Thiopheneazo dye based on a coupling component of the thiazole series

Abstract

Thiopheneazo dyes of the formula ##STR1## where R.sup.1 is cyano, C.sub.1 -C.sub.4 -alkoxycarbonyl, phenylazo, phenylsulfonyl, formyl or the radical ##STR2## where R.sup.7 and R.sup.8 are independently of the other cyano or C.sub.1 -C.sub.4 -alkoxycarbonyl,R.sup.2 is C.sub.1 -C.sub.4 -alkyl, phenyl, halogen, C.sub.1 -C.sub.4 -alkoxy or C.sub.1 -C.sub.4 -alkoxycarbonyl, or R.sup.1 and R.sup.2 together are the radical (CH.sub.2).sub.3 --CO, which may be substituted by 1 or 2 methyl groups and whose carbonyl group is bonded to the thiophene ring in the ortho position relative to the sulfur atom,R.sup.3 is cyano or C.sub.1 -C.sub.4 -alkoxycarbonyl,R.sup.4 is C.sub.1 -C.sub.8 -alkyl, cyclohexyl, phenoxy-C.sub.1 -C.sub.4 -alkyl, substituted or unsubstituted phenyl, or substituted or unsubstituted thienyl,R.sup.5 is C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.7 -alkyl whose alkyl chain is interrupted by 1 or 2 oxygen atoms, or C.sub.1 -C.sub.4 -alkoxy andR.sup.6 is cyanoethyl, phenylethyl or C.sub.3 -C.sub.12 -alkyl whose alkyl chain is interrupted by from 1 to 4 oxygen atoms and which may be substituted by phenyl or phenoxy,with the proviso that, when R.sup.5 and R.sup.6 are each oxygen-interrupted alkyl, R.sup.6 has 2 or more carbon atoms more than R.sup.5, are used for dyeing textile fibers.

Description

The present invention relates to a novel thiopheneazo dye of the formula I ##STR3## where R.sup.1 is cyano, C.sub.1 -C.sub.4 -alkoxycarbonyl, phenylazo, phenylsulfonyl, formyl or the radical ##STR4## where R.sup.7 and R.sup.8 are identical or different and each is independently of the other cyano or C.sub.1 -C.sub.4 -alkoxycarbonyl,

R.sup.2 is C.sub.1 -C.sub.4 -alkyl, phenyl, halogen, C.sub.1 -C.sub.4 -alkoxy or C.sub.1 -C.sub.4 -alkoxycarbonyl, or R.sup.1 and R.sup.2 together are the radical (CH.sub.2).sub.3 --CO, which may be substituted by 1 or 2 methyl groups and whose carbonyl group is bonded to the thiophene ring in the ortho position relative to the sulfur atom, R.sup.3 is cyano or C.sub.1 -C.sub.4 -alkoxycarbonyl, R.sup.4 is C.sub.1 -C.sub.8 -alkyl, cyclohexyl, phenoxy-C.sub.1 -C.sub.4 -alkyl, substituted or unsubstituted phenyl, thienyl, C.sub.1 -C.sub.4 -alkylthienyl or halothienyl, R.sup.5 is C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.7 -alkyl whose alkyl chain is interrupted by 1 or 2 oxygen atoms, or C.sub.1 -C.sub.4 -alkoxy and R.sup.6 is cyanoethyl, phenylethyl or C.sub.3 -C.sub.12 -alkyl whose alkyl chain is interrupted by from 1 to 4 oxygen atoms and which may be substituted by phenyl or phenoxy, with the proviso that, when R.sup.5 and R.sup.6 are each oxygen-interrupted alkyl, R.sup.6 has 2 or more carbon atoms more than R.sup.5, and to use thereof for dyeing textile fibers.

EP-A 269,953 already discloses azo dyes whose diazo components are derived from an aminothiophene and whose coupling components are derived from thiazole derivatives. However, it has been found that the compounds mentioned therein are defective in their application properties.

It is an object of the present invention to provide novel azo dyes based on a diazo component of the thiophene series and a coupling component of the thiazole series, which have an advantageous application profile.

We have found that this object is achieved by the thiopheneazo dye of the formula I defined at the beginning.

All the alkyl groups appearing in the abovementioned formula I can be not only straight-chain but also branched.

If substituted phenyl groups appear in the abovementioned formula I, suitable substituents are for example C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, halogen, in particular chlorine or bromine, C.sub.1 -C.sub.4 -alkanoylamino, sulfamoyl, C.sub.1 -C.sub.4 -monoalkylsulfamoyl or C.sub.1 -C.sub.4 -dialkylsulfamoyl, where the alkyl chain may be interrupted by an oxygen atom.

