Dyes containing thiophene radicals

Abstract

The compounds of the general formula I ##STR1## where X is fluorine, chlorine, bromine, SO.sub.2 E or unsubstituted or substituted hydroxyl or mercapto, E is alkyl, alkenyl, cycloalkyl, aralkyl, aryl, chlorine or unsubstituted or substituted hydroxyl or amino, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, T is hydrogen, C.sub.1 -C.sub.4 -alkyl, a radical which can be introduced by electrophilic substitution or a radical of the formula --CH.dbd.B, in which B is a radical of a methylene-active compound or of an amine, and K is a radical of a coupling component, are very useful for dyeing synthetic fibers or plastics.

Description

The present invention relates to compounds of the general formula I ##STR2## where X is fluorine, chlorine, bromine, SO.sub.2 E or unsubstituted or substituted hydroxyl or mercapto, E is alkyl, alkenyl, cycloalkyl, aralkyl, aryl, chlorine or unsubstituted or substituted hydroxyl or amino, Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl, T is hydrogen, C.sub.1 -C.sub.4 -alkyl, a radical which can be introduced by electrophilic substitution or a radical of the formula --CH.dbd.B, in which B is a radical of a methylene-active compound or of an amine, and K is a radical of a coupling component.

Examples of radicals X, in addition to those stated above, are alkoxy, cycloalkoxy, aralkoxy and aryloxy, as well as the corresponding mercapto radicals. Specific examples are OH, OCH.sub.3, OC.sub.2 H.sub.5, OC.sub.3 H.sub.7, OC.sub.4 H.sub.9, OCH.sub.2 C.sub.6 H.sub.5, OC.sub.6 H.sub.11, OC.sub.6 H.sub.5, OC.sub.6 H.sub.4 CH.sub.3, OC.sub.6 H.sub.4 Cl, SH, SCH.sub.3, SC.sub.2 H.sub.5, SC.sub.3 H.sub.7, S.sub.4 H.sub.9, SCH.sub.2 C.sub.6 H.sub.5, SC.sub.2 H.sub.4 OH, SCH.sub.2 COOCH.sub.3, SH.sub.2 COOC.sub.2 H.sub.5, SC.sub.6 H.sub.11, SC.sub.6 H.sub.5 and SC.sub.6 H.sub.4 CH.sub.3.

E is, for example, CH.sub.3, C.sub.2 H.sub.5, C.sub.3 H.sub.7, C.sub.4 H.sub.9, C.sub.6 H.sub.13, C.sub.6 H.sub.11, C.sub.8 H.sub.17, C.sub.6 H.sub.5 --CH.sub.2, C.sub.6 H.sub.5 --CH.sub.2 --CH.sub.2, C.sub.6 H.sub.5, Cl--C.sub.6 H.sub.4, C.sub.4 H.sub.9 --C.sub.6 H.sub.4, Cl, OH, CH.sub.3 O, C.sub.2 H.sub.5 O, C.sub.3 H.sub.7 O, C.sub.4 H.sub.9 O, C.sub.6 H.sub.5 --CH.sub.2 O, C.sub.6 H.sub.5 --CH.sub.2 --CH.sub.2 O, C.sub.6 H.sub.5 O, ClC.sub.6 H.sub.4 O, CH.sub.3 C.sub.6 H.sub.4 O, NH.sub.2, NHCH.sub.3, N(CH.sub.3).sub.2, NHC.sub.2 H.sub.5, N(C.sub.2 H.sub.5).sub.2, NHC.sub.4 H.sub.9, N(C.sub.4 H.sub.9).sub.2, NHC.sub.6 H.sub.5, NHC.sub.6 H.sub.4 --CH.sub.3, NHC.sub.6 H.sub.4 Cl or NCH.sub.3 C.sub.6 H.sub.4.

Specific examples of radicals Y, in addition to those stated above, are: ##STR3##

Examples of radicals T which can be introduced by electrophilic substitution are Cl, Br, NO, NO.sub.2, SO.sub.3 H, CHO, CN and acyl, where acyl is, for example CH.sub.3 CO, C.sub.2 H.sub.5 CO, C.sub.6 H.sub.5 CO, CH.sub.3 SO.sub.2, C.sub.2 H.sub.5 SO.sub.2 or C.sub.6 H.sub.5 SO.sub.2.

Methylene-active compounds of the formula H.sub.2 B are, for example, compounds of the formula ##STR4## where Z is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl or is a radical of a compound of the formula ##STR5##

Specific examples of important compounds of the formula ##STR6##

Examples of amine radicals B are .dbd.N--C.sub.6 H.sub.5, .dbd.N--C.sub.6 H.sub.4 CH.sub.3 or generally radicals of Schiff's bases of the amines.

Alkyl radicals T are, for example, CH.sub.3, C.sub.2 H.sub.5, C.sub.3 H.sub.7 or C.sub.4 H.sub.9.

The diazo components in which T is H or C.sub.1 -C.sub.4 -alkyl alkyl can be prepared by reacting a compound of the formula II ##STR7## with a sulfur donor. Radicals T may be introduced into the diazo components in which T is H by electrophilic substitution by a conventional method.

Furthermore, the diazo component in which T is H and X is OH may be prepared by reacting the compound of the formula

CLCH.sub.2 COCL with malodinitrile and then reacting the product with a sulfide.

The preparation of the diazo components is described in detail in European Patent Application 86102603.7.

The coupling components of the formula HK are preferably derived from the aniline, .alpha.-naphthylamine, pyrazole, aminopyrazole, indole, thiazole, thiophene, phenol, naphthol, tetrahydroquinoline, pyridone or pyridine series, those of the aniline, pyrazole, pyridine, thiophene and thiazole series being preferred.

The coupling components HK are in particular of the general formula ##STR8## where B.sup.1 is hydrogen or B.sup.2, B.sup.2 is unsubstituted or substituted alkyl, cycloalkyl, alkenyl, aryl or acyl, R.sup.1 is hydrogen, alkyl, aralkyl or aryl, R.sup.2 is hydrogen or R.sup.3, R.sup.3 is unsubstituted or substituted alkyl, cycloalkyl, alkenyl, aralkyl or aryl, R.sup.4 and R.sup.5 independently of one another are each hydrogen, alkyl, alkoxy, phenoxy, halogen, alkylsulfonylamino, dialkylaminosulfonylamino or acylamino, R.sup.6 is cyano, carbamyl, nitro, acetyl or carbalkoxy and R.sup.7 is unsubstituted or substituted phenyl, alkyl, aralkyl, halogen, substituted hydroxyl or mercapto.

Examples of radicals B.sup.2, in addition to those stated above, are C.sub.1 -C.sub.6 -alkyl which may be substituted by chlorine, bromine, hydroxyl, C.sub.1 -C.sub.8 -alkoxy, phenoxy, phenyl, cyano, carboxyl, C.sub.1 -C.sub.8 -alkanoyloxy, C.sub.1 -C.sub.8 -alkoxy-C.sub.1 -C.sub.4 -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C.sub.1 -C.sub.8 -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C.sub.1 -C.sub.8 -alkoxycarbonyloxy, C.sub.1 -C.sub.8 -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C.sub.1 -C.sub.8 -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C.sub.1 -C.sub.8 -alkoxycarbonyl, C.sub.1 -C.sub.8 -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C.sub.1 -C.sub.4 -alkoxy or phenylethoxycarbonyl, and phenyl and cyclohexyl.

Specific examples of radicals B.sup.2 are:

1) Unsubstituted or substituted alkyl, such as ##STR9## and the corresponding radicals in which two C.sub.2 H.sub.4 O, C.sub.3 H.sub.6 O, ##STR10## groups are present, and ##STR11##

2. Unsubstituted or substituted cycloalkyl: ##STR12##

3. Unsubstituted or substituted aralkyl: ##STR13## and those radicals containing C.sub.6 H.sub.4 CH.sub.3 and C.sub.6 H.sub.4 OCH.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.3 (OCH.sub.3).sub.2, C.sub.6 H.sub.4 Cl and C.sub.6 H.sub.2 (OCH.sub.3).sub.2 Cl.

5. The radicals CH.sub.2 CH=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, ##STR14## where n is 2, 3, 4 or 6.

6. Acyloxy radicals: (CH.sub.2).sub.2 OCHO, (CH.sub.2).sub.2 OCO(CH.sub.2).sub.n CH.sub.3, (C.sub.2 H.sub.4 O).sub.2 CHO, (C.sub.2 H.sub.4 O).sub.2 CO(CH.sub.2).sub.n CH.sub.3, (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCHO, (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCO(CH.sub.2).sub.n CH.sub.3, (CH.sub.2).sub.2 O(CH.sub.2).sub.4 OCHO and (CH.sub.2).sub.2 O(CH.sub.2).sub.4 OCO(CH.sub.2).sub.n CH.sub.3, where n is 0 to 7, ##STR15## and the corresponding radicals containing (CH.sub.2).sub.3 or (CH.sub.2).sub.4 instead of (CH.sub.2).sub.2.

7. Acyl radicals: CHO and CH.sub.3 (CH.sub.2).sub.n CO, where n is from 0 to 7, C.sub.6 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.

Specific examples of radicals R.sup.1, in addition to those stated above, are methyl, ethyl, propyl, butyl, benzyl, phenethyl, phenyl, o-, m- and p-tolyl and o-, m- and p-chlorophenyl.

