GB2104909A - Azo disperse dyes - Google Patents

Abstract

There are disclosed water insoluble azo dyes having the general formula: <IMAGE> wherein D represents a disperse dye diazo component radical, R represents an alkenyl group or an optionally substituted linear or branched chain alkyl group, R<1> represents a substituted or unsubstituted alkyl or aryl group, R<2> represents a hydrogen atom or a substituted or unsubstituted alkyl or aryl group, R<3> represents a cyano, cyanoalkoxy, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, arylaminocarbonyl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl in which the alkyl and aryl groups may be optionally further substituted, or a group of the formula OCOR<4>R<5>, R<4> represents an oxygen or an imino group or a direct link, R<5> represents a substituted or unsubstituted alkyl, cycloalkyl, aryl or heterocyclic group, n represents 0 or 1 and ring A may be further substituted with the proviso that when R<1> represents a methyl group and R<2> represents a hydrogen atom and n = 0, R<3> may not represent an alkoxycarbonyl, cycloalkoxycarbonyl or aryloxycarbonyl group or a group of formula OCOR<4>R<5>. There are also disclosed processes for preparing such dyes and their use in dyeing hydrophobic fibres.

Description

SPECIFICATION Azo disperse dyes The present invention concerns improvements in and relating to azo disperse dyes.

According to the present invention, water insoluble azo dyes are provided having the general formula:

wherein D represents a disperse dye diazo component radical, R represents an alkenyl group or an optionally substituted linear or branched chain alkyl group, R' represents a substituted or unsubstituted alkyl or aryl group, R2 represents a hydrogen atom or a substituted or unsubstituted alkyl or aryl group, R3 represents a cyano, cyanoalkoxy, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, arylaminocarbonyl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl in which the alkyl and aryl groups may be optionally further substituted, or a group of the formula OCOR4R5, R4 represents an oxygen or an imino group or a direct link, R5 represents a substituted or unsubstituted alkyl, cycloalkyl, aryl or heterocyclic group, n represents 0 or 1 and ring A may be further substituted with the proviso that when R1 represents a methyl group and R2 represents a hydrogen atom and n=O, R3 may not represent an alkoxycarbonyl, cycloalkoxycarbonyl or aryloxycarbonyl group or a group of formula OCOR4R5.

The preferred dyes have the formula:

wherein R6 represents an alkenyl group or an optionally substituted alkyl or aralkyl group, R7 represents a hydrogen, chlorine or bromine atom or an alkyl, alkoxy or acylamino group, R8 represents a hydrogen, chlorine or bromine atom or an alkyl or alkoxy group, D, R', R2, R3 and n have the meanings given above and the alkyl, alkenyl, alkoxy and alkylene groups contain 1-4 carbon atoms.

The invention also includes a process for the preparation of dyes of general formula I which comprises coupling one mole of the diazo compound of an amine of general formula: D-NH2 Ill with one mole of a tertiary amine of general formula:

and particularly one mole of a tertiary amine ot general formula:

wherein D, R, R', R2, R3, R6, R7, R8, A and n have the meanings given above.

The amines of general formula IV and V wherein R3 represents a group of formula OCOR4R5 may be prepared for example by reacting one mole of a tertiary amine of general formula:

and particularly one mole of a tertiary amine of general formula:

w@e@e@@ R,R1,R2,R6,R7,R8, n and A have the meanings given above with one or more moles of the appropriate carboxylic acid chloride or anhydride, chloroformate or isocyanate.

