.sub.3, c.sub.2 h.sub.5, n-- and i--C.sub.3 H.sub.7, n-- and i--C.sub.4 H.sub.9, C.sub.6 H.sub.13, ##STR3## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH, (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH, (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH, (CH.sub.2).sub.2 CN, (CH.sub.2).sub.5 CN, (CH.sub.2).sub.6 CN, (CH.sub.2).sub.7 CN, (CH.sub.2).sub.2 O(CH.sub.2).sub.2 CN, (CH.sub.2).sub.3 O(CH.sub.2).sub.2 CN, (CH.sub.2).sub.2 O(CH.sub.2).sub.2 O(CH.sub.2).sub.2 CN, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH.sub.3, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5, (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH(CH.sub.3).sub.2, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OCH.sub.2 C.sub.6 H.sub.5, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4 C.sub.6 H.sub.5, ##STR4## CH.sub.2 CH.sub.2 COOH, (CH.sub.2).sub.5 COOH, (CH.sub.2).sub.6 COOH, the corresponding radicals in which the groupings: --O(CH.sub.2).sub.2 --, ##STR5## are present two or three times; CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5, CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7, CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9, CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5, (CH.sub.2).sub.3 OCH.sub.3, (CH.sub.2).sub.3 OC.sub.2 H.sub.5, (CH.sub.2).sub.3 OC.sub.4 H.sub.9, ##STR6## (CH.sub.2).sub.3 OC.sub.3 H.sub.7, (CH.sub.2).sub.3 OC.sub.6 H.sub.13, (CH.sub.2).sub.3 OC.sub.8 H.sub.17, (CH.sub.2).sub.3 O--, (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5, (CH.sub.2).sub.3 OC.sub.2 H.sub.4 C.sub.6 H.sub.5, (CH.sub.2).sub.3 OC.sub.6 H.sub.5, ##STR7## 2. unsubstituted or substituted cycloalkyl and polycycloalkyl: ##STR8## 3. aralkyl: CH.sub.2 C.sub.6 H.sub.5, C.sub.2 H.sub.4 C.sub.6 H.sub.5, ##STR9## as well as C.sub.6 H.sub.4 CH.sub.3 instead of C.sub.6 H.sub.5 ; 4. unsubstituted or substituted phenyl; C.sub.6 H.sub.5, C.sub.6 H.sub.4 CH.sub.3, C.sub.6 H.sub.3 (CH.sub.3).sub.2, C.sub.6 H.sub.4 OCH.sub.3, C.sub.6 H.sub.4 OC.sub.2 H.sub.5, C.sub.6 H.sub.4 OCH.sub.2 CH.sub.2 OH or C.sub.6 H.sub.4 Cl; 5. The radicals CH.sub.2 CH.dbd.CH.sub.2, CH.sub.2 COOCH.sub.3, (CH.sub.2).sub.5 COOCH.sub.3, (CH.sub.2).sub.5 COOC.sub.2 H.sub.5, (CH.sub.2).sub.5 COOC.sub.4 H.sub.9, ##STR10## n being 2, 3, 4 or 6. 6. acyloxy: (CH.sub.2).sub.2 OCHO, (CH.sub.2).sub.2 OCOCH.sub.3, (C.sub.2 H.sub.4 O).sub.2 CHO, (C.sub.2 H.sub.4 O).sub.2 COCH.sub.3, (CH.sub.2).sub.2 OCOC.sub.3 H.sub.7, ##STR11## (CH.sub.2).sub.2 OCOC.sub.6 H.sub.5, (CH.sub.2).sub.2 OCOC.sub.6 H.sub.4 CH.sub.3, (CH.sub.2).sub.2 OCOC.sub.6 H.sub.4 Cl, (CH.sub.2).sub.2 OCOC.sub.10 H.sub.7, (CH.sub.2).sub.2 OCONHCH.sub.3, (CH.sub.2).sub.2 OCONHC.sub.4 H.sub.9, ##STR12## (CH.sub.2).sub.2 OCONHC.sub.6 H.sub.5, (CH.sub.2).sub.2 OCONHC.sub.6 H.sub.4 Cl, (CH.sub.2).sub.2 OCONHC.sub.6 H.sub.3 Cl.sub.2, and the corresponding radicals with (CH.sub.2).sub.3 ; (CH.sub.2).sub.4 or (CH.sub.2).sub.6 in each case. 7. acyl: Cho, ch.sub.3 co, c.sub.2 h.sub.5 co, c.sub.3 h.sub.7 co, ##STR13## c.sub.2 h.sub.5 co, ch.sub.3 c.sub.6 h.sub.4 co, c.sub.6 h.sub.5 ch.sub.2 co, c.sub.6 h.sub.5 och.sub.2 co, ch.sub.3 so.sub.2, c.sub.2 h.sub.5 so.sub.2, c.sub.6 h.sub.5 so.sub.2 and CH.sub.3 C.sub.6 H.sub.4 SO.sub.2. Examples of preferred substituents are hydrogen, CH.sub.3, C.sub.2 H.sub.5, n-- and i--C.sub.3 H.sub.7, n-- and i--C.sub.4 H.sub.9, C.sub.6 H.sub.13, CH.sub.2 CH.sub.2 OH, (CH.sub.2).sub.3 OH, ##STR14## (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH, (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OH, (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH, (CH.sub.2).sub.3 O(CH.sub.2).sub.6 OH, ##STR15## CH.sub.2 CH.sub.2 OCH.sub.3, CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5, CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9, (CH.sub.2).sub.3 OCH.sub.3, (CH.sub.2).sub.3 OC.sub.2 H.sub.5, (CH.sub.2).sub.3 OC.sub.3 H.sub.7, (CH.sub.2).sub.3 OC.sub.4 H.sub.9, ##STR16## C.sub.6 H.sub.5, C.sub.6 H.sub.4 CH.sub.3, C.sub.6 H.sub.4 OCH.sub.3, C.sub.6 H.sub.4 OC.sub.2 H.sub.4 OH and (CH.sub.2).sub.5 COOH. Examples of radicals R.sup.1 --N--R.sup.2 and R.sup.3 --N--R.sup.4 are: pyrrolidino, piperidino, morpholino, piperazino and hexamethyleneimino.

