Azo dyes containing 2-amino-3-cyano-5-formylthiophene derivatives as diazo components and substituted aniline compounds as coupling components

Abstract

The compounds of the formula I ##STR1## where R is unsubstituted or substituted phenyl or naphthyl, R.sup.1 and R.sup.2 are each unsubstituted or substituted alkyl, alkenyl or cycloalkyl, and one of the radicals may furthermore be hydrogen, R.sup.3 is hydrogen, methyl, methoxy, ethoxy or chlorine, and R.sup.4 is acylamino, are particularly useful for dyeing polyesters.

Description

The present invention relates to compounds of general formula I ##STR2## where R is unsubstituted or substituted phenyl or naphthyl, R.sup.1 and R.sup.2 are each unsubstituted or substituted alkyl, alkenyl or cycloalkyl, and one of the radicals may furthermore be hydrogen, R.sup.3 is hydrogen, methyl, methoxy, ethoxy or chlorine and R.sup.4 is acylamino.

The radicals R may be substituted by, for example, fluorine, chlorine, bromine, trifluoromethyl, C.sub.1 -C.sub.4 -alkyl or -alkoxy, nitro or cyano, chlorine, methyl and methoxy being preferred.

R.sup.1 and R.sup.2 are each, for example, C.sub.1 -C.sub.6 -alkyl which may furthermore be substituted by hydroxyl, C.sub.1 -C.sub.4 -alkoxy, phenoxy, phenyl, cyano, alkanoyl, alkanoyloxy, alkoxycarbonyl, aroyloxy, alkoxycarbonyloxy, alkylaminocarbonyloxy, arylaminocarbonyloxy or alkoxy-alkoxy, or are each C.sub.2 -C.sub.4 -alkenyl or C.sub.5 -C.sub.7 -cycloalkyl.

Specific examples of radicals R.sup.1 and R.sup.2 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-.beta.-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl, and one of the radicals may furthermore be hydrogen.

Examples of suitable radicals R.sup.4 are unsubstituted or substituted C.sub.1 -C.sub.6 -alkanoylamino, unsubstituted or substituted benzoylamino and C.sub.1 -C.sub.4 -alkylsulfonylamino or -dialkylaminosulfonylamino.

Specific examples of radicals R.sup.4 are methylcarbonylamino, ethylcarbonylamino, n- and isopropylcarbonylamino, n-, iso- and sec-butylcarbonylamino, benzylcarbonylamino, benzoylamino, o-, m- and p-methylbenzoylamino, o-, m- and p-chlorobenzoylamino, o-, m- and p-methoxybenzoylamino, o-, m- and p-nitrobenzoylamino, methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, methoxymethylcarbonylamino and ethoxy-, phenoxy-, cyano-, chloro- and bromomethylcarbonylamino.

The compounds of the formula I can be prepared by reacting a diazonium salt of a compound of the formula I ##STR3## with a coupling component of the formula ##STR4## by a conventional method. The Examples which follow illustrate the preparation. Parts and percentages are by weight, unless stated otherwise.

The compounds of the formula I are preferably used for dyeing synthetic polyesters; essentially blue hues are obtained, some of them possessing very good fastness properties.

Of particular importance are compounds of the formula I in which R is phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy or ethoxy, R.sup.1 and R.sup.2 are each allyl, benzyl, phenylethyl or C.sub.1 -C.sub.4 -alkyl which is unsubstituted or substituted by hydroxyl, cyano, C.sub.1 -C.sub.4 -alkanoyloxy, C.sub.1 -C.sub.4 -alkoxycarbonyl or C.sub.1 -C.sub.4 -alkoxy, and one of the radicals may furthermore be hydrogen, R.sup.3 is hydrogen, methyl, methoxy or ethoxy and R.sup.4 is C.sub.1 -C.sub.4 -alkanoylamino, methoxy-, ethoxy-, phenoxy-, cyano- or chloromethylcarbonylamino, C.sub.1 -C.sub.4 -alkylsulfonylamino or benzoylamino.

