GB1561241A

GB1561241A - Monoazo disperse dyes

Info

Publication number: GB1561241A
Application number: GB1056177A
Authority: GB
Original assignee: Yorkshire Chemicals Ltd
Current assignee: Yorkshire Chemicals Ltd
Priority date: 1978-02-24
Filing date: 1978-02-24
Publication date: 1980-02-13

Description

(54) MONOAZO DISPERSE DYES (71) We, YORKSHIRE CHEMICALS LIMITED, a British company of Black Bull Street, Leeds, LS10 1HP, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention concerns improvements in and relating to monoazo disperse dyes, and to methods for their preparation and use.

Monoazo disperse dyes are known which have good affinity for hydrophobic fibres and which are fast to light and wet treatments and which possess excellent fastness to sublimation and thermofixation.

The dyestuffs of the present invention, which are modifications of U.K. patent Specification 1,159, 355, not only possess excellent fastness to light and wet treatments and excellent fastness to sublimation and thermofixation on hydrophobic fibres, but also possess unexpectedly good affinity for cellulose acetate fibres.

According to the present invention therefore, water-insoluble monoazo dyes are provided having the general formula:

wherein D represents a radical of the benzene, benzthiazole, benzisothiazole, thiadiazole or thiophene series, X represents a hydrogen or a halogen atom, and alkyl or alkoxy group or a group of formula - NHCOR1 or NHSO2Rt, wherein Rl represents an alkyl or phenyl group, Y represents a hydrogen or halogen atom or an alkyl or alkoxy group, A1 and A2 each independently represent alkylene groups, A3 represents an alkyl group, and R represents an alkyl group which may be substituted by a cyano, alkoxy, phenyl or alkoxycarbonyl group or by a group of formula::

where A2 and A3 are as described above, with the proviso that when D represents a radical of the benzthiazole series the group R does not represent an alkyl group substituted by a group of formula:-

The preferred dyes are those in which the alkyl, alkylene and alkoxy groups represented by the above formulae contain 1-4 carbon atoms.

The invention also includes a process for the preparation of dyes of general formula I which comprises coupling 1 mole of the diazo compound of an aromatic amine of general formula: D - NH2 II with 1 mole of tertiary amine of general formula:-

wherein D, X, Y, R, Al, A2 and A3 have the aforementioned meanings, or alternatively with one mole of tertiary amine of general formula:-

wherein R2 represents an alkyl group which may be substituted by a hydroxyl, cyano, alkoxy, phenyl or alkoxycarbonyl group and X, Y and Al have the aforementioned meanings, followed by esterification of 1 mole of the resulting dye of general formula:-

with one or more moles of a chloroformate.

The tertiary amines of general formula III may be prepared for example by esterifying 1 mole of a tertiary amine of general formula IV with one or more moles of the appropriate chloroformate in the presence of an acid binding agent.