Suitable radicals R.sup.1, R.sup.2 and R.sup.3 are for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl or sec-butoxycarbonyl.

R.sup.1 is also for example CH.dbd.C(CN).sub.2, CH.dbd.C(CN)COOCH.sub.3, CH.dbd.C(CN)COOC.sub.2 H.sub.5, CH.dbd.C(COOCH.sub.3).sub.2 or CH.dbd.C(COOC.sub.2 H.sub.5).sub.2.

R.sup.2 is also for example, like R.sup.4 and R.sup.5, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

R.sup.2 is also for example, like R.sup.5, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.

R.sup.2 is also for example chlorine or bromine.

R.sup.4 is also for example pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, phenoxymethyl, 2-phenoxyethyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-chlorophenyl, 2,4-dichlorophenyl, 2-, 3- or 4-bromophenyl, 2-, 3- or 4-formylaminophenyl, 2-, 3- or 4-acetylaminophenyl, 3- or 4-sulfamoylphenyl, 3 l- or 4-monomethyl- or 3- or 4-dimethyl-sulfamoylphenyl or 3- or 4-[bis(2-methoxyethyl)sulfamoyl]phenyl.

R.sup.5 is also for example, like R.sup.6, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butyoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl or 4,7-dioxanonyl.

R.sup.6 is also for example 2- or 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12-tetraoxatetradecyl, 3-benzyloxypropyl, 6-phenoxy-4-oxahexyl, 2-cyanoethyl or 2-phenylethyl.

Preference is given to a thiopheneazo dye of the formula I where only one of R.sup.1, R.sup.2 and R.sup.3 is C.sub.1 -C.sub.4 -alkoxycarbonyl.

Particular preference is given to a thiopheneazo dye of the formula I where

R.sup.1 is cyano, C.sub.1 -C.sub.4 -alkoxycarbonyl or formyl, R.sup.2 is C.sub.1 -C.sub.4 -alkyl or chlorine, R.sup.3 is cyano, R.sup.4 is phenyl, 2-thienyl or 3-thienyl, R.sup.5 is C.sub.1 -C.sub.4 -alkyl and R.sup.6 is C.sub.3 -C.sub.9 -alkyl whose alkyl chain is interrupted by from 1 to 3 oxygen atoms and which may be substituted by phenoxy.

In a particularly noteworthy thiopheneazo dye of the formula I, R.sup.6 is C.sub.2 H.sub.4 OCH.sub.3, C.sub.3 H.sub.6 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.2 H.sub.5, C.sub.3 H.sub.6 OCH(CH.sub.3)CH.sub.2 OCH.sub.3, CH.sub.2 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3, CH.sub.2 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3, C.sub.3 H.sub.6 O(C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 or C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5.

The thiopheneazo dye according to the invention is prepared in a conventional manner. For example, a 2-aminothiophene of the formula II ##STR5## where R.sup.1 R.sup.2 and R.sup.3 are each as defined above, can be diazotized and coupled with a thiazole of the formula III ##STR6## where R.sup.4 R.sup.5 and R.sup.6 are each as defined above.

2-Aminothiophenes of the formula II are already known and described for example in EP-A-150,034 or can be obtained in similar fashion to the method of preparation described therein.

The thiazoles of the formula III are in general likewise known compounds. They are described for example in U.S. Pat. No. 3,770,719 and in J. V. Metzger, Heterocyclic Compounds--Thiazole and its Derivatives, vol. 34, part 1, Interscience Publishers, John Wiley, New York, 1979, or can be obtained in similar fashion to the methods described therein.

Further details of the preparation of the dye according to the invention may be found in the Examples.

In general, a thiopheneazo dye of the formula I where R.sup.5 and R.sup.6 together have 4 or more oxygen atoms is liquid at room temperature.

The novel thiopheneazo dye of the formula I is advantageously suitable for use as a disperse dye for dyeing textile fibers, in particular cellulose esters or polyesters, but also polyamides or blend fabrics from polyesters and cellulose fibers.

The dyeings obtained have good fastness properties, in particular good light fastness and good fastness to dry heat setting and pleating. The novel dye has good migration properties.

To obtain a favorable color buildup, it can be advantageous in some cases to use a mixture of more than one dye of the formula I according to the invention for dyeing.

The Examples which follow will illustrate the invention in more detail.