Examples of radicals R.sup.3, in addition to those mentioned above, are C.sub.1 -C.sub.6 -alkyl which may be substituted by chlorine, bromine, hydroxyl, C.sub.1 -C.sub.8 -alkoxy, phenoxy, cyano, carboxyl, C.sub.1 -C.sub.8 -alkanoyloxy, C.sub.1 -C.sub.8 -alkoxy-C.sub.1 -C.sub.4 -alkoxy, benzoyloxy, o-, m- and p-methylbenzoyloxy, o-, m- and p-chlorobenzoyloxy, C.sub.1 -C.sub.8 -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C.sub.1 -C.sub.8 -alkoxycarbonyloxy, C.sub.1 -C.sub.8 -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenylethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C.sub.1 -C.sub.8 -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C.sub.1 -C.sub.8 -alkoxycarbonyl, C.sub.1 -C.sub.8 -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C.sub.1 -C.sub.4 -alkoxy or phenylethoxycarbonyl, and phenyl, benzyl, phenethyl and cyclohexyl.

Specific examples of radicals R.sup.3 are methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonlyoxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-.beta.-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl.

Examples of suitable radicals R.sup.4 and R.sup.5 are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy and C.sub.1 -C.sub.4 -alkoxycarbonylamino, and benzoylamino or C.sub.1 -C.sub.6 -alkanoylamino which is unsubstituted or substituted by chlorine, bromine, cyano, methoxy, ethoxy or phenoxy, and C.sub.1 -C.sub.4 -alkylsulfonylamino or -dialkylaminosulfonylamino.

Examples of radicals R.sup.6 in addition to those mentioned above are aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- and isopropoxycarbonyl, n-, iso- and sec.-butoxycarbonyl, methoxyethoxycarbonyl ethoxyethoxycarbonyl, n- and isopropoxyethoxycarbonyl and n-, iso- and sec.-butoxyethoxycarbonyl.

Examples of radicals R.sup.7 are C.sub.1 -C.sub.10 -alkyl, C.sub.1 -C.sub.10 -alkoxy, phenoxy, benzyloxy, phenyl, chlorine, bromine, nitro, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.1 -C.sub.4 -mono-and dialkylamino, C.sub.1 -C.sub.4 -alkoxyethoxy, C.sub.1 -C.sub.4 -alkyl- or phenylmercapto, C.sub.1 -C.sub.5 -alkanoylamino, such as acetylamino, propionylamino, butyrylamino or valerylamino, monosubstituted or polysubstituted phenyl, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxycarbonylmethyl, cyanomethyl and benzyl.

The compounds of the formula I have yellow to greenish blue hues and are particularly useful for dyeing polyesters, nylons, cellulose esters and blends of polyesters and cellulose fibers. As a rule, the dyeings obtained have good or very good fastness properties, particularly on polyesters.

Dyes having a suitable constitution are dischargeable under reduced conditions and/or under alkaline and reducing conditions.

Suitable discharging agents are the conventionally used ones, for example tin(II) chloride, sodium bisulfite, sodium dithionite or hydroxymethanesulfonic acid. The discharge process too can be carried out in a conventional manner.

Some of the compounds of the formula I are very useful for dyeing thermoplastics, such as polystyrene, polymethacrylates, polycarbonates, nylon and styrene/acrylic acid/butadiene copolymers, since they possess high color strength and good lightfastness and heat resistance. Furthermore, many novel dyes can be used for dyeing and/or printing polyester/cotton blends by the process described in German Patent 1,811,796, the resulting dyeings having good lightfastness and fastness to washing.

The compounds of the formula I can be prepared by a conventional method. Details are given in the Examples, in which parts and percentages are by weight, unless started otherwise.

Of particular importance are compounds of the formulae I a ##STR16## and I b ##STR17## where X.sup.1 is chlorine, bromine, hydroxyl, C.sub.1 -C.sub.4 -alkoxy or -alkylthio, methylsulfonyl, phenylsulfonyl, phenoxy or phenylthio, Y.sup.1 and Z.sup.1 are each cyano, a carboxylic ester group or substituted carbamyl, T.sup.1 is formyl, nitro or cyano and K.sup.1 is a radical of a coupling component of the aniline, thiazole, pyrazole, thiophene or pyridine series.

Compounds of the formulae Ia and Ib in which X.sup.1 is chlorine, ethoxy or phenylmercapto, Y.sup.1 is cyano, T.sup.1 is formyl, Z.sup.1 is cyano, a carboxylic ester group or substituted carbamyl and K is a radical of a coupling component of the aniline, thiazole, thiophene or pyridine series, are particularly useful industrially.

Other particularly important dyes are those of the general formula IIa ##STR18## where X.sup.1, Y.sup.1 and T.sup.1 have the stated meanings, B.sup.3 is hydrogen or B.sup.4, and B.sup.4 is C.sub.2 -C.sub.8 -alkyl which may or may not be interrupted by oxygen and is unsubstituted or substituted by hydroxyl, C.sub.1 -C.sub.4 -alkanoyloxy, C.sub.1 -C.sub.4 -alkoxy, benzyloxy or phenoxy, or is phenyl which is unsubstituted or substituted by methyl or methoxy. Preferred carboxylic ester groups Y.sup.1 are COOCH.sub.3 and COOC.sub.2 H.sub.5.

Examples of particularly preferred radicals B.sup.3 and B.sup.4 are hydrogen and C.sub.2 H.sub.5, C.sub.3 H.sub.7, C.sub.4 H.sub.9, ##STR19## C.sub.6 H.sub.11, 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.2 H.sub.4 OH, C.sub.3 H.sub.6 OH, C.sub.2 H.sub.4 OCH.sub.3, C.sub.3 H.sub.6 OCH.sub.3, C.sub.2 H.sub.4 OC.sub.2 H.sub.5, C.sub.2 H.sub.4 OC.sub.4 H.sub.9, C.sub.3 H.sub.6 OC.sub.2 H.sub.5, C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH, C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OH, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH, C.sub.3 H.sub.8 OC.sub.2 H.sub.4 OCH.sub.3, C.sub.3 H.sub.6 OC.sub.2 H.sub.5, C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.2 H.sub.5, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.4 H.sub.9, C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCO(CH.sub.2).sub.m CH.sub.3, C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCO(CH.sub.2).sub.m CH.sub.3, C.sub.3 H.sub.6 OC.sub.4 H.sub. 8 OCO(CH.sub.2).sub.m CH.sub.3, C.sub.2 H.sub.4 OCO(CH.sub.2).sub.m CH.sub.3. C.sub.3 H.sub.6 OCO(CH.sub.2).sub.m CH.sub.3, C.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H.sub.5 and C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5, where m is from 1 to 4.

Examples of particularly preferred combinations of B.sup.3 and B.sup.4 are hydrogen and C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCOCH.sub.3, C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCOC.sub.2 H.sub.5, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH, ,C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3,.C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOC.sub.2 H.sub.5, C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3, C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5, C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.2 H.sub.5, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.4 H.sub.9, C.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H.sub.5, C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5 or C.sub.3 H.sub.6 OCH.sub.2 -CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9, and C.sub.2 H.sub.5, C.sub.2 H.sub.4 OCH.sub.3, C.sub.3 H.sub.6 OCH.sub.3, CH(CH.sub.3).sub.2 or C.sub.4 H.sub.9 in combination with C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCOCH.sub.3, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCHO, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOC.sub.2 H.sub.5, C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.2 H.sub.5, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.4 H.sub.9 or C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5 and furthermore C.sub.2 H.sub.4 OH, C.sub.3 H.sub.6 OH, C.sub.2 H.sub.4 OCOCH.sub.3, C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5, C.sub.3 H.sub.6 OCOCH.sub.3 or C.sub.3 H.sub.6 OCOC.sub.2 H.sub.5 in combination with C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3, C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5, C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 , C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.2 H.sub.5, C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.4 H.sub.9, C.sub.6 H.sub.4 OCH.sub.3 or C.sub.6 H.sub.5.

The process for the preparation of acyloxyalkyl-substituted or acyloxyalkoxyalkyl-substituted 2,6-diaminopyridines which are free of by-products is also particularly important.

Previously, azo dyes containing such coupling components had to be prepared by subsequent acylation of the corresponding hydroxyl-containing dyes in anhydrous organic solvents with acyl halides or anhydrides since the coupling components themselves preferentially undergo N-acylation under these conditions, and the N-acyl-2,6-diaminopyridines are not capable of coupling.

According to the invention, the coupling components are prepared by adding not less than an equivalent amount of sulfuric acid to a solution or suspension of the hydroxyl-containing substituted pyridine in the desired organic acid and stirring the mixture at from 20.degree. to 100.degree. C., preferably from 20.degree. to 50.degree. C. The degree of acylation is dependent on the water content and reaches 100% in an anhydrous medium. However, the absence of water and 100% conversion are not essential in every case in order to achieve optimum dyeing properties. An adequate conversion in most cases is 70-70%, which does not require the absence of water and advantageously allows the acylation to be combined with the preparation of the hydroxyalkylaminopyridine.

EXAMPLE 1

4.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene in 30 parts by volume of 85% strength sulfuric acid were stirred at no higher than 30.degree. C., 8.3 parts of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) were added dropwise at 0.degree.-5.degree. C., and the mixture was then stirred for a further 4 hours at this temperature.

