GB2079303A - Monoazo disperse dyes containing 1,3,4 thiadiazole residues - Google Patents

Abstract

The invention relates to water insoluble monoazo dyes having the general formula: <IMAGE> wherein R represents a halogenoalkyl, arylsulphonyl, aralkylsulphonyl, alkarylsulphonyl, alkoxycarbonyl, aryloxycarbonyl or cyano group, and A represents the residue of a coupling component of the carbocyclic or heterocyclic series. The dyes may be prepared by coupling one mole of the diazonium salt derived from an amine of general formula: <IMAGE> with one mole of a coupling component of general formula AH, wherein A has the meaning defined above. The dyes find use in the dyeing and printing of hydrophobic fibres.

Description

SPECIFICATION Monoazo disperse dyes containing 1,3,4, Thiadiazole residues The present invention relates to monoazo dyes and to a process for their preparation and use.

Azo dyes are known which offer an advantage in economy over red and bluish red dyes of the anthraquinone series and exhibit brightness of shade approaching these dyes but which possess inferior light fastness. We have now discovered a group of azo dyes which combine the desirable properties of these azo dyes together with improved fastness to light According to the present invention therefore water insoluble monoazo dyes are provided having the general formula:

wherein R represents a halogenalkyl, arylsulphonyl, aralkylsulphonyl, alkarylsulphonyl, alkoxycarbonyl, aryloxycarbonyl or cyano group, A represents the residue of a coupling component of the carbocyclic or heterocyclic series.

A particularly valuable group of water insoluble monoazo dyes falling within the scope of the dyes of formula I correspond to the general formula:

wherein R' and R2 each independently represent a hydrogen atom or an optionally substituted alkyl group, R3 represents a hydrogen or halogen atom or an alkyl or alkoxy group, R4 represents a hydrogen or halogen atom or an alkyl, alkoxy or acylamino group as herein defined and R has the meaning given above.

When R' and/or R2 represents alkyl groups these may be substituted with for example a halogen atom or a hydroxy, cyano, alkoxy, alkoxycarbonyl, cyanethoxy, alkylcarbonyl, arylcarbonyl, aryl group or a group of formula OCOR5R6 wherein R5 represents an oxygen atom or an imino group or a direct linkage and RB represents a substituted or unsubstituted alkyl, aryl, cycloalkyl or heterocyclic group.

The acylamino group R4 is defined as being an alkanoylamino, arylcarbonylamino, cycloalkylcarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkysulphonylamino, cycloalkysulphonylamino or arylsulphonylamino group. The preferred dyes are those in which the alkylene and alkyl groups contain 14 carbon atoms.

Specially preferred dyes are those in which R3 represents a hydrogen atom and R4 represents an acylamino group as hereinbefore defined.

The invention also provides a process for the preparation of dyes of general formula I which comprises coupling one mole of the diazonium salt derived from an amine of general formula:

with one mole of a coupling component of general formula AH, wherein A has the meaning given above, and particularly with one mole of a tertiary amine of general formula:

wherein R, R', R2, R3 and R4 have the meanings given above.

The tertiary amines of general formula IV in which R' and/or R2 represents an alkyl group substituted by a group of formula OCORSRB may be prepared for example by condensing one mole of a tertiary amine of general formula:

wherein R7 is an alkylene group with one, two or more moles of the appropriate carboxylic acid chloride or anhydride, chloroformate or isocyanate.