Specific examples of amines of general formula II are:2-nitroaniline 4-nitroaniline 4-chloroaniline 4-cyanoaniline 4-carboethoxyaniline 2-bromo-4-nitroaniline 2,5-dichloroaniline 2-chloro-4-nitroaniline 2-chloro-4-methylsulphonylaniline 2-chloro-4-cyano am line 3-chloro-4-cyanoaniline 2 ,4-dicyanoaniline 2-cyano-4-nitroaniline 2-cyano-5-chloroaniline 2-carbomethoxy-4-nitroaniline 2-methylsulphonyl-4-nitroaniline 2-methoxy-4-nitroaniline 2,4-dinitmaniline 2-trifluoromethyl-4-chloroaniline 2 ,6-dibromo-4-nitroaniline 2-bromo-6-chloro-4-nitroaniline 2-bromo-6-cyano-4-nitroaniline 2-bromo-4 ,6-dinitroaniline 2-chloro-4-nitro-6-cyanoaniline 2,6 dichloro-4-nitroaniline 2-chloro-4,6-dinitroaniline 2,4,6-trichloroaniline 2,5-dichloro-4-dimethylsulphonamidoaniline 2 ,6-dicyano-4-nitroaniline 2-cyano-4,6 dinitroaniline 2-aminobenzthiazole 2-amino-6-chlorobenzthiazole 2-amino-5 ,6-dichlorobenzthiazole 2-amino-6-methylsulphonylbenzthiazole 2-amino-6-methoxybenzthiazole 2-amino-6-nitrobenzthiazole 2-amino-6-thiocyanatobenzthiazole 2-amino-4,6-dinitrobenzthiazole 3-amino-5-nitro-2, 1-benzisothiazole 3-amino-5-nitro-7-bromo-2,1-benzisothiazole 3-amino-5-bromo-7-nitro-2,1-benzisothiazole 5-amino-3-methylmercapto-1,2,4-thiadiazole 5-amino-3-phenyl-1,2,4-thiadiazole 5-amino-2-nitro-1,3,4-thiadiazole 2-amino-3-carbomethoxy-5-nitrothiophene 2-amino-3-nitro-5-methylsulphonylthiophene 2-amino-3,5-dinitrothiophene 2-amino-3-nitro-5-acetylthiophene 2-amino-3-nitro-5-benzoylthiophene Specific examples of tertiary amines of general formula IV which may be used for preparing coupling components of general formula III are:: N ,N - di(ss-hydroxyethyl)aniline N,N - di-(ss-hydroxyethyl)-3-acetylaminoaniline N,N-di-(ss-hydroxyethyl)-3-methylaniline N,N-di-(ss-hydroxyethyl)-3-chloroaniline N,N-di-(ss-hydroxyethyl)-3-acetylamino-6-methoxyaniline N ,N-di-(ss-hydroxyethyl)-3-acetylamine-6-ethoxyaniline N,N-di- y-hydroxypropyl)-3-methylaniline N-(P-hydroxyethyl)-N-methylaniline N-(ss-hydroxyethyl)-N-ethylaniline N-(ss-hydroxyethyl)-n-(n-butyl)aniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)aniline N-(ss-hydroxyethyl)-N-(γ-cyanopropyl)aniline N-(ss-hydroxyethyl)-N-(ss-methoxyethyl)aniline N-(ss-hydroxyethyl)-N-(benzyl)aniline N(ss-hydroxyethyl)-N-(γ;-phenylpropyl)aniline N-(ss-hydroxyethyl)-N-(ss-methoxycarbonylethyl)aniline N-(ss-hydroxyethyl)-N-methyl-3-methylaniline N-(ss-hydroxyethyl)-N-ethyl-3-methylaniline N- (P-hydroxyethyl) -N-ethyl3 -acetylaminoaniline N-(ss-hydroxyethyl)-N-(ethyl)-3-propionylaminoaniline N-(ss-hydroxyethyl)-N-(ethyl)-3-benzoylaminoaniline N-(ss-hydroxyethyl)-N-(ethyl)-3-methylsulphonylaminoaniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)-3-methylaniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)-3-chloroaniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)-3-acetylaminoaniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)-3-propionylaminoaniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)-3-ethylsulphonylaminoaniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)-3-n-butylsulphonylaminoaniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)-3-benzoylaminoaniline N-((3-hydrnxyethyl)-N- P-cyanoethyl)-3-phenylsulphonylaminoaniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)-3-bromoaniline N-(ss-hydroxyethyl)-N-(γ-cyanopropyl)-3-acetylaminoaniline N-(ss-hydroxyethyl)-N-(ss-methoxyethyl)-3-methylaniline N-(ss-hydroxyethyl)-N-(ss-methoxyethyl)-3-acetylaminoaniline N-(ss-hydroxyethyl)-N-(benzyl)-3-methylaniline N-(ss-hydroxyethyl)-N-(benzyl)-3-acethylaminoaniline N-(ss-hydroxyethyl)-N-(γ;-phenylpropyl)-3-methylaniline N-(ss-hydroxyethyl)-N-(ss-methoxycarbonylethyl)-3-acetylaminoaniline N-(ss-hydroxyethyl)-N-(ss-ethoxycarbonylethyl)-3-methylaniline N-(ss-hydroxyethyl)-N-(methyl)-3-acetylamino-6-methoxyaniline N-(ss-hydroxyethyl)-N-(ethyl)-3-methyl-6-methoxyaniline N-(ss-hydroxyethyl)-N-(ethyl)-3-acetylamino-6-methoxyaniline N-(ss-hydroxyethyl)-N-(ethyl)-3-acetylamino-6-ethoxyaniline N-(ss-hydroxyethyl)-N-(ethyl)-3-acetylamino-6-n-butoxyaniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)-3-acetylamino-6-methoxyaniline N-(ss-hydroxyethyl)-N-(ss-cyanoethyl)-3-propionylamino-6-methoxyaniline N-(ss-hydroxyethyl)-N-(ss-methoxyethyl)-3-methyl-6-methoxyaniline N-(ss-hydroxyethyl)-N-(benzyl)-3-acetylamino-6-methoxyaniline N-(ss-hydroxyethyl)-N-(ss-methoxycarbonylethyl)-3,6-dimethylaniline N-(ss-hydroxyethyl)-N-(ss-ethoxycarbonylethyl)-3-acetylamino-6-methoxyaniline N-(ss-hydroxyethyl)-N-(ss-butoxycarbonylethyl)-3-acetylamino-6-methoxyaniline Specific examples of chloroformates which may be used for preparing the coupling components are:methoxymethyl chloroformate ethoxymethyl chloroformate 2-methoxyethyl chloroformate 2-ethoxyethyl chloroformate 2-(n-propoxy)ethyl chloroformate 2-(iso-propoxy)ethyl chloroformate 2-(n-butoxy)ethyl chloroformate 2-(iso-butoxy)ethyl chloroformate 2-(tert-butoxy)ethyl chloroformate 3-methoxypropyl chloroformate 2-(sec-butoxy)ethyl chloroformate 3-ethoxypropyl chloroformate 4-methoxybutyl chloroformate The invention further includes a process for the dyeing or printing of hydrophobic fibres, in which the dye is an azo dye of general formula (I).

