Azo compounds having unsubstituted or substituted 2-phenoxycarbonylethyl groups

Abstract

Compounds of the formula ##STR1## wherein A is C.sub.1-6 alkylene, D is a diazo component radical of the triazolyl, pyrazolyl, cyano(C.sub.1-4 alkyl)-imidazolyl, 4-chlorothiazolyl, 4-chlorotheinyl-2, 3-phenyl-1,2,4-thiadiazolyl-5, isothiazolyl-5, benzoisothiazolyl-3 or 1,3,4-thiadiazolyl-5 series or the phenyl series wherein the phenyl group is free of sulfonyl groups and may be substituted, by a maximum of 3 substituents 5-nitrothiazolyl-2, ##STR2## R.sub.1a is phenyl or phenyl substituted by 1 to 4 substituents each of which is independently halo, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, trifluoromethyl, hydroxy, nitro, formyl, cyano, --SCN, (C.sub.1-4 alkyl)carbonyl, (C.sub.1-4 alkyl)carbonylamino, (C.sub.1-4 alkoxy)carbonyl, (C.sub.1-4 alkyl)carbonyloxy, carbamoyl, (C.sub.1-2 alkoxy)(C.sub.2-3 alkoxy)carbonyl or phenyl, andR.sub.2 -R.sub.4 and R.sub.10 -R.sub.15 are as defined in the specification,and mixtures thereof, useful as disperse dyes particularly for dyeing and printing textile materials made of natural, synthetic or semi-synthetic hydrophobic organic materials.

Description

This invention relates to new disperse dyes.

According to the invention, there is provided compounds of formula I ##STR3## wherein D is a diazo component radical of the triazolyl, pyrazolyl, cyano(C.sub.1-4 alkyl)-imidazolyl, 4-chlorothiazolyl, 4-chlorothienyl-2,3-phenyl-1,2,4-thiadiazolyl-5, isothiazolyl-5, benzoisothiazolyl-3 or 1,3,4-thiadiazolyl-5 series, the phenyl series wherein the phenyl group is free of sulphonyl groups and may be substituted by up to 3 substituents or the 5-nitrothiazolyl-2 series or a group of formula .alpha., .beta. or .gamma. ##STR4## wherein R.sub.10 is cyano, nitro, (C.sub.1-4 alkoxy)carbonyl, aminocarbonyl(carbamoyl), mono- or di-(C.sub.1-4 alkyl)aminocarbonyl or (C.sub.1-4 alkyl)carbonyl,

R.sub.11 is hydrogen, C.sub.1-4 alkyl, phenyl or (C.sub.1-4 alkyl)carbonyl, R.sub.12 is cyano, formyl, --CH.dbd.N--O(C.sub.1-4 alkyl), nitro, phenylazo, (C.sub.1-4 -alkoxy)carbonyl, mono- or di-(C.sub.1-4 alkyl)aminocarbonyl, aminosulphonyl (sulfamoyl), mono- or di-(C.sub.1-4 alkyl)aminosulphonyl or (C.sub.14 alkyl)carbonyl, R.sub.13 is hydrogen, C.sub.1-4 alkyl, halo or nitro, R.sub.14 is hydrogen, halo, C.sub.1-4 alkoxy, cyano or nitro, and R.sub.15 is hydrogen, C.sub.1-4 alkyl or phenyl; R.sub.15 is (C.sub.1-6 alkylene)-CO--O--R.sub.1a, preferably (C.sub.1-4 alkylene)-CO--O--R.sub.1a, and more preferably CH.sub.2 --CH.sub.2 --CO--O--R.sub.1a ; wherein R.sub.1a is phenyl or phenyl substituted by 1 to 4 substituents each of which is independently halo, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, trifluoromethyl, hydroxy, nitro, formyl, cyano, --SCN, (C.sub.1-4 alkyl)carbonyl, (C.sub.1-4 alkyl)carbonylamino, (C.sub.1-4 alkoxy)carbonyl, (C.sub.1-4 alkyl)carbonyloxy, aminocarbonyl, (C.sub.1-2 alkoxy)(C.sub.2-3 alkoxy)carbonyl or phenyl; R.sub.2 is C.sub.1-6 alkyl, C.sub.2-6 alkenyl, halo(C.sub.2-6 alkenyl), C.sub.3-8 alkynyl, cyano(C.sub.2-6 alkyl), benzyl, phenylethyl, phenylpropyl, hydroxy(C.sub.1-6 alkyl), (C.sub.1-4 alkoxy)C.sub.1-4 alkyl, (C.sub.1-4 alkoxy)carbonyl(C.sub.1-4 alkyl), (C.sub.1-4)carbonyloxy(C.sub.1-6 alkyl) or (C.sub.1-4 alkoxy)carbonyloxy(C.sub.1-4 alkyl) or, when D is a 2,4-dinitrophenyl group, unsubstituted or substituted in the 5- and/or 6-position, or a heterocyclic group, then R.sub.2 may also be hydrogen, R.sub.4 is hydrogen, halo, C.sub.1-4 alkoxy or (C.sub.1-4 alkoxy)C.sub.2-4 alkoxy, or R.sub.2 and R.sub.4 taken together with the nitrogen atom and the carbon atom to which they are respectively attached and the carbon atom connecting the said carbon and nitrogen atoms form a cyclic six-membered group, and R.sub.3 is hydrogen, halo, hydroxy or C.sub.1-4 alkyl or, when D is 2-cyano-4-nitrophenyl, a heterocyclic group or a trisubstituted phenyl group, R.sub.3 may also be formylamino (formamido), (C.sub.1-3 alkyl)carbonylamino, (C.sub.2-3 alkenyl)carbonylamino, (C.sub.1-4 alkoxy)(C.sub.1-4 alkyl)carbonylamino, (C.sub.1-4 alkoxy)carbonylamino or C.sub.1-3 alkylsulphonylamino; with the proviso that when D is 2,5-dichloro-4-nitrophenyl, R.sub.4 is hydrogen, R.sub.1 is --CH.sub.2 CH.sub.2 --COOC.sub.6 H.sub.5 and R.sub.2 is --CH.sub.2 CH.sub.2 CN, then R.sub.3 is not --NH--COCH.sub.3.

When D is a diazo component radical of the thiadiazolyl-5 series, it is preferably of the 3-phenyl-1,2,4-thiadiazolyl-5 series.

Any C.sub.1-4 alkyl group is preferably ethyl or methyl and more preferably is methyl. Any C.sub.1-4 alkoxy group is preferably ethoxy or methoxy and is more preferably methoxy. Each halo is independently fluoro, chloro, bromo or iodo, preferably fluoro, chloro or bromo and most preferably chloro or bromo. Any alkylene radical is linear or branched.

In R.sub.1, the alkylene radical is more preferably A', where A' is --CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 --, ##STR5## and most preferably A' is --CH.sub.2 --CH.sub.2 --.

In R.sub.1a, any (C.sub.1-2 alkoxy)(C.sub.2-3 alkoxy)carbonyl is preferably 2- or 3-(C.sub.1-2 alkoxy)(C.sub.2-3 alkoxy)carbonyl.

Preferably D is Da where Da is a diazo compound of the 4-chlorothiazolyl series, 4-chlorothienyl-2; or 5-nitrothiazolyl-2 series, or a group of formula a) below.

Preferably Da is a diazo component selected from 4-chlorothiazolyl, 4-chlorothienyl-2 or 5-nitrothiazolyl or is a group of formula a) below.

Preferably R.sub.1a is R.sub.1a ' where R.sub.1a ' is phenyl, unsubstituted or substituted by one to four substituents selected from C.sub.1-4 alkyl, C.sub.1-4 alkoxy, (C.sub.1-4 alkoxy)carbonyl, C.sub.1-4 alkylcarbonyl and halogen and up to one phenyl group.

Preferably A' is A.sub.a ', where A.sub.a ' is --(CH.sub.2).sub.2-3

Preferably D is D', where D' is selected from groups (a) to (h) ##STR6## or D' is a diazo component of the 5-nitrothiazolyl series; wherein

R.sub.20 is hydrogen, C.sub.1-4 alkyl, halo, --CO--O(C.sub.1-4 alkyl), cyano or nitro, preferably cyano or nitro, R.sub.21 is halo, C.sub.1-4 alkyl, nitro or phenylazo, preferably nitro, R.sub.22 is hydrogen, halo, cyano or (C.sub.1-4 alkoxy)carbonyl, preferably hydrogen, chloro, bromo or cyano, R.sub.23 is formyl, cyano, --CH.dbd.N--O(C.sub.1-4 alkyl) or --CH.dbd.C(CN)R.sub.25a, wherein R.sub.25a a is cyano or (C.sub.1-4 alkoxy)carbonyl, and R.sub.23a is cyano, nitro or --CO--O(C.sub.1-4 alkyl), R.sub.24 is (.sub.1-4 alkoxy)carbonyl, nitro or cyano, R.sub.26 is cyano(C.sub.1-4 alkyl) or phenyl, R.sub.27 is C.sub.1-4 alkyl or cyano(C.sub.1-4 alkyl), and R.sub.29 is C.sub.1-4 alkyl or phenyl.