Specific examples of amines of general formula Ill which may be used for preparing the diazo compounds are: 4-methylaniline 4-chloroaniline 4-nitroaniline 2-bromo-4-nitroaniline 2-chloro-4-nitroaniline 2-cyano-4-nitroaniline 2-methyl-4-nitroaniline 2-methoxy-4-nitroaniline 2-methylsulphonyl-4-nitroaniline 2-carbomethoxy-4-nitroaniline 2,4-dinitroaniline 2,6-dibromo-4-nitroaniline 2,6-dichloro-4-nitroaniline 2-bromo-6-chloro-4-nitroaniline 2,6-dicyano-4-nitroaniline 2-bromo-6-cyano-4-nitroaniline 2-chloro-6-cyano-4-nitroaniline 6-bromo-2,4-dinitroaniline 6-chloro-2,4-dinitroaniline 6-cyano-2 ,4-dinitroaniline 6-methylsulphonyl-2,4-dinitroaniline 2,4-dibromoaniline 2,5-dichloroaniline 2,4,6-trichloroaniline 2-chloro-4-methylsulphonylaniline 2-cyano-5-chloroaniline 3-chloro-cyanoaniline 2-trifluoromethyl-4-chloroaniline 2,4-dicyanoaniline 2,5-dicyanoaniline 2-aminothiazole 2-amino-5-nitrothiazole 2-amino-5-methylsulphonylthiazole 5-amino-3-phenyl-1 ,2,4-thiadiazole 2-amino-5-methylthio-1 ,3,4-thiadiazole 2-amino-5-ethylthio-1 ,3,4-thiadiazole 2-amino-5-benzylthio-i ,3,4-thiadiazole 2-amino-5-phenylthio-1 ,3,4-thiadiazole 2-amino-5-methyl-l ,3,4-thiadiazole 2-amino-S-ethyl-i ,3,4-thiadiazole 2-amino-5-phenyl-1 ,3,4-thiadiazole 2-amino-5-chloro-1 ,3,4-thiadiazole 2-amino-5-bromo-l ,3,4-thiadiazole 2-amino-5-methylsulphonyl-1 ,3,4-thiadiazole 2-amino-5-ethylsulphonyl-l ,3,4-thiadiazole 2-amino-5-benzylsulphonyl-1 ,3,4-thiadiazole 2-amino-5-phenylsulphonyl-l 3,4-thiadiazole 2-amino-5-trifluoromethyl-1 ,3,4-thiadiazole 2-amino-5-cyano-l ,3,4-thiadiazole 2-amino-3,5-dinitrothiophene 2-a mino-3-nitro-5-acetylthiophene 2-amino-3-nitro-5-benzoylthiophene 3-amino-2, 1 -isobenzthiazole 3-amino-5-nitro-2, 1 -isobenzthiazole 3-amino-5-nitro-7-bromo-2,1 -isobenzthiazole 2-aminobenzthiazole 2-amino-5,6-dichlorobenzthiazole 2-amino-6-methoxybenzthiazole 2-amino-6-nitrobenzthiazole 2-amino-4-methoxy-6-nitrobenzthiazole 2-amino-6-methylsulphonylbenzthiazole 2-a mino-6-thiocyanatobenzthiazole 4-aminoazobenzene 4-amino-2',3-dimethylazobenzene 4'-nitro-4-aminoazobenzene Specific examples of amines of general formula IV which may be used as coupling components are:: N-ethyl-N-(2-cyano-1 -methylethyl)aniline N-n-propyl-N-(2-cyano-1 -methylethyl)aniline N-benzyl-N-(2-cyano-1 -ethylethyl)aniline N-ethyl-N-(2-methylca rbonyl- 1 -methylethyl)aniline N-ethyl-N-(2-ethylaminocarbonyl-1-methyethyl)anillne N-allyl-N-(2-ethylcarbonyl-1 -methylethyl)-3-bromoaniline N-ethyl-N-(2-methylca rbonyl-1 -methylethyl)-3-methylaniline N-(2-phenylethyl)-N-(2-methylcarbonyl-1-methylethyl)-3-methylaniline N-(3-phenylpropyl)-N-(2-ethylca rbonyl-1 -methylethyl)-3-methylaniline N-ethyl-N-(2-methylcarbonyl- 1 -methylethyl)-3-acetylaminoaniline N-ethyl-N-(2-ethylcarbonyl-1 -methylethyl)-3-acetyla minoaniline N-ethyl-N-(2-phenylcarbonyl-1 -phenylethyl)-3-acetylaminoaniline N-ethyl-N-[2-(2,5-dimethoxy-4-chlorophenyl)aminocarbonyl-methylethyl]-3-methylaniline N-ethyl-N-[2-(2,5-dichlorophenyl)aminocarbonyl-1-methylethyl]-3-methylaniline N-ethyl-N-[2-(2-methoxyphenyl)aminocarbonyl-1 -methylethyl]-3-acetylaminoaniline N-allyl-N-[2-(2,5-dimethoxyphenyl)aminocarbonyl-1-methylethyl]-3-acetylaminoaniline N-ethyl-N-[2-(2,5-dichlorophenyl)aminocarbonyl-1-methylethyl]-3-acetylaminoaniline N-ethyl-N-[2-(2-methoxyphenyl)aminocarbonyl-1-methylethyl]-3-acetylaminoaniline N-ethyl-N-(2-methylaminocarbonyl-1-methylethyl)-3-acetylaminoaniline N-ethyl-N-(2-phenylaminocarbonyl-1 -methylethyl)-3-propionylaminoaniline N-ethyl-N-(2-cyclohexylaminocarbonyl-1-methylethyl)-3-propionylaminoaniline N-ethyl-N-(2-ethylaminocarbonyl-1 -methylethyl)-3-acetyla minoaniline N-n-butyl-N-(2-ethylaminocarbonyl-1-methylethyl)-2-methoxy-5-acetylaminoaniline N-allyl-N-(2-ethylaminocarbonyl-1 -methylethyl)-2-ethoxy-5-acetyla minoaniline N-allyl-N-(2-methylca rbonyl-1 -methylethyl)-2-methoxy-5-acetylaminoaniline N-ethyl-N-(2-phenylaminocarbonyl-1 -methylethyl)-2-methoxy-5-acetylaminoaniline N-allyl-N-(2-phenylaminocarbonyl-1 -methylethyl)-2,5-dichloroaniline N-ethyl-N-(2-phenylaminocarbonyl-1-[methoxyethyl]ethyl)-2,5-dichloroaniline N-benzyl-N-(2-cyanoethoxyethyl- 1 -n-propoxyethyl)-3-chloroaniline N-ethyl-N-(2-cya nopropoxyethyl- 1 -methylethyl)-3-methylaniline N-2-cyanoethyl-N-(2-methylcarbonyl-1-methylethyl)aniline N-2-acetoxyethyl-N-(2-methylcarbonyl-1-methylethyl)aniline N-ethyl-N-[2-(2-cyanoethoxy)-1 -methylethyl]aniline N-allyl-N-[2-(2-cyanoethoxy)-1 -methylethyl] aniline N-ethyl-N-[2-(2-cyanoethoxy)- 1 -methyiethyl]-3-methylaniline N-ethyl-N-[2-(2-cyano-1 -methylethoxy)-1 -methylethyl]-3-methylaniline N-ethyl-N-[2-(2-cyanoethoxy)-1 -methylethyl]-3-acetyla minoaniline N-allyl-N-[2-(2-cyanoethoxy)-1 -methylethyl]-3-acetylaminoaniline N-ethyl-N-[2-(2-cya noethoxy)-1 -methylethyl]-2-methoxy-5-acetyla minoa nil ine N-ethyl-N-[2-(2-cyanoethoxy)-1 -methylethyl]-2,5-dichloroaniline N-ethyl-N-(2-methoxycarbonyl-1 -ethylethyl)an iline N-ethyl-N-(2-ethoxycarbonyl-1 -ethylethyl)aniline N-n-propyl-N-(2-ethoxyca rbonyl-1 -ethylethyl)aniline N-ethyl-N-(2-methoxycarbonyl-1 -n-propylethyl)aniline N-ethyl-N-(2-methoxycarbonyl-1-ethylethyl)-3-acetylaminoaniline N-ethyl-N-(2-cyclohexyloxycarbonyl- 1 -ethylethyl)-3-acetyla minoa niline N-ethyl-N-(2-methoxyethoxycarbonyl- 1 -ethylethyl)aniline N-ethyl-N-(2 -ethylaminocarbonyl-1 -ethylethyl)-3-acetylaminoaniline N-ethyl-N-2-(2,5-dimethoxy-4-chlorophenyl)aminocarbonyl-1 -ethyiethyl-3-acetyla minoaniline N-ethyl-N-(2-methoxycarbonyl-1 ,2-di methylethyl)-3-acetyla minoaniline N-ethyl-N-(2-ethoxycarbonyl-1,2-dimethylethyl)-3-methylaniline N-n-butyl-N-(2-phenoxycarbonyl-2-ethyl- 1 -methylethyl)-3-acetyla minoaniline N-ethyl-N-(2-phenylaminocarbonyl-2-n-propyl-l -methylethyl)-3-acetylaminoaniline N-ethyl-N-[2-(2,5-dichlorophenyl)aminocarbonyl-1 ,2-dimethylethyl]-3-acetylaminoaniline N-allyl-N-(2-ethylaminocarbonyl-1 ,2-dimethylethyl)-3-acetylaminoaniline N-ethyl-N-(3-methoxyca rbonyl-1 -methylpropyl -3-methylaniline N-ethyl-N-(3-ethoxyca rbonyl-1 -methylpropyl)-3-acetyla minoa niline N-n-butyl-N-(3-ethylaminocarbonyl-l -methylpropyl)-3-bromoaniline N-ethyl-N-(3-phenylaminocarbonyl-1 -methylpropyl)-3-methylaniline N-ethyl-N-[3-(2,5-dichlorophenyl)aminocarbonYl-1 -methylpropyl]-3-acetylaminoaniline N-ethyl-N-(3-methylcarbonyl-1 -methylpropyl)-aniline N-ethyl-N-(3-methylcarbonyl-1 -methylpropyl)-3-acetylaminoaniline N-ethyl-N-(3-phenylcarbonyl-1 -methylpropyl)-3-propionylaminoaniline Specific examples of tertiary amines of general formula VI and particularly tertiary amines of general formula VII which may be used for preparing the other coupling components of general formula IV and particularly of general formula V in which R3 represents a group of formula OCOR4R5 are: N-ethy-N-(2-hydroxy-1 -ethylethyl)aniline N-ethyl-N-(2-hydroxy-1 -n-propylethyl)aniline N-ethyl-N-(2 -hydroxy- 1 -ethylethyl)-3-acetylaminoaniline N-allyl-N-(3-hydroxy-1 -methylpropyl)-3-bromoaniline N-ethyl-N-(3-hydroxy-1 -methylpropyl)-3-acetylaminoaniline N-ethyl-N-(2-hydroxy-1 ,2-dimethylethyl)-3-acetylaminoaniline Specific examples of carboxylic acid chlorides and anhydrides which may be used for preparing the coupling components of general formula IV and particularly of general formula V wherein R3 represents a group of formula OCOR4R5 are benzoyl chloride, 3-methylbenzoyl chloride, 4 methoxybenzoylchloride, 4-chlorobenzoylchloride, acetic anhydride, propionic anhydride and 2-furoyl chloride. Specific examples of chloroformates which may be used for preparing the coupling components are methylchloroformate, ethyl chloroformate, phenyl chloroform ate and benzyl chloroformate whilst specific examples of isocyanates which may be used for preparing the coupling components are methyl isocyanate, ethyl isocyanate, phenyl isocyanate and cyclohexyl isocyanate.