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

The dyes are preferably dispersed by grinding with water and a suitable dispersing agent e.g. a formaldehyde/cresolsulphonic acid condensation product such as that sold as "Dyapol PT". Dyeing may be carried out on polyester fibres from, for example, an aqueous bath at 95-100 C. containing a carrier eg. an emulsion of 2-phenylphenol such as that sold as "Optinol B", or in pressurised vessels at 125-140 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 by printing with a roller or through a screen. After drying the fabric, the dye is fixed for example by steaming at 15-251b. per sq.in. or by heating the fabric at 160-220 C for 30-90 seconds. The dyes may also be applied by dyeing or printing on to secondary cellulose acetate, cellulose triacetate, 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 and Colourists, Bradford, England). In addition 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, advantageous ly under reduced pressure. The colourations so obtained are orange to blue in shade and have good fastness to light, washing, sublimation, rubbing, dry cleaning and gas fumes.

Alternatively, the dyes may be dispersed in an organic solvent, for example, trichloroethylene, 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 equivaient 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 I 17.25 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 7"C by the addition of ice and 69.0 parts of a 10% solution of sodium nitrite is added. After stirring for 30 minutes at 7"C 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 34.9 parts of N-(ss-cyanoethyl)-N-[ss-(ss1- ethoxyethoxycarbonyloxy)ethyl]-3-acetylaminoaniline in 20 parts of 100% sulphuric and 500 parts of iced water at 0 C. The mixture is stirred for four hours at OOC when the suspension is neutralised to pH 6-7 at OOC with the appropriate quantities of ice-cold dilute sodium hydroxide solution.The precipitated dye of formula:-

is filtered off, washed acid free and dried.

One part of the dyestuff so obtained and two parts of a formaldehyde/cresol sulphonic acid condensation product, such as that sold as "Dyapol PT" are added to 20 parts of water and milled in a ball mill until the average particle size of the dye is reduced to 1-51l, before dilution to 1000 parts with water to form a dyebath. 100 parts of polyester yarn are introduced into this dyebath at room temperature, and the temperature is raised to 1300C 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 red shades of very good fastness to light, washing, sublimation and thermofixation.

Alternatively, one part of the above dyestuff may be milled as previously described, followed by dilution to 5,000 parts with water to form a dyebath. The dyebath temperature is then raised to 60"C and 100 parts of cellulose secondary acetate cloth are introduced. The temperature is increased to 85"C over 30 minutes and maintained at 80-850C for 1 hour.

After this time the cloth is removed, rinsed with water and dried. The cellulose secondary acetate cloth is dyed a red shade of very good fastness to light and washing.

Preparation 1.

The N-(-cyanoethyl)-N- [t3-I3 , -methoxyethoxycarbonyloxy)ethyl]-3-acetylaminoaniline used in example 1 may be prepared as follows: N-(ss-cyanoethyl)-N-(ss-hydroxyethyl)-3-acetylaminoaniline is prepared in a known manner by the reaction of 3-acetylaminoaniline and acrylonitrile in the presence of a catalyst such as hydrochloric acid or acetic acid followed by further condensation with ethylene oxide.

24.7 parts of the N-(P-cyanoethyl)-N- (P-hydroxyethyl)3 -acetylaminoaniline so obtained are dissolved in 100 parts of pyridine. To this mixture are added dropwise 15-25 parts of 2-methoxyethyl chloroformate at a temperature of 15-20"C. The mixture is then stirred at a temperature of 15-20"C for 8 hours. The product is isolated by pouring the mixture into 1000 parts iced water, followed by neutralisation to pH 5-6 by the dropwise addition of dilute hydrochloric acid. The resulting oil is separated, washed with cold water and dried over anhydrous sodium sulphate. The product is sufficiently pure for use in the preparation of the dyestuff in example 1.

Example 2.

6.9 parts of sodium nitrite are added with stirring to 140 parts of 100% sulphuric acid, the temperature being held at 30"C by external cooling. The temperature is raised to 70"C before cooling to 20"C. 21.75 parts of 2-chloro-4,6-dinitroaniline are then added during 30 minutes at 20"C and the mixture stirred for 3 hours at this temperature. The diazo solution so obtained is added to a solution of 39.3 parts of N-(3-cyanoethyl-N-[P-('- ethoxyethoxycarbonyloxy)ethylj-3-acetylamino-6-methoxyaniline in 40 parts of 100% sulphuric acid and 500 parts of iced water at OOC. The mixture is stirred for one hour when the suspension is neutralised to pH 6-7 at OOC with the appropriate quantities of ice cold dilute sodium hydroxide solution.

The precipitated dye of formula:

is filtered off, washed acid free and dried.

One part of the dyestuff so obtained and two parts of a formaldehyde/cresolsulphonic acid condensation product, such as that sold as "Dyapol PT" 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,u. This is then added to a mixture of 5 parts of a galactomannan thickening agent such as that sold as "Indalca - PA3" (Indalca is a registered Trade Mark), 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 20 p.s.i. After this time the fabric is removed, washed and dried. The bright reddish-blue print so obtained has very good fastness to light, washing, sublimation and thermofixation.

Alternatively, one part of the above dyestuff may be milled and a printing paste prepared as previously described, followed by printing through a screen onto cellulose secondary acetate cloth. After drying, the print is fixed by steaming for 30 minutes at 3 p.s.i. The bright reddish-blue print so obtained has very good fastness to light and washing.

Preparation 2.