In R.sub.21, the phenyl group may be substituted by 1 to 4, preferably not more than 3, substituents each of which is independently C.sub.1-4 alkyl, nitro, halo or C.sub.1-4 alkoxy. D is most preferably D", where D" is 2 cyano-4-nitrophenyl, 2,4-dinitro-6-bromophenyl,,2,6-dichloro-4-nitro phenyl or 2,4-dinitro-6-chlorophenyl.

Preferably, R.sub.1 is R.sub.1 ', where R.sub.1 ' is a group of formula (j) ##STR7## wherein each R.sub.26a is independently hydrogen, fluoro, chloro, (C.sub.1-2 alkoxy)carbonyl, methyl, methoxy or ethoxy,

R.sub.27a is hydrogen, fluoro, chloro, bromo, methyl, methoxy, ethoxy, (C.sub.1-2 alkoxy)carbonyl or phenyl, and R.sub.28 is hydrogen, methyl, methoxy or ethoxy.

Preferably, the phenyl ring of the group of formula (j) contains a maximum of three substituents, more preferably a maximum of two substituents.

Preferably, there are at least two carbon atoms between any oxygen atom in R.sub.2 and the nitrogen atom to which R.sub.2 is attached and no carbon atom of R.sub.2 that is part of a double or triple bond is directly attached to the nitrogen atom to which R.sub.2 is attached. R.sub.2 is more preferably R.sub.2 ', where R.sub.2 ' is methyl, ethyl, allyl, 2-methylallyl, chloroallyl, propynyl, (C.sub.1-2 alkyl)carbonyloxyethyl or (C.sub.1-2 alkoxy)carbonyloxyethyl and most preferably methyl.

R.sub.3 is preferably R.sub.3 ', where R.sub.3 ' is hydrogen, methyl or (C.sub.1-2 alkyl)carbonylamino, and more preferably R.sub.3 ", where R.sub.3 " is hydrogen or methyl.

The C.sub.1-4 alkoxy group of any (C.sub.1-4 alkoxy)(C.sub.2-4 alkoxy) group as R.sub.4 is preferably in other than the 1-position. R.sub.4 is preferably R.sub.4 ', where R.sub.4 ' is hydrogen or C.sub.1-4 alkoxy (preferably methoxy or ethoxy), and most preferably hydrogen.

When R.sub.2 and R.sub.4 are part of a six-membered heterocyclic ring, the ring preferably contains no hetero atom other than the nitrogen atom to which R.sub.2 is attached and is unsubstituted or substituted by 1 to 4, more preferably 1, 2 or 3, substituents each of which is independently C.sub.1-2 alkyl and most preferably methyl.

The preferred compounds of formula I are those wherein D is D', the alkylene radical in R.sub.1 is A', R.sub.1a ' is a phenyl or substituted phenyl group as in formula (j), R.sub.2 is R.sub.2 ', R.sub.3 is R.sub.3 ', and R.sub.4 is R.sub.4 '. Those of this group wherein R.sub.1 is a group of formula (j) are more preferred, with those of this group wherein D is D" being even more preferred. The compounds of formula I wherein D is D', R.sub.1 is a group of formula (j) the phenyl ring of which has not more than three (more preferably not more than two) substituents, R.sub.2 is R.sub.2 ', R.sub.3 is R.sub.3 ", and R.sub.4 is hydrogen are also more preferred, with those of this group wherein D is D" being most preferred.

Especially preferred compounds of formula I are of formulae Ia to Ic ##STR8## wherein n is 0 or 1;

R.sub.50 is C.sub.1-4 alkyl; R.sub.51 is NO.sub.2 or CN; R.sub.52 is halogen (preferably CI or Br) or CN; R.sub.53 is a significance of R.sub.2 other than hydrogen; and R.sub.54 is C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.1-4 alkoxycarbonyl or C.sub.1-4 alkylcarbonyl.

The compounds of formula I can be synthesized by reacting a diazotized amine of formula II

D--NH.sub.2 (II) with one mole of a compound of formula III per mole of the compound of formula II ##STR9## The compounds of formulae II and III are known or can be synthesized from known compounds by known methods.

The compounds of formula I can be incorporated into dyeing preparations by known methods, for example by milling in the presence of a dispersing agent and/or filler. The preparations can then be granulated (optionally under vacuum) by the use of a fluidized bed or by atomizing to form dry preparations. These dry preparations can then be dispersed in a little or a lot of water to form short or long dyebaths for use in exhaust dyeing, padding or printing processes.

The compounds of formula I can be exhausted from an aqueous liquor onto textile materials of natural, semi-synthetic or fully synthetic hydrophobic, high molecular weight organic materials. In particular, the compounds of formula I can be used to dye and print textile materials of linear aromatic polyesters as well as of cellulose 21/2 acetate and cellulose triacetate.

Dyeing, printing and padding can be carried out by known methods, for example as described in French Patent 1,445,371.

The dyeings that result from application of the compounds of formula I have good properties, for example good thermomigration, fastness, good light fastness, good thermofixation, good sublimation and good blistering fastness properties as well as good wet fastness properties, especially using a permanent press machine. The compounds of formula I have good fastness properties, especially thermomigration properties (for example, in the Marks & Spencer's (M&S) C4A 60.degree. C. Test).

The invention will now be illustrated by the following examples in which all temperatures are in .degree.C.

EXAMPLE 1

16.3 parts of 2-amino-5-nitrobenzonitrile are stirred into 100 parts of cold sulfuric acid (93%) and then reacted at 0.degree.-5.degree. C. over 30 minutes with 30 parts nitrosyl sulfuric acid (40%). The mixture is stirred for a further 3 to 4 hours at 0.degree.-5.degree. C. and is poured while stirring well, onto a mixture of 26.9 parts 3-(N-methyl-N-phenylamino)propionic acid 2-methylphenyl ester, 100 parts glacial acetic acid, 2 parts of amidosulfonic acid, 200 parts water and 500 parts ice. The resulting dyestuff is filtered, washed acid-free with water and dried under vacuum at 60.degree. C.

The resulting dyestuff is of formula 1a ##STR10## and has a .lambda..sub.max. of 532 nm. It dyes polyester fiber material a ruby-red tone. The dyeing has excellent fastness properties.

EXAMPLE 2

Example 1 is repeated except that the 26.9 parts of 3-(N-methyl-N-phenylamino)propionic acid 2'-methylphenyl ester is replaced by 29.9 parts 3-(N-ethyl-N-phenylamino)propionic acid 2'-methoxyphenyl ester. The resulting dyestuff of formula 2a ##STR11## has a .lambda..sub.max. =of 535 nm. It dyes polyester fiber material a bluish-ruby red tone. The dye has excellent fastness properties and is particularly useful in the rapid dyeing process.

EXAMPLE 3

20.7 parts of 1-amino-2,6-dichloro-4-nitrobenzene is stirred into 100 parts of sulfuric acid (93%) and reacted at 30.degree. C. over 1 hour with 32 parts nitrosylsulfuric acid (40%). The mixture is stirred for 2-3 hours at 30-32.degree. C. and the resulting diazonium salt solution is added drop-wise to a mixture to 28.5 parts 3-(N-methyI-N-phenylamino)propionic acid 4'-methoxyphenyl ester, 50 parts of glacial acetic acid, 20 parts of water, 300 parts ice and 0.5 parts amidosulfonic acid. The mixture is then slowly diluted with 500 parts water. The resulting dyestuff is filtered, washed acid free with water and dried under vacuum at 60.degree. C.

The resulting dyestuff of formula 3a ##STR12## has a .lambda..sub.max. =439 nm. It dyes polyester fiber material a yellow-brown tone and is particularly useful for rapid dyeing. The resulting dyeings have excellent fastness properties.

EXAMPLE 4

4.1 parts 2-amino-4-chloro-5-formylthiazole are added to 50 parts of 85% phosphoric acid at -10.degree. to -5.degree. C. over 30 minutes and are then reacted with 8 parts nitrosylsulfuric acid (40%). This is stirred for a further 3-4 hours at -5.degree. C. and then the resulting mixture is poured while stirring well into a mixture of 7.9 parts of 3-(N-ethyl-N-3'-methylphenylamino)propionic acid 3"-methoxyphenyl ester, 50 parts glacial acetic acid, 20 parts water and 250 parts ice. This mixture is then stirred for 30 minutes and diluted by the slow addition of 500 parts ice water. The resulting dyestuff is filtered, washed acid-free with water and dried under vacuum.