The resulting diazonium salt solution was slowly run, at 0.degree. C., into a solution of 5.8 parts of N,N-diallyl-3-aminoacetanilide in a mixture of 25 parts by volume of dimethylformamide, 125 parts of water, 300 parts of ice, 20 parts by volume of 32% strength hydrochloric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried to give 9 parts of the dye of the formula ##STR20## which dyes polyester fibers in fast blue hues.

EXAMPLE 2

4.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene were diazotized by a method similar to that described in Example 1. The diazonium salt solution was added dropwise at 0.degree. C., to a solution of 8.8 parts of o-(bisacetoxyethyl)-amino-p-acetanisidine in a mixture of 125 parts of water, 350 of ice, 1 part of 96% strength sulfuric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered under suction, washed until neutral and dried to give 9.5 parts of a greenish black powder of the formula ##STR21## which dyes polyester fabric in fast greenish blue hues.

The dyes characterized in the Table below are obtained similarly to Examples 1 and 2.

__________________________________________________________________________ ##STR22##Example Dyeing onNo. T X Y K polyester__________________________________________________________________________ 3 CHO Cl CN ##STR23## blue 4 CHO Cl CN ##STR24## bluish violet 5 CHO Cl CN ##STR25## blue 6 CHO Cl CN ##STR26## blue 7 CHO Cl CN ##STR27## blue 8 CHO Cl CN ##STR28## blue 9 CHO Cl CN ##STR29## blue10 CHO Cl CN ##STR30## blue11 CHO Cl CN ##STR31## reddish blue12 CHO Cl CN ##STR32## reddish blue13 CHO Cl CN ##STR33## bluish violet14 CHO Cl CN ##STR34## violet15 CHO Cl CN ##STR35## greenish blue16 CHO Cl CN ##STR36## greenish blue17 CHO Cl CN ##STR37## greenish blue18 CHO Cl CN ##STR38## greenish blue19 CHO Cl CN ##STR39## greenish blue20 CHO Cl CN ##STR40## greenish blue21 CHO Cl CN ##STR41## greenish blue22 CHO Cl CN ##STR42## blue23 CHO Cl CN ##STR43## blue24 CHO Cl CO.sub.2 C.sub.2 H.sub.5 ##STR44## blue25 CHO Cl CN ##STR45## blue26 CHO Cl CN ##STR46## blue27 CHO Cl CN ##STR47## blue28 CHO Cl CN ##STR48## blue29 CHO Cl CN ##STR49## blue30 CHO Cl CN ##STR50## blue31 CHO Cl COOCH.sub.3 ##STR51## blue32 CHO Cl SO.sub.2 CH.sub.3 ##STR52## blue33 CHO Cl CONH.sub.2 ##STR53## reddish blue34 CHO Cl CON(CH.sub.3).sub.2 ##STR54## blue35 CHO Cl CO.sub.2 C.sub.2 H.sub.5 ##STR55## blue36 CHO Cl CO.sub.2 C.sub.2 H.sub.5 ##STR56## bluish violet37 CHO Cl CO.sub.2 C.sub.2 H.sub.5 ##STR57## blue38 CHO Cl CO.sub.2 C.sub.2 H.sub.5 ##STR58## greenish blue39 CHO Br CN ##STR59## violet40 CHO Br CN ##STR60## bluish violet41 CHO Br CN ##STR61## blue42 CHO Br CN ##STR62## greenish blue43 CHO Br CO.sub.2 C.sub.2 H.sub.5 ##STR63## blue44 CHO F CN ##STR64## blue45 CHO F CN ##STR65## reddish blue46 CHO F CN ##STR66## blue47 CHO F CO.sub.2 C.sub.2 H.sub.5 ##STR67## reddish blue48 CHO Cl CO.sub.2 C.sub.2 H.sub.5 ##STR68## blue49 CHO Cl CONH.sub.2 ##STR69## blue50 CHO Cl NO.sub.2 ##STR70## blue51 CHO Cl CON(CH.sub.3).sub.2 ##STR71## blue52 CHO Cl SO.sub.2 CH.sub.3 ##STR72## blue53 CHO Br CO.sub.2 C.sub.2 H.sub.5 ##STR73## blue54 CHO Cl CN ##STR74## blue55 CHO Cl CN ##STR75## blue56 CHO Br CN ##STR76## blue57 CHO Cl CN ##STR77## violet58 CHO Cl CN ##STR78## blue59 CHO Cl CO.sub.2 C.sub.2 H.sub.5 ##STR79## blue60 CHO Cl CN ##STR80## yellowish brown61 CHO Cl CN ##STR81## red62 CHO Cl CN ##STR82## red63 CHO Cl CN ##STR83## blue64 CHO Cl CN ##STR84## blue65 CHO Br CN ##STR85## blue66 CHO Cl CN ##STR86## blue67 CHO Cl CN ##STR87## violet68 CHO Cl CN ##STR88## red69 CHO Cl CN ##STR89## red70 CHO Cl CN ##STR90## blue71 CHO Cl CN ##STR91## blue72 H Cl CN ##STR92## red73 CH.sub.3 Cl CN ##STR93## red74 CH.sub.3 Cl CN ##STR94## red75 CH.sub.3 Cl CN ##STR95## reddish violet76 C.sub.2 H.sub.5 Cl CN ##STR96## red77 CH.sub.3 Br CN ##STR97## red78 CN Cl CN ##STR98## blue79 CN Cl CN ##STR99## blue80 CN Cl CN ##STR100## greenish blue81 CN Br CN ##STR101## reddish blue82 CN Cl CN ##STR102## blue83 NO.sub.2 Cl CN ##STR103## reddish blue84 NO.sub.2 Cl CN ##STR104## blue85 NO.sub.2 Cl CN ##STR105## greenish blue86 NO.sub.2 Cl CN ##STR106## greenish blue87 ##STR107## Cl CN ##STR108## blue88 NO.sub.2 Br CN ##STR109## blue89 NO.sub.2 Cl CN ##STR110## greenish blue90 NO.sub.2 Cl CN ##STR111## greenish blue91 Br Cl CN ##STR112## bluish red92 Br Cl CN ##STR113## bluish violet93 Br Cl CN ##STR114## red94 Br Cl CN ##STR115## red95 Br Cl CN ##STR116## bluish violet96 Cl Cl CN ##STR117## bluish red97 Cl Cl CN ##STR118## reddish blue98 Br Br CN ##STR119## reddish blue__________________________________________________________________________

EXAMPLE 99

11.7 parts of 2-amino-3-cyano-4-ethoxy-5-formylthiophene in 200 parts by volume of a 3:1 glacial acetic acid/propionic acid mixture and 25 parts by volume of 96% strength sulfuric acid were stirred at no higher than 20.degree. C. 23 parts of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) were added dropwise at 0.degree.-5.degree. C., and the mixture was then stirred for 1 hour.

The resulting diazonium salt solution was added dropwise, at 0.degree. C., to a solution of 21 parts of o-(bisacetoxyethyl)-amino-p-acetanisidine in a mixture of 100 parts by volume of dimethylformamide, 500 parts of water, 25 parts by volume of 18% strength hydrochloric acid, 250 parts of ice and 1 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried to give 25 parts of the dye of the formula ##STR120## which dyes polyester fibers in fast greenish blue hues.

The dyes shown in the Table below were obtained similarly to Example 99.