The N-(P-cyanoethyl)-N- [ss ssl -ethoxyethoxycarbonyloxy)ethyl] -3-acetylamino-6 methoxyaniline used in examDle 2 is Drepared as follows: 27.7 parts of N-(ss-cyanoethyl)-N-(ss-hydroxyethyl)-3-acetylamino-6-methoxyaniline are dissolved in 100 parts of pyridine. To this mixture are added dropwise 16-79 parts of 2-ethoxyethyl chloroformate at a temperature of 15-20"C. The product is isolated by pouring the mixture into 1000 parts of iced water, followed by neutralisation of pH 5-6 by the dropwise addition of dilute hydrochloric acid. The resulting oil is separated, washed with cold water and dried over anhydrous sodium sulphate. The product is sufficiently pure for use in the preparation of the dyestuff in example 2.

The N-(ss-cyanoethyl)-N-(ss-hydroxyethyl)-3-acetylamino-6-methoxyaniline is prepared by the reaction of 3-acetylamino-6-methoxyaniline with acrylonitrile in the presence of a catalyst such as hydrochloric acid or acetic acid, followed by further condensation with ethylene oxide.

Example 3 6.9 parts of sodium nitrite are added with stirring to 140 parts of 100% sulphuric acid, the temperature being held at 30"C by external cooling. The temperature is then raised to 700C, before cooling to 200C. 25.2 parts of 2-bromo-6-chloro-4-nitroaniline are then added during 1 hour at 20"C, and the mixture stirred for 2 hours at this temperature, before pouring onto 1000 parts of ice and water. The mixture is filtered and the filtrate so obtained is added to a solution of 38.5 parts N,N-di[P-((31-methoxyethoxycarbonyloxy)-ethyl] aniline in 200 parts of glacial acetic acid and 200 parts iced water at 0 C. The mixture is stirred for two hours at 0 C when the precipitated dye of formula:

is filtered off, washed and dried.

One part of a dyestuff so obtained and 2.0 parts of a formaldehyde/cresolsulphonic acid condensation product, such as that sold as 'Dyapol PT", are added to 20 parts of water and milled in a ball mill, until the average particle size is reduced to 1-5y, before dilution to 5,000 parts with water to form a dyebath. The dyebath temperature is raised to 70"C and 100 parts of cellulose triacetate cloth are introduced. The temperature is increased to 95 100"C for 90 minutes. After this time the cloth is removed, rinsed with water and dried. The cellulose triacetate cloth is dyed a yellowish brown shade of very good fastness to light, washing, sublimation and thermofixation.

Alternatively, one part of the above dyestuff is milled as described above and added to a mixture of 5 parts of a galactomannan thickening agent such as that sold as "Indalca - PA3" and 5 parts of urea in 50 parts of water to form a paste which is then printed through a screen onto cellulose triacetate cloth. After drying the print is fixed by steaming for 25 minutes at 18 p.s.i. After this time the fabric is removed, washed and dried. The bright yellow-brown print so obtained has very good fastness to light, washing, sublimation and thermofixation.

Preparation 3 The N,N-di[ss-ssl-methoxyethoxycarbonyloxy)ethyl]aniline used in example 3 is obtained as follows: 30.5 parts of 2-methoxyethyl chloroformate are added with stirring to a solution of 18.1 parts of N,N-(di-ss-hydroxyethyl)aniline in 100 parts of pyridine. The mixture is stirred at 15-20"C for 8 hours and the product isolated by distillation under reduced pressure.

Example 4 6.9 parts of sodium nitrite are added with stirring to 150 parts of 100% sulphuric acid, the temperature being held at 300C by external cooling. The temperature is then raised to 700C before cooling to 0 C, when a previously prepared solution of 22.8 parts of 2-amino-6methylsulphonyl benzthiazole in 250 parts of 50% sulphuric acid is added. Diazotisation is completed by stirring the mixture at 0 C for 2 hrs. The diazo solution is then added to a previously prepared solution of 28.1 parts N-ethyl-N-[ss-(ss'-methoxyethoxycarbonyloxy)- ethyl]-3-methylaniline in 40 parts of hydrochloric acid and 60 parts of iced-water at 0 C, and stirring is continued at this temperature for two hours. The dye suspension is neutralised to pH 6-7 with dilute caustic soda.The precipitated dye of formula:

is filtered off, washed and dried.

The resulting dyestuff dyes and prints hydrophobic fibres bright reddish blue shades of good excellent fastness to light, washing, sublimation and thermofixation.

Preparation 4 The N-ethyl-N-[ss-(ssl-methoxyethoxycarbonyloxy)ethyl]-3-methylaniline used in Example 4 is prepared as follows: 15.25 parts of 2-methoxyethyl chloroformate are added with stirring to a solution of 17.9 parts of N-ethyl-N-(ss-hydroxyethyl)aniline in 100 parts of pyridine. The mixture is stirred at 15-20"C for 8 hours and the product isolated by distillation under reduced pressure.

Example 5 15.25 parts of 2-methoxyethyl chloroformate are added dropwise 15-20"C with stirring to a solution of 44.45 parts of the dye of formula:

in a 100 parts of pyridine. The mixture is stirred at 15-200C for 8 hours. This is followed by drowning the mixture into 1000 parts of iced water and neutralising to pH 5-6 with dilute hydrochloric acid, whereupon the precipitated dye of formula:

is filtered, washed acid free and dried. The dyestuff dyes and prints hydrophobic fibres bright red shades of excellent fastness to washing sublimation and thermofixation.