EXAMPLE 1

18.7 g of 2-amino-3-cyano-4-chloro-5-formylthiophene where introduced into a 0.degree. C. mixture of 111 g of 80% strength by weight sulfuric acid, 15 ml of glacial acetic acid and 32 g of 42% strength by weight nitrosylsulfuric acid. This was followed by stirring at 0.degree.-5.degree. C. for 4 hours. The diazonium salt solution was then added to a mixture at 0.degree. C. prepared from 36.4 g of a coupling component of the formula ##STR7## 200 g of glacial acetic acid, 40 g of propionic acid and 30 ml of 10% strength by weight amidosulfuric acid solution. After the two solutions had been combined, about 160 g of ice were added, and the mixture was then buffered with sodium acetate solution (about 30% strength by weight) to pH 0.2-0.7. The dye formed was then precipitated in full by the addition of water, filtered off with suction, washed until neutral and dried. This gave 52 g of dark blue powder of the formula ##STR8## The dye forms a blue solution in acetone and dyes polyethylene terephthalate fabric in bright medium blue shades of excellent buildup potential. The dyeings have high light fastness properties and a high fastness to dry heat setting and pleating. .lambda..sub.max : 604 nm (9:1 v/v N,N-dimethylformamide/glacial acetic acid).

EXAMPLE 2

A mixture of 110 g of 80% strength by weight sulfuric acid, 15 g of glacial acetic acid and 32 g of 42% strength by weight nitrosylsulfuric acid was cooled down to 0.degree. C. 21 g of ethyl 2-amino-3-cyano-4-methylthiophene-5-carboxylate were then sprinkled in with thorough stirring and cooling at such a rate that the reaction temperature was maintained at 0.degree.-5.degree. C. Stirring for 3-4 hours gave a clear diazonium salt solution. It was added to a solution prepared from 36.4 g of the coupling component of the formula ##STR9## in 15 ml of concentrated hydrochloric acid, 350 ml of water and 0.5 g of an acidic dispersant. Before the diazonium salt solution was added, 300 g of ice were added to bring the temperature down to .ltoreq.0.degree. C., and 1 g of amidosulfuric acid was added. At the same time as the diazonium salt solution water and ice were added in such a way that the coupling mixture stayed stirrable and does not exceed 5.degree. C. The mixture was subsequently stirred for 15 minutes, the pH of the suspension was then raised to 0.5-0.8 by the addition of ice-cold dilute sodium hydroxide solution, and the product obtained was isolated as described in Example 1. This gave 57.5 g of violet powder of the formula ##STR10## which gives a reddish blue solution in acetone and dyes polyester fabric in light-fast, deep reddish blue to navy shades. .lambda..sub.max : 576 nm (9:1 v/v N,N-dimethylformamide/glacial acetic acid).

The dyes listed in the tables below are obtained in a similar manner.