Specific examples of amines of general formula III which may be used for preparing the diazo compounds are: 2 - amino - 5 - trifluoromethyl - 1,3,4 - thiadiazole 2- amino - 5 - pentafluoroethyl -1,3,4 - thiadiazole 2 - amino - 5 - trichloromethyl - 1,3,4 - thiadiazole 2 - amino - 5 - phenylsulphonyl -1,3,4 - thiadiazole 2 - amino - 5 - (4 - methyl)phenylsulphonyl - 1,3,4 - thiadiazole 2-amino-5- benzvlsulphonyl -1,3,4 - thiadiazole 2 - amino - 5 - methoxycarbonyl -1,3,4 - thiadiazole 2 - amino - 5 - ethoxycarbonyl - 1,3,4 -thiadiazole 2 - amino - 5 - butoxycarbonyl -1,3,4 - thiadiazole 2 - amino - 5 - dichloromethyl - 1,3,4 - thiadiazole Specific examples of amines of general formula IV which may be used as coupling components are: N - benzyl - 3 - acetylaminoaniline N-ethyl-N-P- cyanoethyl-3- acetylaminoaniline N,N - diethyl - 3 - acetylaminoaniline N,N - diisopropyl -3 - acetylaminoaniline N,N - diisobutyl - 3 - acetylaminoaniline N,N - diisobutyl - 3 - propionylaminoaniline N,N - diisopropyl - 3 - methylaniline N, N - diisobutyl - 3 - chloroaniline N,N - diisopropyl - 2 - methyl - 5 acetylaminoaniline N - ethyl - N - benzyl - 3 - acetylaminoaniline N-'3-cyanoethyl-N-benzyl-3- acetylaminoaniline N-'3-ethoxyeThyl-N-benzyl-3- acetylaminoaniline N - ss - (ethoxycarbonyl)ethyl - N - benzyl - 3 - acetylaminoaniline N - ss - (ss' - cyanoethoxy)ethyl - N - phenylethyl - 3 benzoylaminoaniline N - ss - (ethylcarbonyl)ethyl - N - benzyl - 3 - methoxycarbonylaminoaniline N - ss - benzoylethyl - N - benzyl - 3 - methylsulphonylaminoaniline N - ss - cyanoethyl - N - ss - (ss' - cyanoethoxy)ethyl 3 - acetylaminoaniline N - '3 - hydroxyethyl - N - benzyl - 3 - acetylamino aniline N - '3 - hydroxyethyl - N - ethyl - 3- methylsulphonylaminoaniline N - ethyl - N - benzyl - 2,5 - dimethoxyaniline N-ethyl-N-benn/l-2- methyl-5- acetylaminoaniline N - ethyl - N - benzyl - 2 - chloroaniline N - ethyl - N - benzyl - 3 - chloroaniline Specific examples of tertiary amines of general formulae V and VI which may be used for preparing the other coupling components of general formula IV are: N-'3- hydroxyethyl-N benzyl-3- acetylaminoaniline N-ss-hydroxyethyl-N-benzyl-2-methyl-5- acetylaminoaniline N - z - hydroxypropyl - N - ss - (methoxycar bonyl)ethyl - 5- phenylsu Iphonylaminoaniline N - ss - hydroxyethyl - N -'3 - cyanoethyl - 2 - methoxy - 5 - acetylaminoaniline N - ss - hydroxyethyil - N - ss - cyanoethyl - 2 - ethoxy - 5 - acetylaminoaniline N - ss - hydroxyethyl - N - '3 - ethoxyethyl - 3 - acetylaminoaniline N - ss - hydroxyethyl - N - '3- cyanoethyl - 3 - propionylaminoaniline N - ss - hydroxyethyl - N -'3-cyanoethyl -3-cyc- lohexylsulphonylaminoaniline N - ss - hydroxyethyl - N - benzyl - 3 - phenylsul- phonylaminoaniline N - ss - hydroxyethyl - N - benzyl - 3 - cyclohexylcarbonylaminoaniline N - '3 - hydroxyethyl - N - benzyl - 3 - methoxycarbonylaminoaniline N - '3 - hydroxyethyl - N - phenylpropyl - 3 phenoxycarbonylaminoaniline N -ss- hydroxyethyl - N - benzyl-3- ethylsulphonylaminoaniline N - '3 - hydroxyethyl - N - ethyl - 3 acetylaminoaniline N,N - dihydroxyethyl - 3 - acetylaminoaniline N,N - dihydroxypropyl - 3 - methylsul- phonylaminoaniline Specific examples of carboxylic acid chlorides and anhydrides which may be used for preparing the coupling components of general formula IV wherein the alkyl groups R1 and/or R2 are substituted with a group of formula OCOR5R5 are benzoyl chloride, 3 methylbenzoyl chloride, 4 - methoxybenzoyl chloride, 4 - chlorobenzoyl chloride, acetic anhydride, propionix anhydride and 2 - furoylchloride.