Dyes of the formula (I) may be prepared by reacting a diazo compound of an amine of the formula (II):

d--nh.sub.2 (ii) with a coupling component of the formula (III): ##STR17## in which D, R, X, and R.sup.1 to R.sup.4 have the above meanings.

The amines are diazotized by the usual methods. Coupling is also carried out as usual in an aqueous medium, with or without the addition of a solvent, at a strongly acid to weakly acid pH.

The invention relates particularly to dye formulations which contain, in addition to the conventional dispersing agents water rentention agents and water, a dye of the formula (I) in which:

D is phenyl substituted by cyano, trifluoromethyl, methyl, fluoro, chloro, bromo, C.sub.1 to C.sub.4 alkylsulfonyl, phenylsulfonyl, ##STR18## anthraquinonyl; anthraquinonyl substituted by methyl, chloro, bromo or carboxyl; or benzoisothiazolyl substituted by nitro, chloro or bromo; R is hydrogen, C.sub.1 to C.sub.3 alkyl or phenyl; X is cyano, carbamoyl or ##STR19## R.sup.1 and R.sup.3 independently of one another are hydrogen; C.sub.1 to C.sub.8 alkyl; C.sub.2 to C.sub.8 alkyl substituted by hydroxy, C.sub.1 to C.sub.8 alkoxy, phenoxy, tolyloxy, cyclohexyloxy, benzyloxy, .beta.-phenylethoxy, carboxyl, carboxylic ester with a total of 2 to 9 carbon atoms, carboxylic acyloxy with a total of 1 to 11 carbon atoms, C.sub.1 to C.sub.8 alkylaminocarbonyloxy, benzoylaminocarbonyloxy, tolylaminocarbonyloxy, chlorophenylaminocarbonyloxy, dichlorophenylaminocarbonyloxy or pyrrolidonyl; cyclohexyl; norbornyl; phenyl-C.sub.1 to C.sub.4 -alkyl; tolyl-C.sub.1 to C.sub.4 -alkyl; .beta.-phenyl-.beta.-hydroxy-ethyl; phenyl; phenyl substituted by fluoro, chloro, bromo, methyl, trifluoromethyl, ethyl, methoxy, ethoxy or pyrrolidonyl; CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH; or (CH.sub.2).sub.3 (OC.sub.2 H.sub.4).sub.n OB; n is zero, 1 or 2; B is hydrogen, C.sub.1 to C.sub.4 alkyl, cyclohexyl, benzyl, phenylethyl, phenyl or tolyl; R.sup.2 and R.sup.4 independently of one another are hydrogen or C.sub.1 to C.sub.4 alkyl; R.sup.1 and R.sup.2 together with the nitrogen are pyrrolidino, piperidino, morpholino or hexamethyleneimino; T.sup.1 is hydrogen, chloro, bromo or methyl; T.sup.2 is hydrogen or methyl; T.sup.3 is hydrogen, ##STR20## or COOB.sup.1 ; B.sup.1 is hydrogen, C.sub.1 to C.sub.8 alkyl, phenyl-C.sub.1 to C.sub.4 -alkyl or (OC.sub.2 H.sub.4).sub.n OB; Y is --SO.sub.2 -- or --CO--; T.sup.4 is hydrogen or chloro; and T.sup.5 is hydrogen, methyl or ethyl.

Dye formulations which contain a dye or dye mixture of the formula (Ia): ##STR21## in which D.sup.1 is a diazo component devoid of nitro groups of the benzene, phthalimide, naphthalimide, anthraquinone or azobenzene series or a nitrobenzoisothiazolyl radical;

A is hydrogen or C.sub.1 to C.sub.3 alkyl; and X.sup.1 is cyano or carbamoyl; and R.sup.1 and R.sup.3 have the meanings given above, are particularly important industrially.

The substituents are conveniently chosen so that the molecule contains either in the diazo component or in the coupling component at least one aryl radical and preferably a phenyl radical.

We have special preference for A to be methyl and X.sup.1 to be cyano and also for the combination A.dbd.H and X.sup.1 = CONH.sub.2.

Dyes are moreover preferred in which at least one of the radicals R.sup.1 and R.sup.3 contains an oxygen-containing amine radical, preferably the radical of one of the amines:

phenoxyethoxypropylamine, phenoxyethoxyethoxypropylamine, benzyloxypropylamine, phenylethoxypropylamine, butoxyethoxypropylamine, benzoyloxyethylamine, benzoyloxypropylamine, benzoyloxyethoxyethylamine, H.sub.2 N(CH.sub.2).sub.3 O(CH.sub.2).sub.4 OCOC.sub.6 H.sub.5, H.sub.2 N(CH.sub.2).sub.2 OCONHC.sub.6 H.sub.5, H.sub.2 N(CH.sub.2).sub.3 OCONHC.sub.6 H.sub.5 and H.sub.2 N(CH.sub.2)OCONHC.sub.6 H.sub.4 Cl and the combination of one of these radicals with phenylamino or amino. The radical D.sup.1 may be derived for example specifically from the following amines: o-cyanoaniline, m-cyanoaniline, p-cyanoaniline, 2,4-dicyanoaniline, 2,4,6-tribromoaniline, 2,4-dichloroaniline, 2-cyano-4,6-dibromoaniline, 2,4-dicyano-6-bromoaniline, 4-cyano-2-chloroaniline, 1-amino-2-trifluoromethyl-4-chlorobenzene, 2-chloro-5-aminobenzonitrile, 2-amino-5-chlorobenzonitrile, 1-aminobenzene-4-methylsulfone, 1-amino-2,6-dibromobenzene-4-methylsulfone, 1-amino-2-chloro-4-methylsulfone, 1-amino-2,6-dichlorobenzene-4-methylsulfone, propyl 3,5-dichloroanthranilate, .beta.-methoxyethyl 3,5-dibromoanthranilate, 4-aminoacetophenone, 4-aminobenzophenone, 2-aminobenzophenone, 2-aminodiphenylsulfone, 4-aminodiphenylsulfone, 3-aminophthal-.beta.-hydroxyethylimide, 4-aminophthalic phenylimide or p-tolylimide, 3-amino-6-chlorophthalimide and its N-substitution products, 3-amino-4-cyano-5-methylphthalimide and 3-amino-4-cyano-5-ethylphthalimide and their N-substitution products, 1-amino-2-chloroanthraquinone, 1-amino-2-bromoanthraquinone, 1-amino-2,4-dibromoanthraquinone, 1-amino-2-acetyl-4-chloroanthraquinone, 1-aminoanthraquinone-6-carboxylic acid, its ethyl ester, the ethyl ester of 1-aminoanthraquinone-6-carboxylic acid, 1-amino-4-methoxyanthraquinone, 1-amino-4-hydroxyanthraquinone, 1-amino-2-chloro-4-p-toluidinoanthraquinone, 2-amino-1-chloroanthraquinone, 2-amino-3-chloroanthraquinone, 2 -amino-3-bromoanthraquinone, 2-amino-1,3-dibromoanthraquinone, 2-amino-1-cyano-3-bromoanthraquinone, 1-aminobenzanthrone, 6-aminobenzanthrone, 7-aminobenzanthrone, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-amino-4-chloroanthraquinone, 2,4-dicyano-3,5-dimethylaniline, the imide, methylimide, n-butylimide, 2-hydroxyethylimide, 3'-methoxypropylimide or phenylimide of 4-aminonaphthalic acid, 5-nitro-3-aminobenzoisothiazole-(2,1) or 5-nitro-7-bromo-3-aminobenzoisothiazole-(2,1).

Examples of suitable diazo components of the aminoazobenzene series are:

4-aminoazobenzene, 3-chloro-4-aminoazobenzene, 3-bromo-4-aminoazobenzene, 2',3-dimethyl-4-aminoazobenzene, 3',2-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene, 2-methyl-5-methoxy-4-aminoazobenzene, 2-methyl-4',5-dimethoxy-4-aminoazobenzene, 4'-chloro-2-methyl-5-methoxy-4-aminoazobenzene, 4'-chloro-2-methyl-4-aminoazobenzene, 2,5-dimethoxy-4-aminoazobenzene, 4'-chloro-2,5-dimethoxy-4-aminoazobenzene, 4'-chloro-2,5-dimethyl-4-aminoazobenzene, 4'-methoxy-2,5-dimethyl-5-aminoazobenzene, 3,5-dibromo-4-aminoazobenzene, 2,3'-dichloro-4-aminoazobenzene, 3-methoxy-4-aminoazobenzene, 2',3-dimethyl-5-bromo-4-azobenzene, 4'-amino-2',5'-dimethylazobenzene-4-sulfonic amide, 4'-amino-2',5'-dimethylazobenzene-4-sulfonic amide and the aminoazobenzenes of the formula: ##STR22## in which T.sup.1 is hydrogen, chloro, bromo or methyl; T.sup.2 is hydrogen or methyl; and T.sup.3 is a radical of the formula ##STR23## or --COOB.sup.1 where Y is CO or SO.sub.2 and B.sup.1 is an alcohol radical and R.sup.1 and R.sup.2 have the meanings given above.

The dyes of the formula (I) may from their constitution be termed disperse dyes whose application for example to cotton is not as a rule possible. A process is described however in U.S. Pat. No. 3,706,525 which makes printing on cellulose and cellulosic textile material possible. Details given therein concerning process conditions are applicable to the dye formulations of the present invention. Other methods are specified in the commonly assigned copending application Ser. No. 691,496, filed June 1, 1976, by Hermann Schwab and Adolph Blum, now U.S. Pat. No. 4,049,377, according to which the dye formulations according to the invention may be applied. Printing processes are preferred. The above two patents are incorporated herein by reference.

The dye formulations according to the invention give dyeings and prints having excellent fastness properties among which wet fastnesses (particularly fastness to washing, water, perspiration and sea water) and in some cases lightfastness may be emphasized. In the case of prints for example no staining of any white ground present occurs in washing.

In the following Examples, which illustrate the invention, parts and percentages are by weight unless specified otherwise.

EXAMPLE 1

Cotton cloth is printed by a rotary screen printing method with an ink consisting of 10 parts of the dye of the formula: ##STR24## 100 parts of polyethylene oxide of a molecular weight of 300 to 790 parts of a 3% alginate thickening and the print is dried at 100.degree. C. The print is then treated for one minute at 200.degree. C. with hot air, rinsed cold, soaped at the boil, again rinsed cold and dried. A light-fast and wash-fast yellow orange print is obtained on a white ground.

