.alpha.-methine substituted thiophene monoazo dye

Abstract

A compound of the formula: ##STR1## wherein K is a radical of a coupling component, R is a radical of a methylene-active compound, X is hydrogen or unsubstituted or substituted alkyl, aryl, or hetaryl and Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl. The present compound is useful for the dyeing of polyesters, nylons, cellulose esters and blends of polyesters and cellulose fibers.

Description

The present invention relates to compounds of the general formula I ##STR2## where K is a radical of a coupling component, R is a radical of a methylene-active compound, X is hydrogen or unsubstituted or substituted alkyl, aryl or hetaryl and Y is cyano, nitro, alkanoyl, aroyl, alkylsulfonyl, arylsulfonyl, carboxyl, a carboxylic ester group or unsubstituted or substituted carbamyl.

X is hydrogen or, for example, C.sub.1 -C.sub.8 -alkyl which may be further substituted by chlorine, bromine or phenyl, or thienyl, furyl or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy or nitro.

Specific examples of alkyl radicals are CH.sub.3, C.sub.2 H.sub.5, C.sub.3 H.sub.7, C.sub.4 H.sub.9, C.sub.5 H.sub.11, C.sub.6 H.sub.13, C.sub.8 H.sub.17 and ##STR3## the abbreviated formula also embracing the n- and iso-radicals.

Specific examples of radicals Y, in addition to those stated above, are CH.sub.3 CO, C.sub.2 H.sub.5 CO, C.sub.3 H.sub.7 CO, C.sub.4 H.sub.9 CO, C.sub.5 H.sub.11 CO, C.sub.7 H.sub.15 CO, ##STR4## C.sub.6 H.sub.5 CO, CH.sub.3 C.sub.6 H.sub.4 CO, ClC.sub.6 H.sub.4 CO, (CH.sub.3).sub.2 C.sub.6 H.sub.3 CO, H.sub.3 COC.sub.6 H.sub.4 CO, Cl.sub.2 C.sub.6 H.sub.3 CO, CH.sub.3 SO.sub.2, C.sub.2 H.sub.5 SO.sub.2, C.sub.4 H.sub.9 SO.sub.2, C.sub.6 H.sub.5 SO.sub.2, CH.sub.3 C.sub.6 H.sub.4 SO.sub.2, ClC.sub.6 H.sub.4 SO.sub.2, COOCH.sub.3, COOC.sub.2 H.sub.5, COOC.sub.3 H.sub.7, COOC.sub.4 H.sub.9, COOC.sub.6 H.sub.13, COOC.sub.8 H.sub.17, ##STR5## COOC.sub.2 H.sub.4 OCH.sub.3, COOC.sub.2 H.sub.4 OC.sub.2 H.sub.5, COOC.sub.2 H.sub.4 OC.sub.4 H.sub.9, COOC.sub.6 H.sub.5, COOC.sub.6 H.sub.4 CH.sub.3, CONH.sub.2, CONHCH.sub.3, CONHC.sub.2 H.sub.5, CONHC.sub.4 H.sub.9, CONHC.sub.6 H.sub.13, CONHC.sub.8 H.sub.17, CON(CH.sub.3).sub.2, CON(C.sub.2 H.sub.5).sub.2, CON(C.sub.4 H.sub.9)2, ##STR6##

Methylene-active compounds of the formula H.sub.2 R are, for example, compounds of the formula ##STR7## where Y has the stated meanings, and the compounds of the formulae: ##STR8##

Examples of very important specific compounds of the formula ##STR9##

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

The coupling components HK are, in particular, of the general formulae ##STR10## where 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.2 and R.sup.3 together with the nitrogen form a saturated heterocyclic structure, 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 or carbalkoxy and R.sup.7 is unsubstituted or substituted phenyl, alkyl or aralkyl.