In the following table data are given referring to other monoazo dyes of the present invention corresponding to general formula I, which may be prepared, and used, in accordance with the general methods described in the previous examples It must be understood that the invention is not limited to the examples given in the following table. Example D-NH2 X Y R A1 A2 A3 Shade on No.Hydrophobic Fibres

6 2-nitroasiline cH3 H QHs c2H4 c2H4 CH3 RED 7 4-nitroaniline NHcOcH H a < 4 n 2 g : 8 4-nitwaniline NHcOCH1 g CH2 X X Vn Y 9 nitwaniIine H H C2H4CN c2H4 C2H4 c2H5 ORANGE X 4-nitroaniline H u u" Ii 4cHowaniline H H C2H5 c2H4 c2HA cH3 YELLOW 12 4-chloroaniline H H q4OcH C2H4 c2H4 cH3 d 13 4-cyanoaniline NHcOcH3 OcH3 QH c2H4 C2H4 cu3 RED 14 4carboethoxyaniline NHC0 H e" QH- c2H4 C2H4 cH3 RED is 2-bromo-4-nitroaniline NHcOcH5 H C2H'. c2H4 c2H4 cu3 RED 16 2-beorno-4-nitwaniiine CH3 H C2H4OCH3 C2H4 c2H4 cH3 RED 17 2,5-dichlocaniline NHcOcH3 OCH3 CH3 C2H4 C2H4 c2H5 U is 2-ebiocoA-nitroaniline H H C2H5 c2H4 C2H4 cH3 RED 19 2-eHow-4-nitwaniline H H C2H C2H4 C3H6 CH3 RED 8 21 2-eblowA-nitroaniline v r CH2 = 31 m CH3 RED 22 2-chiowA-nitroaniline H H C3H6 C2H4 C2H4 cn3 RED 23 2-chiowA-nitroaniline CH3 H C2H4CN C2H4 C2H4 CH3 RED 3 2-cbioro4-nitroaniline CH3 H 3= 3= 3= 3= 3 3= 3E - 3 3 3 = 3 - = O = 2 c a 2 c ,:: c c 2 2 2 2 2 2 s X 2 n = ,= i = e = m O b 00 0 0 ~ N n t m s g g n a Example D-NH2 X Y R A1 A2 A3 Shade on No.Hydrophobic Fibres

N 2-cbloro-4-nitroaniline N H C2H4CN C2H4 CH2 CH3 SCARLET 26 2-ehloro-4-nitroaniline H CI C2H4CN C2H4 c2H4 cH3 SCARLET 27 2-chloro-4-nitrosniline NHCOCH.' H C2H4CN C2H4 C2H4 Q RED 28 2-chloro-4-nitroaniline NHCOCH3 H C2HCN c2H4 C3H6 C2Hs RED 29 2-ebloro-4-nitcoaniline NHCOC2Hs H C2HCN c2H4 c2H4 C2H3 RED 30 2-cbloro-4-nitroaniline NHSO2C2H5 U C2H3CN E c2H4 CH3 RED 31 2-ehloro-4-nitroanitine NHSO2-n-C4H H C2H4CN C2H4 CH2 C2H3 RED 32 2-cbloro-4-nitcoaniline N U CO H U' Ui 6 a Ui 5 Ú Ú RED 33 2-ehloro-4-nitroasiiine NH S O2 C2H4CN C2H4 CH2 CH3 RED a 2-cbloro-4-nitcoanitine Br H Ú U Ú Ú Ú U a a U U U 35 2-cbloro-4-nitroaniline NHCOCH3 H C3H6CN C2H4 C2H4 CH3 RED 36 2-ebioro-4-nitroaniline NHCOCH3 81'14 c2H4 C2H4 CH3 RED 37 2-chloro-4-nitroanitine 00 Z c2H4 uZ u ú CH3 RED 38 2-ch!oro-4-nitcoanitine NHCOCH.' H ú u t) C2H3 RED 39 2-ebloro-4-metbytsntpbonylaniline H H C2H4OCOOC2H4OCH3 C2H4 Cd2H4 CH3 ORANGE 40 2-chloro-4-metbylsnlpltonylaniiine H H c-,H4cOOCH3 C2H4 c2H4 cu3 ORANGE 41 2-cbloro-4-cyanoaniline NHCOCH3 H C2H4CN c2H4 2H4 iso-C3H7 RED Ú 3-ebloro-4-cyanoaniline Ú C O O U U U C2H4COOCH3 c2H4 8888CH3 RED 3-ehloro-4-cyanoanitine NHCOCH3 H C2H4OcOOC2H4OC2H5 C2H4 C2H4 C2H3 RED 44 2A-dicyanoaniline NHCOCH3 = r z m z z xz z z: = z nZ Z z = = 3 3= 3= = 3= 3 = 3 3 3gw 3 < 3= 30 30 30 = 40 2 40 40 40 40 40 o 2 o o o o o 2 o o 2 & BR< v N o & u U Ú Ú ú oC o e N N no X N ^ t e e n on o t S W 4 Example No. D-NH2 X Y R A1 A2 A3 Shade on No.Hydrophobic Fibres 45 2,4-dicyanoaniline NHCOCH3 H C2H5 C2H4 C2H4 CH3 RED 46 2-cyano-4-nitroaniline CH3 H C2H4CN C2H4 C2H4 C2H5 RED 47 2-cyano-4-nitroaniline NHCOCH3 H C2H5 C2H4 C2H4 CH3 VIOLET 48 2-cyano-4-nitroaniline NHCOC2H5 H C2H4CN C2H4 C2H4 CH3 VIOLET 49 2-cyano-4-nitroaniline CH3 CH3 C2H4COOCH3 C2H4 C2H4 CH3 RED 50 2-cyano-4-nitroaniline NHCOCH3 OCH3 C2H5 C2H4 C2H4 C2H5 VIOLET 51 2-cyano-5-chloroaniline NHCOCH3 H C2H5 C2H4 C2H4 n-C4H9 RED 52 2-carbomethoxy-4-nitroanilne H H C2H4CN C2H4 C2H4 C2H5 SCARLET 53 2-methylsulphonyl-4-nitroaniline CH3 H C2H5 C2H4 C2H4 CH3 BLUISH-RED 54 2-methoxy-4-nitroaniline CH3 H C2H4OCH3 C2H4 C2H4 CH3 SCARLET 55 2-methoxy-4-nitroaniline Cl H C2H4CN C2H4 C2H4 CH3 ORANGE 56 2,4-dinitroaniline NHCOCH3 OCH3 C2H5 C2H4 C2H4 CH3 REDDISH-BLUE 57 2-trifluoromethyl-4-chloroaniline NHCOCH3 H C2H5 C2H4 C2H4 CH3 RED 58 2,6-dibromo-4-nitroaniline H H C2H4OCOOC2H4OCH3 C2H4 C2H4 CH3 YELLOW BROWN 59 2-bromo-4-nitro-6-chloroaniline H H C2H4CN C2H4 C2H4 C2H5 YELLOW BROWN 60 2-bromo-4-nitro-6-chloroaniline H H C2H5 C2H4 C2H4 CH3 YELLOW 61 2-bromo-4-nitro-6-chloroaniline NHCOCH3 H C2H4OCOOC2H4OCH3 C2H4 C2H4 CH3 REDDISH BLUE 62 2-bromo-4-nitro-6-cyanoaniline NHCOCH3 H C2H5 C2H4 C2H4 CH3 BLUE 63 2-bromo-4-nitro-6-cyanoaniline CH3 H C2H5 C2H4 C2H4 CH3 VIOLET C2H4 CH3 VIOLET Example D-NH2 X Y R A1 A2 A3 Shade on No.Hydrophobic Fibres