The resulting dyestuff of formula 4a ##STR13## has a .lambda..sub.max. =586 nm. It dyes polyester fiber material a bluish-violet tone, and the resulting dyeings have good fastness properties. The dye of formula 4a is particularly useful for rapid dyeing.

EXAMPLE 5

14.5 parts of 2-amino-5-nitrothiazole are stirred into a mixture of 75 parts of sulfuric acid (93%), 85 parts of glacial acetic acid and 15 parts of propionic acid. This is then reacted at 0.degree.-2.degree. C. over 30 minutes with 32 parts of nitrosylsulfuric acid (40%). This is stirred for a further 1-2 hours at 0.degree.-2.degree. C. and then is poured while stirring slowly onto a mixture of 28.5 parts of 3-(N-methyI-N-phenylamino)propionic acid 3'-methoxyphenyl ester, 50 parts of glacial acetic acid, 20 parts of water, 300 parts of ice and 0.5 parts of amidosulfonic acid. This mixture is then slowly diluted with about 500 parts of water. The resulting dyestuff is filtered, washed acid-free with water and added under vacuum at 60.degree. C.

The resulting dyestuff is a compound of formula 5a ##STR14## and has a .lambda..sub.max. =584 nm. It dyes polyester fiber material a bluish-violet tone and the resulting dyeings have excellent fastness properties. The dye is particularly useful for rapid dyeing.

EXAMPLE 6

19.6 parts of 1-amino-2-methoxycarbonyl-4-nitrobenzene are dissolved at 60.degree. C. in 70 parts of glacial acetic acid. The resulting solution is poured while stirring well onto a mixture of 150 parts of ice and 30 parts of hydrochloric acid (ca. 30%). To the resulting fine suspension, a solution of 7 parts of sodium nitrite in 100 parts of water is added drop-wise at 0-5.degree. C. over 1 hour. This is then stirred for a further 3 hours at 0-5.degree. C. The resulting solution is then reacted with 0.5 parts amidosulfonic acid and then added drop-wise over 15-20 minutes to a solution of 28.5 parts 3-(N-methyI-N-phenylamino)propionic acid 3'-methoxyphenyl ester in 50 parts of glacial acetic acid. Sodium acetate is added to assist in completing the coupling reaction. The resulting dyestuff is filtered, washed with water and dried under vacuum.

The resulting compound is of formula 6a ##STR15## and has a .lambda..sub.max. =493 nm. It dyes polyester fiber material a scarlet red tone with good fastness properties. The dyestuff is particularly useful for rapid dyeing.

EXAMPLES 7-53

Compounds of the formula ##STR16## in which R.sub.2 and R.sub.29 are given in Table 1 below can be prepared from known compounds by a method analogous to that of Example 1.

TABLE 1__________________________________________________________________________Example Nuance onNumber R.sub.2 R.sub.29 polyester__________________________________________________________________________ 7 C.sub.2 H.sub.5 ##STR17## rubine 8 CH.sub.3 ##STR18## " 9 " ##STR19## "10 " ##STR20## "11 " ##STR21## "12 " ##STR22## "13 " ##STR23## "14 C.sub.2 H.sub.5 " "15 CH.sub.3 ##STR24## "16 " ##STR25## "17 C.sub.2 H.sub.5 ##STR26## "18 CH.sub.3 " "19 C.sub.2 H.sub.5 ##STR27## "20 CH.sub.2 CH.sub.2 OCOOCH.sub.3 ##STR28## red.21 CH.sub.2 CH.sub.2 OCOOC.sub.4 H.sub.9 n " "22 CH.sub.3 ##STR29## rubine23 C.sub.2 H.sub.5 " rubine24 CH.sub.3 ##STR30## "25 " ##STR31## "26 C.sub.2 H.sub.5 ##STR32## "27 " ##STR33## "28 CH.sub.3 ##STR34## "29 " ##STR35## "30 CH.sub.3 ##STR36## "31 C.sub.2 H.sub.5 " "32 " ##STR37## "33 CH.sub.3 " "34 CH.sub.3 ##STR38## "35 C.sub.2 H.sub.5 " "36 CH.sub.3 ##STR39## "37 " ##STR40## "38 " ##STR41## "39 " ##STR42## "40 C.sub.2 H.sub.5 ##STR43## "41 CH.sub.3 ##STR44## rubine42 " ##STR45## "43 " ##STR46## "44 " ##STR47## "45 CH.sub.2 CH.sub.2 OCOOCH.sub.3 ##STR48## red46 CH.sub.3 ##STR49## rubine47 " ##STR50## "48 " ##STR51## "49 C.sub.2 H.sub.5 ##STR52## "50 CH.sub.3 ##STR53## "51 " ##STR54## "52 " ##STR55## "53 " ##STR56## "__________________________________________________________________________

EXAMPLES 54-151

Compounds of the formula ##STR57## in which the symbols are defined in Table 2 can be prepared from known compounds by a method analogous to that of Example 1.