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 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, cyano, carboxyl, C.sub.1 -C.sub.8 -alkanoyloxy, C.sub.1 -C.sub.8 -alkoxy-C.sub.1 -C.sub.4 -alkoxy, benzyoloxy, 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, phenethyloxycarbonyloxy, 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 phenethyloxycarbonyl, 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-phenoxymethylcarbonyloxyethyl, 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- -phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl.

R.sup.2 and R.sup.3 together with the nitrogen form, for example, pyrrolidino, piperidino or morpholino.

Examples of suitable radicals R.sup.4 and R.sup.5 are hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, C.sub.1 -C.sub.6 -alkanoylamino, benzylamino, C.sub.1 -C.sub.4 -alkylsulfonylamino and C.sub.1 -C.sub.4 -dialkylaminosulfonylamino.

Examples of radicals R.sup.6 in addition to those stated 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.

R.sup.7 is, for example, phenyl which is monosubstituted or polysubstituted by 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 -monoalkylamino, C.sub.1 -C.sub.4 -dialkylamino, C.sub.1 -C.sub.4 -alkoxyethoxy, C.sub.1 -C.sub.4 -alkylmercapto, phenylmercapto or C.sub.1 -C.sub.5 -alkanoylamino, such as acetylamino, propionylamino, butyrylamino or valerylamino, or is, for example, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxycarbonylmethyl, cyanomethyl or benzyl.

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

The compounds of the formula I can be prepared by a method in which a 5-formyl compound of the diazo component of the formula ##STR11## is condensed with a compound of the formula

H.sub.2 R by a conventional method to give a compound of the formula II ##STR12## this compound is diazotized in a conventional manner, and the product is reacted with a coupling component KH.

However, it is also possible first to diazotize a diazo component of the formula ##STR13## and react the product with a coupling component KH to give a monoazo dye of the formula III ##STR14## and then to condense this dye with a compound of the formula

H.sub.2 R to give a methineazo dye of the formula I

The Examples which follow illustrate the preparation. Parts and percentages are by weight, unless stated otherwise.

Of particular importance are compounds of the formula Ia ##STR16## where K.sup.1 is a radical of a coupling component of the aniline or thiazole series, X.sup.1 is hydrogen, C.sub.1 -C.sub.8 -alkyl, benzyl, phenethyl or thienyl, furyl or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy, and Y.sup.1 is cyano, a carboxylic ester group or substituted carbamyl.

EXAMPLE 1

(a) 8.3 parts of 2-amino-3-cyano-4-methyl-5-formylthiophene in a mixture of 56.3 parts by volume of glacial acetic acid and 18.7 parts by volume of propionic acid were stirred. 25 parts by volume of 85% strength sulfuric acid were added, after which 16 parts of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) were run slowly into the stirred solution at 0.degree.-5.degree. C. and stirring was continued for 4 hours at the same temperature. The diazonium salt solution thus obtained was run slowly 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 to give 15 parts of the dye of the formula ##STR17## which dyes polyester fibers in violet hues.

(b) 6.2 parts of the dye described in Example 1a were dissolved in 45 parts by volume of dioxane, 3.8 parts of ethyl cyanoacetate, 1.5 parts of glacial acetic acid and 1.5 parts 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 with water and dried at 40.degree. C. under reduced pressure to give 7 parts of the dye of the formula ##STR18## which dyes polyester fibers in dark blue hues having good lightfastness and fastness to dry heat pleating and setting.

EXAMPLE 2

Using a method similar to that described in Example 1(a), 7.6 parts of 2-amino-3-cyano-5-formylthiophene were reacted with 9.7 parts of N-cyanoethyl-N-ethyl-m-toluidine to give 13 parts of the dye of the formula ##STR19## 3.8 parts of ethyl cyanoacetate, 1.5 parts of glacial acetic acid and 1.5 parts of piperidine were added to 6.0 parts of this dye in 45 parts by volume of dioxane, and the mixture was stirred for 16 hours at room temperature. Thereafter, the dye was precipitated by adding 50 parts of water and 50 parts of ice, the mixture was stirred for 1 hour and the product was filtered off under suction, washed neutral with water and dried to give 7 parts of the dye of the formula ##STR20## which dyes polyesters in fast dark blue hues.

