Azo dyes with a diazo component of the 3-amino thiophene series and a coupling component of the pyridine, pyridone or pyrazole series

Abstract

Thien-3-ylazo dyes of the formula: ##STR1## where X is cyano, nitro, C.sub.1 -C.sub.6 -alkanoyl, substituted or unsubstituted benzoyl, substituted or unsubstituted phenyl or the radical COOR.sup.1 or CONR.sup.1 R.sup.2 where R.sup.1 and R.sup.2 are identical or different and each is independently of each other substituted or unsubstituted C.sub.1 -C.sub.8 -alkyl, C.sub.5 -C.sub.7 -cycloalkyl, C.sub.3 -C.sub.4 -alkenyl, substituted or unsubstituted phenyl or together with the nitrogen atom linking them a 5- or 6-membered saturated heterocyclic radical, and R.sup.2 may additionally be hydrogen, Y is hydrogen, cyano, C.sub.1 -C.sub.6 -alkanoyl, substituted or unsubstituted benzoyl, C.sub.1 -C.sub.4 -alkylsulfonyl, substituted or unsubstituted phenylsulfonyl, substituted or unsubstituted phenyl or the radical COOR.sup.1 or CONR.sup.1 R.sup.2 where R.sup.1 and R.sup.2 are each as defined above, Z is hydrogen, substituted or unsubstituted C.sub.1 -C.sub.8 -alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C.sub.1 -C.sub.6 -alkylthio, substituted or unsubstituted phenylthio, substituted or unsubstituted C.sub.1 -C.sub.6 -alkylsulfonyl or phenylsulfonyl or together with the radical Y a fused benzo ring which may be substituted, and K is the radical of a coupling component of the 2,6-diaminopyridine, 6-hydroxypyrid-2-one or 5-aminopyrazole series, are used for dyeing synthetic fiber materials, in particular synthetic polyesters, in yellow to red shades and are notable for good light fastness, fastness to dry heat setting and pleating and for good affinity.

Description

The present invention relates to novel thien-3-ylazo dyes whose coupling components are derived from the pyridine, pyridone or pyrazole series and to the use of these dyes for dyeing synthetic fiber materials.

GB-A-2,011,937, DD-A-157,911 and JP-A-226,556/1985 disclose thien-3-ylazo dyes. Furthermore, DE-A-2,441,524 describes benzothien-3-ylazo dyes, including a case where the coupling component is 3-cyano-4-methyl-6-hydroxypyrid-2-one. However, it has been found that the known dyes have application defects.

It is an object of the present invention to provide new azo dyes whose diazo components are derived from 3-aminothiophene derivatives and which have a favorable range of application properties.

We have found that this object is achieved with novel thien-3-ylazo dyes of the formula I ##STR2## where

X is cyano, nitro, C.sub.1 -C.sub.6 -alkanoyl, substituted or unsubstituted benzoyl, substituted or unsubstituted phenyl or the radical COOR.sup.1 or CONR.sup.1 R.sup.2 where R.sup.1 and R.sup.2 are identical or different and each is independently of each other substituted or unsubstituted C.sub.1 -C.sub.8 -alkyl, C.sub.5 -C.sub.7 -cycloalkyl, C.sub.3 -C.sub.4 -alkenyl, substituted or unsubstituted phenyl or together with the nitrogen atom linking them a 5- or 6- membered saturated heterocyclic radical, and R.sup.2 may additionally be hydrogen,

Y is hydrogen, cyano, C.sub.1 -C.sub.6 -alkanoyl, substituted or unsubstituted benzoyl, C.sub.1 -C.sub.4 -alkylsulfonyl, substituted or unsubstituted phenylsulfonyl, substituted or unsubstituted phenyl or the radical COOR.sup.1 or CONR.sup.1 R.sup.2 where R.sup.1 and R.sup.2 are each as defined above,

Z is hydrogen, substituted or unsubstituted C.sub.1 -C.sub.8 -alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C.sub.1 -C.sub.6 -alkylthio, substituted or unsubstituted phenylthio, substituted or unsubstituted C.sub.1 -C.sub.6 -alkylsulfonyl or phenylsulfonyl or together with the radical Y a fused benzo ring which may be substituted, and

K is the radical of a coupling component of the pyridine, pyridone or pyrazole series.

All the alkyl groups appearing in the abovementioned formula I can be either straight-chain or branched.

If substituted phenyl radicals 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, cyano, fluorine, chlorine, bromine and nitro.

If substituted alkyl radicals appear in the above-mentioned formula I, suitable substituents are for example, unless otherwise stated, hydroxyl, C.sub.1 -C.sub.4 -alkoxy, phenoxy, C.sub.1 -C.sub.4 -alkoxycarbonyl, cyano and phenyl.