3 2-bromo-4-nitro-6-cyonoaniline NHCOCH3 3 C2H4OCOOC2H4OCH3 C2H4 C2H4 CH3 REDDISH BLUE 65 2-bromo-4,6-dinitrooniline CH3 3 Wa 3 0 g C2H4 H4 C2H5 VIOLET 66 2-bromo-4,6-dinitroaniline N H Co H C2H C2H4 C2H4 CH3 BLUE 67 2-broroo-4,6-dinitroanilixe CH3 H C2H, c2H4 c2H4 CH3 a BLUE 68 2-broroo-4, & initroaniline NHCOCH,1 uB C2H5 C2H4 C2H4 CH3 NAVY-BLUE 69 2-browo-4,6-dinitroaoiline N H Co H C2H4CN C2H4 c2H4 CH3 NAVY-BLUE 70 2-bromoA,6-dinitroaniline NIlCOCH3 0C2H3 C2H5 ui C2H4 CH3 NAVY-BLUE 71 2-bromo-4,6-dinitroaniline NHcOCH3 OC2H C2Hs c2H4 C2H4 c2u5 NAVY-BLUE 72 2-bromo-4,6-dinltroaniline NHcOCH3 OCH3 c2H4CN c2H4 H4 CR3 NAVY-BLUE 0 0t 0= 0 ú 2-bromo-4,6-dinitroaniline NHCOCH3 OcR3 C2H4CN C2H4 u CR3 NAVY-BLUE U O 2-broroo-4,dinitcoanili:. NHcOcH3 o-n-C4H5 0 ú ú ú c2H4 c2R4 CR3 uz 80 76 2-bromo-4,6-dinitroaniline NHCOcH3 ocli3 CH2 c2u4 I ur- CH3 NAVY-BLUE a 78 2-chloro-4-nitro-6-cyanoaniline CH3 H C2H4OCOOC2H4OC2H5 C2H4 U C2H5 U 79 2-chloro-4-nitro-6-cyanoaniline : H c3H60C00C2H40CH3 C3H5 C2H4 CR3 VIOLET 80 2-chloro-4-nitro-6-cyanoaniline CR3 H C2CN C2H4 C2H4 CH3 VIOLET X 2-chloro-4-nitro-6cyanoanHne NHCOCH3 H U C2H4 U U U Ú CH3 BLUE 82 2,dieb!oroA-nitroanHne H H C2H40c00c2R40CR3 ui ux xz S 8 8888 ,u 2 e 2 e 2 2 2 2 e g e e ,u vuO Q fiuO uO '-C aO , XO O O O , XO O O a ,a a ,a a e tE tE E É E E É É É É tE É E e O e e u ,eO ,eO ,Oe eO ,eO ,eO ,eO eO ,eO ,eO zeO eO o2 Ú Ú Ú ú C \ *0 vO Fo S 0 oÒ R g cs [2 g > g 0 Example D-HN2 X Y R A1 A2 A3 Shade on No.Hydrophobic Fibres 83 2,6-dichloro-4-nitroaniline Cl H C2H4OCOOC2H4OCH3 C2H4 C2H4 CH3 YELLOW BROWN 84 2,6-dichloro-4-nitroaniline H H C2H4CN C2H4 C2H4 CH3 YELLOW BROWN 85 2,6-dichloro-4-nitroaniline H H C2H5 C2H4 CH2 CH3 YELLOW BROWN 86 2,6-dichloro-4-nitroaniline H H n-C4H9 C2H4 C2H4 CH3 YELLOW BROWN 87 2-chloro-4,6-dinitroaniline CH3 H C2H5 C2H4 C2H4 CH3 REDDISH88 2-chloro-4,6-dinitroaniline NHCOCH3 H C2H5 C2H4 C2H4 CH3 BLUE 89 2-chloro-4,6-dinitroaniline NHCOCH3 OCH3 C2H5 C2H4 C2H4 CH3 NAVY-BLUE 90 2-chloro-4,6-dinitroaniline NHCOCH3 OC2H5 C2H4OCOOC2H4OCH3 C2H4 C2H4 CH3 NAVY-BLUE 91 2-chloro-4,6-dinitroaniline CH3 OCH3 C2H5 C2H4 C2H4 C2H5 REDDISH BLUE 92 2-chloro-4,6-dinitroaniline NHCOCH3 OC2H5 C2H5 C2H4 C2H4 CH3 NAVY-BLUE 93 2-chloro-4,6-dinitroaniline HNCOCH3 OCH3 C2H4CN C2H4 C2H4 CH3 NAVY-BLUE 94 2-chloro-4,6-dinitroaniline NHCOC2H5 OCH3 C2H4CN C2H4 C2H4 CH3 NAVY-BLUE 95 2-chloro-4,6-dinitroaniline CH3 OCH3 C2H4OCH3 C2H4 C2H4 CH3 REDDISH BLUE 96 2-chloro-4,6-dinitroaniline NHCOCH3 OCH3 C2H4COOC2H5 C2H4 C2H4 CH3 NAVY-BLUE 97 2-chloro-4,6-dinitroaniline NHCOCH3 OCH3 C2H4COO-n-C4H9 C2H4 C2H4 CH3 NAVY-BLUE 98 2,4,6-trichloroaniline H H C2H4OCOOC2H4OCH3 C2H4 C2H4 CH3 ORANGE 99 2,5-dichloro-4-dimethylsulphonamido H H C2H5 C2H4 C2H4 CH3 ORANGE aniline 100 2,6-dicyano-4-nitroaniline NHCOCH3 OCH3 C2H5 C2H4 C2H4 CH3 GREENISH BLUE 101 2-cyano-4,6-dinitroaniline CH3 H C2H5 C2H4 C2H4 CH3 BLUE 102 2-cyano-4,6-dinitroaniline CH3 H C2H4COOC2H5 C2H4 C2H4 CH3 BLUE Example D-NH2 X Y R A1 A2 A3 Shade on No.Hydrophobic Fibres