EXAMPLE 3

12.4 parts of the dye of the formula ##STR21## in 80 parts by volume of dioxane were stirred with 6.8 parts of ethyl cyanoacetate, 2.5 parts of glacial acetic acid and 2.5 parts of piperidine for 16 hours at room temperature. Thereafter, the mixture was diluted with 200 parts of an ice/water mixture, and the product was filtered off and dried to give 14.7 parts of the dye of the formula ##STR22## which gives, on polyesters, dark blue dyeings which are lightfast and fast to dry heat pleating and setting.

EXAMPLE 4

Using a method similar to that described in Example 1(b), 13.5 parts of the dye of the formula ##STR23## were reacted with 7.5 parts of n-butyl cyanoacetate to give 14 parts of the dye of the formula ##STR24## Dark blue dyeings having good general fastness properties were obtained on polyesters.

EXAMPLE 5

Using a method similar to that described in Example 1(a), 8.3 parts of 2-amino-3-cyano-4-methyl-5-formylthiophene were reacted with 12.3 parts of N,N-diethyl-3-aminoacetanilide to give 14 parts of the dye of the formula ##STR25## 6.5 parts of this compound were dissolved in 45 parts by volume of dioxane, 3.8 parts of ethyl cyanoacetate, 1.5 parts of glacial acetic acid and 1.5 parts of piperidine were added and the mixture was stirred for 16 hours at room temperature. Working up by a procedure similar to that described in Example 1 gave 7 parts of the dye of the formula ##STR26## which, on polyesters, gives clear blue dyeings which in particular possess very good lightfastness and fastness to dry heat pleating and setting.

The dyes defined in the Table below were obtained similarly to Examples 1-5.