If in the abovementioned formula I the radicals Y and Z together are a substituted fused benzo ring, suitable substituents are for example C.sub.1 -C.sub.4 -alkyl, in particular methyl, cyano, chlorine, bromine and nitro.

If the substituents X and/or Y are each COOR.sup.1 or CONR.sup.1 R.sup.2, the individual radicals R.sup.1 and R.sup.2 are each for example hydrogen (not in the case of R.sup.1), methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 4-methoxybutyl, 4-ethoxybutyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or 3-ethoxycarbonylpropyl, 2- or 3-butoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 4-cyanobutyl, benzyl, 1- or 2-phenylethyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, 2-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-(2-ethylhexyl)phenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 4-cyanophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2-bromophenyl, 3-nitrophenyl, 4-nitrophenyl, prop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl or but-3-en-1-yl.

If R.sup.1 and R.sup.2 together with the nitrogen atom linking them are a 5- or 6-membered saturated heterocyclic radical, the possibilities are for example the following radicals: pyrrolidino, piperidino, morpholino, piperazino or N-(C.sub.1 -C.sub.4 -alkyl)piperazino, such as N-methyl- or N-ethyl-piperazino.

Further radicals X and Y are for example phenyl, 4-nitrophenyl, 4-cyanophenyl, 4-methylphenyl, 4-chlorophenyl, 2,4-dichlorophenyl, formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, benzoyl, 2methylbenzoyl, 4-methylbenzoyl, 4-ethylbenzoyl, 4-butylbenzoyl, 4-(2-ethylhexyl)benzoyl, 2,4-dimethylbenzoyl, 4-cyanobenzoyl, 4-chlorobenzoyl, 2-bromobenzoyl, 2,4-dichlorobenzoyl or 3- or 4-nitrobenzoyl.

Further radicals Y are for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, phenylsulfonyl, 2-methylphenylsulfonyl, 4-methylphenylsulfonyl, 4-chlorophenylsulfonyl or 4-bromophenylsulfonyl.

Radicals Z are for example methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, secbutylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, hexylthio, 2-hydroxyethylthio, 2-methoxyethylthio, 2-ethoxyethylthio, 3-methoxypropylthio, 2-phenoxyethylthio, 2- or 3-phenoxypropylthio, methoxycarbonylmethylthio, ethoxycarbonylmethylthio, propoxycarbonylmethylthio, isopropoxycarbonylmethylthio, butoxycarbonylmethylthio, isobutoxycarbonylmethylthio, cyanomethylthio, benzylthio, phenylthio, 2-methylphenylthio, 4-methylphenylthio, 4-chlorophenylthio, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, pentylsulfonyl, isopentylsulfonyl, hexylsulfonyl, 2-hydroxyethylsulfonyl, 2-methoxyethylsulfonyl, 2-ethoxyethylsulfonyl, 2-phenoxyethylsulfonyl, 2-methoxycarbonylethylsulfonyl, 2-ethoxycarbonylethylsulfonyl, 2-cyanoethylsulfonyl or benzylsulfonyl.

If Z is substituted or unsubstituted C.sub.1 -C.sub.8 -alkyl or substituted or unsubstituted phenyl, reference may be made to the radicals listed by way of example under R.sup.1 and R.sup.2.

If Y and Z together form a fused benzo ring which may be substituted, for example the following azo dyes ##STR3## where X and K are each as defined above, come into consideration.

In the formula I, K is the radical of a coupling component KH from the pyridone, pyridine or pyrazole series. Preferably this coupling component KH comes from the 2,6-diaminopyridine, 6-hydroxypyrid-2-one or 5-aminopyrazole series.

More particularly, it conforms to formula II, III or IV ##STR4## where

B.sup.1 and B.sup.2 are identical or different and each is independently of the other hydrogen, C.sub.1 -C.sub.12 -alkyl which is substituted and/or interrupted by one or two oxygen atoms, C.sub.5 -C.sub.7 -cycloalkyl, substituted or unsubstituted phenyl, C.sub.3 -C.sub.6 -alkenyl, substituted or unsubstituted benzoyl, C.sub.1 -C.sub.8 -alkanoyl, C.sub.1 -C.sub.6 -alkylsulfonyl or phenylsulfonyl,

T.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl or phenyl,

T.sup.2 is hydrogen, cyano, nitro, carbamoyl, C.sub.1 -C.sub.4 -monoalkyl- or -dialkyl-carbamoyl, C.sub.1 -C.sub.8 -alkanoyl, C.sub.1 -C.sub.6 -alkoxycarbonyl whose alkyl chain may be interrupted by one or two oxygen atoms, and

T.sup.3 is hydrogen, C.sub.1 -C.sub.12 -alkyl which may be substituted and/or interrupted by one or two oxygen atoms, C.sub.5 -C.sub.7 -cycloalkyl, C.sub.3 -C.sub.6 -alkenyl or substituted or unsubstituted phenyl.