The coupling components of formula IV and particularly of formula V in which R3 represents a cyano, (cyclo)alkyicarbonyl, arylcarbonyl, (cyclo)alkylaminocarbonyl, arylaminocarbonyl, (cyclo)alkoxycarbonyl or aryloxycarbonyl group may be prepared for example by the condensation of a ketone of the formula:

with an amine of the formula:

and particularly of the formula:

wherein R3 represents a cyano, lcyclo)alkylcarbonyl, arylcarbonyl, (cyclo)alkylaminocarbonyl, arylaminocarbonyl, (cyclo)alkoxycarbonyl or aryloxycarbonyl group, and R', R2, R8, R9, A and n have the meanings given above, followed by reduction of the condensation product and alkylation of the resulting secondary amine.

The coupling components of formula IV and particularly of formula V in which R3 represents a cyanoalkoxy group may be prepared by the condensation of a compound of formula R'COCH(R2)CH2)nOH with the appropriate cyanoalkenyl derivative followed by the condensation of the resulting ketone with an amine of the formula IX and particularly of the formula X wherein R', R2 and n have the meanings given above, followed by reduction of the condensation product and alkylation of the resulting secondary amine.

Specific examples of cyanoalkenyl derivatives which may be used for reacting with the ketones of general formula R'COCH(R2)CH2)nOH are acrylonitrile and crotonitrile.

The compounds of formula VI and VII may be prepared by the condensation of an amine of general formula IX and particularly of formula X with a compound of formula R'CO CH(CH2)nOH R2 followed by reduction of the condensation product and alkylation of the resulting secondary amine.

The invention further includes a process for the colouration (e.g. dyeing and printing) of hydrophobic fibres, in which the dye is an azo dye of general formula I.

Instead of using one dye, a mixture of dyes falling within the scope of general formula I may be used to colour the hydrophobic fibres.

Specific examples of hydrophobic fibres are cellulose acetate fibres such as secondary cellulose acetate and cellulose triacetate, polyamide fibres, polyacrylonitrile fibres such as "COURTELLE" ("COURTELLE" is a Registered Trade Mark), and in particular polyester fibres such as "TERYLENE" ("TERYLENE" is a Registered Trade Mark).

The dyes are preferably dispersed by grinding with water and a suitable dispersing agent e.g.