__________________________________________________________________________ ##STR27##Exam-pleNo. X Y Y.sup.1 Y.sup.2 K *__________________________________________________________________________6 H CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR28## dark blue7 H CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR29## bluish violet8 H CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR30## dark blue9 H CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR31## blue10 H CN CN CN ##STR32## dark blue11 H CN COCH.sub.3 COOC.sub.2 H.sub.5 ##STR33## dark blue12 H COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR34## bluish violet13 H COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR35## dark blue14 H COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR36## blue15 H COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 COOC.sub.2 H.sub.5 ##STR37## dark blue16 H COOC.sub.2 H.sub.5 COCH.sub.3 COOC.sub.2 H.sub.5 ##STR38## dark blue17 H COOC.sub.2 H.sub.5 COCH.sub.3 COCH.sub.3 ##STR39## bluish violet18 H COOC.sub.2 H.sub.5 COCH.sub.3 CN ##STR40## dark blue19 H ##STR41## CN COOC.sub.2 H.sub.5 ##STR42## dark blue20 H ##STR43## CN COOC.sub.2 H.sub.5 ##STR44## blue21 H SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR45## dark blue22 H SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR46## dark blue23 H SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR47## blue24 H CN CN COOC.sub.2 H.sub.5 ##STR48## bluish violet25 H CN CN COOC.sub.2 H.sub.5 ##STR49## bluish violet26 H CN CN COOC.sub.2 H.sub.5 ##STR50## dark blue27 H CN CN COOC.sub.2 H.sub.5 ##STR51## dark blue28 H CN CN COOC.sub.2 H.sub.5 ##STR52## dark blue29 H CN CN COOC.sub.2 H.sub.5 ##STR53## dark blue30 H CN CN COOC.sub.2 H.sub.5 ##STR54## dark blue31 H CN CN COOC.sub.2 H.sub.5 ##STR55## blue32 H CN CN COOC.sub.2 H.sub.5 ##STR56## blue33 H CN CN COOC.sub.2 H.sub.5 ##STR57## blue34 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR58## bluish violet35 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR59## bluish violet36 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR60## bluish violet37 CH.sub.3 CN CN COOC.sub. 2 H.sub.5 ##STR61## dark blue38 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR62## dark blue39 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR63## dark blue40 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR64## dark blue41 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR65## dark blue42 CH.sub.3 CN CN COOC.sub.2 H.sub. 5 ##STR66## dark blue43 CH.sub.3 CN CN COOC.sub.4 H.sub.9 (n) ##STR67## dark blue44 CH.sub.3 CN CN COOC.sub.4 H.sub.9 (n) ##STR68## blue45 CH.sub.3 CN CN COOC.sub.4 H.sub.9 (n) ##STR69## blue46 CH.sub.3 CN CN COOC.sub.4 H.sub.9 (n) ##STR70## blue47 CH.sub.3 CN CN COOC.sub.4 H.sub.9 (n) ##STR71## dark blue48 CH.sub.3 CN CN ##STR72## ##STR73## dark blue49 CH.sub.3 CN CN ##STR74## ##STR75## dark blue50 CH.sub.3 CN CN ##STR76## ##STR77## dark blue51 CH.sub.3 CN CN CONH.sub.2 ##STR78## dark blue52 CH.sub.3 CN COOC.sub.2 H.sub.5 COOC.sub.2 H.sub. 5 ##STR79## navy53 CH.sub.3 CN COCH.sub.3 COOC.sub.2 H.sub.5 ##STR80## dark blue54 CH.sub.3 CN CN CONHCH.sub.3 " dark blue55 CH.sub.3 COOC.sub.2 H.sub.5 CN CN ##STR81## blue56 CH.sub.3 COOC.sub.2 H.sub.5 CN COOC.sub.4 H.sub.9 ##STR82## dark blue57 CH.sub.3 COOC.sub.2 H.sub.5 CN CON(CH.sub.3).sub.2 ##STR83## bluish violet58 CH.sub.3 CONH.sub.2 CN COOC.sub.2 H.sub.5 ##STR84## dark blue59 CH.sub.3 SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR85## dark blue60 CH.sub.3 CON(CH.sub.3).sub.2 CN COOC.sub.2 H.sub.5 ##STR86## dark blue61 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR87## dark blue62 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR88## navy63 CH.sub.3 CN CN COOCH.sub.3 ##STR89## navy64 CH.sub.3 CN CN COOCH.sub.3 ##STR90## navy65 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR91## navy66 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR92## violet67 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR93## violet68 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR94## violet69 CH.sub.3 CN CN CONHCH.sub.3 ##STR95## dark blue70 CH.sub.3 CN CN CONHC.sub.2 H.sub.5 ##STR96## dark blue71 CH.sub.3 CN CN SO.sub.2 CH.sub.3 ##STR97## dark blue72 CH.sub.3 CN CN COCH.sub.3 ##STR98## dark blue73 CH.sub.3 CN CN COOCH.sub.3 ##STR99## dark blue74 CH.sub.3 CN CN ##STR100## ##STR101## dark blue75 C.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR102## dark blue76 C.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR103## dark blue77 C.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR104## dark blue78 C.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR105## dark blue79 C.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR106## dark blue80 C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 CN COOC.sub.2 H.sub.5 ##STR107## dark blue81 4-CH.sub.3 OC.sub.6 H.sub.4 CN CN COOC.sub.2 H.sub.5 ##STR108## navy82 4-CH.sub.3C.sub.6 H.sub.4 CN CN COOC.sub.2 H.sub.5 ##STR109## navy83 4-ClC.sub.6 H.sub.4 CN CN COOC.sub.2 H.sub.5 ##STR110## navy__________________________________________________________________________ *Dyeing on polyesters

EXAMPLE 84

(a) 25 parts of 2-amino-3-cyano-4-methyl-5-formylthiophene were dissolved in 200 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. and then stirred 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 31.5 parts of 2-amino-3-cyano-4-methyl-5-((.beta.-cyano-.beta.-carboethoxy)-vinyl)-thiophene of the formula ##STR111## which was reacted without further purification.