EXAMPLE 2

A cloth from a blend of polyester and cotton (ratio by weight 67:35) is printed with a paste consisting of 20 parts of the dye of the formula ##STR25## 120 parts of the reaction product from polyethylene oxide having a molecular weight of 300 with boric acid in the molar ratio 3:1 and 860 parts of a 10% alginate thickening. The print is dried at 105.degree. C. and treated for six minutes at 180.degree. C. with superheated steam. The print is then rinsed with cold water, soaped at 80.degree. C., again rinsed cold and dried.

A red print which is fast to light and washing is obtained on a white ground.

EXAMPLE 3

A cotton cloth is printed by the roller printing method with a print paste consisting of 15 parts of the dye of the formula: ##STR26## 110 parts of polyethylene oxide of the molecular weight 350, 30 parts of the diethanolamide of oleic acid and 845 parts of a 10% alginate thickening. The print is dried at 100.degree. C. and then fixed by a treatment with hot air for one minute at 195.degree. C. The print is finished off as described in Example 1 and a fast organic print is obtained on a white ground.

EXAMPLE 4

Cloth of a blend of polyester and cellulose (ratio by weight 67:35) is printed on a screen printing machine with an ink consisting of 30 parts of the dye of the formula: ##STR27## 100 parts of the reaction product of polyethylene oxide of the molecular weight 300 with boric acid in the molar ratio 3:1, 30 parts of the diethanolamide of oleic acid and 840 parts of a 3% alginate thickening and the print is dried at 110.degree. C. It is then treated for five minutes at 185.degree. C. with superheated steam and finished off as described in Example 2. A fast scarlet print on a white ground is obtained.

EXAMPLE 5

Cotton cloth is padded on a padding mangle with a solution containing 20 parts of the dye of the formula: ##STR28## 300 parts of a 3% alginate thickening, 550 parts of water and 130 parts of polyethylene oxide of the molecular weight 300. The cloth should take up 80% liquor. It is dried at 100.degree. C. To fix the dye it is treated for five minutes with superheated steam at 190.degree. C. The cloth is then rinsed cold, washed at 90.degree. C. in a liquor containing 3 parts of the condensation product of a long chain alcohol with ethylene oxide to 997 parts of water.

A yellow dyeing is obtained.

Cloth of a blend of polyester and cotton in the ratio by weight 67:33 may be padded with the said solution instead of cotton cloth. A yellow dyeing is obtained in which the two phases are equal in tone. Fixation with hot air at 195.degree. C. may also be carried out instead of the treatment with superheated steam.

EXAMPLE 6

Cotton cloth is padded on a padding mangle with a solution of 150 parts of polyethylene oxide in 850 parts of water so that the wet pickup is 80% and the padded cloth is dried at 100.degree. C. The cloth treated in this way is printed by the rotary screen printing method with a color consisting of 30 parts of the dye of the formula: ##STR29## and 970 parts of a 10% alginate thickening. After the print has been dried at 105.degree. C. it is treated for seven minutes at 185.degree. C. with superheated steam and finished off by rinsing and soaping as described in Example 1.

A fast red print on a white ground is obtained.

The dyes specified in the following Examples may be converted as follows into a commercial dye formulation:

30 parts of dye, 6 parts of dispersing agent, 10 parts of a water retention agent, 1 part of a disinfectant and about 53 parts of water are ground in an agitator mill to a particle size of about 0.5 micron. A dispersion of the dye is thus obtained which is stable in storage.

EXAMPLE 7

20 parts of 4-aminoazobenzene is stirred overnight with 80 parts by volume of 5N hydrochloric acid. Then it is diluted with ice and water to a volume of 500 parts by volume at 10.degree. C. 30 parts by volume of a 23% sodium nitrite solution is added and the whole is stirred for two hours at 15.degree. C. The filtrate, in which excess nitrous acid has been removed in the conventional manner by adding sulfamic acid, is allowed to flow into a solution of 53 parts of 2,6-bis(phenoxyethoxypropylamino)-3-cyano-4-methylpyridine in 4000 parts by volume of dimethylformamide at 15.degree. C. 150 parts by volume of a 50% aqueous sodium acetate solution is then added to this coupling mixture and the whole is stirred at 15.degree. C. until coupling is completed. The dye formed is suction filtered, washed first with alcohol and then with hot water and dried at 90.degree. C. A red powder is obtained which readily dissolves in dimethylformamide and polyethylene glycols with a yellowish red color and when printed in the form of these solutions or as an aqueous dispersion on cloth of polyester or cotton or a blend of the two types of fiber and aftertreated with hot air or superheated steam gives deep and clear scarlet hues.

EXAMPLE 8

35 parts of 3-chloro-4-aminoazobenzene is stirred overnight with 7 parts of an oxyethylated sperm oil alcohol containing about 23 ethylene oxide radicals and 120 parts by volume of 5N hydrochloric acid. A volume of 750 parts by volume and a temperature of 10.degree. C. are set up with ice and water and 450 parts by volume of a 23% aqueous sodium nitrite solution is introduced. After stirring for two hours at 15.degree. C. a small amount of insoluble matter is filtered off and nitrous acid is removed in the usual way by adding an aqueous solution of sulfamic acid.

The diazonium salt solution thus obtained is then allowed to flow at 10.degree. C. into 385 parts by volume of an isobutanol solution containing 0.16 mole of 2,6-bis-(phenoxyethoxypropylamino)-3-cyano-4-methylpyridine. Complete coupling is achieved after stirring for several hours at 15.degree. to 25.degree. C. without adding the usual acid-binding agents. The dye formed is suction filtered, washed first with 100 parts by volume of isobutanol and then with 100 parts of hot water and then dried at 100.degree. C.

