DYES CONTAINING A 2,4,5-TRIFLUORO-3,6-DICYANOPHENYL REACTIVE GROUP AND USE THEREOF

Abstract: Dyes having at least one 2,4,5-trifluoro-3,6-dicyanophenyl group and their use in the coloration of substrates, particularly cellulosic textile materials.

Description: DYES CONTAINING A2, 4,5-TRIFLU0R0-3,6-DICYAN0PHENYL REACTIVE GROUP AND USE THEREOF This invention relates to dyes having a 2,4,5-trifluoro-3,6-dicyanophenyl reactive group (hereinafter a TFDC group), to a process for their manufacture, to a process for the coloration of materials using the dyes and to materials when coloured by the dyes. According to the present invention there is provided a dye having at least one 2,4,5-trifluoro-3,6-dicyanophenyl group. It is preferred that the TFDC group is attached to an amine group in the dye, more preferably an amine group of formula -NR 1 - wherein Ft 1 is H or alkyl, especially H or C 1j( -alkyl. The amine group is preferably attached to a carbon atom in an aromatic ring, for example a phenylene or naphthylene ring. Preferably the dye is water-soluble. Preferred dyes according to the invention contain at least two, more preferably at least 3 and preferably less than 1 1 sulpho groups. One class of dye according to the invention contains a group of the Formula (1): wherein: 1 is an arylene group; and R 1 is as hereinbefore defined. In addition to the TFDC group the dye may contain a further reactive group, for example a pyrimidinyl amino group, a vinyl sulphone group or a triazinylamino reactive group. The pyrimidinylamino reactive group is preferably halopyrimidinylamino, especially trichloropyrimidinylamino, and more especially a difluorochloropyrimidinylamino group. The term vinyl sulphone group includes vinyl sulphonyl and groups which are convertible to vinyl sulphonyl in the presence of aqueous alkali, for example -CH 2 CH 2 OSO 3 H and -CH 2 CH 2 SSO 3 H. The triazinylamino reactive group is preferably a 2,4,6,-s-triazinylamino group carrying a labile atom or group and either an alkoxy group, especially C^-alkoxy, or an optionally substituted alkylamino group, especially optionally substituted phenylamino or optionally substituted alkylamino. Preferred optional substituents are selected from sulpho and DFDC. The preferred optionally substituted alkylamino group is an optionally substituted C, ^-alkylamino group, for example CH 3 -NH- and CH 3 CH 2 -NH-. By a labile atom or group it is meant an atom or group which is bound by a chemical bond to the triazine nucleus, which atom or group is displaceable by a hydroxyl group of cellulose under mildly alkaline aqueous conditions to form a covalent bond between the triazine nucleus and cellulose. As examples of such atoms or groups there may be mentioned halogen atoms such as F and Cl; sulphonic acid groups; thiocyano groups; quaternary ammonium groups such as trialkylammonium groups; and optionally substituted pyridinium groups such as 3- and 4-carboxy pyridinium groups. The water-soluble dye according to the invention is preferably a water- soluble azo, anthraquinone, phthalocyanine, triphenodioxazine or formazan dye. Thus preferred dyes of the present invention are of the formula D-(NR'-Z) n wherein Z is 2,4,5- trifluoro-3,6-dicyanophenyl, n is 1 , 2 or 3, D is the residue of an azo, anthraquinone, phthalocyanine, triphenodioxazine or formazan chromophore and R 1 is as hereinbefore defined. Examples of groups represented by D are given in the following pages in Formulae (2) to (9) wherein D is the portion of the illustrated molecules other than group -NR 1 Z. Preferred water-soluble azo dyes are monoazo and disazo dyes. Preferred monoazo dyes are formula L-N=N-L 1 -NR 1 -Z wherein L is an aryl or heteroaryl group, L 1 is an arylene group and Z and R 1 are as hereinbefore defined. It is preferred that each aryl or arylene group independently is a mono- or di-cyclic aryl or arylene group. Preferred aryl groups are optionally substituted phenyl and naphthyl, and preferred arylene groups are optionally substituted phenylene and optionally substituted naphthylene. Preferred heteroaryl groups are pyridinyl and pyrazolonyl. A first preferred monoazo dye is of the Formula (2) or salt thereof: wherein: X is H or sulpho; and L, R 1 and Z are as hereinbefore defined. L is preferably optionally substituted phenyl or naphthyl, especially a phenyl or naphthyl group having at least one sulpho substituent. Further optional substituents which may be present on L include a halogen atom, especially chlorine; an alkyl radical, especially C 1j( -alkyl, more especially methyl; an acylamino radical, especially acetylamino, benzamido or sulphonated benzamido; amino; hydroxy; and an alkoxy radical, especially C^-alkoxy, more especially methoxy. As examples of phenyl groups having at least one sulpho substituent there may be mentioned 2-, 3- or 4-sulphophenyl; 2-sulpho-4-nitrophenyl; 2-sulpho-5- nitrophenyl; 4-sulpho-2-methylphenyl; 5-sulpho-2-methylphenyl; 2-sulpho-4-methylphenyl; 5-sulpho-2-methoxyphenyl; 2- sulpho-4-methoxyphenyl; 4-sulpho-2-chlorophenyl; 