(b) 13 parts of 2-amino-3-cyano-4-methyl-5-((.beta.-cyano-.beta.-carboethoxy)-vinyl)-thiophene 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 of the formula ##STR112## described in Example 1(b).

EXAMPLE 85

16.2 parts of 2-amino-3-cyano-4-phenyl-5-((.beta.-cyano-.beta.-carboethoxy)-vinyl)-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, using a procedure similar to Example 84(b), to give 23 parts of the dye of the formula ##STR113## which gives, on polyesters, navy dyeings possessing good lightfastness and fastness to dry heat pleating and setting.

EXAMPLE 86

11.6 parts of 2-amino-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 slowly run 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 product was washed neutral and dried to give 16 parts of the dye of the formula ##STR114## which, on polyesters, gives dark blue dyeings possessing good general fastness properties.

The compounds defined in the Table below were also obtained similarly to Examples 84-86.

__________________________________________________________________________ ##STR115##Exam-ple No. X Y Y.sup.1 Y.sup.2 K *__________________________________________________________________________87 H CN CN COOCH.sub.3 ##STR116## dark blue88 H CN CN COOCH.sub.3 ##STR117## dark blue89 H CN CN COOCH.sub.3 ##STR118## blue90 H CN CN COOCH.sub.3 ##STR119## blue91 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR120## dark blue92 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR121## dark blue93 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR122## dark blue94 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR123## dark blue95 CH.sub.3 CN CN CONHCH.sub.3 ##STR124## dark blue96 CH.sub.3 COOCH.sub.3 CN COOC.sub.2 H.sub.5 ##STR125## dark blue97 CH.sub.3 SO.sub.2 CH.sub.3 CN COOC.sub.2 H.sub.5 ##STR126## dark blue98 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR127## bluish violet99 C.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR128## dark blue100 C.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR129## dark blue101 C.sub.6 H.sub.5 CN CN COOC.sub.2 H.sub.5 ##STR130## navy__________________________________________________________________________ *Dyeing on polyesters

The dyes characterized by the substituents in the Table below were prepared similarly to the methods described for Example No. 7.

__________________________________________________________________________Example No. X Y Y.sup.1 Y.sup.2 K (*)__________________________________________________________________________102 H CN CN COOC.sub.2 H.sub.5 ##STR131## dark blue103 H CN CN COOC.sub.2 H.sub.5 ##STR132## blue104 H CN CN CN ##STR133## blue105 H CN CN COOC.sub.2 H.sub.5 ##STR134## blue106 H CN CN COOC.sub.2 H.sub.5 ##STR135## dark blue107 H CN CN COOC.sub.2 H.sub.5 ##STR136## blue108 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR137## navy109 CH.sub.3 CN CN COOC.sub.2 H.sub.5 ##STR138## navy110 CH.sub.3 CN CN CN ##STR139## blue__________________________________________________________________________ (*) Dyeing on polyesters

The dyes below were obtained using N,N-dimethylbarbituric acid as the starting material:

______________________________________ ##STR140##Exam-ple No. X Y K (*)______________________________________111 H CN ##STR141## dark blue112 CH.sub.3 CN ##STR142## bluish violet113 C.sub.6 H.sub.5 CN ##STR143## dark blue114 CH.sub.3 CN ##STR144## blue115 H CN ##STR145## bluish violet______________________________________ (*) Dyeing on polyesters