Dyapol SL. Dyeing may be carried out on cellulose triacetate fibres from an aqueous bath at 95--1000C containing a carrier e.g. an emulsion of diethyl phthalate such as that sold as "Optinol TR". Dyeing may be carried out on polyester fibres from, for example, an aqueous bath at 95--1000C containing a carrier, e.g. an emulsion of 2-phenylphenol such as that sold as "Optinol B" or in pressurised vessels at 125-1 400 C. Alternatively, the dye dispersion may be thickened with sodium alginate or other thickeners commonly used in textile printing and applied to polyester fabrics in the usual way by padding or printing with a roller or through a screen.After drying the fabric, the dye is fixed for example by steaming at 1.0-1.7 bar pressure or by heating the fabric in dry air at 1 6O-2200C for 30-90 seocnds or by heating at 1 70-1 800C for 4-8 minutes with high temperature (superheated) steam.

The dyes may also be applied by dyeing or printing on to secondary cellulose acetate, polyamide and polyacrylonitrile fibres by the typical methods of application to these fibres described in the Colour Index, Third Edition, 1971 (published by the Society of Dyers 8 Colourists, Bradford, England).

In addition some of the dyes may also be applied by transfer printing whereby a paper or foil is printed with the dye contained in a printing ink composition.

The printed paper or foil is then heated in contact with a secondary cellulose acetate, cellulose triacetate, polyamide, polyacrylonitrile or polyester fabric, advantageously under reduced pressure. The colourations so obtained are orange to greenish blue and have good fastness to light, washing, sublimation, rubbing and dry cleaning.

The dyes of the present invention are characterised by their good build-up properties on cellulose triacetate fibres.

Alternatively, the dyes may be dispersed in an organic solvent, for example, chloroethylene, tetrachloroethylene or carbon tetrachloride, and colouration carried out from such a dispersion to the same fibres and under conditions of time and temperature similar to those used for aqueous application.

The colourations so obtained are equivalent in hue and fastness properties to those obtained by aqueous methods of application.

The invention will be more clearly understood by reference to the following examples, in which parts and percentages are by weight.

EXAMPLE 1 6.9 parts of sodium nitrite are added with stirring to 140 parts of 100% sulphuric acid, the temperature being held at 300C by external cooling. The temperature is then raised to 700C before cooling to below 1 50C when a mixture of 57.2parts of acetic acid and 8.9 parts of propionic acid is added dropwise at this temperature. After cooling to 0-50C, 1 6.1 g of 2-amino-5-ethylthio-1 3,4- thiadiazole are added during 30 minutes at 0--50C and the mixture stirred for three hours at this temperature.The diazo solution so obtained is added to a solution of 26.2 parts of N-ethyl-N-(2methylcarbonyl-1 -methylethyl)3-acetylaminoaniline in 40 parts of 100% sulphuric acid and 500 parts of iced water at O"C. The pH of the mixture is adjusted to 3 with sodium hydroxide solution and stirring is continued for one hour. The product which has the formula:

is filtered off, washed and dried.

One part of the dyestuff so obtained and two parts of Dyapol SL are added to 20 parts of water and milled in a ball mill until the average particle size of the dye is reduced to 1--5 Fcm, before dilution to 1 000 parts with water to form a dyebath. 100 parts of polyester yarn are introduced into the dyebath at room temperature and the temperature is then raised to 1 300C and maintained for one hour in a pressurised dyeing machine. After this time the yarn is removed, rinsed and dried. The polyester fibres are dyed bright bluish red shades of very good fastness to light, washing and sublimation.

If 100 parts of cellulose triacetate are added to the dyebath prepared as above at room temperature with the addition of 3 parts of Optinol TR and dyeing is carried out for 1 - hours at 95--1000C the cellulose triacetate fibres are dyed bluish red shades characterised by very good build up properties. The fibres also possess very good fastness to light, washing and sublimation.

The N-ethyl-N-(2-methylcarbonyl-1 -methylethyl)-3-acetylaminoaniline used in Example 1 may be prepared by hydrogenating an equimolar mixture of 3-acetylaminoaniline and acetylacetone in isopropanol in the presence of a 5% palladium on charcoal catalyst and p toluene sulphonic acid followed by ethylation with diethyl sulphate in the presence of an acid binding agent.

EXAMPLE 2 6.9 parts of sodium nitrite are added with stirring to 140 parts of 100% sulphuric acid, the temperature being held at 300C by external cooling. The temperature is then raised to 700C before cooling to 200C when a mixture of 57.2 parts of acetic acid and 8.9 parts of propionic acid is added dropwise. 20.8 parts of 6-cyano-2,4-dinitroaniline are then added during 30 minutes at 20 OC and the mxiture stirred for three hours at this temperature.The diazo solution so obtained is added to a solution of 26.2 parts of N-ethyl-N-(2-methylcarbonyl-1 -methylethyl)-3-acetylaminoaniline in 40 parts of 100% sulphuric acid and 500 parts of iced water at 00 C. The mixture is stirred for one hour when the precipitated dye of formula:

Is tiltered ott, washed acid tree and dried.

One part of the dyestuff so obtained and two parts of Dyapol SL are added to 20 parts of water and milled in a ball mill until the average particle size of the dye is reduced to 1-5 Hm. This is then added to a mixture of 5 parts of a galactomannan thickening agent, such as that sold as "lndalca PA3", and 5 parts of urea in 50 parts of water to form a paste which is then printed through a screen onto polyester fabric. After drying, the print is fixed by steaming for 20 minutes at 1.4 bar pressure. After this time the fabric is removed, washed and dried. The blue print so obtained has very good fastness to light, washig and sublimation.