__________________________________________________________________________ ##STR121##Example No. T X Y K Dyeing on polyester__________________________________________________________________________100 CHO OC.sub.2 H.sub.5 CN ##STR122## blue101 CHO OC.sub.2 H.sub.5 CN ##STR123## bluish violet102 CHO OC.sub.2 H.sub.5 CN ##STR124## blue103 CHO OC.sub.2 H.sub.5 CN ##STR125## blue104 CHO OC.sub.2 H.sub.5 CN ##STR126## blue105 CHO OC.sub.2 H.sub.5 CN ##STR127## blue106 CHO OC.sub.2 H.sub.5 CN ##STR128## reddish blue107 CHO OC.sub.2 H.sub.5 CN ##STR129## reddish blue108 CHO OC.sub.2 H.sub.5 CN ##STR130## bluish violet109 CHO OC.sub.2 H.sub.5 CN ##STR131## violet110 CHO OC.sub.2 H.sub.5 CN ##STR132## greenish blue111 CHO OC.sub.2 H.sub.5 CN ##STR133## greenish blue112 CHO OC.sub.2 H.sub.5 CN ##STR134## greenish blue113 CHO OC.sub.2 H.sub.5 CN ##STR135## greenish blue114 CHO OC.sub.2 H.sub.5 CN ##STR136## blue115 CHO OC.sub.2 H.sub.5 CO.sub.2 C.sub.2 H.sub.5 ##STR137## blue116 CHO OC.sub.2 H.sub.5 COOCH.sub.3 ##STR138## blue117 CHO OC.sub.2 H.sub.5 SO.sub.2 CH.sub.3 ##STR139## blue118 CHO OC.sub.2 H.sub.5 CONH.sub.2 ##STR140## reddish blue119 CHO OC.sub.2 H.sub.5 CON(CH.sub.3).sub.2 ##STR141## blue120 CHO OC.sub.2 H.sub.5 CO.sub.2 C.sub.2 H.sub.5 ##STR142## blue121 CHO OC.sub.2 H.sub.5 CO.sub.2 C.sub.2 H.sub.5 ##STR143## bluish violet122 CHO OC.sub.2 H.sub.5 CO.sub.2 C.sub.2 H.sub.5 ##STR144## blue123 CHO OC.sub.2 H.sub.5 CO.sub.2 C.sub.2 H.sub.5 ##STR145## greenish blue124 CHO OCH.sub.3 CN ##STR146## violet125 CHO OCH.sub.3 CN ##STR147## bluish violet126 CHO OCH.sub.3 CN ##STR148## blue127 CHO OCH.sub.3 CN ##STR149## greenish blue128 CHO OCH.sub.3 CO.sub.2 C.sub.2 H.sub.5 ##STR150## blue129 CHO OC.sub.6 H.sub.5 CN ##STR151## blue130 CHO OC.sub.6 H.sub.5 CN ##STR152## bluish violet131 CHO SC.sub.6 H.sub.5 CO.sub.2 C.sub.2 H.sub.5 ##STR153## blue132 CHO SC.sub.2 H.sub.5 CN ##STR154## bluish violet133 CHO SC.sub.6 H.sub.5 CN ##STR155## blue134 CHO OC.sub.2 H.sub.5 CN ##STR156## blue135 CHO OC.sub.2 H.sub.5 CN ##STR157## blue136 CHO OC.sub.2 H.sub.5 CN ##STR158## blue137 CHO OC.sub.2 H.sub.5 CN ##STR159## reddish blue138 CHO OC.sub.2 H.sub.5 CN ##STR160## blue139 CHO OCH.sub.3 CO.sub.2 C.sub.2 H.sub.5 ##STR161## blue140 CHO OC.sub.2 H.sub.5 CN ##STR162## yellowish brown141 CHO OC.sub.2 H.sub.5 CN ##STR163## red142 CHO OC.sub.2 H.sub.5 CN ##STR164## red143 CHO OC.sub.2 H.sub.5 CN ##STR165## blue144 CHO OC.sub.2 H.sub.5 CN ##STR166## blue145 CHO OCH.sub.3 CN ##STR167## blue146 CHO OC.sub.6 H.sub.5 CN ##STR168## blue147 CH.sub.3 OC.sub.2 H.sub.5 CN ##STR169## red148 CH.sub.3 OC.sub.2 H.sub.5 CN ##STR170## red149 CH.sub.3 OC.sub.2 H.sub.5 CN ##STR171## reddish violet150 C.sub.2 H.sub.5 OC.sub.2 H.sub.5 CN ##STR172## red151 CH.sub.3 OC.sub.2 H.sub.5 CN ##STR173## red152 CN OC.sub.2 H.sub.5 CN ##STR174## blue153 CN OC.sub.2 H.sub.5 CN ##STR175## blue154 NO.sub.2 OC.sub.2 H.sub.5 CN ##STR176## blue__________________________________________________________________________

EXAMPLE 155

5.8 parts of the dye described in Example 12 were dissolved in 60 parts by volume of dioxane, 3.4 parts of ethyl cyanoacetate, 1 part of glacial acetic acid and 1 part of piperidine were added, and the mixture was stirred for 16 hours at room temperature, after which 50 parts of water and 50 parts of ice were added. Stirring was continued for 15 minutes, and the product was filtered off under suction, washed neutral and dried at 50.degree. C. under reduced pressure to give 6.6 parts of the dye of the formula ##STR177## which dyes polyester fibers in medium blue hues.

EXAMPLE 156

5.1 parts of the dye described in Example 13 were dissolved in 65 parts by volume of dioxane, 4.2 parts of butyl cyanoacetate, 1 part of glacial acetic acid and 1 part of piperidine were added and the mixture was stirred for 16 hours at room temperature. Thereafter, 50 parts of water and 50 parts of ice were added, stirring was continued for 1 hour and the product was filtered off under suction, washed neutral and dried to give 5.9 parts of the dye of the formula ##STR178## which dyes polyester in fast blue hues.

The dyes listed in the Table below were obtained similarly to Examples 155 and 156.

__________________________________________________________________________ ##STR179##Example Dyeing onNo. X Y Y.sup.1 Y.sup.2 K polyester__________________________________________________________________________157 Cl CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR180## blue158 Cl CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR181## reddish blue159 Cl CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR182## blue160 Cl CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR183## blue161 Cl CN CN CN ##STR184## blue162 Cl CN COCH.sub.3 COOC.sub.2 H.sub.5 ##STR185## blue163 Cl COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR186## blue164 Cl COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR187## blue165 Cl COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR188## blue166 Cl COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR189## dark blue167 Cl COOC.sub.2 H.sub.5 COCH.sub.3 COOC.sub.2 H.sub.5 ##STR190## dark blue168 Cl COOC.sub.2 H.sub.5 COCH.sub.3 COCH.sub.3 ##STR191## blue169 Cl COOC.sub.2 H.sub.5 COCH.sub.3 CN ##STR192## dark blue170 Cl ##STR193## CN COOC.sub.2 H.sub.5 ##STR194## dark blue171 Cl ##STR195## CN COOC.sub.2 H.sub.5 ##STR196## blue172 Cl SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR197## dark blue173 Cl SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR198## blue174 Cl SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR199## blue175 Cl CN CN COOC.sub.2 H.sub.5 ##STR200## reddish blue176 Cl CN CN COOC.sub.2 H.sub.5 ##STR201## dark blue177 Cl CN CN COOC.sub.2 H.sub.5 ##STR202## dark blue178 Cl CN CN COOC.sub.2 H.sub.5 ##STR203## dark blue179 Cl CN CN COOC.sub.2 H.sub.5 ##STR204## dark blue180 Cl CN CN COOC.sub.2 H.sub.5 ##STR205## dark blue181 Cl CN CN COOC.sub.2 H.sub.5 ##STR206## blue182 Cl CN CN COOC.sub.2 H.sub.5 ##STR207## blue183 Cl CN CN COOC.sub.2 H.sub.5 ##STR208## blue184 Cl CN CN COOC.sub.2 H.sub.5 ##STR209## blue185 Cl CN CN COOC.sub.2 H.sub.5 ##STR210## violet186 Cl CN CN COOC.sub.2 H.sub.5 ##STR211## violet187 Cl CN CN COOC.sub.2 H.sub.5 ##STR212## violet188 Cl CN CN CONHCH.sub.3 ##STR213## dark blue189 Cl CN CN CONHC.sub.2 H.sub.5 ##STR214## dark blue190 Cl CN CN SO.sub.2 CH.sub.3 ##STR215## dark blue191 Cl CN CN COCH.sub.3 ##STR216## dark blue192 Cl CN CN COOCH.sub.3 ##STR217## dark blue193 Cl CN CN COOC.sub.4 H.sub.9 (n) ##STR218## blue194 Cl CN CN COOC.sub.4 H9(n) ##STR219## blue195 Cl CN CN COOC.sub.4 H.sub.9 (n) ##STR220## blue196 Cl CN CN COOC.sub.4 H.sub.9 (n) ##STR221## dark blue197 Cl CN CN ##STR222## ##STR223## dark blue198 Cl CN CN ##STR224## ##STR225## dark blue199 Cl CN CN ##STR226## ##STR227## dark blue200 Cl CN CN CONH.sub.2 ##STR228## dark blue201 Cl CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR229## navy blue202 Cl CN COCH.sub.3 COOC.sub.2 H.sub.5 ##STR230## dark blue203 Cl CN CN CONHCH.sub.3 ##STR231## dark blue204 Br CN CN COOC.sub.2 H.sub.5 ##STR232## reddish blue205 Br CN CN COOC.sub.2 H.sub.5 ##STR233## reddish blue206 Br CN CN COOC.sub.2 H.sub.5 ##STR234## blue207 Br CN CN COOC.sub.2 H.sub.5 ##STR235## dark blue208 Br CN CN COOC.sub.2 H.sub.5 ##STR236## dark blue209 Br CN CN COOC.sub.2 H.sub.5 ##STR237## dark blue210 Br CN CN COOC.sub.2 H.sub.5 ##STR238## dark blue211 Br CN CN COOC.sub.2 H.sub.5 ##STR239## dark blue212 Br CN CN COOC.sub.2 H.sub.5 ##STR240## dark blue213 Br CN CN COOC.sub.4 H.sub.9 (n) ##STR241## dark blue214 Br COOC.sub.2 H.sub.5 CN CN ##STR242## blue215 Br COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.9 ##STR243## dark blue216 Br COOC.sub.2 H.sub.5 CN CON(CH.sub.3).sub.2 ##STR244## bluish violet217 Br CONH.sub.2 CN COOC.sub.2 H.sub.5 ##STR245## dark blue218 Br SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR246## dark blue219 Br CON(CH.sub.3).sub.2 CN COOC.sub.2 H.sub.5 ##STR247## dark blue220 Br CN CN COOC.sub.2 H.sub.5 ##STR248## dark blue221 Br CN CN COOC.sub.2 H.sub.5 ##STR249## blue222 Br CN CN COOCH.sub.3 ##STR250## blue223 Br CN CN COOCH.sub.3 ##STR251## navy blue224 Cl CN CN ##STR252## ##STR253## dark blue225 F CN CN COOC.sub.2 H.sub.5 ##STR254## dark blue226 F CN CN COOC.sub.2 H.sub.5 ##STR255## dark blue227 F CN CN COOC.sub.2 H.sub.5 ##STR256## dark blue228 F COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR257## dark blue229 OC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR258## dark blue230 OC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR259## blue231 OC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR260## dark blue232 OC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR261## blue233 OC.sub.2 H.sub.5 CN CN CN ##STR262## dark blue234 OC.sub.2 H.sub.5 CN COCH.sub.3 COOC.sub.2 H.sub.5 ##STR263## dark blue235 OC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR264## blue236 OC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR265## dark blue237 OC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR266## blue238 OC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR267## dark blue239 OC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 COCH.sub.3 COOC.sub.2 H.sub.5 ##STR268## dark blue240 OC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 COCH.sub.3 COCH.sub. 3 ##STR269## bluish violet241 OC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 COCH.sub.3 CN ##STR270## dark blue242 OC.sub.2 H.sub.5 ##STR271## CN COOC.sub.2 H.sub.5 ##STR272## dark blue243 OC.sub.2 H.sub.5 ##STR273## CN COOC.sub.2 H.sub.5 ##STR274## blue244 OC.sub.2 H.sub.5 SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR275## dark blue245 OC.sub.2 H.sub.5 SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR276## dark blue246 OC.sub.2 H.sub.5 SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR277## blue247 OC.sub.2 H.sub.5 CN CN CON(CH.sub.3).sub.2 ##STR278## reddish blue248 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR279## reddish blue249 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR280## dark blue250 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR281## dark blue251 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR282## dark blue252 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR283## dark blue253 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR284## dark blue254 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR285## blue255 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR286## blue256 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR287## blue257 OC.sub.2 H.sub.5 CN CN COOC.sub.4 H.sub.9 (n) ##STR288## blue258 OC.sub.2 H.sub.5 CN CN COOC.sub.4 H.sub.9 (n) ##STR289## blue259 OC.sub.2 H.sub.5 CN CN COOC.sub.4 H.sub.9 (n) ##STR290## blue260 OC.sub.2 H.sub.5 CN CN COOC.sub.4 H.sub.9 (n) ##STR291## dark blue261 OC.sub.2 H.sub.5 CN CN ##STR292## ##STR293## dark blue262 OC.sub.2 H.sub.5 CN CN ##STR294## ##STR295## dark blue263 OC.sub.2 H.sub.5 CN CN ##STR296## ##STR297## dark blue264 OC.sub.2 H.sub.5 CN CN CONH.sub.2 ##STR298## dark blue265 OC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR299## navy blue266 OC.sub.2 H.sub.5 CN COCH.sub.3 COOC.sub.2 H.sub.5 ##STR300## dark blue267 OC.sub.2 H.sub.5 CN CN CONHCH.sub.3 ##STR301## dark blue268 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR302## navy blue269 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR303## violet270 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR304## violet271 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR305## violet272 OC.sub.2 H.sub.5 CN CN CONHCH.sub.3 ##STR306## dark blue273 OC.sub.2 H.sub.5 CN CN CONHC.sub.2 H.sub.5 ##STR307## dark blue274 OC.sub.2 H.sub.5 CN CN SO.sub.2 CH.sub.3 ##STR308## dark blue275 OC.sub.2 H.sub.5 CN CN COCH.sub.3 ##STR309## dark blue276 OC.sub.2 H.sub.5 CN CN COOCH.sub.3 ##STR310## dark blue277 OCH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR311## bluish violet278 OC.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR312## bluish violet279 SC.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR313## bluish violet280 SC.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR314## dark blue281 OCH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR315## dark blue282 OCH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR316## blue283 OCH.sub.3 CN CN COOC.sub.4 H.sub.9 (n) ##STR317## blue284 OC.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR318## dark blue285 SC.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR319## dark blue286 SC.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR320## dark blue287 SC.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR321## dark blue288 SC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR322## dark blue289 SC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR323## dark blue__________________________________________________________________________