Claims

1. A compound of formula I: ##STR146## wherein X.sup.2 is cyano and Y.sup.2 is CN, NO.sub.2, CH.sub.3 CO, C.sub.2 H.sub.5 CO, C.sub.3 H.sub.7 CO, C.sub.4 H.sub.9 CO, C.sub.5 H.sub.11 CO, C.sub.7 H.sub.15 CO, (C.sub.4 H.sub.9)(C.sub.2 H.sub.5)CHCO, C.sub.6 H.sub.5 CO, CH.sub.3 C.sub.6 H.sub.4 CO, ClC.sub.6 H.sub.4 CO, (CH.sub.3).sub.2 C.sub.6 H.sub.3 CO, CH.sub.3 OC.sub.6 H.sub.4 CO, Cl.sub.2 C.sub.6 H.sub.2 CO, CH.sub.3 SO.sub.2, C.sub.2 H.sub.5 SO.sub.2, C.sub.4 H.sub.9 SO.sub.2, C.sub.6 H.sub.5 SO.sub.2, CH.sub.3 C.sub.6 H.sub.4 SO.sub.2, ClC.sub.6 H.sub.4 SO.sub.2, carboxyl, COOCH.sub.3, COOC.sub.2 H.sub.5, COOC.sub.3 H.sub.7, COOC.sub.4 H.sub.9, COOC.sub.6 H.sub.13, COOC.sub.8 H.sub.17, (C.sub.4 H.sub.9)(C.sub.2 H.sub.5)CHCH.sub.2 OOC, CH.sub.3 OC.sub.2 H.sub.4 OOC, C.sub.2 H.sub.5 OC.sub.2 H.sub.4 OOC, C.sub.4 H.sub.9 OC.sub.2 H.sub.4 OOC, C.sub.6 H.sub.5 OOC, CH.sub.3 C.sub.6 H.sub.4 OOC, CONH.sub.2, CONHCH.sub.3, CONHC.sub.2 H.sub.5, CONHC.sub.4 H.sub.9, CONHC.sub.6 H.sub.5, CONHC.sub.6 H.sub.13, CONH(C.sub.6 H.sub.4 --CH.sub.3 --p), CONHC.sub.8 H.sub.17, CON(CH.sub.3).sub.2, CON(C.sub.2 H.sub.5).sub.2, CON(C.sub.4 H.sub.9).sub.2, (CH.sub.3)(C.sub.2 H.sub.5)NOC, CONH(C.sub.6 H.sub.4 --OCH.sub.3 --p), CONH(C.sub.6 H.sub.3 --OCH.sub.3 --m, --OCH.sub.3 --p), CONH(C.sub.6 H.sub.4 --Cl--p), C.sub.6 H.sub.5, C.sub.6 H.sub.4 --NO.sub.2 --p, C.sub.6 H.sub.4 --Cl--p, C.sub.6 H.sub.4 --OCH.sub.3 --p, ##STR147## or group ##STR148## is a member selected from the group consisting of ##STR149## X is hydrogen C.sub.1 -C.sub.8 -alkyl, C.sub.1 -C.sub.8 -alkyl substituted by chlorine, bromine or phenyl, thienyl, furyl, phenyl or phenyl substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy or nitro; Y is cyano, nitro, CH.sub.3 CO, C.sub.2 H.sub.5 CO, C.sub.3 H.sub.7 CO, C.sub.4 H.sub.9 CO, C.sub.5 H.sub.11 CO, C.sub.7 H.sub.15 CO, ##STR150## C.sub.6 H.sub.5 CO, CH.sub.3 C.sub.6 H.sub.4 CO, ClC.sub.6 H.sub.4 CO, (CH.sub.3).sub.2 C.sub.6 H.sub.3 CO, H.sub.3 COC.sub.6 H.sub.4 CO, Cl.sub.2 C.sub.6 H.sub.3 CO, CH.sub.3 SO.sub.2, C.sub.2 H.sub.5 SO.sub.2, C.sub.4 H.sub.9 SO.sub.2, C.sub.6 H.sub.5 SO.sub.2, CH.sub.3 C.sub.6 H.sub.4 SO.sub.2, ClC.sub.6 H.sub.4 SO.sub.2, carboxyl, COOCH.sub.3, COOC.sub.2 H.sub.5, COOC.sub.3 H.sub.7, COOC.sub.4 H.sub.9, COOC.sub.6 H.sub.13, COOC.sub.8 H.sub.17, COOCH.sub.2 CH(C.sub.4 H.sub.9)(C.sub.2 H.sub.5), COOC.sub.2 H.sub.4 OCH.sub.3, COOC.sub.2 H.sub.4 OC.sub.2 H.sub.5, COOC.sub.2 H.sub.4 OC.sub.4 H.sub.9, COOC.sub.6 H.sub.5, COOC.sub.6 H.sub.4 CH.sub.3, CONH.sub.2, CONHCH.sub.3, CONHC.sub.2 H.sub.5, CONHC.sub.4 H.sub.9, CONHC.sub.6 H.sub.13, CONHC.sub.8 H.sub.17, CON(CH.sub.3).sub.2, CON(C.sub.2 H.sub.5).sub.2, CON(C.sub. 4 H.sub.9).sub.2, CON(CH.sub.3)(C.sub.2 H.sub.5), ##STR151## and K is derived from HK which is a compound selected from the group consisting of: ##STR152## where R.sup.1 is hydrogen, C.sub.1 -C.sub.8 -alkyl, phenyl, o-, m- or p-tolyl, o-, m- or p-chlorophenyl, benzyl or phenethyl; R.sup.2 is hydrogen or R.sup.3 ; R.sup.3 is C.sub.1 -C.sub.6 -alkyl, allyl, methallyl, cyclohexyl, phenethyl, benzyl, phenyl, or C.sub.1 -C.sub.6 -alkyl 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, benzyoloxy, 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 -alkoxy-alkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, 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 phenethoxycarbonyl; R.sup.2 and R.sup.3 together with the nitrogen form pyrrolidino, piperidino or morpholino; R.sup.4 and R.sup.5 independently of one another are each hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, phenoxy, halogen, C.sub.1 -C.sub.4 -alkylsulfonylamino, C.sub.1 -C.sub.4 -dialkylaminosulfonylamino, C.sub. 1 -C.sub.6 -alkanoylamino; R.sup.6 is cyano, carbamyl, nitro, methoxycarbonyl, ethoxycarbonyl, n- or isopropoxycarbonyl, n-, iso- or sec-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- or isopropoxyethoxycarbonyl or n-, iso- or sec-butoxyethoxycarbonyl, and R.sup.7 is phenyl, C.sub.1 -C.sub.4 -alkyl, benzyl or phenyl mono- or polysubstituted by C.sub.1 -C.sub.10 -alkyl, C.sub.1 -C.sub.10 -alkoxy, phenoxy, benzoyloxy, phenyl, chlorine, bromine, nitro, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.1 -C.sub.4 -monoalkylamino, C.sub.1 -C.sub.4 -dialkylamino, C.sub.1 -C.sub.4 -alkoxyethoxy, C.sub.1 -C.sub.4 -alkylmercapto, phenylmercapto or C.sub.1 -C.sub.5 -alkanoylamino.