EXAMPLE 1

22.8 parts of 2-amino-3-cyano-4-phenyl-5-formylthiophene were introduced into a mixture of 150 parts by volume of glacial acetic acid/propionic acid (3:1) and 50 parts by volume of 85% strength sulfuric acid. 17.5 parts by volume of nitrosylsulfuric acid (11.5% of N.sub.2 O.sub.3) were added dropwise at 0.degree.-5.degree. C., after which the mixture was stirred for 4 hours at this temperature.

24.6 parts of 3-diethylaminoacetanilide were dissolved in 100 parts by volume of dimethylformamide, and the solution was added to 250 parts of water, 50 parts by volume of 32% strength hydrochloric acid, 1000 parts of ice and 2.5 parts of amidosulfonic acid. The diazo solution obtained beforehand was added in the course of 0.5 hour, with external cooling with ice/water, and the mixture was stirred for 4 hours at 0.degree.-5.degree. C. and overnight without further cooling. The product was filtered off under suction, washed neutral with water and dried at 60.degree. C. in a drying oven under reduced pressure to give 38 parts of a blueish black powder of the formula ##STR5## which dyes polyesters in fast blue hues.

The dyes defined in the Table below were obtained by a similar method.

__________________________________________________________________________ ##STR6##Example No. R R.sup.1 R.sup.2 R.sup.3 R.sup.4 Color on__________________________________________________________________________ PES 2 C.sub.6 H.sub.5 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 H NHCOCH.sub.3 blue 3 C.sub.6 H.sub.5 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 H NHCOC.sub.6 H.sub.5 blue 4 C.sub.6 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOC.sub.6 H.sub.5 blue 5 C.sub.6 H.sub.5 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) H NHCOCH.sub.3 blue 6 C.sub.6 H.sub.5 C.sub.6 H.sub.13 (n) C.sub.6 H.sub.13 (n) H NHCOCH.sub.3 blue 7 C.sub.6 H.sub.5 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 H NHCOCH.sub.3 blueish violet 8 C.sub.6 H.sub.5 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 H NHCOC.sub.6 H.sub.5 blueish violet 9 C.sub.6 H.sub.5 C.sub.2 H.sub.4 CN CH.sub.2 CHCH.sub.2 H NHCOC.sub.6 H.sub.5 blueish violet10 C.sub.6 H.sub.5 C.sub.2 H.sub.4 CN C.sub.4 H.sub.9 (n) H NHCOC.sub.6 H.sub.5 blue11 C.sub.6 H.sub.5 C.sub.2 H.sub.4 CN ##STR7## H NHCOC.sub.6 H.sub.5 blueish violet12 C.sub.6 H.sub.5 C.sub.2 H.sub.4 OCH.sub.3 C.sub.2 H.sub.4 CN H NHCOCH.sub.3 blue13 C.sub.6 H.sub.5 CH.sub.2 CO.sub.2 CH.sub.3 CH.sub.2 CO.sub.2 CH.sub.3 CH.sub.3 NHSO.sub.2 CH.sub.3 blueish violet14 C.sub.6 H.sub.5 H C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OC.sub.6 H.sub.5 H NHCOCH.sub.3 blueish violet15 C.sub.6 H.sub.5 H C.sub.2 H.sub.4 OC.sub.2 H.sub.5 Cl NHCOCH.sub.3 blue16 C.sub.6 H.sub.5 C.sub.2 H.sub. 4 CN CH.sub.2 CHCH.sub.2 OCH.sub.3 NHCOCH.sub.3 greenish blue17 C.sub.6 H.sub.5 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 CO.sub.2 CH.sub.3 H NHCOCH.sub.3 violet18 C.sub.6 H.sub.5 C.sub.2 H.sub.4 OH C.sub.2 H.sub.4 CO.sub.2 CH.sub.3 H NHCOCH.sub.3 blue19 C.sub.6 H.sub.5 C.sub.2 H.sub.4 OH CH.sub.2 C.sub.6 H.sub.5 H NHCOCH.sub.3 blue20 C.sub.6 H.sub.5 C.sub.2 H.sub.4 OCOCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 H NHCOCH.sub.3 blue21 C.sub.6 H.sub.5 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 OCH.sub.3 NHCOCH.sub.3 greenish blue22 C.sub.6 H.sub.5 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 OCH.sub.3 NHCOCH.sub.3 greenish blue23 C.sub.6 H.sub.5 H C.sub.2 H.sub.4 CO.sub.2 C.sub.4 H.sub.9 OCH.sub.3 NHCOCH.sub.3 greenish blue24 C.sub.6 H.sub.5 H C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OC.sub.4 H.sub.9 H NHCOCH.sub.3 reddish blue25 p-CH.sub.3 OC.sub.6 H.sub.4 C.sub. 2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.3 