EXAMPLE 3 1 7.25 parts of 2-chloro-4-nitroaniline are added to a solution of 40 parts of 36.5% hydrochloric acid in 130 parts of water and the mixture is stirred for 2 hours. The temperature is then adjusted to 70C by the addition of ice and 69.0 parts of a 10% solution of sodium nitrite is added. After stirring for 30 minutes at 70C any excess sodium nitrite is destroyed by the addition of sulphamic acid. The mixture is filtered and the filtrate so obtained is added to a solution of 20.5 parts of N-ethyl-N-2methylcarbonyl-1 -methylethylaniline in 20 parts of 100% sulphuric acid and 500 parts of iced water at 00 C. The mixture is stirred for four hours at 00 C when the precipitated dye of formula:

is filtered off, washed acid free and dried.It dyes polyester and cellulose triacetate fibres red shades of very good fastness to light, washing and sublimation.

EXAMPLE 4 If the 26.2 parts of N-ethyl-N-(2-methylcarbonyl- 1 -methylethyl)-3-acetylaminoaniline used in example 1 is replaced by 28.7 parts of N-ethyl-N-[2-(2-cyanoethoxy)-1 -methylethyl]-3- acetylaminoaniline the dye obtained has the formula:

It dyes polyester and cellulose triacetate fibres bright red shades of very good fastness to light, washing and sublimation.

The N-ethyl-N-[2 -(2-cyanoethoxy)-l -methylethyl]-3-acetyla minoaniline used in example 4 may be prepared by condensing hydroxyacetone with acrylonitrile at room temperature in the presence of sodium hydroxide solution, hydrogenating an equimolar mixture of the product and 3acetylaminoaniline in isopropanol in the presence of a 5% palladium on charcoal catlayst and p-toluene sulphonic acid follovved by ethylation with diethyl sulphate in the presence of an acid binding agent.

EXAMPLE 5 21.7 parts of ethyl chloroformate are added with stirring to a solution of 25.0 parts of N-ethyl-N (2-hydroxy-1 -ethylethyl)-3-acetylaminoaniline in 100 parts of pyridine. The mixture is stirred at 1 5-200C until thin layer chromatography shows the reaction to be complete. After cooling the mixture is added slowly to a solution of 100 parts of 100% sulphuric acid in 1000 parts of iced water at OOC.

20.8 parts of 6-cyano-2,4-dinitroaniline are diazotised by the method described in example 2 and added to the coupling component mixture at OOC. The mixture is stirred for one hour when the precipitated dye of formula:

is filtered off, washed acid-free and dried. It dyes polyester and cellulose triacetate fibres blue of good fastness to light, washing and sublimation.

In the following table data are given referring to other monoazo dyes of the present invention corresponding to general formula II, which may be prepared by the general methods described in the previous examples, and which may be used for the dyeing and printing of hydrophobic fibres in accordance with the methods described in the previous examples.

=xample D,NH2 P1 P2 P3 P6 P7 P8 n Shade on Polyester and Cellulose Tri acetate Fibres. 6 4-methyl aniline CH3 H ON C2H5 H H 0 Orange 7 4-chloroaniline CH3 H CN C2H8 H H 0 Orange 8 e O &commat; CH3 H C C ON nC3H7 H H L Orange EII 9 o a, o O 0 0 O o) cn v, CH3 m ON CH2 H cr m m m C 2-bromo-4-nitroaniline OH3 H O O O O O O O O H H 0 O O O 11 2-bromo-4-nitroaniline OH3 H O0NHC2H8 O2H5 H H 0 Scarlet 12 2-chloro-4-nitroaniline OH3 H O0NHO3H8 O2H8 H H 0 Scarlet N O 2-chloro-4-nitroaniline CH3 H OOO2H5 C H2OH=OH2 Br H 0 Scarlet I 2-chloro-4-nitroaniline I I I I COCH3 C2H5 OH3 z Z Z Z Z Z Red 1 5 2-cyano-4-nitroaniline OH3 H COCH3 C2H8 OH3 H 0 Bluish-Ped P\11 16 2-cyano-4-nitroaniline OH3 H COCH3 cH2cH2 OH3 H N Ped z 2-methyl-4-nitroaniline H C0C2H8 CH2CH2CH2 I bo m N Ped r IN IN IN In IN IN N r ON UN ON N N Y ON N N N N 6 N N N N N N 18 2-methoxy-4-nitroaniline OH3 H COCH3 C2H5 3 u o" H 0 Red 19 2-methylsulphonyl-4-nitroaniline o" H COCH3 C2H5 I"IOIOlo N Ped U 2-carbomethoxy-4-nitroaniline OH3 H C2H5 H 0 Ped 21 2,4-dinitroaniline H O O O U O O U O H O I I I I Red 22 2,6-dibromo-4-nitroaniline OH3 H C0NHOH3 C2H8 NHCOCH3 H 0 Bluish Red 23 2,6-dichloro-4-nitroaniline OH3 H CONHOH3 C2H8 NHO0CH3 H I I I Red mc ~ &commat; &commat; c &commat; - C XC X = = t t t t t t st , E O -s 2 E É 2 2 o2 o > c > n c Q c IE O Ic c n Q cJ y O O > E E E w > Q E CD b co oz o c o N 7) I W CN CS N CS

