Isothiazolylazo dyes having aminophenyl and aminonaphthyl components

Abstract

An isothiazolylazo dye of the formula I ##STR1## wherein R is an alkyl group or unsubstituted aryl or substituted aryl group selected from the group consisting of ##STR2## and K is a radical of the formula ##STR3## where B is C.sub.1 -C.sub.4 alkyl or a substituted amino radical selected from the group consisting of ##STR4## R.sup.1 is hydrogen, methyl, methoxy or ethoxy, R.sup.2 and R.sup.3 independently of one another are each unsubstituted C.sub.1 -C.sub.4 alkyl or substituted alkyl groups selected from the group of C.sub.1 -C.sub.4 alkyls which are substituted by chlorine, bromine, cyano, hydroxyl, C.sub.1 -C.sub.4 -alkoxy, benzyloxy, phenoxy, phenyl, C.sub.1 -C.sub.4 -alkylcarbonyloxy which is unsubstituted or substituted by C.sub.1 -C.sub.4 -alkoxy, phenoxy or phenyl, phenycarbonyloxy which is unsubstituted or substituted by chlorine, bromine, methoxy, ethoxy, methyl or ethyl, oxycarbonyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.1 -C.sub.4 -alkoxycarbonyloxy, carbamyl, phenalkyloxycarbonyloxy, phenoxyalkyloxycarbonyloxy, C.sub.1 -C.sub.4 -alkoxyalkoxycarbonyloxy, phenylaminocarbonyloxy which is unsubstituted or substituted by chlorine, methoxy or methyl, C.sub.1 -C.sub.4 -alkoxyalkoxycarbonyl, phenylalkyloxycarbonyl or C.sub.1 -C.sub.4 -alkylaminocarbonyloxy which is unsubstituted or substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, chlorine or bromine; or R.sup.3 is hydrogen, R.sup.4 is a radical of the formula --A--OCO--Y--R, Z is hydrogen or methyl, X is hydrogen, methyl, methoxy, chlorine or an acylamino radical selected from the group consisting of A is C.sub.2 - or C.sub.3 -alkylene and Y is --O-- or --NH--. The dyes are very useful for dyeing cellulose esters and synthetic polyesters; the dyeings obtained are from yellow to blue, and very fast.

Description

The present invention relates to compounds of the general formula I ##STR5## where R is alkyl or unsubstituted or substituted aryl and K is a radical of the formula ##STR6## B is C.sub.1 -C.sub.4 -alkyl or substituted amino, R.sup.1 is hydrogen, methyl, methoxy or ethoxy, R.sup.2 and R.sup.3 independently of one another are each unsubstituted or substituted alkyl, R.sup.3 may furthermore be hydrogen, R.sup.4 is a radical of the formula --A--OCO--Y--R, Z is hydrogen or methyl, X is hydrogen, methyl, methoxy, chlorine or acylamino, A is C.sub.2 - or C.sub.3 -alkylene and Y is --O-- or --NH--.

Alkyl R is preferably of 1 to 8 carbon atoms, specific examples being methyl, ethyl, n-propyl, i-propyl, butyl, hexyl and 2-ethylhexyl. Unsubstituted or substituted aryl radicals R are, for example, ##STR7## Substituted amino radicals B are, for example, N(CH.sub.3).sub.2, N(C.sub.2 H.sub.5).sub.2, ##STR8##

Unsubstituted or substituted alkyl radicals R.sup.2 and R.sup.3 are, for example, alkyl which is of 1 to 4 carbon atoms and can be substituted by chlorine, bromine, cyano, hydroxyl, C.sub.1 -C.sub.4 -alkyoxy, benzyloxy, phenoxy, phenyl, C.sub.1 -C.sub.4 -alkylcarbonyloxy which may be unsubstituted or further substituted by C.sub.1 -C.sub.4 -alkoxy, phenoxy or phenyl, phenylcarbonyloxy which is unsubstituted or substituted by Cl, Br, OCH.sub.3, OC.sub.2 H.sub.5, CH.sub.3 or C.sub.2 H.sub.5, oxycarbonyl, C.sub.1 -C.sub.4 -alkoxycarbonyl, C.sub.1 -C.sub.4 -alkoxycarbonyloxy, carbamyl, phenalkyloxycarbonyloxy, phenoxyalkyloxycarbonyloxy, C.sub.1 -C.sub.4 -alkoxyalkoxycarbonyloxy, phenylaminocarbonyloxy which is unsubstituted or substituted by Cl, methoxy or methyl, C.sub.1 -C.sub.4 -alkoxyalkoxycarbonyl, phenylalkyloxycarbonyl or C.sub.1 -C.sub.4 -alkylaminocarbonyloxy which is unsubstituted or substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, chlorine or bromine.

Specific examples of such 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.2 H.sub.4 Cl, C.sub.2 H.sub.4 CN, C.sub.2 H.sub.4 OH, CH.sub.2 --CHOH--CH.sub.3, CH.sub.2 --CHOH--C.sub.2 H.sub.5, ##STR9## C.sub.3 H.sub.6 --OCH.sub.3, C.sub.2 H.sub.4 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,

R.sup.2 and R.sup.4 together can form a saturated heterocyclic ring, eg. a piperidine or morpholine ring.