TABLE 1__________________________________________________________________________ ##STR11##Ex.No. R.sup.1 R.sup.2 X R.sup.5 R.sup.6 Hue__________________________________________________________________________ 3 CN CH.sub.3 H CH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 reddish blue 4 CN CH.sub.3 H C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 reddish blue 5 CN CH.sub.3 p-OCH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 navy 6 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 reddish blue 7 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 reddish blue 8 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 navy 9 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 navy10 CN CH.sub.3 m-Cl C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 reddish blue11 CN CH.sub.3 p-Cl C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 reddish blue12 CN CH.sub.3 m-SO.sub.2 N(CH.sub.3).sub.2 C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 reddish blue13 CN CH.sub.3 m-SO.sub.2 N(CH.sub.3).sub.2 C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 reddish blue14 CN CH.sub.3 p-OCH.sub.3 C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 reddish blue15 CO.sub.2 CH.sub.3 CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 bluish violet16 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 bluish violet17 CN Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 navy18 CN Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 navy19 CN Cl H C.sub.3 H.sub.6 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 navy20 CN H H C.sub.3 H.sub.6 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 reddish blue21 CHO H H C.sub.3 H.sub.6 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue22 CHO H H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue23 CN C.sub.2 H.sub.5 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 reddish blue24 CHO Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue25 CHO Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue26 CHO Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 blue27 CHO Cl H C.sub.2 H.sub.5 (C.sub. 2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 blue28 CHO Cl H C.sub.3 H.sub.7 (n) (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue29 CHO Cl H C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 blue30 CHO Cl H C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 blue31 CHO Cl H CH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 blue32 CHO Cl H CH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 blue33 CHO Cl H CH.sub.3 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 blue34 CHO Cl H C.sub.3 H.sub.7 (n) (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 blue35 CHO Cl H C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n) (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 blue36 CHO Cl H C.sub.2 H.sub.4 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue37 CHO Cl H C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 blue38 CHO Cl H C.sub.2 H.sub.4 OC.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue39 CHO Cl H C.sub.3 H.sub.6 OC.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 blue40 CHO Cl H C.sub.3 H.sub.6 OC.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 blue41 CHO Cl H CH(CH.sub.3).sub.2 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue42 CHO Cl m-SO.sub.2 N(CH.sub.3).sub.2 C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue43 CHO Cl m-SO.sub.2 N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue44 CHO Cl m-Cl C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue45 CHO Cl p-Cl C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue46 CHO Cl p-Cl C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 blue47 ##STR12## Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH greenish blue48 ##STR13## Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 greenish blue__________________________________________________________________________ TABLE 2__________________________________________________________________________ ##STR14##Ex. No. R.sup.1 R.sup.2 X R.sup.5 R.sup.6 Hue__________________________________________________________________________49 CN CH.sub.3 H CH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 blue50 CN CH.sub.3 H C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 blue51 CN CH.sub.3 H C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 blue52 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue53 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 blue54 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue55 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 blue56 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue57 CN CH.sub.3 H C.sub.3 H.sub.7 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue58 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 blue59 CN CH.sub.3 H C.sub.3 H.sub.7 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 blue60 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue61 CO.sub.2 CH.sub.3 CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue62 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue63 CN CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 blue64 CHO Cl H C.sub.3 H.sub.6 OC.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub. bluish green65 CN Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue66 CN Cl H C.sub.3 H.sub.6 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue67 CN C.sub.6 H.sub.5 H C.sub.3 H.sub.6 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue68 CHO H H C.sub.3 H.sub.6 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 greenish blue69 CHO H H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 greenish blue70 CN C.sub.2 H.sub.5 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue71 CHO Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 turquoise72 CHO Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 bluish green73 CHO Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 bluish green74 CHO Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 bluish green75 CHO Cl H C.sub.3 H.sub.7 (n) (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 bluish green76 CHO Cl H C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 bluish green77 CHO Cl H C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 bluish green78 CHO Cl H CH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 bluish green79 CHO Cl 2-CH.sub.3 CH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 bluish green80 CHO Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 bluish green81 CHO Cl H C.sub.3 H.sub.7 (n) (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 bluish green82 CHO Cl H C.sub.2 H.sub.4 OC.sub.4 H.sub.9 (n) (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 bluish green83 CHO Cl H C.sub.2 H.sub.4 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 bluish green84 CHO Cl H C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n) (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 bluish green85 CHO Cl H C.sub.2 H.sub.4 OC.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 bluish green86 CHO Cl H C.sub.3 H.sub.6 OC.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 bluish green87 CHO Cl H C.sub.2 H.sub.4 OC.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 bluish green88 CHO Cl H CH(CH.sub.3).sub.2 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 bluish green89 CHO Cl H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 bluish green90 CHO Cl H C.sub.3 H.sub.6 OC.sub.3 H.sub.7 (n) (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 turquoise91 CHO Cl H C.sub.3 H.sub.7 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 turquoise92 CHO OC.sub.2 H.sub.5 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 turquoise93 CHO OC.sub.2 H.sub.5 H C.sub.3 H.sub.7 (n) (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 turquoise94 CHO H H C.sub.3 H.sub.7 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 bluish green95 CO.sub.2 CH.sub.3 CH.sub.3 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 blue96 CO.sub.2 CH.sub.3 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 blue__________________________________________________________________________ TABLE 3__________________________________________________________________________ ##STR15##Ex. No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 Hue__________________________________________________________________________ 97 CH.sub.3 O.sub.2 C CH.sub.3 CN ##STR16## C.sub.4 H.sub.8 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 blue 98 ##STR17## H CN C.sub.6 H.sub.5 C.sub.3 H.sub.6 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.3 CH.sub.3 blue 99 C.sub.2 H.sub.5 O.sub.2 C C.sub.2 H.sub.5 O.sub.2 C CN C.sub.6 H.sub.5 C.sub.3 H.sub.7 (n) C.sub.3 H.sub.6 OC.sub.2 reddish blue100 C.sub.2 H.sub.5 O.sub.2 C C.sub.2 H.sub.5 CN ##STR18## C.sub.3 H.sub.7 (n) C.sub.3 H.sub.6 OC.sub.2 blueb.5101 CN CH.sub.3 CN C.sub.6 H.sub.5 C.sub.3 H.sub.7 (n) (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 reddish blue102 CN CH.sub.3 CN C.sub.6 H.sub.5 C.sub.3 H.sub.7 (l) (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 reddish blue103 CN CH.sub.3 CN C.sub.6 H.sub.5 C.sub.4 H.sub.9 (n) (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 reddish blue104 CN CH.sub.3 CN ##STR19## C.sub.3 H.sub.7 (n) (C.sub.2 H.sub.4 O).sub.2 CH.sub.3 blue105 CN CH.sub.3 CN ##STR20## C.sub.3 H.sub.7 (n) ##STR21## blue106 C.sub.2 H.sub.5 O.sub.2 C C.sub.2 H.sub. 5 O.sub.2 C CN C.sub.6 H.sub.5 C.sub.2 H.sub.4 OC.sub.3 H.sub.7 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 reddish blue107 C.sub.2 H.sub.5 O.sub.2 C CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 C.sub.6 H.sub.5 C.sub.2 H.sub.4 OC.sub.4 H.sub.9 C.sub.3 H.sub.6 OC.sub.3 H.sub.4 OC.sub.2 H.sub.5 violet108 C.sub.2 H.sub.5 O.sub.2 C CH.sub.3 CO.sub.2 C.sub.2 H.sub.5 C.sub.6 H.sub.5 C.sub.3 H.sub.7 (n) C.sub.3 H.sub.6 OC.sub.2 violet5109 CHO CH.sub.3 CN C.sub.6 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3 blue110 CHO CH.sub.3 CN C.sub.6 H.sub.5 C.sub.2 H.sub.5 (C.sub.2 H.sub.4 O).sub.3 C.sub.2 H.sub.5 blue111 CHO CH.sub.3 CN C.sub.6 H.sub.5 C.sub.3 H.sub.6 OCH.sub.3 (C.sub.2 H.sub.4 O).sub.2 C.sub.2 H.sub.5 blue__________________________________________________________________________ TABLE 4______________________________________ ##STR22## .lambda..sub.maxEx. No. L.sup.1 L.sup.2 L.sup.3 [nm]______________________________________112 CO.sub.2 CH.sub.3 CH.sub.3 ##STR23## 580113 CO.sub.2 CH.sub.3 CH.sub.3 ##STR24## 594114 CHO Cl ##STR25## 638115 CHO Cl ##STR26## 592116 CHO Cl C.sub.6 H.sub.5 606117 CN CH.sub.3 ##STR27## 609______________________________________