(((3 2-cyno-4,6-1initroa.niline NHCOCH H C2H3 C2R4 C2R4 CR3 GREENISH BLUE 11(4 2-n3irobcnthi.o(c CH3 H C2lI4CN C2R4 C2H4 CR3 RED (((5 2-xmino-h-chk3ro1cx'..1hi3c)L ('H3 H C3H6 C2H4 C2R4 CR3 RED o 2-xm(no-6ch(xrobenzthixzo(c CH m &commat;;x 5 B 3 3 3 ! (((7 2-arsix5.6-dich(robcxz1hi3zt)I (I H C2l(4CN C2H4 C2R4 CR3 SCARLET (08 2-amino-6-methy(sa(ph()ny( H H C2Hs C2R4 C2R4 CR3 RED benztbixzo(c U 2-amix-6-cthy(sa(phony( H H C2(i5 C2H4 C2H4 n-C3H7 RED bcnflhi3o(e 110 2-amino-h-mcthylsnlphonyl CH H C2H4OCH3 C2R4 C2H4 CR3 RED bexzth(aco(e Ú 2-amino-6-methy(sx(phony( NIlCOCH H B u B G C2H4 C2H4 CR3 U Ú bex2thiazxlc RED (12 2-xmino-6-methylxn(phony( NHCOCH3 OCR C2Hs. C2H4 C2R4 CR3 VIOLET o 113 2-amino-6-methoxybexzthiazo(e O H C2R4COOC2R3 C2H4 C2H4 CR3 RED 114 2-amino-6-methoxybenz1hi.o(c CR3 H CH2 C2R4 C2R4 CR3 RED 115 2-xm(xo-6-nitrobenzth(aro(c H H C2H4CN C2H4 C2R4 CR3 RED ((6 2-arn(no-8-nitrobexzthixzo(e CR3 H C2H C2R4 C2R4 CR3 BLUISH RED 117 . 2-amino-6-th(ocyanatobenzthiaro(e C111 H C2H3 C2R4 C2R4 E z 6 RED 118 2-xminx-4,6-dixitrobcnzthixco(c H H C2H5 C2H3 C2H4 CR3 BLUE 119 3-amino-5-nitro-2,l-benzixotbiaco(e H H C2R3 C2H4 C2H4 CR3 VIOLET 120 3-arnino-I-n(tro-2,1-benz(xothiszo(e NRCOCR3 H QH4OCOOC2R3OCR3 C2H4 C2H4 CR3 GREENISH BLUE b 3-amino-5-nitro-7-brorno-2.1- CR H bencixothiazole Z 3-arnino-5-nitro.7-bromo.2,( H T T i Y 1: CR3 BLUE 2 Z U 3-amino-5-bronio-7-nitro-2,1- u y N N bexzixoth(azo(e c c c c cE Ê E E E E E E E rq ra rl rl rl rl r rl rl ru l rl rz o rW 3 rl rq ~ rz Example D-NH2 X Y R A1 A2 A3 Shade on No. Hydrophobic Fibres 124 5-amino-3-methylmercapto-1,2,4- NHCOCH3 H C2H4OCOOC2H4OCH3 C2H4 C2H4 CH3 RED thiadiazole 125 5-amino-3-phenyl-1,2,4-thiadiazole CH3 H C2H5 C2H4 C2H4 C2H5 RED 126 5-amino-2-nitro-1,3,4-thiadiazole H H C2H5 C2H4 C2H4 sec-C4H9 VIOLET 127 2-amino-3-carbomethoxy-5-nitro- CH3 H C2H5 C2H4 C2H4 C2H5 REDDISHthiophene BLUE 128 2-amino-3-nitro-5-methylsulphonyl- CH3 H C2H4CN C2H4 C2H4 CH3 BLUE thiophene 129 2-amino-3,5-dinitrothiophene CH3 H C2H4OCOOC2H4OCH3 C2H4 C2H4 CH3 GREENISH BLUE 130 2-amino-3,5-dinitrothiophene NHCOCH3 OCH3 C2H5 C2H4 C2H4 CH3 GREEN 131 2-amino-3-nitro-5-acetylthiophene H H C2H5 C2H4 C2H4 CH3 NAVY-BLUE 132 2-amino-3-nitro-5-benzoylthiophene NHCOCH3 OCH3 C2H5 C2H4 C2H4 CH3 GREENISH BLUE