5-sulpho-2-carboxyphenyl; 2,4-disulphophenyl; 2,5-disulphophenyl; and 3,5- disulphophenyl. As examples of naphthyl groups having at least one sulpho substituent there may be mentioned 1-sulphonaphth-2-yl; 1 ,5,7-trisulphonaphth-2-yl; 3,6,8- trisulphonaphth-2-yl; 5,7-disulphonaphth-2-yl; 6-sulphonaphth-2-yl; 4-, 5-, 6-, or 7- sulphonaphth-1-yl; 4,8-disulphonaphth-1-yl; 3,8-disulphonaphth-1-yl; 2,5,7-trisulphonaphth-1-yl; and 3,5,7- trisulphonaphth-1 -yl. Preferred optional substituents which may be present on L 1 are those mentioned above for L. In dyes of Formula (2) -NR*Z is preferably at the 6-, 7- or 8-position, especially the 6- or 8- position. When -NR 1 Z is at the 8-position, it is preferred that X is a sulpho group at the 5- or 6- position. A second preferred monoazo dye is of the Formula (3) or a salt thereof: wherein: R 3 is H or C M -alkyl; R is H, C^-alkyl; C, ^-alkanoyl; optionally substituted benzoyi, especially benzoyi or sulphobenzoyi, acetyl, propanoyl, n-butanoyl or iso- butanoyl; and Z, R and each X is as hereinbefore defined. A third preferred monoazo dye is of the Formula (4) or salt thereof: wherein: Ph is an optionally substituted phenyl group, especially sulphophenyl; R 4 is CN, CH 3 or carboxy; and R\ X and Z are as hereinbefore defined. A preferred disazo dye is of Formula (5) or salt thereof: L-N=N-A-N=N-B-NR 1 Z (5) wherein: A and B are each independently optionally substituted phenylene or naphthylene; and R\ L and Z are as hereinbefore defined. It is preferred that B is optionally substituted naphthylene and A is optionally substituted phenylene. The optional substituents which may be present on A or B are preferably independently selected from halo, especially chloro; alkoxy, especially C lJ( -alkoxy; alkyl, especially methyl; sulpho; carboxy; hydroxy; amino; acylamino especially as acetamido, benzamido and sulphonated benzamido, and pyrimidinylamino or triazinylamino cellulose-reactive groups. As Examples of groups represented by A and B there may be mentioned phenylene, sulphophenylene, ureidophenylene, 7-sulpho-1 , 4-naphthylene, 6-sulpho-1,4-naphthylene and 8-sulpho-1 ,4-naphthylene. A preferred anthraquinone dye is of the Formula (6) or a salt thereof: wherein the anthraquinone nucleus optionally contains a sulphonic acid group in the 5-, 6-, 7-, or 8-position; V is a divalent organic linking group, preferably of the benzene series; and R 1 and Z are as hereinbefore defined. V is preferably phenylene, diphenylene, or 4,4'-divalent stilbene or azobenzene radicals which are optionally sulphonated. It is preferred that V contains one sulphonic acid group for each benzene ring present therein. A preferred phthalocyanine dye is of the Formula (7) or a salt thereof: wherein Pc is a metallo-phthalocyanine nucleus, preferably copper or nickel phthalocyanine; each R 1 and Z is as hereinbefore defined; each W independently is a hydroxy or a substituted or unsubstituted group, V 1 is a divalent organic linking group, preferably a C -alkylene or phenylene linking group; and a and b are each independently 1 , 2 or 3 provided that a + b is not greater than 4. A preferred triphenodioxazine dye is of the Formula (8) or a salt thereof wherein : each Y independently is a covalent bond, C 2J( -alkylene, phenylene or sulphophenylene; U is H or SO 3 H; T 1 and T 2 are halo, especially chloro, C -alkyl, or C -alkoxy; and each Z and R 1 independently is as hereinbefore defined. Each Y is preferably -C 2 H 4 - or -C 3 H 6 -, U is preferably SO 3 H, and T 1 and T 2 are preferably Cl, methyl or ethyl. A preferred formazan dye is of the Formula (9) or a salt thereof : wherein : X 1 is H, SO 3 H or Cl; m and p each independently have a value of 0, 1 or 2; and Z and R 1 as hereinbefore defined; provided that the formazan group has at least one, and preferably at least two, sulpho groups. It is preferred that m and p each have a value of 1. Dyes according to the invention may be prepared by a process comprising condensation of 1 ,2,4,5-tetrafluoro-3,6-dicyanobenzene and a dye having a nucleophilic group, especially a -NR 1 H group, preferably in a liquid medium. It is preferred that the condensation is performed at 10-90°C, especially 20-90°C, more especially 40-90°C. The liquid medium is preferably an aqueous medium or comprises dimethylsulphoxide. The condensation is preferably performed in the presence of an acid- binding agent. The function of the acid-binding agent is to neutralise hydrogen fluoride as it is formed during the condensation. Accordingly any acid-binding agent may be used provided that it is not present in such a concentration that it causes hydrolysis of the reactants or causes some other side-reaction. It is preferred to use an alkali metal hydroxide, carbonate or bicarbonate, added at such a rate that the pH of the mixture stays within the range of 5.0 to 6.0. According to a further aspect of the present invention there is provided a compound of the Formula (10) and use thereof for the preparation of a dye : wherein : R 1 , R 2 and B are as hereinbefore defined. In a compound of