=xample D.NH2 R1 P2 P3 P6 P7 P6 n Shade on Polyester and Cellulose Tri acetate Fibres. 24 2,6-dichloro-4-nitroaniline CH3 H CONH C2H5 NHC0C2H8 H r Bluish Red 25 2-bromo-6-chloro-4-nitroaniline CH3 H C0NH C2H5 o a, H 0 Bluish Red U ~3 3 3 3 U U 3 3 mom m m m m a, m m iZ O 26 2,6-dicyano-4-nitroaniline CH3 H O O O O O C2H8 NHC0CH3 H 0 o o o O o D I 2,6-dicyano-4-nitroaniline I I I I I C2H8 NHCOC2H6 H 0 Blue O I I I O 28 2,6-dicyano-4-nitroaniline CH3 H C0NHC2H5 C2H5 NHC0CH3 H I Blue o" " r" I,IIIII 29 2-bromo-4-nitro-6-cyanoaniline CH3 H C0NHC2H5 C2H5 NHC0CH3 H 0 O r o O 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Z 2-chloro-4-nitro-6-cyanoaniline CH3 H CONHC2H5 Z NHC0CH3 H O ZiL 31 6-bromo-2,4-dinitroaniline CH3 H C0NHC2H5 nC4H9 NHC0CH3 OCH3 0 Blue oo o 32 6-bromo-2,4-dinitroaniline CH3 H CONHC2H5 CH2CH=CH2 NHC0CH3 OC2H5 0 Blue o" 6-bromo-2,4-dinitroaniline CH3 o" COCH3 NHC0CH3 OCH3 0 ON 34 6-chloro-2,4-dinitroaniline CH3 H C2H5 NHC0CH3 W3 I Blue 35 6-cyano-2,4-dinitroaniline CH3 H C2H5 NHC0CH3 H Z Blue Z S"zI o o I SZ Zo o ,Z 36 6-cyano-2,4-dinitroaniline CH3 H ....... C2H5 NHC0CH3 H 0 Blue I 'I I'I I I I I I I 37 CH3 H C0NHCH3 C2H5 NHC0CH3 rl rw I I I I I I I 38 2,4-dibromoaniline CH3 H C0NH CH2CH=CH2 Cl Cl 0 Orange O C .c o c c c O O C C C C C C C 2 2 2 2 2 < 0 ,c, 2 2 2 2 2 > * n - c 2 2 c > 2, < 0 2, ? Q, Q, Q, Q O O Y sP ZD Q E t tD (D rs oD O O ~ - cS 7) t tD ç > ao Xx cs N cS CS CS cS X X or X X tr) o) X X lll

Example D.NH2 P1 P2 P3 P8 P7 P8 n Shade on Polyester and t'C Tri to F D 39 2,5-dichloroaniline C2H4OCH3 H U C3H8 Cl Cl L Orange v, no a, a, I 0 0 0 0 0 O rr rr O m u 40 2,4,6-trichloroaniline C3H4OCH2CH3CH3 O 0C3H4CN O O O Cl H 0 Orange a: 2-chloro-4-methylsulphonylaniline CH3 I OC2H2CN2CN C2H I I I I I I I 42 2-cyano-5-chloroaniline CH3 H CONH C2H8 H H 0 Orange IN r 2-trifluoromethyl-4-chloroaniline CH3 H C0NHC3H7 C2H5 I I N N CH3 H IN IN LN IN H H N N Red O 2,5-dicyanoaniline CH3 H COCH3 C3H8 CH3 H U Ped 47 2-aminothiazole CH3 H 0CHCH2CN C2H5 H H 0 Orange CH3 o o o o o o--u o o o o u u 48 2-amino-5-nitrothiazole I I I I I I C2H8 I I I I I Blue ra Cl 49 2-amino-5-methylsulphonylthiazole CH3 H COHN C2H8 CH3 H 0 Red 00 a F o o 0 q qqq 9 N N &commat; ao .- c eg g c ~ > X > I s c C r N = c ., O O O O =" > O o o D t c > c &verbar; x: n E E E t O O Q ~ S ur X X az Q E a) o sN n ç uz eD N 00 x co ç e < q ç w t ç t t uj

Example D.NH2 P1 P2 P3 P6 P7 P8 n Shade on Polyester and c- O 5 F D (u)j;; c 5-amino-3-phenyl-1 ,2,4-thiadiazole CH3 H COHN C2H5 CH3 H O Ped F O O o O O o 51 2-amino-5-methylthio-1,3,4-thiadiazole CH3 H COHN C2H8 NHC0CH3 H 0 Ped Io Io o o o o o o o o o o o o C: 2-amino-5-ethylthio-1 3,4-thiadiazole CH3 O CONH CH2CH=CH2 NHC0CH3 H Z Ped OCH3 I I CH3O C: 2-amino-5-phenylthio-1 3,4-thiadiazole CH3 H COHN XU NHC0CH3 H 0 Ped Cl 55 2-amino-S-methyl-i 3,4-thiadiazole CH3 H CONH C2H8 NHCOCH3 H 0 Ped 56 CH3 H CONH C2H5 O O O O ap O O a E O 2 a ,E ap o o o o o o o E E E E E E E X X X X X r X [D CS N (9 N c9 N Q E o cs m s S eD x ur ul S Lro uz S LO uJ

Example D.NH2 R1 R2 R3 R6 R7 R8 n Shade on Polyester and CEllulose Triacetate Fibres. 57 2-amino-5-phenyl-1,3,4-thiadiazole CH3 H COC2H5 C2H5 NHCOCH3 H O Red 58 2-amino-5-chloro-1,3,4-thiadiazole CH3 H COCH3 C2H5 NHCOCH3 H O red 59 2-amino-5-bromo-1,3,4-thiadiazole CH3 H COC2H5 C2H5 NHYCOCH3 H O red 60 2-amino-5-methylsulphonyl-1,3,4-thiadiazole CH3 H COC2H5 C2H5 H H O Orange 61 2-amino-5-ethylsulphonyl-1,3,4-thiadiazole CH3 H COC2H5 C2H5 Cl Cl O Orange 62 2-amino-5-benzylsulphonyl-1,3,4-thiadiazole CH3 H COC2H5 C2H5 NHCOCH3 H O Red 63 2-amino-5-phenylsulphonyl-1,3,4-thiadiazole CH3 H COCH3 C2H5 CH3 H O Orange Red 64 2-amino-5-trifluoromethyl-1,3,4-thiadiazole CH3 H COC2H5 C2H5 NHCOCH3 H O Red 65 2-amino-5-cyano-1,3,4-thiadiazole CH3 H COC2H5 C2H5 NHCOCH3 H O Red 66 2-amino-3,5-dinitrothiophene CH3 H COCH3 C2H4CN H H O Blue 67 2-amino-3,5-dinitrothiophene CH3 H COCH3 C2H4OCOOCH3 CH H O Blue 68 2-amino-3-nitro-5-acetylthiophene CH3 H COCH3 C2H4OCOOCH3 CH3 H O Blue 69 2-amino-3-nitro-5-benzoylthiophene CH3 H COCH3 C2H4CN H H O Reddish Blue 70 3-amino-2,1-isobenzthiazole CH3 H COCH3 C2H4OCOCH3 H H O Reddish Blue 71 3-amino-5-nitro-2,1-isobenzthiazole CH3 H COCH3 C2H4OCOCH3 H H O Blue 72 3-amino-5-nitro-7-bromo-2,1-isobenzthiazole CH3 H COCH3 C2H5 H H O Blue