If the radicals B.sup.1, B.sup.2 and/or T.sup.3 are each substituted C.sub.1 -C.sub.12 -alkyl which may be interrupted by one or two oxygen atoms, suitable substituents are for example phenyl, cyano, C.sub. 1 -C.sub.8 -alkoxycarbonyl, phenoxycarbonyl, halogen, in particular chlorine or bromine, hydroxyl, C.sub.1 -C.sub.8 -alkanoyloxy, benzoyloxy, C.sub.5 -C.sub.7 -cycloalkoxy and phenoxy.

Radicals T.sup.2 are for example mono- or dimethylcarbamoyl, mono- or diethylcarbamoyl, mono- or dipropylcarbamoyl, mono- or diisopropylcarbamoyl, mono- or dibutylcarbamoyl, mono- or diisobutylcarbamoyl, N-methyl-N-ethylcarbamoyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, hexyloxycarbonyl, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, 2-propoxyethoxycarbonyl, 2- or 3-methoxypropoxycarbonyl, 2- or 3-ethoxypropoxycarbonyl, 4-methoxybutoxycarbonyl or 4-ethoxybutoxycarbonyl.

Radicals B.sup.1, B.sup.2, T.sup.1 and T.sup.3 are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl or secbutyl.

Radicals B.sup.1, B.sup.2 and T.sup.3 are each further for example, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl (the designations isooctyl, isononyl and isodecyl are trivial names and come from the alcohols obtained by the oxo process - cf. Ullmanns Enzyklopadie der technischen Chemie, 4th edition, volume 7, pages 215 to 217, and also volume 11, pages 435 and 436), 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-(2-ethylhexyloxy)ethyl, 2-methoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-(2-ethylhexyloxy)propyl, 2-methoxybutyl, 4-methoxybutyl, 2-ethoxybutyl, 4-ethoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 3,6-dioxadecyl, 4,9-dioxatridecyl, benzyl, 1- or 2-phenylethyl, 8-phenyl-4,7-dioxaoctyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, 5-cyano-3-oxapentyl, 6-cyano-4-oxahexyl, 8-cyano-4-oxahexyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2,3-dihydroxypropyl, 2-hydroxybutyl, 4-hydroxybutyl, 5-hydroxy-3-oxapentyl, 6-hydroxy-4-oxahexyl, 8-hydroxy-4-oxaoctyl, 8-hydroxy-3,6-dioxaoctyl, 2-phenyl-2-hydroxyethyl, 2-chloroethyl, 2-bromoethyl, 2-phenoxyethyl, 3-phenoxypropyl, 4-phenoxybutyl, 5-phenoxy-3-oxapentyl, 6-phenoxy-4-oxahexyl, 8-phenoxy-4-oxaoctyl, 2-cyclohexyloxyethyl, 3-cyclohexyloxypropyl, 4-cyclohexyloxybutyl, 5-cyclohexyloxy-3-oxapentyl, 6-cyclohexyloxy-4-oxahexyl, 8-cyclohexyloxy-4-oxaoctyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, 5-methoxycarbonyl-3-oxapentyl, 6-methoxycarbonyl-4-oxahexyl, 8-methoxycarbonyl-4-oxaoctyl, 2-phenoxycarbonylethyl, 2- or 3-phenoxycarbonylpropyl, 4-phenoxycarbonylbutyl, 5-phenoxycarbonyl-3-oxapentyl, 6-phenoxycarbonyl-4-oxahexyl, 8-phenoxycarbonyl-4-oxaoctyl, 2-formyloxyethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-(2-ethylhexanoyloxy)ethyl, 2- or 3-acetyloxypropyl, 2- or 3-propionyloxypropyl, 2- or 3-(2-ethylhexanoyloxy)-propyl, 4-acetyloxybutyl, 4-propionyloxybutyl, 4-(2-ethylhexanoyloxy)-butyl, 5-acetyl-oxy-3-oxapentyl, 5-propionyloxy-3-oxapentyl, 5-(2-ethylhexanoyloxy)-3-oxapentyl, 6-acetyloxy-4-oxahexyl, 6-propionyloxy-4-oxahexyl, 6-(2-ethylhexanoyloxy)-4-oxahexyl, 8-acetyloxy-4-oxaoctyl, 8-propionyloxy-4-oxaoctyl, 8-(2-ethylhexanoyloxy)-4-oxaoctyl, 2-benzoyloxyethyl, 2- or 3-benzoyloxypropyl, 4-benzoyloxybutyl, 5-benzoyloxy-3-oxapentyl, 6-benzoyloxy-4-oxahexyl, 8-benzoyloxy-4-oxaoctyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, 2-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 4-isopropylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2-ethoxyphenyl, 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 4-bromophenyl, allyl or methallyl.