EXAMPLE 290

a) 18.6 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene were suspended in 140 parts by volume of ethanol, and 2 parts of glacial acetic acid and 2 parts of piperidine were added. Thereafter, 50 parts by volume of ethyl cyanoacetate were added dropwise at room temperature and the mixture was stirred for 7 hours at 60.degree. C. It was then introduced into 500 parts of an ice/water mixture, and the precipitate was filtered off under suction, washed with water and dried at 60.degree. C. under reduced pressure to give 20 parts of 2-amino-4-chloro-3-cyano-5-(.beta.-cyano-.beta.-carboethoxyvinyl)-thiophene of the formula ##STR324## which was reacted without further purification.

b) 14 parts of this product were suspended in 100 parts by volume of 85% strength phosphoric acid, and 16 parts of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) were added slowly at 0.degree.-5.degree. C. After 2 hours at this temperature, the diazonium salt solution was run into a solution of 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 125 parts of water, 500 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried under reduced pressure to give 20 parts of the dye described in Example 155, of the formula ##STR325## On polyesters, this dye gives dark blue dyeings having generally good fastness properties.

EXAMPLE 291

14.5 parts of 2-amino-3-cyano-4-ethoxy-5-(.beta.-cyano-.beta.-carboethoxyvinyl)-thiophene were suspended in 160 parts by volume of 85% strength phosphoric acid and diazotized with 16 parts of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) at 0.degree.-5.degree. C. After 2 hours at this temperature, the diazonium salt solution was reacted with 9.75 parts of N-cyanoethyl-N-ethyl-m-toluidine similarly to Example 290 to give 20 parts of the dye of the formula ##STR326## which, on polyesters, gives blue dyeings possessing good lightfastness and fastness to dry heat pleating and setting.

EXAMPLE 292

14 parts of 2-amino-4-chloro-3-cyano-5-(.beta.-cyano-.beta.-methylaminocarbonyl)-vinyl)-thiophene were suspended in 120 parts by volume of 85% strength phosphoric acid and reacted with 16 parts of nitrosylsulfuric acid at 0.degree.-5.degree. C., and the mixture was stirred for 2 hours at this temperature. The diazonium salt solution was run slowly into a mixture of 7.5 parts of N,N-diethylaniline, 100 parts of water, 300 parts of ice, 25 parts by volume of 32% strength hydrochloric acid and 1 part of amidosulfonic acid. When coupling was complete, the suspension was filtered and the residue was washed neutral and dried to give 16 parts of the dye of the formula ##STR327## which, on polyesters, gives dark blue dyeings possessing generally good fastness properties.

The compounds characterized in the Table below were obtained similarly to Examples 290-292.

__________________________________________________________________________ ##STR328##ExampleNo. X Y Y.sup.1 Y.sup.2 K *.sup.)__________________________________________________________________________293 Br CN CN COOCH.sub.3 ##STR329## dark blue294 Br CN CN COOCH.sub.3 ##STR330## dark blue295 Br CN CN COOCH.sub.3 ##STR331## blue296 Br CN CN COOCH.sub.3 ##STR332## blue297 Cl CN CN COOC.sub. 2 H.sub.5 ##STR333## dark blue298 Cl CN CN COOC.sub.2 H.sub.5 ##STR334## dark blue299 Cl CN CN COOC.sub.2 H.sub.5 ##STR335## dark blue300 Cl CN CN COOC.sub.2 H.sub.5 ##STR336## dark blue301 Cl CN CN CONHCH.sub.3 ##STR337## dark blue302 Cl COOCH.sub.3 CN COOC.sub.2 H.sub.5 ##STR338## dark blue303 Cl SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR339## dark blue304 Cl CN CN COOC.sub.2 H.sub.5 ##STR340## reddish blue305 F CN CN COOC.sub.2 H.sub.5 ##STR341## dark blue306 F CN CN COOC.sub.2 H.sub.5 ##STR342## dark blue307 F CN CN COOC.sub.2 H.sub.5 ##STR343## blue308 Cl CN CN CN ##STR344## blue309 OC.sub.2 H.sub.5 CN CN COOCH.sub.3 ##STR345## dark blue310 OC.sub.2 H.sub.5 CN CN COOCH.sub.3 ##STR346## blue311 OCH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR347## dark blue312 OC.sub.2 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR348## dark blue313 SC.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR349## dark blue314 OC.sub.2 H.sub.5 CN CN COOCH.sub.3 ##STR350## dark blue315 SC.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR351## dark blue__________________________________________________________________________ *.sup.) Dyeing on polyester

The following dyes characterized by the substituents can also be prepared similarly to the methods described:

__________________________________________________________________________Example Color onNo. T X Y K polyester__________________________________________________________________________316 CHO Cl CN ##STR352## blue317 CHO Cl CN ##STR353## greenish blue318 CHO Cl CN ##STR354## blue319 CHO Cl CN ##STR355## blue320 CHO Cl CN ##STR356## blue321 CHO Cl CN ##STR357## blue322 CHO Br CN ##STR358## blue323 CHO Cl CN ##STR359## blue324 CHO Cl CN ##STR360## blue325 CHO Cl CN ##STR361## reddish blue326 CHO Cl CN ##STR362## blue327 CHO Cl CN ##STR363## reddish blue328 CHO Cl CN ##STR364## blue329 CHO Cl CN ##STR365## blue330 CHO Cl CN ##STR366## blue331 CHO Cl CN ##STR367## blue332 CHO Cl CN ##STR368## blue333 CN Cl CN ##STR369## blue334 CN Cl CN ##STR370## blue335 NO.sub.2 Cl CN ##STR371## greenish blue336 NO.sub.2 Cl CN ##STR372## blue337 NO.sub.2 Cl CN ##STR373## blue338 CN Cl CN ##STR374## blue339 CN Cl CN ##STR375## blue340 CN Cl CN ##STR376## blue341 CHO Cl CN ##STR377## blue342 CHO Cl CN ##STR378## blue343 CHO Cl CN ##STR379## reddish blue344 CHO Cl CN ##STR380## blue345 CHO Cl CN ##STR381## blue346 CHO Br CN ##STR382## blue347 CHO Br CN ##STR383## blue348 CHO C.sub.6 H.sub.5 S CN ##STR384## reddish blue349 CHO C.sub.6 H.sub.5 S CN ##STR385## greenish blue350 CHO OC.sub.2 H.sub.5 CN ##STR386## reddish blue351 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR387## blue352 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR388## blue353 CN Cl CN ##STR389## reddish blue354 CN Cl CN ##STR390## blue355 H.sub.5 C.sub.2 O.sub.2 C(CN)CCH Cl CN ##STR391## blue__________________________________________________________________________

EXAMPLE 356

2 parts of the dye described in Example 3, in 30 parts by volume of dimethylformamide and 50 parts by volume of glacial acetic acid, were stirred and 0.7 part of aniline was added. Stirring was continued for 12 hours at room temperature and 500 parts of water were added and the mixture was filtered under suction to give 2.2 parts of a powder of the formula ##STR392## which dyes polyester fabric in fast blue hues.