UIC D.NH2 P1 R2 R3 P6 R7 R6 n Shade on Polyester and Cellulose Tri acetate r- r L' r 0 0 0 73 2-aminobenzthiazole O O O O CONH O O O O O O O V) O I 2-amino-5,6-dichlorobenzthiazole CH3 H COCH3 C2H4CN H H 0 75 2-amino-6-methoxybenzthiazole OH3 H COCH3 C2H40C00CH3 H H 0 Red 76 2-amino-6-nitrobenzthiazole CH3 H COCH3 C2H5 Cl Cl 0 Red G 2-amino-4-methoxy-6-nitrosniline I I I C2H5 H I I Red IO 79 2-amino-6-thiocyanatebenzthiazole OH3 9 ON IN m r I H 0 Red o" 4-aminoszobenzene O H COCH3 O2H8 H H o Orange 81 4-aminoazobenzene z rl H ON rl TX T '82 4-amino-2',3dimethylazobenzene CH3 H CONH O2H5 H H 0 Orange 83 4'-nitro-4-aminoazobenzene .... O U O O U U 84 2-bromo-4-nitroaniline O2H5 H COOCH3 O2H8 H H 0 Yellowish Red 85 2-chloro-4-nitroaniline O2H8 H O00O2H8 O2H5 H H 0 Yellowish Red 86 2-cyano-4-nitroaniline C2H5 H O00O2H8 nO3H7 H H 0 Red ~ I I I IX I I I I I X I IN IN IN O U O O O O O O C) T S 5 5 s 2 c P . 2 2 2 c az E Y E E sv nO nO E Y = n X t W , ns w sl t t EF g g ' É g ' g ~ E 2 0 ,w ,w ew T ,w w ,w ,w w X l n y o Q E X X (o N co o . N X ç S en $ b b b b b N b 00 CD OD CD OD CO 00

Dco~ D. NH2 a) P2 P3 P8 P7 P3 n Shade on s5 F n w Cellulose Tri mt-Il 3 87 2-cyano-4-nitroaniline 3 3 m 3 3 H o a, C2H5 m m 5 r r r 88 6-cyano-2,4-dinitroaniline o o o o H COOCH2 C2H5 NHCOCH2 H 0 Blue 89 6-cyano-2,4-dinitroaniline C2H5 H I C2H8 NHCOCH3 H 0 Blue U 2,6-dichloro-4-nitroaniline C2H5 H COOC2H4OCH3 C2H5 H H O Brown oo O 0 0 00 O0 2 t CONHC H C H G 2,6-dicyano-4-nitroaniline C z Z 2 Z 0 Z Z Z Z 0 CH3O IN OCH3 I I I" I" I" I" I" I" I ,1 , 0 N N N N N Nl N N ( ) N N I N 93 2,6-dicyano-4-nitroaniline CH3 ( COOCH3 C2H5 t) C (~) H 0 Blue 94 2,6-dibromo-4-nitroaniline OH2 OH3 COOC2H5 C2H5 OH2 H 0 Brown 95 2-bromo-6-cyano-4-nitroaniline OH2 C2H5 CO0 nC4H8 NHC0CH3 H 0 Reddish Blue 96 2-bromo-6-cyano-4-nitroaniline CH3 CH2CH2OH2 CONH C2H5 g U O 0 Reddish Blue N 2-chloro-6-cyano-4-nitroaniline OH2 CH2 I N C2H5 NHCOCH2 H 0 Reddish Blue I 6-bromo-2,4-dinitroaniline I I CONHO2H5 CH3CH=0H2 I I I O t) H 0 Reddish Blue 2 COOCH2 C H 99 2,5-dichloroaniline CH H 2 5 OH3 H 1 Reddish Orange I . U I N Ir) I a) O ao oC .-C C ,c ,c ,c ,c C C ,C O O O .C t (N sN o C E ED eD s É O U O CO (D CO (D (D D S O r' LD CL E > OD CD o cs n t S eD rs co n X oo co X cn ar n 01 ar O uJ

Example D.NH2 P1 P2 P2 P6 P7 P8 n Shade on Polyester and Cellulose Tri acetate Fibres. 100 2-trifluoromethyl-4-chloroaniline OH2 H COOC2H5 02H5 NHCOCH2 H 1 Red o 2-trifluoromethyl-4-chloroaniline OH2 o CONHC2H5 C2H5 Br H s Yellowish Red a, o = = m 3 o e, 102 2-chloro-4-methylsulphonyaniline r r H CONH C2H5 O H 1 M m Ir G I 103 2,5-dicyanoaniline OH2 H COHN C2H5 NHCOCH2 H 1 Red u o o o" Z 2,4-dibromoaniline OH2 H COCH2 C2H5 I H 1 Orange 105 2-trifluoromethyl-4-nitroaniline OH2 H COCH2 C2H5 4n H 1 Red 1 N 2-truoromethyl-4-nitroaniline OH H CO N H 2 2 5 NHCOC2H8 H 1 Red " 2-amino-5-nitrothiazole T t OCOCH2 C2H5 H H C Blue 108 2-amino-5-nitrothiazole 02H5 H 000 C2H5 H H 0 Blue 109 2-cyano-4-nitroaniline n03H7 H ooo C2H5 H H 0 Red OH3 O O O O O O O U O c O &commat; Oc c C O O C C w ,~ w X > c C e 9 , e " ~ o cs o b oo E o o o o o o O o O O r r r r