blue26 p-CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 H NHCOCH.sub.3 blue27 p-CH.sub.3 OC.sub.6 H.sub.4 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) H NHCOCH.sub.3 blue28 p-CH.sub.3 OC.sub.6 H.sub.4 C.sub.6 H.sub.13 (n) C.sub.6 H.sub.13 (n) H NHCOCH.sub.3 blue29 p-CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2 CHCHCl CH.sub.2 CHCHCl H NHCOCH.sub.3 reddish blue30 p-CH.sub.3 OC.sub.6 H.sub.4 C.sub.2 H.sub.4 CN C.sub.4 H.sub.9 (n) H NHCOC.sub.6 H.sub.5 blue31 p-CH.sub.3 OC.sub.6 H.sub.4 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 H NHCOC.sub.6 H.sub.5 reddish blue32 p-CH.sub.3 OC.sub.6 H.sub.4 C.sub.2 H.sub.4 CN CH.sub.2 CHCH.sub.2 OCH.sub.3 NHCOCH.sub.3 greenish blue33 p-CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 OCH.sub.3 NHCOCH.sub.3 greenish blue34 p-ClC.sub. 6 H.sub.4 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.3 blue35 p-ClC.sub.6 H.sub.4 CH.sub.2 CHCHCl CH.sub.2 CHCHCl H NHCOCH.sub.3 reddish blue36 p-ClC.sub.6 H.sub.4 C.sub.6 H.sub.13 (n) C.sub.6 H.sub.13 (n) H NHCOCH.sub.3 blue37 p-ClC.sub.6 H.sub.4 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 H NHCOCH.sub.3 blueish violet38 p-ClC.sub.6 H.sub.4 C.sub.2 H.sub.4 CN ##STR8## H NHCOC.sub.6 H.sub.5 blueish violet39 p-ClC.sub.6 H.sub.4 C.sub.2 H.sub.4 CN CH.sub.2 CHCH.sub.2 OCH.sub.3 NHCOCH.sub.3 greenish blue40 p-ClC.sub.6 H.sub.4 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 OCH.sub.3 NHCOCH.sub.3 greenish blue41 p-CH.sub.3C.sub.6 H.sub.4 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.3 blue42 p-CH.sub.3C.sub.6 H.sub.4 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 H NHCOCH.sub.3 blue43 p-CH.sub.3C.sub.6 H.sub.4 C.sub. 4 H.sub.9 (n) C.sub.4 H.sub.9 (n) H NHCOCH.sub.3 blue44 p-CH.sub.3C.sub.6 H.sub.4 C.sub.6 H.sub.13 (n) C.sub.6 H.sub.13 (n) H NHCOCH.sub.3 blue45 p-CH.sub.3C.sub.6 H.sub.4 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 H NHCOC.sub.2 H.sub.5 blue46 p-CH.sub.3C.sub.6 H.sub.4 C.sub.2 H.sub.4 CN CH.sub.2 CHCH.sub.2 OCH.sub.3 NHCOCH.sub.3 greenish blue47 p-CH.sub.3C.sub.6 H.sub.4 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 OCH.sub.3 NHCOCH.sub.3 greenish blue48 o,p-(CH.sub.3).sub.2C.sub.6 H.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.3 blue49 o,p-(CH.sub.3).sub.2C.sub.6 H.sub.3 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) H NHCOCH.sub.3 blue50 o,p-(CH.sub.3).sub.2C.sub.6 H.sub.3 CH.sub.2 CHCH.sub.2 CH.sub.2 CHCH.sub.2 H NHCOCH.sub.3 blue51 o,p-(CH.sub.3).sub.2C.sub.6 H.sub.3 C.sub.6 H.sub.13 (n) C.sub.6 H.sub.13 (n) H NHCOCH.sub.3 blue52 o,p-(CH.sub.3).sub.2 C.sub.6 H.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 C.sub.2 H.sub.4 OCOCH.sub.3 H NHCOC.sub.6 H.sub.5 blue53 o,p-(CH.sub.3).sub.2C.sub.6 H.sub.3 C.sub.2 H.sub.4 CN CH.sub.2 CHCH.sub.2 OCH.sub.3 NHCOCH.sub.3 blue54 ##STR9## C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.3 blue55 ##STR10## C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) H NHCOCH.sub.3 blue56 ##STR11## C.sub.6 H.sub.13 (n) C.sub.6 H.sub.13 (n) H NHCOCH.sub.3 blue57 C.sub.6 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.2 OCH.sub.3 blue58 C.sub.6 H.sub.5 C.sub.3 H.sub.7 (n) C.sub.3 H.sub.7 (n) H NHCOCH.sub.2 OCH.sub.3 blue59 C.sub.6 H.sub.5 C.sub.4 H.sub.9 (n) C.sub.4 H.sub.9 (n) H NHCOCH.sub.2 OCH.sub.3 blue60 C.sub.6 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.2 OC.sub.2 blueb.561 C.sub.6 H.sub. 5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.2 Cl blue62 C.sub.6 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.2 CN blue63 C.sub.6 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H NHCOCH.sub.2 OC.sub.6 blueb.5__________________________________________________________________________