EXAMPLE 357

A suspension of 4 parts of the dye described in Example 3 in 50 parts by volume of dimethylformamide and 2 drops of concentrated sulfuric acid were added to 1.1 parts of phenylhydrazine in 40 parts by volume of ethanol. The mixture was stirred for 12 hours at 25.degree. C., after which 500 parts of water were added and the dye of the formula ##STR393## was filtered off under suction and dried. 5 parts of a black powder which dyes polyester fabric in fast blue hues were obtained.

EXAMPLE 358

2.3 parts of the dye described in Example 23 were stirred in 50 parts by volume of formic acid, 0.5 part of hydroxylamine hydrochloride and 0.5 part of sodium formate for 12 hours at room temperature. 400 parts of water were added, after which the mixture was filtered under suction to give 2.4 parts of the dye of the formula ##STR394## which dyes polyester fabric in fast blue hues.

EXAMPLE 359

18.7 parts of 2-amino-3-cyano-4-chloro-5-formylthiophene in 120 parts by volume of glacial acetic acid and 40 parts by volume of propionic acid were stirred for 1 hour at room temperature, after which the mixture was cooled to 0.degree.-5.degree. C., 31 parts of 42% strength nitrosylsulfuric acid were added and stirring was continued for about one hour at this temperature.

The coupling component employed was obtained as follows: a thoroughly stirred mixture of 17 parts (based on dry substance) of water-moist 2-chloro-3-cyano-4-methyl-6-aminopyridine (obtained, for example, by the process described in German Patent 2,260,827), 20 parts by volume of isobutanol, 18 parts of 3-aminopropyl 4-hydroxybutyl ether and 8 parts of sodium carbonate was heated under a descending condenser for 5 hours at 145.degree.-150.degree. C. until a thin layer chromatogram showed that conversion was complete. The mixture was cooled to about 100.degree. C., after which 35 parts of acetic acid were added dropwise and 15 parts of 96% strength sulfuric acid were introduced dropwise at 35.degree.-40.degree. C. with further slight cooling. Stirring was continued for 3 hours, after which about 92% of the hydroxy compound were found to be acetylated. The solution of the diazonium salt was run into a thoroughly stirred mixture of 100 parts of the resulting coupling component, 300 parts of ice and 100 parts of water, and stirring was continued for about 2 hours at 0.degree.-5.degree. C. until the diazonium salt solution had been consumed. Thereafter, the coupling mixture was filtered under suction and the residue was washed neutral and dried at 80.degree. C. The greenish black powder contains about 90% of the compound of the formula ##STR395## [.lambda..sub.max : 546 nm (9:1 dimethylformamide/acetic acid)] as well as about 10% of the non-acetylated hydroxy compound.

The dye mixture possesses very good tinctorial properties and, on polyester, gives very deep, brilliant, reddish violet dyes possessing very good lightfastness and fastness to plating.

EXAMPLE 360

When an equivalent amount of the coupling component described below was used under the preparation conditions of the above example, the reddish blue dye 9.lambda..sub.max : 572 nm, 9:1 dimethylformamide/acetic acid) of the formula ##STR396## was obtained. The product still contained about 5% of the hydroxy compound.

The coupling component used was obtained as follows: 45 parts of 2-chloro-3-cyano-4-methyl-6-(3'-hydroxypropylamino)-pyridine (obtained as described in German Patent 2,260,827) were stirred in the presence of one part of p-toluenesulfonic acid in 37 parts of aniline for one hour at 125.degree. C. A total of 10 parts of sodium carbonate were added at 135.degree. C. in three portions at 10 minute intervals, and stirring was continued for about 4 hours at 145.degree. C. until a thin layer chromatogram showed that conversion was complete. Excess aniline was distilled off under reduced pressure, and the hot melt was discharged on to 200 parts by volume of hot water. The aqueous solution was decanted, and the remaining melt was stirred several times with hot water containing acetic acid and was separated off cold. After drying, 14.2 parts of the melt, consisting of 2-phenylamino-3-cyano-4-methyl-6-(3'-hydroxypropylamino)pyridine, were dissolved in 50 parts by volume of glacial acetic acid, and 6 parts of 96% strength sulfuric acid were added dropwise. The mixture was stirred for 3 hours at 60.degree. C., after which the solution was used directly in the coupling reaction described.

The dyes listed in Table I were also obtained in a similar manner, these dyes having a similar property spectrum. The .lambda..sub.max values were determined in a 9:1 mixture of dimethylformamide and acetic acid.

TABLE 1__________________________________________________________________________ ##STR397##Example .lambda.maxNo. X Y R.sup.1 R.sup.2 [nm]__________________________________________________________________________361 Cl CN H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOC.sub.2 H.sub.5 545.5362 Cl CN H C.sub.3 H.sub.6 OC.sub.2 H.sub.7 OC.sub.2 547ub.5363 Cl CN H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4 546.8.9364 Cl CN C.sub.2 H.sub.4 OCH.sub.3 ##STR398## 565365 Cl CN ##STR399## ##STR400## 567366 Cl CN ##STR401## ##STR402## 573367 OC.sub.2 H.sub.5 CN H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 538368 OC.sub.2 H.sub.5 CN H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 540ub.5369 OC.sub.2 H.sub.5 CN C.sub.3 H.sub.6 OCOCH.sub.3 ##STR403## 560.5370 OC.sub.2 H.sub.5 CN C.sub.3 H.sub.6 OH ##STR404## 569371 ##STR405## CN H C.sub.3 H.sub.6 OC.sub.4 H.sub.6 OCOCH.sub.3 540372 ##STR406## CN H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 540__________________________________________________________________________

EXAMPLE 373

14.6 parts of 2-amino-3-cyano-4-ethoxy-5-(2'-cyano-2'-carbethoxyvinyl)-thiophene were diazotized similarly to the procedure described in Example 359 but using half the amount of reagents and assistants, and the product was coupled to 2-(4'-acetoxybutoxy)-3'-propylamino-3-cyano-4-methyl-6-aminopyridine. This gives a bluish black powder of the formula ##STR407## which still contains about 10% of the hydroxy compound and dyes polyester materials in medium blue hues which have very good lightfastness, fastness to washing and fastness to plating.

The diazo component was obtained as follows: 60 parts of 2-amino-3-cyano-4-ethoxythiophene-5-carbaldehyde in 200 parts by volume of dimethylformamide and 57 parts of ethyl cyanoacetate were stirred at room temperature. 10 parts by volume of a saturated aqueous sodium acetate solution were added dropwise, and stirring was continued for 2 hours at 40.degree. C. Precipitation was completed by adding 1,000 mL of ice-cold methanol, and the product was filtered off, washed first with ice-cold methanol and then with water, and dried at 60.degree. C. Yield: 60 parts (67.4%).

EXAMPLE 374

The procedure described in Example 359 was used, but with half the amount of reagents and assitants, and 14.1 parts of 2-amino-3-cyano-4-chloro-5-(2'-cyano-2'-carbethoxyvinyl)-thiophene were diazotized and the product coupled to 2-(4'-acetoxybutoxy)-3'-propylamino-3-cyano-4-methyl-6-(3'-acetoxypropylamino)-pyridine.

This gives a black powder which consists of 90% of the compound of the formula ##STR408## (.lambda..sub.max =585.5 nm; acetone) and dyes polyester in medium blue hues which have very good lightfastness, fastness to washing and fastness to plating.

The diazo component was obtained by a method similar to that described in Example 373, and the coupling component was obtained as follows:

45 parts of 2-chloro-3-cyano-4-methyl-6-(3'-hydroxypropylamino)-pyridine (obtained as described in German Patent 2,260,827) were stirred for 5 hours at 145.degree. C. in the presence of 14 parts of sodium carbonate in 33 parts of 3-aminopropyl 4-hydroxybutyl ether, and the mixture was cooled to 100.degree. C. and discharged on to 120 parts by volume of glacial acetic acid. 41 g of 96% strength sulfuric acid were then added dropwise at 30.degree. C. The mixture was stirred for 3 hours at 40.degree. C., after which a quarter of the solution was converted to the dye, as described above.

The dyes in Table 2, which have similar properties, were obtained in a similar manner. The .lambda..sub.max values were determined in acetone, except for those marked with *, which were measured in a 9:1 dimethylformamide/acetic acid mixture.