Example D.NH3 P1 P2 R3 R8 P7 P8 n Shade on Polyester and Cellulose Tri 10 F 0 G G Q 2-cyano-4-nitroaniline en H OCOQCI C2H5 s v, a v, '5 111 6-cyano-2 4-dinitroaniline W G m m H S NHC0OH3 H 0 Blue 112 6-cyano-2,4-dinitroaniline O O O O H OCOOCH3 C2H5 NHC0CH3 r - Blue 113 C2H8 n 0C00C3H8 C2H8 rz Blue U000 00 0 0000 00 0 UUUO 00 0 I 2,6-dicyano-4-nitroaniline Z Z Z Z Z ocoo 02H5 NHCOOH2 m Z Blue 11 5 2 ,6-dicyano-4-nitroaniline N H 0COOCH2 C2H5 NHC0CH2 H N Blue 11 6 2,6-dicyano-4-nitroaniline OH3 H OCONHCH3 C2H8 NHC0CH3 H 1 Blue 11 7 2-chloro-4-nitroaniline OH3 H OC0NHC2H5 CH3CH=CH3 Br H 1 Yellowish Red o 8 2-chloro-4-nitroaniline OH3 H OCONH CH3CH=CH3 Br o ò u o Uo o o , , o o o U , U 8 8 00 0 G I 2-bromo-4-nitroaniline I I OCONH C2H8 I I I I O Red I zm ~ r I N C c C c c c c: 2 r rc r j C 2 2 2 t Cq X (n t t t y y y y ( D y y n N tD a7 ~ o CS CN W N ) E exu us

Claims (16)

1. A water insoluble azo dye having the general formula:

wherein D represents a disperse dye diazo component radical, R represents an alkenyl group or an-optionally substituted linear or branched chain alkyl group, R1 represents a substituted or unsubstituted alkyl or aryl group, R2 represents a hydrogen atom or a substituted or unsubstituted alkyl or aryl group, R3 represents a cyano, cyanoalkoxy, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, a Ikylaminocarbonyl, cycloalkylaminocarbonyl, arylaminocarbonyl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl in which the alkyl and aryl groups may be optionally further substituted, or a group of the formula OCOR4R5, R4 represents an oxygen or an imino group or a direct link, R5 represents a substituted or unsubstituted alkyl, cycloalkyl, aryl or heterocyclic group.

n represents 0 or 1 and ring A may be further substituted with the proviso that when R1 represents a methyl group and R2 represents a hydrogen atom and n=O, R3 may not represent an alkoxycarbonyl, cycloalkoxycarbonyl or aryloxycarbonyl group or a group of formula OCOR4R5.

2. A dye as claimed in claim 1, having the formula:

wherein R6 represents an alkenyl group or an optionally substituted alkyl or aralkyl group, R7 represents a hydrogen, chlorine or bromine atom or an alkyl, alkoxy or acylamino group, R3 represents a hydrogen, chlorine or bromine atom or an alkyl or alkoxy group, and D, R1, R2, R3 and n have the meanings given in claim 1 and the alkyl, alkenyl, alkoxy and alkylene groups contain 1-4 carbon atoms.

3. A water insoluble dye as claimed in claim 1, substantially as hereinbefore described in any one of the foregoing examples.

4. A process for the preparation of a dye of general formula I as defined in claim 1, which comprises coupling one mole of-the diazo compound of an amine of general formula: D-NH2 Ill wherein D has the meaning given in claim 1, with one mole of a tertiary amine of general formula:

wherein R, R1, R2, R3 and A have the meanings given in claim 1.

5. A process as claimed in claim 4, in which the tertiary amine is

wherein R1, R2, R3, R6, R7, R3 and n have the meanings given in claim 2.

6. A process for the preparation of a dye of the general formula I as defined in claim 1, substantially as hereinbefore described in any one of the foregoing examples.

7. A process for the colouration of hydrophobic fibres, in which the dye is an azo dye of general formula I as claimed in any one of claims 1 to 3, or a mixture of such dyes.

8. A process as claimed in claim 7, in which the hydrophobic fibres are cellulose acetate fibres, polyamide fibres, polyacrylonitrile fibres, or polyester fibres.

9. A process as claimed in claim 7 or 8, in which the dye is dispersed by grinding with water and a dispersing agent.

10. A process as claimed in any one of claims 7 to 9 in which dyeing is carried out on cellulose triacetate fibres from an aqueous bath at 95--1000C containing a carrier.

11. A process as claimed in any one of claims 7 to 9 in which dyeing is carried out on polyester fibres from an aqueous bath at 95100 C containing a carrier, or in a pressurised vessel at 12S14O0O.

12. A process as claimed in claim 7 or 8, in which a dispersion of the dye is thickened with a thickener and applied to a polyester fabric by padding or printing with a roller or through a screen, the fabric is dried and the dye is fixed.

13. A process as claimed in claim 7 or 8, in which the dye is applied by transfer printing whereby a paper or foil is printed with the dye contained in a printing ink composition, the printed paper or foil is then heated in contact with a secondary cellulose acetate, cellulose triacetate, polyamide, polyacrylonitrile or polyester fabric.

14. A process as claimed in claim 7 or 8, in which the dye is dispersed in an organic solvent.

1 5. A process for the colouration of hydrophobic fibres substantially as hereinbefore described in any one of the foregoing examples.

16. Hydrophobic fibres whenever coloured by a process as claimed in any one of claims 7 to 1 5.