Claims

1. A compound of the formula ##STR12## where R is phenyl or naphthyl; R.sup.1 and R.sup.2 are each selected from the group consisting of 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-.beta.-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl and 2-benzoylethyl, and one of R.sup.1 and R.sup.2 may be hydrogen,

R.sup.3 is hydrogen, methyl, methoxy, ethoxy or chlorine and

R.sup.4 is selected from the group consisting of methylcarbonylamino, ethylcarbonylamino, n- and iso-propylcarbonylamino, n-, iso- and sec-butylcarbonylamino, benzylcarbonylamino, benzoylamino, o-, m- and p-methylbenzoylamino, o-, m- and p-chlorobenzoylamino, o-, m- and p-methoxybenzoylamino, o-, m- and p-nitrobenzoylamino, methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, methoxymethylcarbonylamino and ethoxy-, phenoxy-, cyano-, chloro- and bromomethylcarbonylamino.

2. A compound as claimed in claim 1, wherein R is phenyl, R.sup.1 and R.sup.2 are each allyl, benzyl, phenylethyl or C.sub.1 -C.sub.4 -alkyl which is unsubstituted or substituted by hydroxyl, cyano, C.sub.1 -C.sub.4 -alkanoyloxy, C.sub.1 -C.sub.4 -alkoxycarbonyl or C.sub.1 -C.sub.4 -alkoxy, and one of said radicals may be hydrogen, R.sup.3 is hydrogen, methyl, methoxy or ethoxy and R.sup.4 is C.sub.1 -C.sub.4 -alkanoylamino, methoxy-, ethoxy-, phenoxy-, cyano- or chloromethylcarbonylamino, C.sub.1 -C.sub.4 -alkylsulfonylamino or benzoylamino.