Radicals B.sup.1, B.sup.2 and T.sup.2 are each further for example formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl or 2-ethylhexanoyl.

Radicals B.sup.1 and B.sup.2 are each further for example benzoyl, 2-chlorobenzoyl, 4-chlorobenzoyl, 4-bromobenzoyl, 4-methylbenzoyl, 4-methoxybenzoyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl or hexylsulfonyl.

Preference is given to thien-3-ylazo dyes of the formula I where

X is cyano, nitro, C.sub.1 -C.sub.2 -alkanoyl, benzoyl or the radical COOR.sup.1 where R.sup.1 is as defined above,

Y is hydrogen, cyano, C.sub.1 -C.sub.4 -alkanoyl, phenyl or the radical COOR.sup.1 where R.sup.1 is as defined above,

Z is C.sub.1 -C.sub.4 -alkyl, benzyl, phenyl, C.sub.1 -C.sub.4 -alkylthio, phenylthio or C.sub.1 -C.sub.4 -alkylsulfonyl which may each be substituted by cyano, C.sub.1 -C.sub.4 -alkoxycarbonyl, methoxy, chlorine or bromine, or phenylsulfonyl or together with the radical Y is a fused benzo ring which may be substituted, and

K is the radical of a coupling component of the 2,6-diaminopyridine, 6-hydroxypyrid-2-one or 5-aminopyrazole series.

Particular preference is given to thien-3-ylazo dyes of the formula I where

X is cyano, C.sub.1 -C.sub.4 -alkanoyl or the radical COOR.sup.1 where R.sup.1 is C.sup.1 -C.sup.4 -alkyl or phenyl,

Y is hydrogen, cyano, C.sub.1 -C.sub.4 -alkanoyl, phenyl or the radical COOR.sup.1 where R.sup.1 is C.sub.1 -C.sub.4 -alkyl or phenyl,

Z is C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkylthio or C.sub.1 -C.sub.4 -alkylsulfonyl, which may each be substituted by cyano, C.sub.1 -C.sub.4 -alkoxycarbonyl, methoxy, chlorine or bromine, or is benzyl, phenyl, phenylthio or phenylsulfonyl,

K is the radical of a coupling component of the 2,6-diaminopyridine, 6-hydroxypyrid-2-one or 5-aminopyrazole series.

There may be mentioned in particular thien-3-ylazo dyes of the formula V, VI or VII ##STR5## where

X is cyano, C.sub.1 -C.sub.4 -alkanoyl or the radical COOR.sup.1 where R.sup.1 is C.sub.1 -C.sub.4 -alkyl or phenyl,

Y is hydrogen, cyano, C.sub.1 -C.sub.4 -alkanoyl, phenyl or the radical COOR.sup.1 where R.sup.1 is C.sub.1 -C.sub.4 -alkyl or phenyl,

Z is C.sub.1 -C.sub.4 -alkyl or C.sub.1 -C.sub.4 -alkylthio, which may each be substituted by cyano, C.sub.1 -C.sub.4 -alkoxycarbonyl, methoxy, chlorine or bromine, or is benzyl, phenyl, phenylthio, C.sub.1 -C.sub.4 -alkylsulfonyl or phenylsulfonyl, and

T.sup.2 is hydrogen, cyano, carbamoyl or C.sub.1 -C.sub.4 -alkoxycarbonyl and B.sup.1, B.sup.2, T.sup.1 and T.sup.3 are each as defined above.

Industrially particularly useful thien-3-ylazo dyes are of the formula V, VI or VII where

X is cyano or the radical COOR.sup.1 where R.sup.1 is C.sub.1 -C.sub.4 -alkyl,

Y is cyano, phenyl or the radical COOR.sup.1 where R.sup.1 is C.sub.1 -C.sub.4 -alkyl,

Z is phenyl or unsubstituted or cyano- or C.sub.1 -C.sub.4 -alkoxycarbonyl-substituted C.sub.1 -C.sub.4 -alkyl,

T.sup.1 is hydrogen, methyl or phenyl,

T.sup.2 is hydrogen, cyano or C.sub.1 -C.sub.4 -alkoxycarbonyl and B.sup.1, B.sup.2 and T.sup.3 are each as defined above.

To prepare the thien-3-ylazo dyes of the formula I according to the invention, a conventionally obtainable diazonium compound of an amine of the formula VIII ##STR6## where X, Y and Z are each as defined above, may be reacted with a coupling component HK as described above in a conventional manner.

Further details of the preparation may be found in the examples.

3-Aminothiophenes of the formula VIII are known and described for example in Liebigs Ann. Chem. 656 (1962), 90; Pharm. Zentralhalle 107 (1968), 348; GB-A-2,011,937; or Synthesis 1982, 1056. Further information about ways of synthesizing 3-aminothiophenes is given in Heterocyclic Compounds, vol. 44, John Wiley & Sons, Inc., 1986, Thiophene and its Derivatives, parts 1 and 2.