Examples of acylamino radicals X are NH--CHO, NHCOCH.sub.3, NHCOC.sub.2 H.sub.5, NH--CO-aryl, NHCOCH.sub.2 -aryl, ##STR10## and CO--CH.sub.2 --O--CH.sub.3.

The compounds of the formula I can be prepared by reacting a diazonium compound of an amine of the formula ##STR11## with a coupling component of the formula

H--K

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

The compounds of the formula I are useful for dyeing cellulose esters and in particular synthetic polyesters; the dyeings obtained are from yellow to blue, and as a rule very fast. It may be advantageous to use a mixture of compounds of the formula I for this purpose.

Of particular industrial importance are compounds of the formula Ia ##STR12## where K.sup.1 is a radical of the formula ##STR13## B.sup.1 is C.sub.1 -C.sub.4 -alkyl, and R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and X have the above meanings.

R.sup.1 is preferably H, CH.sub.3 or OCH.sub.3, and R.sup.2 is preferably CH.sub.3, C.sub.2 H.sub.5, C.sub.3 H.sub.7, C.sub.4 H.sub.9, C.sub.2 H.sub.4 CN, C.sub.2 H.sub.4 OH, CH.sub.2 --CHOHCH.sub.3, CH.sub.2 CHOHC.sub.2 H.sub.5, C.sub.3 H.sub.6 OCH.sub.3, C.sub.2 H.sub.4 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, ##STR14##

EXAMPLE 1

7 parts of 5-amino-4-cyano-3-methylisothiazole were dissolved in 75 parts by volume of a mixture of 17 parts of glacial acetic acid and 3 parts of propionic acid, 20 parts of 85% strength sulfuric acid were added, 16 parts of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) were allowed to run in slowly into the stirred mixture at 0-5.degree. C., and stirring was continued at this temperature for 4 hours. The diazonium salt solution thus obtained was allowed to run slowly into a mixture of 11.2 parts of N-ethyl-N-methoxycarbonyloxyethylaniline, 20 parts by volume of 32 percent strength hydrochloric acid, 250 parts of water, 250 parts of ice and one part of amidosulfonic acid. After coupling was complete, the product was filtered off under suction, washed neutral and dried under reduced pressure at 50.degree. C. to give 16.5 parts of the dye of the formula ##STR15## This dye dyes polyester fibers in fast, clear bluish red hues.

EXAMPLE 2

A diazo solution prepared as described in Example 1 from 7 parts of 5-amino-4-cyano-3-methylisothiazole was added to a mixture of 16 parts of N-ethyl-N,.beta.-phenylethoxycarbonyloxyethylaniline, 30 parts by volume of 32% strength hydrochloric acid, 250 parts of water and 250 parts of ice. After coupling was complete, the product was filtered off under suction, washed neutral, and dried under reduced pressure at 50.degree. C. to give 18.8 parts of the dye of the formula ##STR16## This dye dyes polyesters in bluish red hues.

EXAMPLE 3

11.1 parts of N-ethyl-N-propylaminocarbonyloxyethylaniline in 10 parts by volume of dimethylformamide and 20 parts by volume of 32% strength hydrochloric acid were added to a mixture of 250 parts of water, 250 parts of ice and one part of amidosulfonic acid. A diazonium salt solution prepared as described in Example 1 was allowed to run slowly into the above mixture. After coupling was complete, the product was filtered off under suction, washed neutral and dried under reduced pressure at 20.degree. C. to give 17.2 parts of the dye of the formula ##STR17## This dye dyes polyesters in clear bluish red hues.

EXAMPLE 4

14.2 parts of N-ethyl-N-phenylaminocarbonyloxyethylaniline in 8 parts by volume of dimethylformamide and 30 parts by volume of hydrochloric acid were coupled, by a procedure similar to that described in Example 3, with the diazonium salt obtained from 7 parts of 5-amino-4-cyano-3-methylisothiazole. After the product had been dried, 20.3 parts of the dye of the formula ##STR18## were obtained. This dye dyes polyester fibers in bluish red hues.

EXAMPLE 5

16 parts of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) were added slowly to 10.1 parts of 5-amino-4-cyano-3-phenylisothiazole in a mixture of 75 parts by volume of glacial acetic acid/propionic acid (17:3 v/v) and 20 parts by volume of 85% strength sulfuric acid at 0.degree.-5.degree. C., while stirring, and stirring was continued for 4 hours at this temperature. The diazo solution thus obtained was added dropwise to a mixture of 15.7 parts of 4-chloro-3-methoxyethoxycarbonylethylaminoacetanilide, 30 parts by volume of 32% strength hydrochloric acid, 250 parts of ice, 250 parts of water and one part of amidosulfonic acid. After coupling was complete, the product was filtered off under suction, washed neutral and dried under reduced pressure at 50.degree. C. to give 21.9 parts of the dye of the formula ##STR19## This dye dyes polyesters in fast bluish red hues.