TABLE 2__________________________________________________________________________ ##STR409##Example .lambda.maxNo. T X Y R.sup.1 R.sup.2 [nm]__________________________________________________________________________375 COOC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CN H C.sub.3 H.sub.6 OCH.sub.3 583376 COOC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CN H ##STR410## 580.5377 COOC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CN H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 594*378 COOC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CN C.sub.3 H.sub.6 OCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 597*379 COOC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CN C.sub.2 H.sub.4 OH C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 602.3*380 COOC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CN C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 C.sub.3 H.sub.4 OCOCH.sub.3 591.5381 COOC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CN C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 591.5382 COOC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CN C.sub.3 H.sub.6 OCOCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 594383 COOC.sub.2 H.sub.5 OC.sub.2 H.sub.5 CN C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 594384 CN OC.sub.2 H.sub.5 CN H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 583385 CN OC.sub.2 H.sub.5 CN C.sub.3 H.sub.6 OCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.6 OCOCH.sub.3 595386 CN OC.sub.2 H.sub.5 CN C.sub.3 H.sub.6 OCOCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 595387 CN Cl CN C.sub.3 H.sub.6 OCOCH.sub.3 ##STR411## 613.5*388 CN Cl CN C.sub.3 H.sub.4 OH C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 605.3*389 CN Cl CN H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 578390 COOCH.sub.3 Cl CN H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 577391 COOC.sub.2 H.sub.5 Cl CN H C.sub.3 H.sub.6 OCH.sub.3 578392 COOC.sub.2 H.sub.5 Cl CN H ##STR412## 575.5393 COOC.sub.2 H.sub.5 Cl CN H ##STR413## 588394 CN Cl CN C.sub.3 H.sub.6 OCOCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 586395 COOC.sub.2 H.sub.5 Cl CN C.sub.3 H.sub.6 OCH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 588396 COOC.sub.2 H.sub.5 Cl CN C.sub.3 H.sub.6 OCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 585.5397 COOC.sub.2 H.sub.5 Cl CN C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 586398 COOC.sub.2 H.sub.5 Cl CN C.sub.3 H.sub.8 OC.sub.4 H.sub.8 OCOCH.sub.3 ##STR414## 612*399 CN Cl CN C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.3 C.sub.3 H.sub.8 OC.sub.4 H.sub.8 OCOCH.sub.3 586__________________________________________________________________________

EXAMPLE 400

7.3 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene in 30 parts by volume of 85% strength sulfuric acid were stirred at no higher than 30.degree. C. 8.3 parts of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) were added dropwise at 0.degree.-5.degree. C., after which stirring was continued for 4 hours at this temperature.

This diazonium salt solution was diluted with 20 ml of concentrated sulfuric acid and then run slowly, at 0.degree. C., into a solution of 6.6 parts of 3-[N,N-di-n-butylamino]-acetanilide in a mixture of 25 parts by volume of dimethylformamide, 125 parts of water, 300 parts of ice and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried, and 12 parts of the dye of the formula ##STR415## were obtained. This dye dyes polyester fibers in fast blue hues.

EXAMPLE 401

7.3 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene were diazotized by a method similar to that described in the Example above.

The diazonium salt solution was added dropwise, at 0.degree. C., to a solution of 5.2 parts of 3-(N,N-diethylamino)-acetanilide in a mixture of 125 parts of water, 350 parts of ice, 10 parts by volume of 32% strength hydrochloric acid and 0.5 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried, and 10.5 parts of a powder of the formula ##STR416## were obtained. This dye dyes polyester fabric in fast blue hues.

The dyes shown in the Table below were obtained in a similar manner.

__________________________________________________________________________ ##STR417##Example No. T X Y K Dyeing on__________________________________________________________________________ polyester402 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR418## greenish blue403 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR419## bluish violet404 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR420## blue405 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR421## blue406 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR422## blue407 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR423## reddish blue408 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR424## bluish violet409 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR425## greenish blue410 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR426## blue411 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR427## blue412 CHO C.sub. 6 H.sub.5 SO.sub.2 CO.sub.2 C.sub.2 H.sub.5 ##STR428## blue413 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR429## blue414 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR430## blue415 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR431## blue416 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR432## blue417 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR433## blue418 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR434## blue419 CHO ##STR435## CO.sub.2 C.sub.2 H.sub.5 ##STR436## reddish blue420 CHO C.sub.6 H.sub.5 SO.sub.2 CO.sub.2 C.sub.2 H.sub.5 ##STR437## blue421 CHO C.sub.6 H.sub.5 SO.sub.2 CONH.sub.2 ##STR438## blue422 CHO C.sub.6 H.sub.5 SO.sub.2 NO.sub.2 ##STR439## blue423 CHO C.sub.6 H.sub.5 SO.sub.2 CON(CH.sub.3).sub.2 ##STR440## blue424 CHO C.sub.6 H.sub.5 SO.sub.2 SO.sub.2 CH.sub.3 ##STR441## blue425 CHO CH.sub.3 SO.sub.2 CO.sub.2 C.sub.2 H.sub.5 ##STR442## blue426 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR443## blue427 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR444## blue428 CHO CH.sub.3 SO.sub.2 CN ##STR445## blue429 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR446## violet430 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR447## blue431 CHO C.sub.6 H.sub.5 SO.sub.2 CO.sub.2 C.sub.2 H.sub.5 ##STR448## blue432 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR449## yellowish brown433 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR450## red434 CHO C.sub.6 H.sub. 5 SO.sub.2 CN ##STR451## red435 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR452## blue436 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR453## blue437 CHO p-ClC.sub.6 H.sub.4 SO.sub.2 CN ##STR454## blue438 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR455## blue439 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR456## violet440 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR457## red441 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR458## red442 CN C.sub.6 H.sub.5 SO.sub.2 CN ##STR459## blue443 CN C.sub.6 H.sub.5 SO.sub.2 CN ##STR460## blue444 CN C.sub.6 H.sub.5 SO.sub.2 CN ##STR461## greenish blue445 CN CH.sub.3 SO.sub.2 CN ##STR462## reddish blue446 CN C.sub.6 H.sub.5 SO.sub.2 CN ##STR463## blue447 NO.sub.2 C.sub.6 H.sub.5 SO.sub.2 CN ##STR464## reddish blue448 NO.sub.2 C.sub.6 H.sub.5 SO.sub.2 CN ##STR465## blue449 NO.sub.2 C.sub.6 H.sub.5 SO.sub.2 CN ##STR466## blue450 NO.sub.2 C.sub.6 H.sub.5 SO.sub.2 CN ##STR467## greenish blue451 ##STR468## C.sub.6 H.sub.5 SO.sub.2 CN ##STR469## blue452 Cl C.sub.6 H.sub.5 SO.sub.2 CN ##STR470## reddish blue453 Br CH.sub.3 SO.sub.2 CN ##STR471## reddish__________________________________________________________________________ blue

EXAMPLE 454

1.2 parts of sodium phenylsulfinate were added to 2.3 parts of 4-chloro-3-cyano-5-formyl-2-(4'-N,N-dibutylamino-2'-acetylaminophenylazo)-thiophene in 50 parts by volume of dimethylformamide, and the mixture was stirred at room temperature. When the reaction was complete (thin layer chromatogram), the reaction mixture was poured on to 300 parts of water, and the dye formed was isolated. 2.4 parts of the dye of the formula ##STR472## were obtained. This dye dyes polyester fibers in fast blue hues.

The dyes shown in the Table below were obtained by a method similar to Example 454.

__________________________________________________________________________ ##STR473##Example Dyeing onNo. T X Y K polyester__________________________________________________________________________455 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR474## blue456 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR475## bluish violet457 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR476## blue458 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR477## blue459 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR478## blue460 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR479## blue461 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR480## reddish blue462 CHO C.sub.6 H.sub.5 SO.sub.2 CN ##STR481## reddish blue463 CHO C.sub.6 H.sub.5 SO.sub.2 CO.sub.2 C.sub.5 H.sub.5 ##STR482## blue__________________________________________________________________________

EXAMPLE 464

2.6 parts of the dye described in Example 413 were dissolved in 80 parts by volume of dioxane, 1.1 parts of ethyl cyanoacetate, 0.4 part of glacial acetic acid and 0.4 part of piperidine were added, and the mixture was stirred for 16 hours at room temperature. 50 parts of water and 50 parts of ice were then added, stirring was continued for 15 minutes, and the product was filtered off under suction, washed neutral and dried at 50.degree. C. under reduced pressure to give 2.8 parts of the dye of the formula ##STR483## which dyes polyester fibers in fast blue hues.

EXAMPLE 465

2.3 parts of the dye described in Example 403 were dissolved in 70 parts by volume of dioxane, 1.4 parts of butyl cyanoacetate, 0.4 part of glacial acetic acid and 0.4 part of piperidine were added and the mixture was stirred for 16 hours at room temperature. 50 parts of water and 50 parts of ice were then added, stirring was continued for 1 hour and the product was filtered off under suction, washed neutral and dried to give 2.5 parts of the dye of the formula ##STR484## which dyes polyester fabric in fast blue hues.

The dyes shown in the Table below were obtained similarly to the above Examples.