Claims

1. A thiopheneazo dye of the formula I ##STR28## where R.sup.1 is cyano or formyl,

R.sup.2 is methyl, phenyl or chlorine,

R.sup.3 is cyano,

R.sup.4 is C.sub.1 -C.sub.8 -alkyl, cyclohexyl, phenoxy-C.sub.1 -C.sub.4 -alkyl;, unsubstituted phenyl or thienyl,

R.sup.5 is C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.7 -alkyl whose alkyl chain is interrupted by 1 or 2 oxygen atoms, each oxygen atom being attached to only a carbon atom, or C.sub.1 -C.sub.4 -alkoxy and

R.sup.6 is phenylethyl, or C.sub.3 -C.sub.12 -alkyl whose alkyl chain is interrupted by from 1 to 4 oxygen atoms, each oxygen atom being attached to only a carbon atom, or said interrupted C.sub.3 -C.sub.12 -alkyl substituted by phenyl or phenoxy,

with the proviso that, when R.sup.5 and R.sup.6 are each oxygen-interrupted alkyl, R.sup.6 has 2 or more carbon atoms more than R.sup.5.

2. A thiophene dye as claimed in claim 1, wherein R.sup.6 is methoxyethyl, methoxypropyl or 3,5-dioxaoctyl.

3. A thiophene dye as claimed in claim 2, wherein R.sup.1 is formyl and R.sup.2 is methyl or phenyl.

4. A thiophene dye as claimed in claim 1, wherein R.sup.1 is formyl and R.sup.2 is methyl or phenyl.

5. A thiopheneazo dye as claimed in claim 1, wherein

R.sup.2 is methyl or chlorine,

R.sup.3 is cyano,

R.sup.4 is phenyl, 2-thienyl or 3-thienyl,

R.sup.5 is C.sub.1 -C.sub.4 -alkyl and

R.sup.6 is C.sub.3 -C.sub.9 -alkyl whose alkyl chain is interrupted by from 1 to 3 oxygen atoms, or said interrupted C.sub.3 -C.sub.9 -alkyl substituted by phenoxy.

6. A method of dyeing textile fibers comprising applying thereto a thiopheneazo dye as claimed in claim 1.