The dyes according to the invention are yellow to red and are notable for good light fastness, fastness to dry heat setting and pleating and for good affinity. They are suitable for dyeing synthetic fiber materials, such as polyamides, cellulose esters or blends of polyesters and cellulose fibers. But particularly, they are suitable for dyeing synthetic polyesters.

The Examples which now follow serve to illustrate the invention in more detail. Percentages are by weight, unless otherwise stated.

EXAMPLE 1

4.9 g of 3-amino-4-cyano-2-methoxycarbonyl-5-methylthiophene were added to 37.5 ml of 17:3 glacial acetic acid/propionic acid. 10 ml of 85% strength sulfuric acid were added dropwise at 10.degree.-20.degree. C., followed at 0.degree.-5.degree. C. by 4.3 ml of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3), and the mixture was stirred at 0.degree. -5.degree. C. for 4 hours.

The diazonium salt solution prepared above was added dropwise to 6.6 g of 2,6-bis(2-methoxyethylamino)-3-cyano-4-methylpyridine dissolved in 20 ml of N,N-dimethylformamide, 20 ml of dilute hydrochloric acid, 100 g of ice and 0.5 g of sulfamic acid at 0.degree. C. The mixture was stirred at 0.degree.-5.degree. C. for 4 hours, slowly warmed to room temperature and filtered with suction, and the precipitate was washed and dried.

Yield: 10.5 g of the dye of the formula ##STR7## which dyes polyester material in fast orange shades.

.lambda..sub.max (CH.sub.2 CL.sub.2): 485 nm.

EXAMPLE 2

The diazonium salt solution prepared in Example 1 was added dropwise with stirring to 5.85 g of 3-cyano-6-hydroxy-1-hexyl-4-methylpyrid-2-one dissolved in 20 ml of N,N-dimethylformamide, 20 ml of dilute hydrochloric acid, 100 g of ice and 0.5 g of sulfamic acid at 0.degree. -3.degree. C. After 4 hours at 0.degree. -5.degree. C. and warming to room temperature, the precipitate was filtered off with suction, washed and dried to leave 10.3 g of the dye of the formula ##STR8## which dyes polyester fiber material in fast yellow shades.

.lambda..sub.max (CH.sub.2 CL.sub.2): 431 nm.

EXAMPLE 3

4.9 g of 3-amino-2,4-dicyano-5-methylthiothiophene were suspended in 50 ml of 3:1 glacial acetic acid/propionic acid. 8.2 g of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) were added dropwise at 0.degree.-59.degree. C., and the mixture was stirred at 0.degree. -5.degree. C. for 3 hours.

This diazonium salt solution was added dropwise to 7.7 g of 2,6-bis(3-methoxypropylamino)-3-cyano-4-methylpyridine dissolved in 100 ml of N,N-dimethylformamide, 0.5 g of sulfamic acid and 100 g of ice at 0.degree.-5.degree. C. in the course of 20 minutes. The mixture was stirred at 0.degree.-5.degree. C. for 4 hours and at room temperature for 8 hours. The dye product was filtered off with suction, washed and dried. Yield: 6.2 g of the dye of the formula ##STR9## which dyes polyester material in fast orange shades.

.lambda..sub.max (CH.sub.2 CL.sub.2): 491 nm.

EXAMPLE 4

5.5 g of 3-amino-2-cyano-5-nitrobenzothiophene were diazotized as described in Example 1 and added dropwise to a solution of 6.6 g of 2,6-bis(2-methoxyethylamino)-3-cyano-4-methylpyridine in 20 ml of N,N-dimethylformamide, 100 ml of water, 20 ml of hydrochloric acid, 100 g of ice and 0.5 g of sulfamic acid with stirring at 0.degree.-5.degree. C. Workingup as described in Example 1 left 10.4 g of the dye of the ##STR10## which dyes polyester in fast yellowish red shades.

.lambda..sub.max (CH.sub.2 CL.sub.2): 506 nm

The same method was used to obtain the dyes listed in the following tables 1 to 4:

TABLE 1__________________________________________________________________________ ##STR11## Hue onEx. X Y Z R.sup.1 R.sup.2 R.sup.3 PES__________________________________________________________________________ 5 CO.sub.2 CH.sub.3 CN CH.sub.3 H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub .3 H orange 6 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub .3 H orange 7 CO.sub.2 CH.sub.3 CN CH.sub.3 H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCOCH.sub .3 H orange 8 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 H (1) H orange 9 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 H C.sub.3 H.sub.6 OC.sub. 4 H.sub.8 OCOC.sub.2 H.sub.5 H orange10 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 H (2) H orange11 CO.sub.2 CH.sub.3 CN C.sub.2 H.sub.5 H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub .3 H orange12 CN CN CH.sub.3 H (2) H orange13 CN CN CH.sub.3 H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 1 H orange14 COCH.sub.3 CN CH.sub.3 H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 H orange15 COC.sub.6 H.sub.5 CN CH.sub.3 H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 H orange16 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.2 H.sub.5 H orange17 CO.sub.2 C.sub.2 H.sub.5 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.4 H.sub.9 H orange18 CO.sub.2 CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 H orange19 CO.sub. 2 CH.sub.3 CO.sub.2 CH.sub.3 C.sub.2 H.sub.5 H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 O H orange20 COCH.sub.3 CN CH.sub.3 H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub .3 H orange21 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH H orange22 CN CN CH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub .3 H orange23 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 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 H orange24 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 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 H orange25 CO.sub.2 CH.sub.3 CN C.sub.6 H.sub.5 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 OC.sub.2 H.sub.5 H orange26 CO.sub.2 CH.sub.3 CN CH.sub.3 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 H orange27 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.3 H.sub.6 OCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH H orange28 CO.sub.2 CH.sub.3 H CH.sub.3 C.sub.3 H.sub.6 OCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH H orange29 CO.sub.2 CH.sub.3 H CH.sub.3 H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 T H orange30 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.3 H.sub.6 OCOCH.sub.3 ##STR12## H yellowish red31 CO.sub.2 CH.sub.3 CN CH.sub.3 ##STR13## C.sub.3 H.sub.6 OCOCH.sub.3 H yellowish red32 CN CN CH.sub.3 ##STR14## C.sub.3 H.sub.6 OCOCH.sub.3 H red33 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH ##STR15## H orange34 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 C.sub.3 H.sub.6 OH ##STR16## H yellowish red35 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 C.sub.3 H.sub.6 OH ##STR17## H red36 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 ##STR18## H red37 CO.sub.2 CH.sub.3 CO.sub.2 CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 OCH.sub.3 C.sub.3 H.sub.6 OCH.sub.3 H orange38 CO.sub.2 C.sub.2 H.sub.5 CN C.sub.4 H.sub.9 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 H orange39 COCH.sub.3 CN CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOC.sub. 2 H.sub.5 H orange40 COC.sub.6 H.sub.5 CN CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 H orange41 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.2 H.sub.5 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OH H orange42 CO.sub.2 CH.sub.3 H CH.sub.3 C.sub.3 H.sub.6 OH ##STR19## H yellowish red43 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 C.sub.3 H.sub.6 OCOCH.sub.3 ##STR20## H yellowish red44 CO.sub.2 CH.sub.3 CN CH.sub.3 H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.4 H.sub.9 H orange45 COCH.sub.3 CN CH.sub.3 C.sub.3 H.sub.6 OCH.sub.3 C.sub.3 H.sub.6 OCH.sub.3 H orange46 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 C.sub.3 H.sub.6 OCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.4 H.sub.9 H orange47 CN CN CH.sub.3 H ##STR21## H orange48 CN CN CH.sub.3 H ##STR22## H orange49 CO.sub.2 CH.sub.3 CN CH.sub.3 H ##STR23## H orange50 CO.sub.2 CH.sub.3 CN CH.sub.3 H ##STR24## H reddish orange51 CO.sub.2 CH.sub.3 CN CH.sub.3 H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOC.sub. 2 H.sub.5 H orange52 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 CH.sub.3 reddish orange53 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.3 H.sub.6 OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 reddish orange54 CN CN SCH.sub.3 H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub .3 H orange55 CN CN SCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH H orange56 CN CN SCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 H orange57 CN CN SCH.sub.3 H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OC.sub.2 H.sub.5 H orange58 CO.sub.2 CH.sub.3 CN (3) H C.sub.3 H.sub.6 