EXAMPLE 6

A diazonium salt solution prepared as described in Example 5 from 10.1 parts of 5-amino-4-cyano-3-phenylisothiazole was added dropwise to a mixture of 16.8 parts of N-cyanoethyl-N-ethoxyethoxycarbonyloxyethylaniline, 20 parts by volume of 32% strength hydrochloric acid, 250 parts of water, 250 parts of ice and one part of amidosulfonic acid. After coupling was complete, the product was filtered off under suction, washed neutral, and dried under reduced pressure at 50.degree. C. to give 21.3 parts of the dye of the formula ##STR20## This dye dyes polyesters in fast red hues.

The compounds below were prepared by similar procedures.

__________________________________________________________________________Example R K Hue on polyesters__________________________________________________________________________ 7 CH.sub.3 ##STR21## bluish red 8 CH.sub.3 ##STR22## bluish red 9 CH.sub.3 ##STR23## bluish red10 CH.sub.3 ##STR24## bluish red11 CH.sub.3 ##STR25## bluish red12 CH.sub.3 ##STR26## bluish red13 CH.sub.3 ##STR27## bluish red14 CH.sub.3 ##STR28## bluish red15 CH.sub.3 ##STR29## violet16 CH.sub.3 ##STR30## red17 CH.sub.3 ##STR31## red18 CH.sub.3 ##STR32## bluish red19 CH.sub.3 ##STR33## yellowish red20 CH.sub.3 ##STR34## yellowish red21 CH.sub.3 ##STR35## yellowish red22 ##STR36## ##STR37## yellowish red23 ##STR38## ##STR39## yellowish red24 ##STR40## ##STR41## red25 ##STR42## ##STR43## bluish red26 ##STR44## ##STR45## bluish red27 ##STR46## ##STR47## bluish red28 ##STR48## ##STR49## bluish red29 ##STR50## ##STR51## bluish red30 ##STR52## ##STR53## bluish red31 ##STR54## ##STR55## bluish red32 ##STR56## ##STR57## bluish red33 ##STR58## ##STR59## red34 ##STR60## ##STR61## bluish red35 ##STR62## ##STR63## bluish red36 ##STR64## ##STR65## bluish red37 ##STR66## ##STR67## yellowish red38 ##STR68## ##STR69## red39 ##STR70## ##STR71## bluish red40 ##STR72## ##STR73## bluish red41 ##STR74## ##STR75## red42 ##STR76## ##STR77## red43 ##STR78## ##STR79## red44 ##STR80## ##STR81## yellowish red45 ##STR82## ##STR83## yellowish red46 ##STR84## ##STR85## red47 ##STR86## ##STR87## bluish red48 ##STR88## ##STR89## bluish red49 ##STR90## ##STR91## bluish red50 ##STR92## ##STR93## red51 ##STR94## ##STR95## bluish red52 ##STR96## ##STR97## red53 CH.sub.3 ##STR98## blue54 CH.sub.3 ##STR99## bluish red55 CH.sub.3 ##STR100## violet56 CH.sub.3 ##STR101## red57 ##STR102## ##STR103## bluish red58 ##STR104## ##STR105## red59 ##STR106## ##STR107## violet60 ##STR108## ##STR109## violet61 ##STR110## ##STR111## violet62 ##STR112## ##STR113## bluish red63 ##STR114## ##STR115## bluish red64 ##STR116## ##STR117## bluish red65 ##STR118## ##STR119## violet66 ##STR120## ##STR121## violet67 ##STR122## ##STR123## violet68 ##STR124## ##STR125## violet69 ##STR126## ##STR127## bluish red70 CH(CH.sub.3).sub.2 ##STR128## red71 CH(CH.sub.3).sub.2 ##STR129## red72 CH(CH.sub.3).sub.2 ##STR130## red73 CH(CH.sub.3).sub.2 ##STR131## red74 CH(CH.sub.3).sub.2 ##STR132## bluish red75 CH(CH.sub.3).sub.2 ##STR133## red76 CH(CH.sub.3).sub.2 ##STR134## red77 CH(CH.sub.3).sub.2 ##STR135## red78 CH(CH.sub.3).sub.2 ##STR136## bluish red79 CH(CH.sub.3).sub.2 ##STR137## bluish red80 CH(CH.sub.3).sub.2 ##STR138## red81 CH.sub.3 ##STR139## violet82 CH.sub.3 ##STR140## violet83 CH.sub.3 ##STR141## bluish red84 CH.sub.3 ##STR142## bluish red85 CH.sub.3 ##STR143## bluish red__________________________________________________________________________

Claims

1. An isothiazolylazo dye of the formula: ##STR144## wherein R is methyl, ethyl or isopropyl, or is phenyl which is unsubstituted or substituted by methyl, methoxy or chlorine, R.sup.2 is a straight-chain or branched C.sub.1 -C.sub.4 alkyl or benzyl, X is hydrogen or methyl, Y is --O-- or --NH-- and T is C.sub.1 -C.sub.4 alkyl, phenyl or chlorophenyl.