Claims

WHAT WE CLAIM IS:1. A water-insoluble monoazo dye of the general formula:

wherein D represents a radical of the benzene, benzthiazole, benzisothiazole, thiadiazole or thiophene series, X represents a hydrogen or a halogen atom, an alkyl or alkoxy group or a group of formula -NHCOR1 or -NHSO2R1, wherein Rl represents an alkyl or phenyl group, Y represents a hydrogen or halogen atom or an alkyl or alkoxy group, A1 and A2 each independently represent alkylene groups, A3 represents an alkyl group, and R represents an alkyl group which may be substituted by a cyano, alkoxy, phenyl or alkoxycarbonyl group or by a group of formula:

wherein A2 and A3 are as defined above, with the proviso that when D represents a radical of the benzthiazole series the group R does not represent an alkyl group substituted by a group of formula::
2. A water-insoluble monoazo dye as claimed in claim 1, in which any alkyl, alkylene and alkoxy groups contain from 1 to 4 carbon atoms.
3. A water-insoluble monoazo dye, 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 1 mole of the diazo compound of an aromatic amine of general formula: D-NH2 II wherein D is as defined in claim 1 with 1 mole of tertiary amine of general formula:

wherein X, Y,R,A1, A2, and A3 are as defined in claim 1.
5. 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 aromatic amine of general formula: D - NH2 wherein D is as defined in claim 1 II with one mole of tertiary amine of general formula:

wherein R2 represents an alkyl group which may be substituted by a hydroxyl, cyano, alkoxy, phenyl or alkoxycarbonyl group and X, Y and A1 are as defined in Claim 1, followed by esterification of 1 mole of the resulting dye of general formula:

with one or more moles of a chloroformate.
6. A process for the preparation of a water-insoluble monoazo dye substantially as hereinbefore described in any one of the foregoing examples
7. A process for the dyeing or printing of hydrophobic fibres, in which the dye is an azo dye as claimed in any one of claims 1 to 3.
8. A process as claimed in claim 7, in which the hydrophobic fibres are cellulose acetate fibres, polyamide fibres, polyester fibres or polyacrylonitrile 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 polyester fibres from an aqueous bath at 95-100"C. containing a carrier, or in a pressurised vessel at 125-140"C.
11. A process as claimed in any one of claims 7 to 9, in which the dye dispersion is thickened and applied to a polyester fabric by padding or by printing with a roller or through a screen, the fabric is dried and the dye is fixed.
12. 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, and the printed paper or foil is then heated in contact with the fabric to be coloured.
13. A process as claimed in claim 7 or 8 in which the dye is dispersed in an organic solvent.
14. A process for the colouration of hydrophobic fibres, substantially as hereinbefore described in any one of the foregoing Examples.
15. Hydrophobic fibres whenever coloured by a process as claimed in any one of claims 7 to 14.