2. The compound as claimed in claim 1, of the formula: ##STR153## wherein K' is derived from HK' which is an aniline compound of the formula: ##STR154## or a thiazole compound of the formula: ##STR155## wherein R.sup.2 is hydrogen or R.sup.3, R.sup.3 is C.sub.1 -C.sub.6 -alkyl, cyclohexyl, allyl, methallyl, phenethyl, benzyl, phenyl or C.sub.1 -C.sub.6 -alkyl 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- 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, phenethyloxycarbonyloxy, 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 phenethyloxycarbonyl; R.sup.2 and R.sup.3 together with the nitrogen form pyrrolidino, piperidino or morpholino; R.sup.4 and R.sup.5 independently of one another are each hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, phenoxy, halogen, C.sub.1 -C.sub.4 -alkylsulfonylamino, C.sub.1 -C.sub.4 -dialkylaminosulfonylamino, or C.sub.1 -C.sub.6 -alkanoylamino; and R.sup.7 is phenyl, mono- or polysubstituted by C.sub.1 -C.sub.10 -alkyl, C.sub.1 -C.sub.10 -alkoxy, phenoxy, benzoyloxy, phenyl, chlorine, bromine, nitro, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.1 -C.sub.4 -monoalkylamino, C.sub.1 - C.sub.4 -dialkylamino, C.sub.1 -C.sub.4 -alkoxyethoxy, C.sub.1 -C.sub.4 -alkylmercapto, phenylmercapto or C.sub.1 -C.sub.5 -alkanoylamino, C.sub.1-4 alkyl, C.sub.1 -C.sub.4 -alkoxycarbonylmethyl, cyanomethyl or benzyl; X is hydrogen, C.sub.1-8 -alkyl, benzyl, phenethyl, or thienyl, furyl or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy, and Y' is cyano, COOCH.sub.3, COOC.sub.2 H.sub.5, COOC.sub.3 H.sub.7, COOC.sub.4 H.sub.9, COOC.sub.6 H.sub.13, COOC.sub.8 H.sub.17, COOCH.sub.2 CH(C.sub.4 H.sub.9 (C.sub.2 H.sub.5), COOC.sub.2 H.sub.4 OCH.sub.3, COOC.sub.2 H.sub.4 OC.sub.2 H.sub.5, COOC.sub.2 H.sub.4 OC.sub.4 H.sub.9, COOC.sub.6 H.sub.5, COOC.sub.6 H.sub.4 CH.sub.3, CONHCH.sub.3, CONHC.sub.2 H.sub.5, CONHC.sub.4 H.sub.9, CONHC.sub.6 H.sub.13, CONHC.sub.8 H.sub.17, CON(CH.sub.3).sub.2, CON(C.sub.2 H.sub.5).sub.2, CON(C.sub.4 H.sub.9).sub.2, CON(CH.sub.3)(C.sub.2 H.sub.5), ##STR156##