TABLE 2__________________________________________________________________________Ex. Nuance on# DK R.sub.2 R.sub.3 R.sub.4 R.sub.29 polyester__________________________________________________________________________54 ##STR58## ##STR59## NHCOCH.sub.3 OCH.sub.3 2-methoxyphenyl navy blue55 " CH.sub.2 CHCHCl " " " "56 ##STR60## CH.sub.2 CH.sub.3 H H " scarlett57 ##STR61## " H H " violet58 ##STR62## " H H 3-methoxyphenyl "59 ##STR63## " NHCOCH.sub.3 H 2-methoxyphenyl reddish violet60 " CH.sub.3 " H " "61 ##STR64## " H H " yellow brown62 ##STR65## C.sub.2 H.sub.5 H H 3-methoxyphenyl "63 ##STR66## C.sub.4 H.sub.9 n CH.sub.3 H " red64 " C.sub.3 H.sub.7 n " H 2-methoxy-phenyl "65 ##STR67## ##STR68## NHCOCH.sub.3 OC.sub.2 H.sub.4 OCH.sub.3 3-methylphenyl navy blue66 " C.sub.2 H.sub.5 NHCHO " 3-methoxyphenyl "67 ##STR69## CH.sub.3 CH.sub.3 H " bluish violet68 ##STR70## C.sub.2 H.sub.5 " H " reddish blue69 " CH.sub.3 " H 3-methylphenyl "70 ##STR71## C.sub.2 H.sub.5 " H 2-methylphenyl red71 " " " H 2-methoxycarbonyl " phenyl72 ##STR72## " " H C.sub.6 H.sub.5 "73 ##STR73## C.sub.2 H.sub.5 " H 3-methoxyphenyl bluish red74 " CH.sub.3 " H 2-methoxyphenyl "75 ##STR74## " H H 4-acetylphenyl yellow brown76 " C.sub.2 H.sub.5 H H " "77 " CH.sub.2 CH.sub.2 OCOCH.sub.3 H H " "78 ##STR75## CH.sub.3 NHCOCH.sub.3 OCH.sub.3 C.sub.6 H.sub.5 navy blue79 " C.sub.2 H.sub.5 " " " "80 " H.sub.2 CHCH.sub.2 " " " "81 " CH.sub.2 CHCHCl " " " "82 " " " " 3-methoxyphenyl "83 ##STR76## " " " " "84 " C.sub.2 H.sub.5 NHCOC.sub.2 H.sub.5 " 2-methoxyphenyl "85 ##STR77## C.sub.2 H.sub.5 NHCOCH.sub.3 OC.sub.2 H.sub.5 2-methoxyphenyl navy blue86 " CH.sub.3 " " 3-methylphenyl "87 " CH.sub.2 CH.sub.2 OCOCH.sub.3 " " " "88 " " " OCH.sub.3 2-methoxycarbonyl- " phenyl89 " ##STR78## NHCOC.sub.2 H.sub.5 " 4-actylphenyl "90 " C.sub.2 H.sub.5 NHCOCHCH.sub.2 " 4-methylphenyl "91 ##STR79## ##STR80## NHCOCH.sub.3 OC.sub.2 H.sub.5 3-methylphenyl "92 ##STR81## " " " " "93 " C.sub.2 H.sub.5 " " " "94 " CH.sub.3 " " 3-methoxyphenyl "95 " C.sub.2 H.sub.5 " OCH.sub.3 2-methoxyphenyl "96 " CH.sub.2 CHCHCl " OC.sub.2 H.sub.5 " "97 ##STR82## ##STR83## NHCOCH.sub.3 " ##STR84## navy blue98 ##STR85## CH.sub.3 H H 2-fluorophenyl yellow brown99 " " H H 4-methoxycarbonyl- " phenyl100 ##STR86## C.sub.2 H.sub.5 CH.sub.3 H ##STR87## reddish blue101 ##STR88## " H H ##STR89## yellow brown102 " " H H 2-methoxyphenyl "103 " " H H 4-methoxy-phenyl "104 " CH.sub.3 H H 3-methoxy-phenyl "105 " " H H 2-methoxy-phenyl "106 ##STR90## " H H 4-methoxy-phenyl "107 " " H H 3-methoxy-phenyl "108 ##STR91## CH.sub.3 H H 4-methoxyphenyl yellow brown109 ##STR92## " H H " "110 ##STR93## " H H " "111 ##STR94## ##STR95## NHCOCH.sub.3 OC.sub.2 H.sub.5 3-methoxyphenyl navy blue112 " C.sub.2 H.sub.5 " " 2-methoxyphenyl "113 ##STR96## C.sub.2 H.sub.5 H H " reddish blue114 " " CH.sub.3 H C.sub.6 H.sub.5 "115 ##STR97## CH.sub.3 " H 3-methoxyphenyl violet116 " C.sub.2 H.sub.5 " H C.sub.6 H.sub.5 "117 ##STR98## " H H " navy blue118 ##STR99## CH.sub.3 CH.sub.3 H 3-methylphenyl navy blue119 ##STR100## CH.sub.2 CH.sub.2 OCH.sub.3 H H 4-chlorophenyl "120 " " H H 2-methoxyphenyl "121 ##STR101## C.sub.2 H.sub.5 H H " red122 " CH.sub.3 H H C.sub.6 H.sub.5 "123 ##STR102## " H H 2-methoxyphenyl red124 " " CH.sub.3 H C.sub.6 H.sub.5 "125 ##STR103## C.sub.2 H.sub.5 H H " red126 " CH.sub.2 CHCH.sub.2 H H 2-methyl-phenyl "127 ##STR104## C.sub.2 H.sub.5 NHCOCH.sub.3 H 3-methoxyphenyl blue128 ##STR105## " " H C.sub.6 H.sub.5 red129 " " NHCOCH.sub.2 OCH.sub.3 H 2-methoxyphenyl "130 ##STR106## " NHSO.sub.2 CH.sub.3 H ##STR107## red131 " CH(CH.sub.3)CH.sub.2 CH.sub.3 " H 2-fluorophenyl "132 ##STR108## CH.sub.3 NHCOOCH.sub.3 H ##STR109## "133 ##STR110## " NHCOCH.sub.3 OCH.sub.3 C.sub.6 H.sub.5 navy blue134 " ##STR111## " OCH.sub.2 CH.sub.3 2-methoxyphenyl "135 " C.sub.2 H.sub.5 " OCH.sub.3 C.sub.6 H.sub.5 "136 ##STR112## CH.sub.2 CH.sub.2 OH H H " "137 ##STR113## C.sub.2 H.sub.5 Cl H " bluish rubine138 " " NHCOCH.sub.3 H 2-methoxy-phenyl reddish violet139 ##STR114## H " OCH.sub.3 " navy blue140 ##STR115## H " " ##STR116## "141 " " NHCOCH.sub.2 CH.sub.3 OC.sub.2 H.sub.5 C.sub.6 H.sub.5 blue142 ##STR117## CH.sub.3 H H 4-ethoxy-phenyl yellow brown143 ##STR118## " CH.sub.3 H 2-methoxy-phenyl bluish violet144 " CH.sub.3 H H 2-fluoro-phenyl violet145 ##STR119## " H OCH.sub.3 3-nitro-phenyl yellow brown146 " " H H 4-fluoro-phenyl "147 " " H H 2-fluoro-phenyl "148 ##STR120## CH.sub.2 CH.sub.2 OCOCH.sub.3 NHCOCH.sub.3 OCH.sub.3 2-methoxy-phenyl navy blue149 " " " OCH.sub.2 CH.sub.2 C.sub.6 H.sub.5 "150 ##STR121## CH.sub.2 CH.sub.2 OCOOCH.sub.3 " OCH.sub.3 2-methyl-phenyl "151 ##STR122## ##STR123## NHCOCH.sub.2 CH.sub.3 " 3-methoxy-phenyl "__________________________________________________________________________

EXAMPLES 152-182

Compounds of the formula ##STR124## in which the symbols are defined in Table 3 can be made by a method analogous to any one of Examples 1-6 from known compounds.

TABLE 3__________________________________________________________________________ nuanceEx. on .lambda.max .multidot.# D R.sub.2 R.sub.3 R.sub.4 R.sub.100 A polyester nm__________________________________________________________________________152 ##STR125## CH.sub.3 H H H CH.sub.2 CH.sub.2 CH.sub.2 rubine 541153 ##STR126## " H H H " yellow 446wn154 " " H H 3-OCH.sub.3 " " 446155 ##STR127## " H H " " rubine 541156 " " H H " ##STR128## "157 " " H H 2-OCH.sub.3 ##STR129## "158 " " H H 3-CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 "159 ##STR130## C.sub.2 H.sub.5 CH.sub.3 H 2-OCH.sub.3 " blue160 " " " H 3-OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 "161 ##STR131## " " H " " bluish violet162 " " NHCOCH.sub.3 OCH.sub.3 " " blue163 ##STR132## ##STR133## " OC.sub.2 H.sub.5 " " blue164 " CH.sub.2 CHCHCl " OCH.sub.3 " " "165 ##STR134## H NHCOCH.sub.3 OC.sub.2 H.sub.5 4-OCH.sub.3 CH.sub.2 CH.sub.2 blue166 " CH.sub.2 CCH " " " " "167 " " " OCH.sub.3 4-COOC.sub.2 H.sub.5 " "168 " " " " 4-COOCH.sub.3 " "169 ##STR135## " " " " " "170 ##STR136## C.sub.2 H.sub.5 CH.sub.3 H 3-CH.sub.3 " reddish blue171 " " " H 2-OCH.sub.3 " "172 " CH.sub.3 H H 3,4-di-CH.sub.3 " violet173 " C.sub.2 H.sub.5 CH.sub.3 H 3-OCH.sub.3 " reddish blue174 " CH.sub.3 " OCH.sub.3 2-CH.sub.3 " blue175 ##STR137## " H H 3-OCH.sub.3 " violet176 " C.sub.2 H.sub.5 CH.sub.3 H 2-OCH.sub.3 " "177 " H NHCOCH.sub.3 OCH.sub.3 3-CH.sub.3 " "178 " ##STR138## " " " " blue179 " " " OC.sub.2 H.sub.5 4-OCH.sub.3 " "180 " C.sub.2 H.sub.5 CH.sub.3 H 3-CH.sub.3 " violet181 " ##STR139## NHCOCH.sub.3 OCH.sub.3 4-OCH.sub.3 " blue182 " " " " 4-OC.sub.2 H.sub.5 " "__________________________________________________________________________

Examples 183-190

Compounds of the formula ##STR140## in which the symbols are defined in Table 4 below can be prepared from known compounds by a method analogous to any one of Example 1-6.

TABLE 4__________________________________________________________________________ Nuance onEx. # D R.sub.3 R.sub.101 polyester__________________________________________________________________________183 ##STR141## CH.sub.3 3-methoxy-phenyl blue184 " NHCOCH.sub.3 2-methoxy-phenyl "185 " " C.sub.6 H.sub.5 "186 ##STR142## " " "187 " " 2-methoxy- " carbonylphenyl188 " CH.sub.3 2-methoxy-phenyl "189 ##STR143## " " "190 " NHCOCHCH.sub.2 4-fluoro-phenyl "__________________________________________________________________________

EXAMPLE 191

16.3 parts of 2-amino-5-nitrobenzonitrile are stirred into 100 parts of cold sulphuric acid (93%) and are then reacted at 0-5.degree. C. over 30 minutes with 32 parts of nitrosylsulphuric acid (40%). This is stirred for 3 to 4 hours at 0-5.degree. C. and this is then poured into a mxiture of 13.5 parts of 3-(N-methyI-N-phenylamino)propionic acid 2'-methylphenyl ester, 13.5 of 3-(N-methyI-N-phenyl-amino)propionic acid 4'-methylphenyl ester, 100 parts of glacial acetic acid, 2 parts of amidosulphonic acid, 200 parts of water and 500 parts of ice. Coupling is terminated by adding sodium acetate. The resulting dyestuff is filtered, washed with water and vacuum dried at 60.degree. C. The resulting mixture comprises a 1:1 mixture of the compounds of the formulae ##STR144##

This mixture dyes polyester fiber material a rubine-red tone and is particularly suitable for rapid dyeing (for example, in the Foron.RTM. RD process). The dyeings have good fastness properties.