Specific examples of chloroformates which may be used for preparing the coupling components are methyl chloroformate, ethyl chloroformate, phenyl chloroformate and benzoyl chloroformate, whilst specific examples of isocyanates which may be used for preparing the coupling components are methyl isocyanate, ethyl isocyanate, phenyl isocyanate and cyclohexylisocyanate.

Specific examples of heterocyclic coupling components formula AH are: 2 - methylindole 1,2 - dimethylindole 2 - phenylindole 1 - methyl - 2 - phenylindole 1 - phenyl - 3 - methyl - 5 - pyrozolone 1 - phenyl - 3 - methyl - 5 - aminopyrazole 2,6 - dihydroxy - 3 - cyano - 4 - methylpyridine 1 - ethyl - 3 - cyano - 4 - methyl - 6 - hydroxypyrid 2-one 1 - methyl - 3- cyano - 4 - methyl - 6- hydroxypyrid -2-one 1 - (ss - hydroxy)ethyl - 3 - cyano - 4 - methyl - 6 - hydroxypyrid - one 1 - phenyl - 3 - cyano - 4 - methyl - 6 - hydroxypyrid - 2 - one barbituric acid 1 - phenyl - 3 - methylbarbituric acid 1 - N - '3- hydroxyethyl -2,2,4,7- tetramethyl 1,2,3,4 - tetrahydroquinoline 1 - N - ss acetoxyothyl 2,2,4,7- tetramethyl -1,2,3,4 - tetrahydroquinoline 1 - N - ss - acetoxyethyl 2,2,4,7- tetramethyl - 7- acetylamino - 1,2,3,4 - tetrahydroquinoline 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 cel lulose 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 Registered Trade Mark).

The dyes are preferably dispersed by grinding with water and a suitable dispersing agent e.g. a formaldehydelcresolsulphonic 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, e.g. 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 orotherthicken- ers 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 dry ing the fabric, the dye is fixed for example by steam ing at 1.0-1.7 bar pressure 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 cellul ose 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, 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 of polyester fabric.The colourations so obtained are yellow to violet in shade and have good fastness to light, washing, sub limation, 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 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 30"C by external cooling. The temperature is then raised to 70"C before cooling to below 15"C when a mixture of 57.2 parts of acetic acid and 8.9 parts of propionic acid is added dropwise at this temperature. After cooling to -10"C, 16.9 g of 2 - amino - 5 - trifluoromethyl - 1,3,4 - thiadiazole are added during 30 minutes at -10 C and the mixture stirred for three hours at this temperature.The diazo solution so obtained is added to a solution of 26.89 of N - benzyl - N - ethyl - 3 - acetylaminoaniline in a mixture of 40 parts of 100% sulphuric acid and 500 parts of iced water at 0 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 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,um, before dilution to 1000 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 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 good fastness, washing, sublimation and thermofixation and excellent fastness to light.

Example 2 28.4 parts of N - benayl - N - ss - hydroxyethyl - 3 acetylaminoaniline are added with stirring to 50 parts of acetic anhydride at 20"C. The mixture is then heated at 100 C for two hours. After cooling, the mixture is added to a solution of 40 parts of 100% sulphuric acid in 500 parts of iced water at 0 C.16.9g of 2 - amino - 5 - trifluoromethyl - 1,3,4 - thiadiazole are diazotised as in example 1 and added to the coupling mixture which is stirred for 4 hours at 0 C. The precipitate 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,um. 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 form a paste which is then printed through a screen on to polyester fabric. After drying, the print is fixed by steaming for 20 minutes at 1.3 bar pressure. After this time the fabric is removed, washed and dried.