OC.sub.4 H.sub.8 C.sub.2 H.sub.5 H orange59 CO.sub.2 CH.sub.3 CN (3) C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 H orange60 CO.sub.2 CH.sub.3 C.sub.6 H.sub.5 (3) H C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3 O H orange61 NO.sub.2 CN SCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 H reddish orange62 CN CN SO.sub.2 CH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 OCH.sub.3 H orange63 CO.sub.2 CH.sub.3 CN SCH.sub.3 H C.sub.3 H.sub.4 OC.sub.4 H.sub.8 OC.sub.2 H.sub.5 H orange64 CO.sub.2 CH.sub.3 CN SCH.sub.3 C.sub.2 H.sub.4 OH C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH H orange__________________________________________________________________________ ##STR25## (2) C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OCOCH.sub.2 CH(CH.sub.3).sub.2 TABLE 2__________________________________________________________________________ ##STR26## Hue onEx. X Y Z R W PES__________________________________________________________________________65 CO.sub.2 CH.sub.3 CN CH.sub.3 CH.sub.3 CN yellow66 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.4 H.sub.9 CN yellow67 CO.sub.2 CH.sub.3 CN CH.sub.3 ##STR27## CN yellow68 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5 CN yellow69 CN CN CH.sub.3 C.sub.6 H.sub.13 CN yellow70 CN CN CH.sub.3 ##STR28## CN yellow71 CN CN CH.sub.3 C.sub.3 H.sub.7 CN yellow72 COCH.sub.3 CN CH.sub.3 CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9 CN yellow73 COCH.sub.3 CN CH.sub.3 CH.sub.3 CN yellow74 COCH.sub.3 CN CH.sub.3 ##STR29## CN yellow75 COC.sub.6 H.sub.5 CN CH.sub.3 ##STR30## CN yellow76 COC.sub.6 H.sub.5 CN CH.sub.3 C.sub.4 H.sub.9 CN yellow77 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 CH.sub.3 CN yellow78 CO.sub.2 C.sub.2 H.sub.5 CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 CN yellow79 CO.sub.2 CH.sub.3 H CH.sub.3 C.sub.4 H.sub.9 CN yellow80 CO.sub.2 CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 ##STR31## CN yellow81 CO.sub.2 CH.sub.3 CN CH.sub.3 CH.sub.3 CONH.sub.2 yellow82 CO.sub.2 CH.sub.3 CN CH.sub.3 CH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9 CONH.sub.2 yellow83 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.3 H.sub.78 CONHC.sub.3 H.sub.7 yellow84 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.9 OC.sub.6 H.sub.5 H yellow85 CO.sub.2 CH.sub.3 CN CH.sub.3 C.sub.4 H.sub.9 CO.sub.2 C.sub.2 H.sub.5 yellow86 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 C.sub.6 H.sub.13 CONH.sub.2 yellow87 CN CN CH.sub.3 C.sub.6 H.sub.13 CONH.sub.2 yellow88 CN CN SCH.sub.3 CH.sub.3 CN yellow89 CN CN SCH.sub.3 C.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H.sub.5 CN yellow90 CN CN SCH.sub.3 C.sub.4 H.sub.9 CN yellow91 CO.sub.2 CH.sub.3 CN SCH.sub.2 CO.sub.2 CH.sub.3 C.sub.4 H.sub.9 CN yellow92 CO.sub.2 CH.sub.3 C.sub.6 H.sub.5 SCH.sub.2 CO.sub.2 CH.sub.3 C.sub.4 H.sub.9 CN yellow93 CO.sub.2 CH.sub.3 CN SCH.sub.3 C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5 CN yellow__________________________________________________________________________ (3) SCH.sub.2 CO.sub.2 CH.sub.3 - TABLE 3__________________________________________________________________________ ##STR32## Hue onEx. X Y Z T.sup.1 T.sup.3 PES__________________________________________________________________________ 94 CO.sub.2 CH.sub.3 CN CH.sub.3 H CH.sub.2 C.sub.6 H.sub.5 yellow 95 CO.sub.2 CH.sub.3 CN CH.sub.3 H C.sub.6 H.sub.5 yellow 96 CO.sub.2 CH.sub.3 CN CH.sub.3 H ##STR33## yellow 97 CO.sub.2 CH.sub.3 CN CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 yellow 98 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 H CH.sub.2 C.sub.6 H.sub.5 yellow 99 CO.sub.2 C.sub.2 H.sub.5 CN CH.sub.3 H CH.sub.3 yellow100 COCH.sub.3 CN CH.sub.3 H C.sub. 6 H.sub.5 yellow101 CN CN CH.sub.3 H ##STR34## yellow102 CO.sub.2 CH.sub.3 CO.sub.2 CH.sub.3 CH.sub.3 H CH.sub.2 C.sub.6 H.sub.5 yellow103 CO.sub.2 CH.sub.3 CO.sub.2 CH.sub.3 C.sub.2 H.sub.5 H CH.sub.2 C.sub.6 H.sub.5 yellow104 CO.sub.2 CH.sub.3 H CH.sub.3 H C.sub.6 H.sub.5 yellow105 COC.sub.6 H.sub.5 CN CH.sub.3 H ##STR35## yellow106 CN CN SCH.sub.3 H ##STR36## yellow107 CN CN SCH.sub.3 H CH.sub.2 C.sub.6 H.sub.5 yellow108 CO.sub.2 CH.sub.3 CN SCH.sub.2 CO.sub.2 CH.sub.3 H CH.sub.2 C.sub.6 H.sub.5 yellow109 CO.sub.2 CH.sub.3 CN SCH.sub.3 H C.sub.6 H.sub.5 yellow110 CO.sub.2 CH.sub.3 C.sub.6 H.sub.5 SCH.sub.2 CO.sub.2 CH.sub.3 H ##STR37## yellow__________________________________________________________________________ TABLE 4__________________________________________________________________________DNNK Hue onEx. D K PES__________________________________________________________________________111 ##STR38## ##STR39## yellowish red112 ##STR40## ##STR41## yellowish red113 ##STR42## ##STR43## yellowish red114 ##STR44## ##STR45## yellowish red115 ##STR46## ##STR47## yellow116 ##STR48## ##STR49## yellow117 ##STR50## ##STR51## yellow118 ##STR52## ##STR53## yellow119 ##STR54## ##STR55## yellow120 ##STR56## ##STR57## yellow121 ##STR58## ##STR59## yellow122 ##STR60## ##STR61## yellow123 ##STR62## ##STR63## yellowish red__________________________________________________________________________