EXAMPLE 192

Example 191 is repeated replacing 13.5 parts of 3-(N-methyI-N-phenyl-amino)propionic acid 2'-methylphenylester with 13.5 parts of 3-(N-methyI-N-phenylamino)propionic acid-3'-methyl-phenyl ester. The resulting precipitate is a 50:50 mix of the compounds of the formulae below ##STR145##

This mixture dyes polyester fiber material a rubine-red tone and is particularly useful in rapid dyeing. The resulting dyeings have good fastness properties.

EXAMPLES 193-575

Compound of the formula ##STR146## in which the symbols are defined in Table 5 below can be made from known compounds by a method analogous to that of Example 1.

__________________________________________________________________________Ex nuance on# DK R.sub.2 R.sub.3 R.sub.4 R.sub.29 polyester__________________________________________________________________________193 ##STR147## ##STR148## NHCOCH.sub.3 OCH.sub.3 ##STR149## navy blue194 " " NHCOC.sub.2 H.sub.5 " 4-methoxy-carbonyl- " phenyl195 " " " OCH.sub.2 CH.sub.3 4-methoxy-carbonyl- " phenyl196 " " NHCOCH.sub.3 " 4-ethoxy-carbonyl- " phenyl197 " " " OCH.sub.3 4-ethoxy-carbonyl- " phenyl198 " " " " 3-methoxy-phenyl "199 " " " OC.sub.2 H.sub.5 " "200 " " NHCOC.sub.2 H.sub.5 " " "201 " " " OCH.sub.3 " "202 " " " " 3-methyl-phenyl "203 " " " OC.sub.2 H.sub.5 " "204 " " NHCOC.sub.2 H.sub.5 " " "205 " " " OCH.sub.3 " "206 " " " OC.sub.2 H.sub.4 CH.sub.3 phenyl "207 " " " OC.sub.2 H.sub.5 " "208 " " NHCOC.sub.2 H.sub.5 " " "209 " " " OC.sub.2 H.sub.5 " "210 " CH.sub.2 CHCH.sub.2 NHCOCH.sub.3 OCH.sub.3 4-methoxycarbonyl- " phenyl211 " " " OC.sub.2 H.sub.5 4-methoxycarbonyl- " phenyl212 " " NHCOC.sub.2 H.sub.5 " 4-methoxycarbonyl- " phenyl213 " " " OCH.sub.3 4-methoxy-carbonyl- " phenyl214 " " " " 4-aethoxy-carbonyl " phenyl215 " " " OC.sub.2 H.sub.5 4-aethoxy-carbonyl- " phenyl216 " " NHCOCH.sub.3 " 4-aethoxy-carbonyl- " phenyl217 " " " OCH.sub.3 4-aethoxy-carbonyl- " phenyl218 " " " " 3-methoxy-phenyl "219 " " " OC.sub.2 H.sub.5 " "220 " " NHCOC.sub.2 H.sub.5 " " "221 " " " OCH.sub.3 " "222 " " " " 3-methyl-phenyl "223 " " " OC.sub.2 H.sub.5 " "224 " " NHCOCH.sub.3 " " "225 " " " OCH.sub.3 " "226 " " NHCOC.sub.2 H.sub.5 " phenyl "227 " " " OC.sub.2 H.sub.5 " "228 " " NHCOCH.sub.3 " " "229 " CH.sub.2 CHCHCl " OCH.sub.3 4-methoxy-carbonyl- " phenyl230 " " " OC.sub.2 H.sub.5 4-methoxy-carbonyl- " phenyl231 " " NHCOC.sub.2 H.sub.5 " 4-methoxy-carbonyl- " phenyl232 " " " OCH.sub.3 4-methoxy-carbonyl- " phenyl233 " " NHCOCH.sub.3 " 4-ethoxy-carbonyl- " phenyl234 " " " OC.sub.2 H.sub.5 4-ethoxy-carbonyl- " phenyl235 " " NHCOC.sub.2 H.sub.5 " 4-ethoxy-carbonyl- " phenyl236 " " " " 4-ethoxy-carbonyl- " phenyl237 " " " " 3-methoxy-phenyl "238 " " " OCH.sub.3 " "239 " " NHCOCH.sub.3 OC.sub.2 H.sub.5 " "240 " " ##STR150## " " "241 " " " OCH.sub.3 " "242 " " " " 3-methyl-phenyl "243 " " " OC.sub.2 H.sub.5 " "244 " " NHCOCH.sub.3 " " "245 " " " OCH.sub.3 " "246 " " NHCOC.sub.2 H.sub.5 " " "247 " " " OC.sub.2 H.sub.5 " "248 " " " " phenyl "249 " " " OCH.sub.3 " "250 " " NHCOCH.sub.3 OC.sub.2 H.sub.5 " "251 " CH.sub.2 CH.sub.2 OCOCH.sub.3 " " 4-methoxy-carbonyl- " phenyl252 " " " OCH.sub.3 4-methoxy-carbonyl- " phenyl253 " " ##STR151## OC.sub.2 H.sub.5 ##STR152## "254 " " NHCOC.sub.2 H.sub.5 " 4-methoxy-carbonyl- " phenyl255 " " " OCH.sub.3 4-methoxy-carbonyl- " phenyl256 " " NHCOCH.sub.3 OC.sub.2 H.sub.4 OCH.sub.3 4-methoxy-carbonyl- " phenyl257 " CH.sub.2 CH.sub.2 OCOCH.sub.3 NHCOCH.sub.3 OCH.sub.3 3-methoxy-phenyl "258 " " " OC.sub.2 H.sub.5 " "259 " " NHCOC.sub.2 H.sub.5 " " "260 " " " " " "261 " " " " 3-methyl-phenyl "262 " " " OCH.sub.3 " "263 " " NHCOCH.sub.3 " " "264 " " " OC.sub.2 H.sub.5 " "265 " " " OC.sub.2 H.sub.4 OCH.sub.3 " "266 " " " " 3-methoxy-phenyl "267 " " " " phenyl "268 " " " OCH.sub.3 " "269 " " " OC.sub.2 H.sub.5 " "270 " " NHCOC.sub.2 H.sub.5 " " "271 " " " OCH.sub.3 " "272 " CH.sub.2 CH(CH.sub.3)OCOCH.sub.3 " " " "273 " " " OC.sub.2 H.sub.5 " "274 " " NHCOCH.sub.3 " " "275 " " " OCH.sub.3 " "276 " " " " 3-methoxy-carbonyl- " phenyl277 " " " OC.sub.2 H.sub.5 3-methoxy-carbonyl- " phenyl278 " " NHCOC.sub.2 H.sub.5 " 3-methoxy-carbonyl- " phenyl279 " " OCH.sub.3 OCH.sub.3 3-methoxy-carbonyl- " phenyl280 " " " " 3-methyl-phenyl "281 " " " OC.sub.2 H.sub.5 " "282 " CH.sub.2 CH(CH.sub.3)OCOCH.sub.3 NHCOCH.sub.3 OCH.sub.3 3-methylphenyl "283 " " " OC.sub.2 H.sub.5 " "284 " " " " 4-methoxycarbonyl- " phenyl285 " " " OCH.sub.3 4-methoxycarbonyl- " phenyl286 " " NHCOC.sub.2 H.sub.5 " 4-methoxycarbonyl- " phenyl287 " " " OC.sub.2 H.sub.5 4-methoxycarbonyl- " phenyl288 " " " " 4-ethoxycarbonyl- " phenyl289 " " " OCH.sub.3 4-ethoxycarbonyl- " phenyl290 " " NHCOCH.sub.3 " 4-ethoxycarbonyl- " phenyl291 " " " OC.sub.2 H.sub.5 4-ethoxycarbonyl- " phenyl292 " CH.sub.2 CH.sub.2 OCOOCH.sub.3 " " 4-ethoxycarbonyl- " phenyl293 " " " OCH.sub.3 4-ethoxycarbonyl- " phenyl294 " " NHCOC.sub.2 H.sub.5 " 4-ethoxycarbonyl- " phenyl295 " " " OC.sub.2 H.sub.5 4-ethoxycarbonyl- " phenyl296 " " " " 4-methoxycarbonyl- " phenyl297 " " " OCH.sub.3 4-methoxycarbonyl- " phenyl298 " " " " 4-methoxycarbonyl- " phenyl299 " " " OC.sub.2 H.sub.5 4-methoxycarbonyl- " phenyl300 " " " " 3-methoxyphenyl "301 " " " OCH.sub.3 " "302 " " NHCOCH.sub.3 " " "303 " " " OC.sub.2 H.sub.5 " "304 " " NHCOOCH.sub.3 " " "305 " " " OCH.sub.3 " "306 " " NHCOCH.sub.3 " 3-methylphenyl "307 " " " OC.sub.2 H.sub.5 " "308 " " NHCOC.sub.2 H.sub.5 " " "309 " " " OCH.sub.3 " "310 " " NHCOOCH.sub.3 " " "311 " CH.sub.2 CH(CH.sub.3)OCOOCH.sub.3 " " " "312 " " NHCOCH.sub.3 " " "313 " " " OC.sub.2 H.sub.5 " "314 " " " " 