The product which is in the form of a red powder may as an aqueous dispersion or dissolved in a polyethylene glycol be printed on cloth of polyester, cotton or a blend of both types of fiber and aftertreated with hot air or superheated steam. Deep and clear red hues of very good light and wet fastness properties are thus obtained.

EXAMPLE 9

The procedure described in Examle 8 is adpted but the coupling component used is 0.15 mole of the substance having the formula: ##STR30## dissolved in 8000 parts by volume of dimethylformamide. The red powder obtained after isolation and drying dissolves in dimethylformamide and polyethylene glycols with a yellowish red color. Deep and clear scarlet hues with very good fastness properties are obtained on cloth of polyester, cotton or blends of the two.

Red hues having similar tinctorial properties are obtained in an analogous manner with the same diazo components and the following coupling components:

__________________________________________________________________________ ##STR31##Ex. R.sup.1 R.sup.2__________________________________________________________________________10 H ##STR32##11 ##STR33## "12 ##STR34## "13 ##STR35## "14 ##STR36## "15 " ##STR37##16 ##STR38## "17 ##STR39## "18 ##STR40## "19 ##STR41## ##STR42##20 ##STR43## ##STR44##21 ##STR45## ##STR46##22 H "__________________________________________________________________________

EXAMPLE 23

16 parts of o-trifluoromethylaniline is dissolved in 30 parts by volume of 10N hydrochloric acid and 200 parts of water. 200 parts of ice is added and then 30 parts by volume of a 23% aqueous solution of sodium nitrite is allowed to flow in below the surface. After stirring for half an hour at 0.degree. to 5.degree. C. the excess of nitrous acid is destroyed as usual by adding an aqueous solution of sulfamic acid.

The solution of the diazonium salt thus obtained is gradually added at 5.degree. to 10.degree. C. to a solution of 54 parts of bis-(phenoxyethoxypropylamino)-3-cyano-4-methylpyridine in 1000 parts by volume of dimethylformamide and then 32 parts by volume of a 50% aqueous sodium acetate solution is added. When coupling is over the yellow dye formed is suction filtered, washed first with alcohol and then with hot water and dried at 100.degree. C. The yellow powder thus obtained dissolves in dimethylformamide or polyglycols with a pure yellow color and when printed on to cloth of cotton, polyester or blends of both and fixed gives deep and clear yellow hues with very good fastness properties.

The following dyes are obtained in a similar manner with the same coupling components:

______________________________________ Hue on cottonEx. Diazo component and polyester______________________________________24 m-trifluoromethylaniline yellow25 4-chloro-2-trifluoromethylaniline "26 2-cyanoaniline "27 4-chloro-2-cyanoaniline "28 2,4-dicyanoaniline yellowish orange29 2-chloroaniline-4-methylsulfone reddish yellow30 2-aminodiphenylsulfone reddish yellow31 3-aminophthalic hydroxyethylimide yellowish orange______________________________________

EXAMPLE 32

25.3 parts of the p-tolylimide of 3-aminophthalic acid is introduced at 15.degree. to 25.degree. C. into 60 parts of 96% sulfuric acid while stirring. The mixture is further stirred at the same temperature until complete solution has taken place. Then 32 parts (0.1 mole) of nitrosylsulfuric acid is allowed to flow in slowly at 0.degree. to 5.degree. C. and the diazotization mixture is stirred for another thirty minutes at 0.degree. to 5.degree. C. and then introduced into a mixture of 125 parts of ice and 25 parts of ice-water.

After the excess of nitrite has been destroyed with sulfamic acid the diazonium salt is stirred while 300 parts by volume of isobutanol and 110 parts by volume of a 10-molar solution of 2,6-bis-(phenoxyethoxypropylamino)-3-cyano-4-methylpyridine in isobutanol are introduced. After coupling is over the dye formed is suction filtered, washed first with isobutanol and then with hot water and dried at 100.degree. C. The reddish powder thus obtained dissolves in polyglycols with a reddish yellow color and gives deep orange hues with very good fastness properties on polyester, cotton or blends of the two after having been printed and fixed.

The following dyes may be obtained by similar methods with the same coupling components:

______________________________________ Hue on polyesterEx. Diazo components and cotton______________________________________33 1-aminoanthraquinone brown34 1-aminoanthraquinone-6-carboxylic acid brown35 1-amino-2-chloroanthraquinone brown36 1-amino-2-bromoanthraquinone brown37 1-amino-2,4-dichloroanthraquinone brown38 4-amino-3-methoxybenzanthrone brown39 2-aminoanthraquinone red40 2-amino-3-chloroanthraquinone red41 2-amino-1-chloroanthraquinone red42 2-amino-1-cyano-3-bromoanthraquinone red43 2-amino-3-bromoanthraquinone red44 1-aminobenzanthrone reddish violet45 5-nitro-3-aminobenzoisothiazole-(2,3) bluish violet46 5-nitro-2-aminothiazole reddish violet______________________________________

The following dyes are obtainable according to the processes of the foregoing Examples:

__________________________________________________________________________Ex. Diazo components Coupling components Hue__________________________________________________________________________47 ##STR47## ##STR48## scarlet48 ##STR49## " red49 ##STR50## " ruby50 ##STR51## " reddish violet51 ##STR52## ##STR53## red52 ##STR54## " red53 ##STR55## " orange54 ##STR56## ##STR57## reddish orange55 ##STR58## " reddish orange56 ##STR59## " scarlet57 ##STR60## " yel- lowish orange58 ##STR61## " red ##STR62##Ex.No. D X R.sup.1 R.sup.2 Hue__________________________________________________________________________59 ##STR63## CN H (CH.sub.2).sub.3 O(CH.sub.2).su b.2 OC.sub.6 H.sub.5 red60 " CN C.sub.2 H.sub.5 " red61 " CN C.sub.3 H.sub.7(n) " red62 ##STR64## CN C.sub.6 H.sub.5 " golden yellow63 " CONH.sub.2 H (CH.sub.2).sub.3 OCH.sub.3 orange64 ##STR65## " H " scarlet65 ##STR66## " H " red66 ##STR67## CN CH.sub.3 " red67 " CONH.sub.2 H " red68 ##STR68## CN CH.sub.3 (CH.sub.2).sub.3 O(CH.sub.2).su b.2 OC.sub.6 H.sub.5 red69 " CN H " red70 " CN CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 red71 " CONH.sub.2 H " bluish red72 ##STR69## CN CH.sub.3 (CH.sub.2).sub.3 O(CH.sub.2).su b.2 OC.sub.6 H.sub.5 bluish red ##STR70##Ex.No. D Hue__________________________________________________________________________73 ##STR71## scarlet74 ##STR72## scarlet75 ##STR73## scarlet76 ##STR74## red77 ##STR75## red78 ##STR76## red79 ##STR77## red80 ##STR78## red81 ##STR79## red82 ##STR80## orange83 ##STR81## orange__________________________________________________________________________ ##STR82##Ex.No. D Hue__________________________________________________________________________84 ##STR83## golden yellow85 ##STR84## golden yellow86 ##STR85## orange87 ##STR86## orange88 ##STR87## ruby ##STR88##Ex.No. D Hue__________________________________________________________________________89 ##STR89## scarlet90 ##STR90## red91 ##STR91## red92 ##STR92## red93 ##STR93## red94 ##STR94## red95 ##STR95## red96 ##STR96## red97 ##STR97## red98 ##STR98## red99 ##STR99## orange100 ##STR100## golden yellow101 ##STR101## orange102 ##STR102## orange ##STR103##Ex.No. D R Hue__________________________________________________________________________103 ##STR104## H reddish orange104 " CH.sub.3 reddish orange105 " COC.sub.6 H.sub.5 reddish orange106 ##STR105## " golden yellow107 ##STR106## " golden yellow108 ##STR107## " reddish orange109 " H reddish orange110 ##STR108## H red111 ##STR109## COC.sub.6 H.sub.5 red112 " ##STR110## red113 " CH.sub.3 red114 " C.sub. 2 H.sub.5 red115 ##STR111## " red116 " CH.sub.3 red117 " H red118 ##STR112## H yellowish orange119 " CH.sub.3 yellowish orange120 " C.sub.2 H.sub.5 yellowish orange121 ##STR113## C.sub.2 H.sub.5 red122 " CH.sub.3 red123 " H red ##STR114##Ex.No. D Hue__________________________________________________________________________124 ##STR115## golden yellow125 ##STR116## orange126 ##STR117## golden yellow127 ##STR118## reddish orange128 ##STR119## red129 ##STR120## red130 ##STR121## reddish orange131 ##STR122## reddish orange132 ##STR123## red133 ##STR124## red134 ##STR125## orange135 ##STR126## orange ##STR127##Ex.No. D Hue__________________________________________________________________________136 ##STR128## bluish red137 ##STR129## bluish red138 ##STR130## Bordeaux139 ##STR131## Bordeaux140 ##STR132## bluish red141 ##STR133## orange142 ##STR134## orange143 ##STR135## reddish orange144 ##STR136## red145 ##STR137## red146 ##STR138## red147 ##STR139## red148 ##STR140## reddish orange149 ##STR141## reddish orange150 ##STR142## golden yellow151 ##STR143## golden yellow152 ##STR144## golden yellow153 ##STR145## golden yellow ##STR146##Ex.No. D Hue__________________________________________________________________________154 ##STR147## reddish orange155 ##STR148## red156 ##STR149## red157 ##STR150## red158 ##STR151## red159 ##STR152## orange160 ##STR153## orange161 ##STR154## golden yellow162 ##STR155## golden yellow163 ##STR156## golden yellow164 ##STR157## golden yellow ##STR158##Ex.No. D Hue__________________________________________________________________________165 ##STR159## reddish orange166 ##STR160## red167 ##STR161## red168 ##STR162## red169 ##STR163## red170 ##STR164## reddish orange171 ##STR165## reddish orange172 ##STR166## golden yellow173 ##STR167## golden yellow174 ##STR168## golden yellow175 ##STR169## golden yellow ##STR170##Ex.No. D Hue__________________________________________________________________________176 ##STR171## reddish orange177 ##STR172## red178 ##STR173## red179 ##STR174## red180 ##STR175## red181 ##STR176## reddish orange182 ##STR177## reddish orange183 ##STR178## golden yellow184 ##STR179## golden yellow185 ##STR180## golden yellow186 ##STR181## golden yellow Coupling components Diazo component ##STR182## ##STR183##Ex.No. R.sup.1 R.sub.2 Hue__________________________________________________________________________187 ##STR184## ##STR185## yellow188 ##STR186## " yellow189 NH.sub.2 " yellow190 ##STR187## ##STR188## yellow191 " ##STR189## yellow192 " ##STR190## yellow ##STR191## ##STR192##Ex.No. R.sup.1 R.sup.2 Hue__________________________________________________________________________193 