The bright red print so obtained has good fastness to washing, sublimation and thermofixation and excellent fastness to light Example 3 21.7 parts of ethyl chloroformate are added with stirring to a solution of 28.4 parts of N - benzyl - N - P hydroxyethyl - 3 - acetylaminoaniline in 100 parts of pyridine. The mixture is stirred at 15-200C 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 100 parts of iced water at ODC. 21.9 parts of 2 - amino - 5 - pentafluoroethyl -1,3,4 - thiadiazole are diazotised by the method described in example 1 and added to the coupling mixture which is stirred for four hours at OOC. The precipitated dye of formula:

is filtered off, washed acid free and dried. It dyes polyester fibres red shades of good fastness to washing and sublimation and excellent fastness to light Example 4 If the 26.8 parts of N - benzyl - N - ethyl - 3 acetylaminoaniline used in example 1 are replaced by 20.6 parts of N,N - diethyl - 3 - acetylaminoaniline the dye obtained has the formula:

5 parts of this dyestuff is pasted with 35 parts of ethanol.To the mixture is gradually added with stir ring, 3.5 parts of ethyl cellulose, followed by 2.5 parts of ethylene glycol. The paste is then milled in a ball mill until the average particle size is reduced to 1-5,um. The paste so obtained is applied to a sheet of paper treated with silicone, in a thickness of 24,am using a wire-wound hand coater bar (K-Bar No.3, R.K. Chemical Co. Ltd.) and air dried. The dyestuff is then transferred from the support material to the polyester by the action of dry heat at 210"C for 30 seconds.

The polyester fibres are printed a bright bluish red shade of very good fastness to light, wet treatments, rubbing and dry cleaning.

In the following table data are given referring to other monoazo dyes of the present invention corresponding to 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.

ple It RZ iii RS Shade on Polyester Fibre, 4 Cr3 C2115 2 4 ii NiiCtJCH3 Red 5 Cr C ii c ii il NilcoC ii Bluish Red 3 25 25 25 6 ar3 al(CH3 )2 oi(c113)2 II ii11C(:i13 Bluish Red 7 CF3 ci12c11(cii ) cii cii(ai ) ii NliCOC2115 Bluish Red 32 2 32 . 25 a CF3 cii(cii ) cii(cii } II c113 Red 32 32 9 Cr3 C112C11(01 ) cli2cii(cii ) ii cl Vellovish Red 32 32 IC CF3 cil(al3)a c11(c1l cir, 2 C113 NIlCOCH3 Violet 32 11 C2F5 C2115 C1120 a NIICOC113 Red 12 CC13 C21l/ CN C112(3 ii NilCCCH3 Red 13 CC13 c2l14OC2115 al2 H NllWCii3 Red 14 CC13 C211zCWC 5 , C2 (9 ii Zit NilCOC113 Red 15 5 z(9 C21140C211XCP CìJ ii NilCO (3 Red

Example It ill R2 R3 R4 Shade on Polyester Fibre, 16 c2114CoC2115 ugO H NllCGCCil3 Red 17 1 3 c21l/co C112(3 ii NliS02Cil3 Red 18 aa3 C2114CN C2IlOC2I14CN II NIICO Yellowish Red 19 CMCIL CoUcil 2 4 U12 cl12 II NIlCOCH Red 3 24 20 COOC2ii5 C2114 H C2115 ii Ni1S02013 Bluish Red 21 COOT 11 C II OI2 U12 foil3 3 Bed 25 25 3 22 CF3 C2115 U125 C1 H Yellowish Red 23 CF3 Cm'15 U12 H C1 Yellowish Red 25 24 CFi C21140COC15 U12 O H Nl'CaC113 Red 25 CP3 C2.14GCGal3 0I2 al3 NllCaC113 Violet 26 C F) C2II4OCo CI12 H NIlcocli3 Red 7 C2F5 C3116UCO Q Cl14C0oC113 11 NRiS02 O Red 3 28 CCl3 (i2114C00 2 4 < 3 C2H4CN Gal3 NiiCQ'i3 Violet 29 5 2 C2114rJCO e C1 C2114CN 0013 NilCOC113 Violet 30 SO2Cll2 C2!I4Rct)C21l5 C2ii4CN Ii NIICGC2115 Red 31 COUP113 Cz1140CoQ C211/CN 11 NlISO2 Red 32 CWC2115 C2114OC0013 U12 II N11502(3 . Red 33 v Ct)uC H C II OCUC H Ii WILCO S NIICO &commat; Red 25 24 25 2 34 CF, C 11 OCO Cli H ii NIIWGC113 Red 24 = 2- 3 35 CF3 C2HIPCOC2'i5 Cll2cI12cH2 Ii NFIcOO Red 96 C Cl3 c2114cC0 (3 al20 It NIlSO C II Red 37 CP3 C2"40C'3 C2115 H NllCOCil3 Red 3 24 3 25 3 38 CCl3 c2'i4ocoo (3 C2il5 H NIICGal3 Red 39 CF3 c2llZi0coocl12 O C2115 H Ii NNCEQI) Red 25 40 0to12 C21140CONLIC13 C211tstlC15 r N''3 Red