3-methoxyphenyl "315 " " " OCH.sub.3 " "316 " " NHCOOCH.sub.3 " " "317 " " " " 4-methoxycarbonyl- " phenyl318 " " " OC.sub.2 H.sub.5 4-methoxycarbonyl- " phenyl319 " " NHCOCH.sub.3 " 4-methoxycarbonyl- " phenyl320 " " " OCH.sub.3 4-methoxycarbonyl- " phenyl321 " " " " 4-ethoxycarbonyl- " phenyl322 " " " OC.sub.2 H.sub.5 4-ethoxycarbonyl- " phenyl323 " " " OC.sub.2 H.sub.4 OCH.sub.3 4-ethoxycarbonyl- " phenyl324 " ##STR153## " OCH.sub.3 4-hydroxyphenyl "325 " CH.sub.2 CHCH.sub.2 " " " "326 " CH.sub.2 CHCHCl " " " "327 " CH.sub.2 CHCH.sub.2 NHCOC.sub.2 H.sub.5 " " "328 ##STR154## ##STR155## NHCOCH.sub.3 OCH.sub.3 ##STR156## "329 " " NHCOC.sub.2 H.sub.5 " 4-methoxycarbonyl- " phenyl330 " " " OCH.sub.2 CH.sub.3 4-methoxycarbonyl- " phenyl331 " " NHCOCH.sub.3 " 4-ethoxycarbonyl- " phenyl332 " " " OCH.sub.3 4-ethoxycarbonyl- " phenyl333 " " " " 3-methoxyphenyl "334 " " " OC.sub.2 H.sub.5 " "335 " " NHCOC.sub.2 H.sub.2 " " "336 " " " OCH.sub.3 " "337 " " " " 3-methylphenyl "338 " " " OC.sub.2 H.sub.5 " "339 " " NHCOCH.sub.3 " " "340 " " " OCH.sub.3 " "341 " " " OC.sub.2 H.sub.4.CH.sub.3 phenyl "342 " " " OC.sub.2 H.sub.5 " "343 " " NHCOC.sub.2 H.sub.5 " " "344 " " " " " "345 " CH.sub.2 CHCH.sub.2 NHCOCH.sub.3 OCH.sub.3 4-methoxycarbonyl- navy blue phenyl346 " " " OC.sub.2 H.sub.5 4-methoxycarbonyl- " phenyl347 " " NHCOC.sub.2 H.sub.5 " 4-methoxycarbonyl- " phenyl348 " " " OCH.sub.3 4-methoxycarbonyl- " phenyl349 " " " " 4-ethoxycarbonyl- " phenyl350 " " " OC.sub.2 H.sub.5 4-ethoxycarbonyl- " phenyl351 " " NHCOCH.sub.3 " 4-ethoxycarbonyl- " phenyl352 " " " OCH.sub.3 4-ethoxycarbonyl- " phenyl353 " " " " 3-methoxyphenyl "354 " " " OC.sub.2 H.sub.5 " "355 " " NHCOC.sub.2 H.sub.5 " " "356 " " " OCH.sub.3 " "357 " " " " 3-methylphenyl "358 " " " OC.sub.2 H.sub.5 " "359 " " NHCOCH.sub.3 " " "360 " " " OCH.sub.3 " "361 " " NHCOC.sub.2 H.sub.5 " phenyl "362 " " " OC.sub.2 H.sub.5 " "363 " " NHCOCH.sub.3 " " "364 " CH.sub.2 CHCHCl " OCH.sub.3 4-methoxycarbonyl- " phenyl365 " " " OC.sub.2 H.sub.5 4-methxoycarbonyl- " phenyl366 " " NHCOC.sub.2 H.sub.5 " 4-methoxycarbonyl- " phenyl367 " " " OCH.sub.3 4-methoxycarbonyl- " phenyl368 " CH.sub.2 CHCHCl NHCOCH.sub.3 OCH.sub.3 4-ethoxycarbonyl- " phenyl369 " " " OC.sub.2 H.sub.5 4-ethoxycarbonyl- " phenyl370 " " NHCOC.sub.2 H.sub.5 " 4-ethoxycarbonyl- " phenyl371 " " " OC.sub.2 H.sub.5 4-ethoxycarbonyl- " phenyl372 " " " " 3-methoxyphenyl "373 " " " OCH.sub.3 " "374 " " NHCOCH.sub.3 OC.sub.2 H.sub.5 " "375 " " NHCOOCH.sub.3 " " "376 " " " OCH.sub.3 " "377 " CH.sub.2 CHCHCl " " 3-methylphenyl "378 " " " OC.sub.2 H.sub.5 " "379 " " NHCOCH.sub.3 " " "380 " " " OCH.sub.3 " "381 " " NHCOC.sub.2 H.sub.5 " " "382 " " " OC.sub.2 H.sub.5 " "383 " " " " phenyl "384 " " " OCH.sub.3 " "385 " " NHCOCH.sub.3 OC.sub.2 H.sub.5 " "386 " CH.sub.2 CH.sub.2 OCOCH.sub.3 " " 4-methoxycarbonyl- " phenyl387 " " " OCH.sub.3 4-methoxycarbonyl- " phenyl388 " " NHCOOCH.sub.3 OC.sub.2 H.sub.5 4-methoxycarbonyl- " phenyl389 " " NHCOC.sub.2 H.sub.5 " 4-methoxycarbonyl- " phenyl390 " " " OCH.sub.3 4-methoxycarbonyl- " phenyl391 " " NHCOCH.sub.3 OC.sub.2 H.sub.4 OCH.sub.3 4-methoxycarbonyl- " phenyl392 " " NHCOCH.sub.3 OCH.sub.3 3-methoxyphenyl "393 " " " OC.sub.2 H.sub.5 " "394 " " NHCOCH.sub.3 " " "395 " " " " " "396 " " " " 3-methylphenyl "397 " " " OCH.sub.3 " "398 " " NHCOCH.sub.3 " " "399 " " " OC.sub.2 H.sub.5 " "400 " " " OC.sub.2 H.sub.4 OCH.sub.3 " "401 " " " " 3-methoxyphenyl "402 " " " " phenyl "403 " " " OCH.sub.3 " "404 " " NHCOOCH.sub.3 OC.sub.2 H.sub.5 " "405 " " NHCOC.sub.2 H.sub.5 " " "406 " " " OCH.sub.3 " "407 " CH.sub.2 CH(CH.sub.3)OCOCH.sub.3 " " " "408 " " " OC.sub.2 H.sub.5 " "409 " " NHCOCH.sub.3 " " "410 " " " OCH.sub.3 " "411 " " " " 3-methoxycarbonyl- " phenyl412 " " " OC.sub.2 H.sub.5 3-methoxycarbonyl- " phenyl413 " " NHCOC.sub.2 H.sub.5 " 3-methoxycarbonyl- " phenyl414 " " " OCH.sub.3 3-methoxycarbonyl- " phenyl415 " " " " 3-methylphenyl "416 " " " OC.sub.2 H.sub.5 " "417 " CH.sub.2 CH(CH.sub.3)OCOCH.sub.3 NHCOCH.sub.3 OCH.sub.3 3-methylphenyl "418 " " " OC.sub.2 H.sub.5 " "419 " " " " 4-methoxycarbonyl- " phenyl420 " " " OCH.sub.3 4-methoxycarbonyl- " phenyl421 " " NHCOC.sub.2 H.sub.5 " 4-methoxycarbonyl- " phenyl422 " " " OC.sub.2 H.sub.5 4-methoxycarbonyl- " phenyl423 " " " " 4-ethoxycarbonyl- " phenyl424 " " " OCH.sub.3 4-ethoxycarbonyl- " phenyl425 " " NHCOCH.sub.3 " 4-ethoxycarbonyl- " phenyl426 " " " OC.sub.2 H.sub.5 4-ethoxycarbonyl- " phenyl427 " CH.sub.2 CH.sub.2 OCOOCH.sub.3 " " 4-ethoxycarbonyl- " phenyl428 " " " OCH.sub.3 4-ethoxycarbonyl- " phenyl429 " " NHCOC.sub.2 H.sub.5 " 4-ethoxycarbonyl- " phenyl430 " " " OC.sub.2 H.sub.5 4-ethoxycarbonyl- " phenyl431 " " " " 4-methoxycarbonyl- " phenyl432 " " " OCH.sub.3 4-methoxycarbonyl- " phenyl433 " " " " 4-methoxycarbonyl- " phenyl434 " " " OC.sub.2 H.sub.5 4-methoxycarbonyl- " phenyl435 " " " " 3-methoxyphenyl "436 " " " OCH.sub.3 " "437 " " NHCOCH.sub.3 " " "438 " " " OC.sub.2 H.sub.5 " "439 " " NHCOOCH.sub.3 " " "440 " " " OCH.sub.3 " "441 " CH.sub.2 CH.sub.2 OCOOCH.sub.3 NHCOCH.sub.3 " 3-methylphenyl "442 " " " OC.sub.2 H.sub.5 " "443 " " NHCOC.sub.2 H.sub.5 " " "444 " " " OCH.sub.3 " "445 " " NHCOOCH.sub.3 " " "446 " CH.sub.2 CH(CH.sub.3)OCOOCH.sub.3 " " " "447 " " NHCOCH.sub.3 " " "448 " " " OC.sub.2 H.sub.5 " "449 " " " " 3-methoxyphenyl "450 " " " OCH.sub.3 " "451 " " NHCOOCH.sub.3 " " "452 " " " " 4-methoxycarbonyl- " phenyl453 " " " OC.sub.2 H.sub.5 4-methoxycarbonyl- " phenyl454 " " NHCOCH.sub.3 " 4-methoxycarbonyl- " phenyl455 " " " OCH.sub.3 4-methoxycarbonyl- " phenyl456 " " " " 4-ethoxycarbonyl- " phenyl457 " " " OC.sub.2 H.sub.5 4-ethoxycarbonyl- " phenyl458 " " " OC.sub.2 H.sub.4 OCH.sub.3 4-ethoxycarbonyl- " phenyl459 " ##STR157## " OCH.sub.3 4-hydroxyphenyl "460 " CH.sub.2 CHCH.sub.2 " " " "461 " CH.sub.2 CHCHCl " " " "462 " CH.sub.2 CHCH.sub.2 NHCOC.sub.2 H.sub.5 " " "463 ##STR158## " NHCOCH.sub.3 " 4-oxycarbonyphenyl "464 " " " " 3-methoxyphenyl "465 ##STR159## CH.sub.2 CH.sub.2 NHCOCH.sub.3 H phenyl "466 " " NHCOC.sub.2 H.sub.5 H " "467 " CH(CH.sub.3)CH.sub.3 " H " "468 " " NHCOCH.sub.3 H " "469 " ##STR160## " H " "470 " " NHCOC.sub.2 H.sub.5 H " "471 " CH(CH.sub.3)C.sub.4 H.sub.9 -n NHCOCH.sub.3 H " "472 " " " H 3-methoxyphenyl "473 " CHCH.sub.3 " H " "474 " " NHCOC.sub.2 H.sub.5 H " "475 " CH.sub.2 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 " H " "476 " " NHCOCH.sub.3 H " "477 " " " H 3-methylphenyl "478 " " NHCOC.sub.2 H.sub.5 H " "479 " CH.sub.2 CH.sub.3 " H " "480 " ##STR161## " H " "481 " CH.sub.2 CH.sub.2 CH.sub.3 NHCOCH.sub.3 H " "482 " " " H 3-methoxyphenyl "483 " CH.sub.2 CH.sub.3 " H 4-methoxyphenyl "484 " " " H 4-methoxycarbonyl- " phenyl485 " " NHCOCH.sub.2 CH.sub.3 H 4-methoxycarbonyl- " phenyl486 " ##STR162## NHCOCH.sub.3 H ##STR163## "487 " CH.sub.2 CH.sub.3 " H 4-ethoxycarbonyl- " phenyl488 " " NHCOC.sub.2 H.sub.5 H 4-ethoxycarbonyl- " phenyl489 " CH.sub.2 CHCH.sub.2 NHCOCH.sub.3 H phenyl "490 " " " H 4-methoxycarbonyl- " phenyl491 " " NHCOC.sub.2 H.sub.5 H 4-methoxycarbonyl- " phenyl492 " " " H 3-methoxyphenyl "493 " " NHCOCH.sub.3 H " "494 " " " H 3-methylphenyl "495 " " NHCOC.sub.2 H.sub.5 H " "496 " " NHCOCH.sub.3 H 4-methoxyphenyl "497 " ##STR164## " H 3-methoxyphenyl ##STR165##498 " " " H phenyl bluish violet499 " " NHCOOCH.sub.3 H " bluish violet500 " " NHCOC.sub.2 H.sub.5 H " bluish violet501 " CH.sub.2 CH.sub.2 COOCH.sub.3 NHCOCH.sub.3 H 3-methyoxyphenyl bluish violet502 " " " H 3-methylphenyl bluish violet503 " CH.sub.2 CH.sub.2 COOCH.sub.3 " H " bluish violet504 " " " H 3-methoxyphenyl bluish violet505 " CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3 " H " bluish violet506 " " " H 4-methoxycarbonyl- bluish phenyl violet507 " CH.sub.2 C.sub.6 H.sub.5 " H 4-methoxycarbonyl- bluish phenyl violet508 " " " H 3-methoxyphenyl bluish violet509 " CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 " H " bluish violet510 " " " H phenyl bluish violet511 " " NHCOC.sub.2 H.sub.5 H " bluish violet512 " CH.sub.2 CHCHCl NHCOCH.sub.3 H 4-methoxycarbonyl- bluish phenyl violet513 " " " H 3-methoxyphenyl bluish violet514 " CH.sub.2 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 " H phenyl bluish violet515 " " " H " bluish violet516 " CH.sub.2 CH.sub.3 " H " bluish violet517 " " " H 4-methxoycarbonyl- bluish phenyl violet518 " " NHCOC.sub.2 H.sub.5 H 4-methoxycarbonyl- bluish phenyl violet519 " ##STR166## NHCOCH.sub.3 H ##STR167## ##STR168##520 " " " H 3-methoxyphenyl bluish violet521 " CH.sub.2 CH.sub.3 " H " bluish violet522 " " NHCOOCH.sub.3 H " bluish violet523 " " NHCOCHCH.sub.2 H " bluish violet524 " " " H phenyl bluish violet525 " " " H 4-methoxycarbonyl- bluish phenyl violet526 " " NHCOCH.sub.2 OCH.sub.3 H 4-methoxycarbonyl- bluish phenyl violet527 " " " H phenyl bluish violet528 " " " H 3-methoxyphenyl bluish violet529 " " " H 4-methoxyphenyl bluish violet530 " " " H 4-ethoxyphenyl bluish violet531 " " " H " bluish violet532 " " " H 3-methoxyphenyl bluish violet533 " " " H phenyl bluish violet534 " CH.sub.2 CH.sub.3 NHCOCHCH.sub.2 H " bluish violet535 " " " H 4-methoxycarbonyl- bluish phenyl violet536 " " " H 3-methoxyphenyl bluish violet537 " " " H " bluish violet538 " " NHCOCH.sub.3 H 4-methylphenyl bluish violet539 " " " H 2-methylphenyl bluish violet540 " " " H 2-methoxyphenyl bluish violet541 " ##STR169## " H " ##STR170##542 " CH.sub.2 CHCH.sub.2 " H " bluish violet543 " CH.sub.2 CHCHCl " H " bluish violet544 " " " H 2-methylphenyl bluish violet545 " ##STR171## " H " ##STR172##546 " CH.sub.2 CHCH.sub.2 " H " bluish violet547 " " " H 2-methoxyphenyl bluish violet548 " " ##STR173## H ##STR174## ##STR175##549 " ##STR176## " H ##STR177## ##STR178##550 " " ##STR179## H ##STR180## ##STR181##551 ##STR182## " " H ##STR183## ##STR184##552 ##STR185## CH.sub.3 H H ##STR186## ##STR187##553 ##STR188## CH.sub.3 H H ##STR189## ##STR190##554 ##STR191## CH.sub.3 H H ##STR192## ##STR193##555 ##STR194## ##STR195## NHCOCH.sub.3 H 3-methoxyphenyl ##STR196##556 ##STR197## " " H " ##STR198##557 " ##STR199## NHCOCHCH.sub.2 H ##STR200## ##STR201##558 ##STR202## " NHSO.sub.2 CH.sub.3 H ##STR203## ##STR204##559 ##STR205## ##STR206## " H ##STR207## ##STR208##560 ##STR209## CH.sub.2 CH.sub.3 H H ##STR210## ##STR211##561 ##STR212## CH.sub.2 CH.sub.2 COCH.sub.3 NHCOCH.sub.3 H ##STR213## ##STR214##562 " CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.3 " H 4-methoxycarbonyl- reddish- phenyl violet563 ##STR215## CH.sub.2 CH.sub.3 " H phenyl ##STR216##564 ##STR217## " " H " ##STR218##565 " CHC.sub.4 H.sub.9 " H " blue566 " " " H 3-methoxyphenyl "567 ##STR219## " " H " "568 " CH.sub.2 CH.sub.3 NHCOCH.sub.2 CH.sub.3 H " "569 ##STR220## CH.sub.2 CH.sub.2 OCOCH.sub.3 H H ##STR221## bluish red570 " CH.sub.2 CH.sub.2 OCOCH.sub.2 CH.sub.3 H H 4-methoxycarbonyl- " phenyl571 " CH.sub.2 CH.sub.2 OCOOCH.sub.3 H H 4-methoxycarbonyl- " phenyl572 " CH.sub.2 CH(CH.sub.3)COOCH.sub.3 H H 4-methoxycarbonyl- " phenyl573 " CH.sub.2 CH(CH.sub.3)COOCH.sub.3 H H 4-methoxycarbonyl- " phenyl574 " " H H 4-ethoxycarbonyl- " phenyl575 " ##STR222## H H ##STR223## "__________________________________________________________________________