NH.sub.2 ##STR193## yellow Coupling components Diazo component ##STR194## ##STR195##Ex.No. R.sup.1 R.sup.2 Hue__________________________________________________________________________194 ##STR196## ##STR197## yellow ##STR198## ##STR199##Ex.No. R.sup.1 R.sup.2 Hue__________________________________________________________________________195 ##STR200## ##STR201## golden yellow196 ##STR202## ##STR203## orange197 " ##STR204## orange198 " ##STR205## orange Coupling components Diazo component ##STR206## ##STR207##Ex.No. R.sup.1 R.sup.2 Hue__________________________________________________________________________199 ##STR208## ##STR209## golden yellow200 ##STR210## ##STR211## orange201 " ##STR212## orange Coupling components Diazo component ##STR213## ##STR214##Ex.No. R.sup.1 R.sup.2 Hue__________________________________________________________________________202 ##STR215## ##STR216## golden yellow203 NH.sub.2 " orange204 ##STR217## ##STR218## orange205 " ##STR219## orange206 " ##STR220## orange207 " ##STR221## golden yellow208 " ##STR222## golden yellow Coupling components Diazo component ##STR223## ##STR224##Ex.No. R.sup.1 R.sup.2 Hue__________________________________________________________________________209 ##STR225## ##STR226## orange210 " ##STR227## orange211 " ##STR228## orange212 " ##STR229## orange213 " ##STR230## orange Coupling components Diazo component ##STR231## ##STR232##Ex.No. R.sup.1 R.sup.2 Hue__________________________________________________________________________214 ##STR233## ##STR234## reddish orange215 ##STR235## ##STR236## "216 ##STR237## ##STR238## "217 " ##STR239## red218 " ##STR240## "219 NH.sub.2 ##STR241## orange Coupling components Diazo component ##STR242## ##STR243##Ex.No. R.sup.1 R.sup.2 Hue__________________________________________________________________________220 ##STR244## ##STR245## red221 ##STR246## " "222 " ##STR247## "223 NH.sub.2 ##STR248## "224 ##STR249## ##STR250## "225 " ##STR251## "226 " ##STR252## "227 " ##STR253## " Coupling components Diazo component ##STR254## ##STR255##Ex.No. R.sup.1 R.sup.2 Hue__________________________________________________________________________228 ##STR256## ##STR257## Bluish violet229 " ##STR258## "230 ##STR259## " "231 NH.sub.2 " violet232 ##STR260## ##STR261## bluish violet233 " ##STR262## blue234 " N "235 " N "Ex.No.236 ##STR263## red ##STR264##Ex.No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 Hue__________________________________________________________________________237 ##STR265## CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 red238 " " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 "239 " " " " C.sub.6 H.sub.5 "240 ##STR266## " " " " "241 ##STR267## " " " " "242 " " " " CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 "243 " H " " " "244 " Cl H " " "245 ##STR268## CH.sub.3 CH.sub.3 " C.sub.6 H.sub.5 "246 " " " " (CH.sub.2).sub.3 O(CH.sub.2 ).sub.2 OC.sub.6 H.sub.5 "247 ##STR269## " " " " "248 ##STR270## " " (CH.sub.2).sub.3 O(CH.sub.2 O(C.sub.6 H.sub.5 " "249 ##STR271## " " " " "250 ##STR272## " " " " "251 " " " (CH.sub.2).sub.3 OCH.sub.3 " "252 H Cl H (CH.sub.2).sub.5COOH " "253 HOOC CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 " "254 H H H (CH.sub.2).sub.5COOH " orange255 H CH.sub.3 CH.sub.3 " " "256 H Cl H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 COCH.sub.3 scarlet257 " " " " SO.sub.2 CH.sub.3 "Coupling component ##STR273## Diazo components Hue__________________________________________________________________________258 ##STR274## yellow259 ##STR275## orange260 ##STR276## "261 ##STR277## scarlet262 ##STR278## "263 ##STR279## "264 ##STR280## bluish red265 ##STR281## "266 ##STR282## reddish violet267 ##STR283## "268 ##STR284## ruby269 trichloroaniline yellow270 tribromoaniline yellowCoupling component ##STR285##Ex Diazo components R X R.sup.3 Hue__________________________________________________________________________271 1-aminoanthraquinone CH.sub.3 CN H brown272 " H CN H brown273 " H CONH.sub.2 H reddish brown274 " CH.sub.3 CN C.sub.6 H.sub.5 brown275 " H CN C.sub.6 H.sub.5 brown276 " H CONH.sub.2 C.sub.6 H.sub.5 reddish brown277 " CH.sub.3 CN C.sub.6 H.sub.4 CH.sub.3 (p) brown278 1-amino-2-chloroanthra- CH.sub.3 CN H brown quinone279 " CH.sub.3 CN C.sub.6 H.sub.5 brown280 " CH.sub.3 CN C.sub.6 H.sub.4 CH.sub.3 (p brown281 " H CN C.sub.6 H.sub.5 brown282 " H CONH.sub.2 C.sub.6 H.sub.5 reddish brown283 1-amino-2-methylanthraquin- CH.sub.3 CN H brown one264 " CH.sub.3 CN C.sub.6 H.sub.5 brown285 3-amino-5-nitro-benzoiso- H CN H violet thiazole-(2,1)286 " H CONH.sub.2 H navy blue287 " H CONH.sub.2 C.sub.6 H.sub.5 blue288 3-amino-5-nitro-7-bromo- H CONH.sub.2 C.sub.6 H.sub.5 blue benzoisothiazole-(2,1)289 " H CONH.sub.2 H navy blue290 " H CN H bluish violet291 ##STR286## CH.sub.3 CN H orange292 " CH.sub.3 CN C.sub.6 H.sub.5 orange293 " H CN H orange294 " H CONH.sub.2 H scarlet295 " H CONH.sub.2 C.sub.6 H.sub.5 scarlet296 ##STR287## CH.sub.3 CN C.sub.6 H.sub.5 orange297 " H CN C.sub.6 H.sub.5 orange298 " H CONH.sub.2 C.sub.6 H.sub.5 scarlet299 " H CONH.sub.2 H orange300 ##STR288## H CN H red301 " H CN C.sub.6 H.sub.5 red302 " H CONH.sub.2 C.sub.6 H.sub.5 ruby303 " H CONH.sub.2 H ruby304 " H CN (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub. 6 H.sub.5 red305 ##STR289## H CONH.sub.2 H ruby306 " H CN H red307 " H CN C.sub.6 H.sub.5 red308 " CH.sub.3 CN (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6 red309 ##STR290## CH.sub.3 CN H orange310 " H CN H orange311 " H CONH.sub.2 H scarletCoupling components ##STR291##Ex. Diazo components R.sup.3 Z Hue__________________________________________________________________________312 ##STR292## H (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5 orange313 " C.sub.6 H.sub.5 " orange314 ##STR293## H " orange315 ##STR294## H " orange316 ##STR295## H " scarlet317 ##STR296## H " scarlet318 3-aminophthalic p-tolyl- imide H " red319 1-aminoanthraquinine H " reddish brown320 aminoazobenzene H " ruby321 chloroaminoazobenzene H " reddish violet322 bromoaminoazobenzene H " reddish violet323 3-amino-5-nitrobenzoiso- thiazole-(2,1) H " navy blue324 " C.sub.6 H.sub.5 " navy blue325 " C.sub.6 H.sub.4 CH.sub.3 (p) " navy blue326 3-amino-5-nitro-7-bromo- benzoisothiazole-(2,1) H " navy blue327 " C.sub.6 H.sub.5 " navy blue328 4-aminoazobenzene H H orange329 4-amino-3-chloroazobenzene H H scarletThe following are also suitable as dyes:Example Hue__________________________________________________________________________330 ##STR297## orange331 ##STR298## yellow332 ##STR299## brown333 ##STR300## red ##STR301##Example R Hue__________________________________________________________________________334 C.sub.6 H.sub.5 red335 C.sub.6 H.sub.4 CH.sub.3 (o) red336 C.sub.6 H.sub.4 CH.sub.3 (p) red337 ##STR302## red ##STR303##Example D R.sup.1 R.sup.3 Hue__________________________________________________________________________338 ##STR304## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 (CH.sub.2).sub.3 (CH.sub.2).sub .2 OC.sub.6 H.sub.5 orange339 ##STR305## " " orange340 ##STR306## " ##STR307## orange341 " " ##STR308## orange342 " " (CH.sub.2).sub.2C.sub.6 H.sub.5 orange343 " ##STR309## (CH.sub.2).sub.3 O(CH.sub.2).su b.2 OC.sub.6 H.sub.5 orange344 ##STR310## (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 orange345 " (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 orange346 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 (CH.sub.2).sub.3 O(CH.sub.2).su b.2 OC.sub.6 H.sub.5 orange347 ##STR311## (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 orange348 " (CH.sub.2 ).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 orange349 " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 (CH.sub.2).sub.3 O(CH.sub.2).su b.2 OC.sub.6 H.sub.5 orange350 ##STR312## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 (CH.sub.2).sub.3 O(CH.sub.2).su b.2 OC.sub.6 H.sub.5 orange351 ##STR313## " " orange352 ##STR314## " " orange353 ##STR315## " " orange354 ##STR316## " " orange355 ##STR317## " " orange356 ##STR318## " " orange357 ##STR319## " " orange358 ##STR320## " " orange359 " NH.sub.2 " orange360 " (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 orange361 " (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 orange362 ##STR321## (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.4 H.sub.9 (CH.sub.2).sub.3 O(CH.sub.2 ).sub.2 OC.sub.4 H.sub.9 red363 ##STR322## " " brown364 ##STR323## " " orange365 ##STR324## " " orange366 ##STR325## " " orange367 ##STR326## " " orange ##STR327##Ex. T.sup.3 T.sup.4 T.sup.5 R.sup.3 R.sup.1 Hue__________________________________________________________________________368 SO.sub.2 NH(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 H H (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 red369 " " (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 red370 " " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 (CH.sub.2).sub.3 O(CH.sub. 2).sub.2 OC.sub.6 redub.5371 " " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 (CH.sub.2).sub.3 O(CH.sub. 2).sub.2 OC.sub.6 redub.5372 " Cl " " " red373 " Cl " (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 red374 " Cl " (CH.sub.2).sub.3 OCH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 red375 CONH(CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 H " " " red376 " H " (CH.sub.2).sub.2 OCH.sub.3 (CH.sub.2).sub.2 OCH.sub.3 red377 " H " (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5 (CH.sub.2).sub.3 O(CH.sub. 2).sub.2 OC.sub.6 redub.5378 Cl Cl SO.sub.2 NH(CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5 red ##STR328##Example R.sup.1 Hue__________________________________________________________________________379 ##STR329## bluish violet380 ##STR330## blue381 ##STR331## blue382 (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.4 H.sub.9 bluish violet383 ##STR332## blue ##STR333##Example D R X Hue__________________________________________________________________________384 ##STR334## CH.sub.3 CN scarlet385 " H CN scarlet386 " H CONH.sub.2 red387 ##STR335## CH.sub.3 CN red388 " H CN red389 " H CONH.sub.2 ruby390 ##STR336## CH.sub.3 CN yellow391 " H CONH.sub.2 orange392 ##STR337## CH.sub.3 CN yellowish orange393 " H CONH.sub.2 reddish orange394 ##STR338## CH.sub.3 CN orange395 " H CONH.sub.2 scarlet__________________________________________________________________________

Claims

1. The dye of the formula ##STR339##