Claims

1. A thien- 3-ylazo dye of the formula I ##STR64## where X is cyano, C.sub.1 -C.sub.6 -alkanoyl, substituted or unsubstituted benzoyl, substituted or unsubstituted phenyl or the radical COOR.sup.1 or CONR.sup.1 R.sup.2 where R.sup.1 and R.sup.2 are identical or different and each is independently of each other, substituted or unsubstituted C.sub.1 -C.sub.8 -alkyl, C.sub.5 -C.sub.7 -cycloalkyl, C.sub.3 -C.sub.4 -alkenyl, substituted or unsubstituted phenyl or together with the nitrogen atom linking them a member selected from the group consisting of pyrrolidino, piperidino, morpholino, piperazino and N-(C.sub.1 -C.sub.4 -alkyl)piperazino, and R.sup.2 may additionally be hydrogen,

Y is hydrogen, cyano, C.sub.1 -C.sub.6 -alkanoyl, substituted or unsubstituted benzoyl, substituted or unsubstituted phenyl or the radical COOR.sup.1 or CONR.sup.1 R.sup.2 where R.sup.1 and R.sup.2 are each as defined above,

Z is hydrogen, substituted or unsubstituted C.sub.1 -C.sub.8 -alkyl, substituted or unsubstituted C.sub.1 -C.sub.6 -alkylthio, substituted or unsubstituted phenyl, substituted or unsubstituted phenylthio or substituted or unsubstituted C.sub.1 -C.sub.6 -alkylsulfonyl or phenylsulfonyl and

K is a group of the formula (II) ##STR65## where B.sup.1 and B.sup.2 are identical or different and each is independently of the other hydrogen, unsubstituted or substituted C.sub.1 -C.sub.12 -alkyl, substituted or unsubstituted C.sub.3 -C.sub.12 -alkoxyalkoxyalkyl or C.sub.2 -C.sub.12 -alkoxyalkyl, C.sub.5 -C.sub.7 -cycloalkyl, substituted or unsubstituted phenyl, C.sub.3 -C.sub.6 -alkenyl, substituted or unsubstituted benzoyl, C.sub.1 -C.sub.8 -alkanoyl, C.sub.1 -C.sub.6 -alkylsulfonyl or phenylsulfonyl,

T.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl or phenyl,

T.sup.2 is hydrogen, cyano, nitro, carbemoyl, C.sub.1 -C.sub.4 -monoalkyl- or dialkyl-carbamoyl, C.sub.1 -C.sub.8 -alkanoyl, C.sub.1 -C.sub.6 -alkanoyl, C.sub.2 -C.sub.6 -alkoxycarbonyl or C.sub.3 -C.sub.6 -alkoxyalkoxyalkoxycarbonyl, and

the substituents on substituted alkyl, alkylthio, alkoxyalkyl, alkoxyalkoxyalkyl or alkylsulfonyl values of X, Y and Z are selected from the group consisting of hydroxy, C.sub.1 -C.sub.4 -alkoxy, phenoxy, C.sub.1 -C.sub.4 -alkoxycarbonyl, cyano and phenyl, the substituents on substituted benzoyl, phenyl, phenylthio and phenylsulfonyl values of X, Y, Z, B.sup.1 and B.sup.2 are selected from the group consisting of C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, cyano, fluoro, chloro, bromo and nitro, and the substituents on substituted alkyl, alkoxyalkoxyalkyl and alkoxyalkyl values of B.sup.1 and B.sup.2 are phenyl, cyano, C.sub.1 -C.sub.8 -alkoxycarbonyl, phenoxycarbonyl, halogen, hydroxyl, C.sub.1 -C.sub.8 -alkanoyloxy, benzoyloxy, C.sub.5 -C.sub.7 -cycloalkoxy and phenoxy.

2. The compound of claim 1 having the formula: ##STR66##

3. The compound of claim 1 having the formula: ##STR67##

4. The compound of claim 1 having the formula: ##STR68##