Application Example

20 parts of the dyestuff of Example 1 in the form of a wet presscake are wet milled with 80 parts of a commercially available dispersing ligninsulphonate dispersing agent and then are dried to a powder.

3.0 parts of the resulting dyeing preparation are added to 2000 parts of demineralized water at 70.degree. C., containing 40 parts of ammonium sulphate to form a dyebath in a dyeing machine. With an 85% aqueous formic acid solution, the pH is brought to 5.

100 parts of a precleaned polyester fiber material is added to the dyebath, the dyeing apparatus is closed, and the bath is heated to 130.degree. C. over 20 minutes. Dyeing is carded out at this temperature for a further 40 minutes. After cooling, the polyester fiber material is removed from the bath, washed, soaped and reductively cleaned with sodium hydrosulphite.

A clear brilliant rubine-red dyeing having good thermomigration, wash fastness, rubbing fastness, light fastness and sublimation fastness properties results.

The Application Example can be repeated using 20 parts of the dyestuff of any one of Examples 2-575 in place of that of Example 1.

Claims

1. A compound of the formula ##STR224## wherein D is ##STR225## wherein R.sub.20 is hydrogen, C.sub.1-4 alkyl, halo, (C.sub.1-4 alkoxy)carbonyl, cyano or nitro,

R.sub.21 is halo, C.sub.1-4 alkyl, nitro, phenylazo or phenylazo the phenyl group of which is substituted by 1 to 4 substituents each of which is independently C.sub.1-4 alkyl, nitro, halo or C.sub.1-4 alkoxy,

R.sub.22 is hydrogen, halo, cyano or (C.sub.1-4 alkoxy)carbonyl,

R.sub.23 is formyl, cyano, --CH.dbd.N--O--C.sub.1-4 alkyl or --CH.dbd.C(CN)R.sub.25a, wherein R.sub.25a is cyano or (C.sub.1-4 alkoxy)carbonyl, and R.sub.24 is (C.sub.1-4 alkoxy)carbonyl, nitro or cyano,

R.sub.1a is phenyl or phenyl substituted by 1 to 4 substituents each of which is independently halo, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, trifluoromethyl, hydroxy, nitro, formyl, cyano, --SCN, (C.sub.1-4 alkyl)carbonyl, (C.sub.1-4 alkyl)carbonylamino, (C.sub.1-4 alkoxy)carbonyl, (C.sub.1-4 alkyl)carbonyloxy, carbamoyl, (C.sub.1-2 alkoxy)(C.sub.2-3 alkoxy)carbonyl or phenyl,

R.sub.2 is hydrogen, C.sub.1-6 alkyl, C.sub.2-6 alkenyl, halo(C.sub.2-6 alkenyl), C.sub.3-8 alkynyl, benzyl, phenylethyl, phenylpropyl, hydroxy(C.sub.1-6 alkyl), (C.sub.1-4 alkoxy)C.sub.1-4 alkyl, (C.sub.1-4 alkoxy)carbonyl(C.sub.1-4 alkyl), (C.sub.1-4 alkyl)carbonyloxy(C.sub.1-4 alkyl) or (C.sub.1-4 alkoxy)carbonyloxy(C.sub.1-4 alkyl), with the proviso that R.sub.2 may be hydrogen only when D is a heterocyclic group, 2,4-dinitrophenyl or 2,4-dinitrophenyl having a substituent in the 6-position, and

R.sub.3 is hydrogen or C.sub.1-4 alkyl,

wherein each halo is independently fluoro, chloro, bromo or iodo.

2. A compound according to claim 1 wherein R.sub.21 is halo, C.sub.1-4 alkyl, nitro or phenylazo.

3. A compound according to claim 2 wherein D is 2-cyano-4-nitrophenyl, 2,4-dinitro-6-bromophenyl, 2,6-dichloro-4-nitrophenyl or 2,4-dinitro-6-chlorophenyl.

4. A compound according to claim 2

wherein

R.sub.1a is ##STR226## wherein each R.sub.26a is independently hydrogen, fluoro, chloro, (C.sub.1-2 alkoxy)carbonyl, methyl, methoxy or ethoxy,

R.sub.27a is hydrogen, fluoro, chloro, bromo, methyl, methoxy, ethoxy, (C.sub.1-2 alkoxy)carbonyl or phenyl, and

R.sub.28 is hydrogen, methyl, methoxy or ethoxy,

R.sub.2 is methyl, ethyl, allyl, 2-methylallyl, chloroallyl, propynyl, (C.sub.1-2 alkyl)carbonyloxyethyl or (C.sub.1-2 alkoxy)carbonyloxyethyl, and

R.sub.3 is hydrogen or methyl.

5. A compound according to claim 4 wherein at least one R.sub.26a, R.sub.27a or R.sub.28 is hydrogen.

6. A compound according to claim 5 wherein at least two of the R.sub.26a 's, R.sub.27a and R.sub.28 are hydrogen.

7. A compound according to claim 6 wherein D is 2-cyano-4-nitrophenyl, 2,4-dinitro-6-bromophenyl, 2,6-dichloro-4-nitrophenyl or 2,4-dinitro-6-chlorophenyl.

8. A compound according to claim 1

wherein

R.sub.1a is ##STR227## wherein each R.sub.26a is independently hydrogen, fluoro, chloro, (C.sub.1-2 alkoxy)carbonyl, methyl, methoxy or ethoxy,

R.sub.27a is hydrogen, fluoro, chloro, bromo, methyl, methoxy, ethoxy, (C.sub.1-2 alkoxy)carbonyl or phenyl, and

R.sub.28 is hydrogen, methyl, methoxy or ethoxy.

9. A compound according to claim 8 wherein at least one R.sub.26a, R.sub.27a or R.sub.28 is hydrogen.

10. A compound according to claim 9 wherein at least two of the R.sub.26a ', R.sub.27a and R.sub.28 are hydrogen.

11. A compound according to claim 1 wherein

R.sub.2 is methyl, ethyl, allyl, 2-methylallyl, chloroallyl, propynyl, (C.sub.1-2 alkyl)carbonyloxyethyl or (C.sub.1-2 alkoxy)carbonyloxyethyl.

12. A compound according to claim 1 wherein R.sub.3 is hydrogen or methyl.

13. A compound according to claim 1 having the formula ##STR228## wherein R.sub.50 is C.sub.1-4 alkyl, and

n is 0 or 1.

14. The compound according to claim 13 having the formula ##STR229##

15. The compound according to claim 13 having the formula ##STR230##

16. A compound according to claim 1 having the formula ##STR231## wherein R.sub.50 is C.sub.1-4 alkyl, and

n is 0 or 1.

17. The compound according to claim 16 having the formula ##STR232##

18. The compound according to claim 13 having the formula ##STR233##

19. A compound according to claim 1 having the formula ##STR234## wherein R.sub.3 is hydrogen or C.sub.1-4 alkyl,

R.sub.51 is nitro or cyano,

R.sub.52 is chloro, bromo or cyano,

R.sub.53 is C.sub.1-6 alkyl, C.sub.2-6 alkenyl, halo(C.sub.2-6 alkenyl), C.sub.3-8 alkynyl, benzyl, phenylethyl, phenylpropyl, hydroxy(C.sub.1-6 alkyl), (C.sub.1-4 alkoxy)C.sub.1-4 alkyl, (C.sub.1-4 alkoxy)carbonyl(C.sub.1-4 alkyl), (C.sub.1-4 alkyl)carbonyloxy(C.sub.1-4 alkyl) or (C.sub.1-4 alkoxy)carbonyloxy(C.sub.1-4 alkyl), and

R.sub.54 is C.sub.1-4 alkyl, C.sub.1-4 alkoxy, (C.sub.1-4 alkoxy)carbonyl or (C.sub.1-4 alkyl)carbonyl.

20. The compound according to claim 1 having the formula ##STR235##

21. A substrate to which a compound according to claim 1 was applied.

22. A substrate according to claim 21 which is a textile material comprising natural, semi-synthetic or fully synthetic hydrophobic, high molecular weight organic material.