Etbpl- R 111- < R 113 114 Shade on Polyester Fibres 41 2 < 3 C2111 CCONliC2115 C4119 H NIlCOCH3 Red 42 SO2C13 C21140COlM (9 C2H5 11 NIICOC2H5 Red 43 Cm13 C2114oCo < 9 C2115 H NIlCOCIl3 Red 44 CF C H c2"5 3 Red 3 CF3 2 4 3 C2114Oc001 H liCoC1i 45 CCI li4OCOOC Ii . 2 ii OCOoC 11 H MICOCI' Red 3 MIWCIL 3 46 Cr3 C21140CO O C140CO ii NI1COC113 Red CHCl U1Cla OCONlIC Ii C 11 OCONlIC 11 N NHWC113 ~.~~~~.~ 5 3 Red

Claims (12)

1. Water insoluble monoazo dyes having the general formula:

wherein R represents a halogenalkyl, arylsulphonyl, aralkylsulphonyl, alkarylsulphonyl, alkoxycarbonyl, aryloxycarbonyl or cyano group, and A represents the residue of a coupling component of the carbocyclic or heterocyclic series.

2. Water insoluble monoazo dyes as claimed in claim 1 having the general formula:

wherein R' and R2 each independently represent a hydrogen atom or an alkyl group which may be substituted with a halogen atom or a hydroxy, cyano, alkoxy, alkoxycarbonyl, cyanoethoxy, alkylcarbonyl, arylcarbonyl or an aryl group or a group of the formula OCORR8wherein Rs represents an oxygen atom or an imino group or a direct linkage and RS represents a substituted or unsubstituted alkyl, aryl, cycloalkyl or heterocyclic group, R3 represents a hydrogen or a halogen atom or an alkyl or alkoxy group, R4 represents a hydrogen or halogen atom or an alkyl or alkoxy group or an acylamino group selected from an alkanoylamino, arylcarbonylamino, cycloalkylcarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkylsulphonylamino, cycloalkylsulphonylamino or arylsulphonylamino groups, and R has the meaning defined in claim 1.

3. Water insoluble monoazo dyes as claimed in claim 2, in which R3 represents a hydrogen atom and R4 represents an acylamino group.

4. Water insoluble monoazo dyes as claimed in any of claims 1 to 3, in which all the alkylene and alkyl groups present in the dye contain from 1 to 4 carbon atoms.

5. A process for the preparation of water insoluble monoazo dyes of general formula I claimed in claim 1, which comprises coupling one mole of the diazonium salt derived from an amine of general formula:

with one mole of a coupling component of general formula AH, wherein A has the meaning defined in claim 1.

6. A process as claimed in claim 5, in which the tertiary amine has the general formula:

wherein R, R', R2, R3 and R4 have the meanings defined in claim 2.

7. A process as claimed in claim 6, in which R3 represents a hydrogen atom and R4 represents an acylamino group.

8. A process as claimed in claim 5,6 or 7, in which all the alkyl groups present in the tertiary amine and the coupling component contain from 1 to4carbon atoms.

9. A process for the dyeing or printing of hydrophobic fibres in which the dye applied to the fibres is a water insoluble monoazo dye claimed in any of claims 1 to 4.

10. Water insoluble monoazo dyes as claimed in claim 1 substantially as hereinbefore described in any of the Examples and the Table.

11. A process as claimed in claim 5 substantially as hereinbefore described in any one of the Examples and the Table.

12. A process as claimed in claim 9, substantially as hereinbefore described in any one of the Examples and the Table.