3. The compound as claimed in claim 2, wherein said radical K is derived from a compound selected from the group consisting of ##STR157## wherein R is hydrogen, alkyl, aralkyl or aryl; R.sup.2 -R.sup.5 and R.sup.7 are as defined in claim 2 and R.sup.6 is cyano, carbamyl, nitro or carbalkoxy.

4. The compound as claimed in claim 2, wherein said radicals R.sup.2 and R.sup.3 together form a pyrrolidino, piperidino or morpholino.

5. The compound as claimed in claim 3, wherein said radicals R.sup.2 and R.sup.3 together form a pyrrolidino, piperidino or morpholino.

6. The compound of claim 2, wherein said R.sup.4 and R.sup.5 radicals are selected from the group consisting of hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, C.sub.1-6 alkanoylamino, benzylamino, C.sub.1-4 alkylsulfonylamino and C.sub.1-4 dialkylaminosulfonylamino.

7. The compound of claim 3, wherein said R.sup.4 and R.sup.5 radicals are selected from the group consisting of hydrogen, methyl, ethyl, propyl, bromine, chlorine, methoxy, ethoxy, phenoxy, benzyloxy, C.sub.1-6 alkanoylamino, benzylamino, C.sub.1-4 alkylsulfonylamino and C.sub.1-4 dialkylaminosulfonylamino.

8. The compound as claimed in claim 3, wherein said R.sup.6 radical is aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- and isopropoxycarbonyl, n-, iso- and sec-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- and isopropoxyethoxycarbonyl or n-, iso- or sec-butoxyethoxycarbonyl.

9. The compound claimed in claim 2, wherein said substituted alkyl is C.sub.1-6 alkyl 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- 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, phenethyloxycarbonyloxy, 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 phenethyloxycarbonyl, said aryl radical is phenyl, said aralkyl radical is benzyl or phenethyl and said cycloalkyl radical is cyclohexyl.