__________________________________________________________________________ ##STR485##Example Dyeing onNo. X Y Y.sup.2 Y.sup.3 K polyester__________________________________________________________________________466 C.sub.6 H.sub.5 SO.sub.2 CN CN CN ##STR486## blue467 C.sub.6 H.sub.5 SO.sub.2 CN COCH.sub.3 COOC.sub.2 H.sub.5 ##STR487## blue468 C.sub.6 H.sub.5 SO.sub.2 COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR488## blue469 C.sub.6 H.sub.5 SO.sub.2 COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR489## blue470 C.sub.6 H.sub.5 SO.sub.2 COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR490## blue471 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR491## reddish blue472 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR492## blue473 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR493## blue474 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR494## blue475 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR495## blue476 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR496## violet477 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR497## violet478 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR498## violet479 C.sub.6 H.sub. 5 SO.sub.2 CN CN CONHCH.sub.3 ##STR499## blue480 C.sub.6 H.sub.5 SO.sub.2 CN CN CONHC.sub.2 H.sub.5 ##STR500## blue481 C.sub.6 H.sub.5 SO.sub.2 CN CN SO.sub.2 CH.sub.3 ##STR501## blue482 C.sub.6 H.sub.5 SO.sub.2 CN CN COCH.sub.3 ##STR502## blue483 C.sub.6 H.sub.5 SO.sub.2 CN CN COOCH.sub.3 ##STR503## blue484 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.4 H.sub.9 (n) ##STR504## greenish blue485 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.4 H9(n) ##STR505## greenish blue486 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.4 H.sub.9 (n) ##STR506## blue487 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.4 H.sub.9 (n) ##STR507## blue488 C.sub.6 H.sub.5 SO.sub.2 CN CN ##STR508## ##STR509## blue489 C.sub.6 H.sub.5 SO.sub.2 CN CN ##STR510## ##STR511## blue490 C.sub.6 H.sub.5 SO.sub.2 CN CN ##STR512## ##STR513## blue491 C.sub.6 H.sub.5 SO.sub.2 CN CN CONH.sub.2 ##STR514## blue492 CH.sub.3 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR515## blue493 CH.sub.3 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR516## blue494 CH.sub.3 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR517## blue495 p-ClC.sub.6 H.sub.4 SO.sub.2 CN CN ##STR518## ##STR519## blue__________________________________________________________________________

EXAMPLE 496

a) 14.6 parts of 2-amino-3-cyano-5-formyl-4-phenylsulfonylthiophene were suspended in 50 parts by volume of ethanol, and 1 part of glacial acetic acid and 1 part of piperidine were added. 13 parts by volume of ethyl cyanoacetate were then added dropwise at room temperature, and the mixture was stirred for 5 hours at 60.degree. C. The reaction mixture was poured on to 800 parts of water, and the precipitate was filtered off under suction, washed with water and dried at 50.degree. C. under reduced pressure to give 16 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(.beta.-cyano-.beta.-carboethoxyvinyl)-thiophene of the formula ##STR520## which was reacted without further purification.

b) 3.9 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(.beta.-cyano-.beta.-carboethoxyvinyl)-thiophene in 35 parts by volume of a 3:1 glacial acetic acid/propionic acid mixture were stirred, and 3.5 parts of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) were slowly added at 0.degree.-5.degree. C. After 2 hours at this temperature, the diazonium salt solution was run into a solution of 2 parts of N-cyanoethyl-N-ethyl-m-toluidine in a mixture of 25 parts of water, 100 parts of ice, 5 parts by volume of 32% strength hydrochloric acid and 0.2 part of amidosulfonic acid. When coupling was complete, the dye was filtered off under suction, washed neutral and dried under reduced pressure. 4.5 parts of the dye of the formula ##STR521## were obtained. On polyester fibers, this dye gives blue dyeings having in general very good fastness properties.

EXAMPLE 497

3.4 parts of 2-amino-3-cyano-4-phenylsulfonyl-5-(.beta.,.beta.-dicyanovinyl)-thiophene were suspended in 25 parts by volume of 85% strength phosphoric acid and slowly reacted with 3.5 parts of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) at 0.degree.-5.degree. C., and the mixture was stirred for 2 hours at this temperature. This diazonium salt solution was run slowly into a mixture of 1.5 parts of N,N-diethylaniline, 20 parts of water, 60 parts of ice, 5 parts by volume of 32% strength hydrochloric acid and 0.2 part of amidosulfonic acid. When coupling was complete, the suspension was filtered and the dye was washed neutral and dried. 4.2 parts of the dye of the formula ##STR522## were obtained. On polyesters, this dye gives blue dyeings having generally good fastness properties.

The compounds shown in the Table below were obtained in a similar manner.

__________________________________________________________________________ ##STR523##Example Dyeing onNo. X Y Y.sup.2 Y.sup.3 K polyester__________________________________________________________________________498 CH.sub.3 SO.sub.2 CN CN COOCH.sub.3 ##STR524## blue499 C.sub.6 H.sub.5 SO.sub.2 CN CN COOCH.sub.3 ##STR525## blue500 C.sub.6 H.sub.5 SO.sub.2 CN CN COOCH.sub.3 ##STR526## greenish blue501 C.sub.6 H.sub.5 SO.sub.2 CN CN COOCH.sub.3 ##STR527## greenish blue502 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR528## blue503 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR529## blue504 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR530## blue505 C.sub.6 H.sub.5 SO.sub.2 CN CN COOC.sub.2 H.sub.5 ##STR531## greenish blue506 C.sub.6 H.sub.5 SO.sub.2 CN CN CONHCH.sub.3 ##STR532## blue507 C.sub.6 H.sub.5 SO.sub.2 COOCH.sub.3 CN COOC.sub.2 H.sub.5 ##STR533## blue__________________________________________________________________________

Examples of suitable dischargeable dyes are the compounds of Examples 21, 22, 113 and 114 and those of Examples 341-355.

Claims

1. A compound of the formula: ##STR534## wherein X is fluorine, chlorine or bromine;

Y is cyano;

T is hydrogen; C.sub.1 -C.sub.4 -alkyl; Cl; Br; NO; NO.sub.2 ; SO.sub.3 H; CHO; CN; CH.sub.3 CO; C.sub.2 H.sub.5 CO; C.sub.6 H.sub.5 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 ; or --CH.dbd.B;

B is C(CN) (Z) where Z is cyano; nitro; alkanoyl; aroyl; alkylsulfonyl; arylsulfonyl; carboxyl; a carboxylic ester group; unsubstituted carbamyl; substituted carbamyl; or a radical of a compound of one of the formulae: ##STR535## and K is a radical derived from a coupling component of the formula: ##STR536## wherein: B.sup.1 is hydrogen or B.sup.2 ;

B.sup.2 is C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkyl substituted by chlorine, bromine, hydroxyl, C.sub.1 -C.sub.8 -alkoxy, phenoxy, phenyl, cyano, carboxyl, C.sub.1 -C.sub.8 -alkanoyloxy, C.sub.1 -C.sub.8 -alkoxy-C.sub.1 -C.sub.4 -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C.sub.1 -C.sub.8 -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C.sub.1 -C.sub.8 -alkoxycarbonyloxy, C.sub.1 -C.sub.8 -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethoxycarbonyloxy, phenoxyethoxycarbonyloxy, C.sub.1 -C.sub.8 -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C.sub.1 -C.sub.8 -alkoxycarbonyl, C.sub.1 -C.sub.8 -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C.sub.1 -C.sub.4 -alkoxy, phenylethoxycarbonyl, phenyl, or cyclohexyl; and R.sup.6 is cyano; carbamyl; nitro; acetyl; alkoxycarbonyl; methylaminocarbonyl; dimethylaminocarbonyl; ethylaminocarbonyl; diethylaminocarbonyl; methoxyethoxycarbonyl; ethoxyethoxycarbonyl; n-propoxyethoxycarbonyl; isopropoxyethoxycarbonyl; n-butoxyethoxycarbonyl; isobutoxyethoxycarbonyl; or sec.-butoxyethoxycarbonyl.

2. The compound of claim 1, wherein X is fluorine.

3. The compound of claim 1, wherein X is chlorine.

4. The compound of claim 1, wherein X is bromine.

5. The compound of claim 1, wherein T is hydrogen or C.sub.1-4 alkyl.

6. The compound of claim 1, wherein T is Cl or Br.

7. The compound of claim 1, wherein T is NO or NO.sub.2.

8. The compound of claim 1, wherein T is SO.sub.3 H, CH.sub.3 SO.sub.2, C.sub.2 H.sub.5 SO.sub.2 or C.sub.6 H.sub.5 SO.sub.2.

9. The compound of claim 1, wherein T is CHO, CH.sub.3 CO, C.sub.2 H.sub.5 CO or C.sub.6 H.sub.5 CO.

10. The compound of claim 1, wherein T is CN.

11. The compound of claim 1, wherein T is --CH.dbd.B, wherein B is as defined above.

12. The compound of claim 1, wherein R.sup.6 is cyano.

13. The compound of claim 1, wherein R.sup.6 is carbamyl.

14. The compound of claim 1, wherein R.sup.6 is nitro.

15. The compound of claim 1, wherein R.sup.6 is acetyl.

16. The compound of claim 1, wherein R.sup.6 is alkoxycarbonyl.

17. The compound of claim 1, wherein R.sup.6 is selected from the group consisting of aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec.-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n-propoxyethoxycarbonyl, isopropoxyethoxycarbonyl, n-butoxyethoxycarbonyl, isobutoxyethoxycarbonyl and sec.-butoxyethoxycarbonyl.