Formula (10) B is preferably C 2J( -alkylene, optionally substituted phenylene, more preferably optionally substituted phen-1 ,3-ylene, wherein the optional substituents are as hereinbefore described for B. A compound of Formula (10) wherein R 2 is H and B is an optionally substituted phenylene or naphthylene group is useful as a diazotisable amine which may be coupled with a coupling component to give an azo dye. Diazotisation may be achieved by treating a solution of the compound of Formula (10) with sodium nitrite and hydrochloric acid at below 5°C. A compound of Formula (10) may be prepared by condensing 1 ,2,4,5- tetrafluoro-3,6-dicyanobenzene with diamine of formula HN(R 2 )-B-HN(R 1 ), preferably in dimethylsulphoxide at 20-90°C, wherein R 1 , R 2 and B are as hereinbefore defined. Although dye formulae have been shown in the form of their free acid in this specification, the invention also relates to the dyes in the salt form, particularly their salts with alkali metals such as the sodium, lithium or mixed sodium/lithium salt. The present invention also provides a process for the coloration of a substrate comprising applying thereto a dye according to the present invention, preferably in aqueous solution. The reactive dyes of the present invention are suitable for colouring natural and artificial textile materials containing amino or hydroxyl groups, for example textile materials such as wool, silk, polyamides and modified polyacrylonitrile fibres, and more especially cotton, viscose rayon and other regenerated cellulosic materials. For this purpose the dyes can be applied to the textile materials by exhaust dyeing, or by padding or by printing using printing pastes containing the conventional thickening agents or oil-in-water emulsions, whereby the textile materials are coloured bright shades and possess good fastness to light and to wet treatments such as washing and also possess good wash off. The new dyes are particularly valuable for colouring cellulosic textile materials. For this purpose the dyes are preferably applied to the cellulosic textile material in conjunction with a treatment with an acid-binding agent, for example, sodium bicarbonate, sodium carbonate, sodium metasilicate, trisodium phosphate or sodium hydroxide, which may be applied to the cellulose textile material before, during and after the application of the dye. The new dyes can be applied to textile materials containing amine groups, such as wool and polyamide textile materials, from a mildly alkaline, neutral or acid dyebath. The dyeing process can be carried out at a constant or substantially constant pH, that is to say the pH of the dyebath remains constant or substantially constant during the dyeing process, or if desired the pH of the dyebath can be altered at any stage of the dyeing process. In the preferred aspect of the present invention the new dyes are applied to a textile material by printing. The invention also provides textile materials coloured using a dye according to the invention. The invention is illustrated but not limited by the following Examples in which all parts and percentages are by weight unless stated otherwise. Example 1 Preparation of (A) Stage a . To a mixture of N-(β-hydroxyethyl)diethylamine (5.86g) and 2,4- diaminobenzene sulphonic acid (7.52g)in dimethylsulphoxide (45ml) was added 1 ,2,4,5- tetrafluoro-3,6-dicyanobenzene (8.25g) portionwise with stirring. The mixture was heated at 75°C for 4 hours then poured into ice/water (140 ml) to give a solution of 2-amino-4- (2,4,5-trifluoro-3,6-dicyanophenylamino)benzene sulphonic acid. Stage b 2N NaNO 2 (27.2ml) was added to a cold solution of 2-amino-4-(2,4,5- trifluoro-3,6-dicyanophenylamino)benzene sulphonic acid in water (about 400ml) containing cone, hydrochloric acid (15ml). The mixture was stirred at <5°C for 1.5 hrs then excess nitrous acid was destroyed by adding a few drops of 10% sulphamic acid solution to give a diazo compound. Stage c The product of stage b was added to a solution of 1-benzoylamino-8- hydroxynaphthalene-1 ,3-disulphonic acid (0.05 M) at <5°C. The pH was adjusted to 6 and the mixture stirred overnight at pH 6.5/<5°C. The mixture was filtered, brine (10% w.v) added to the stirred filtrate and the resultant precipitate was collected and desalinated using Visking tubing. Water was evaporated from the resultant solution to give a small volume of liquid and the title product was precipitated by the addition of methylated spirits. 14.2g title product was obtained having a λmax at 530nm. D ejng The title product was applied to cotton by printing and found to have excellent build up and fastness. Example 2 Preparation of Stage a 1-hydroxy-6-(2,5-dicyano-3,4,6-trifluoropheny!)amino naphthalene-3- sulphonic acid was prepared by condensing tetrafluoro terephalonitrile with 1-hydroxy-6- aminonaphthalene-3-sulphonic acid in dimethylsulphoxide. Stage b A solution of 2-sulpho-4-(4-sulphophenylazo)benzene diazonium chloride (prepared by diazotising 4-amino-3,4'-disulphoazobenzene) (0.1 m) was added at <5°C to a solution of 1-hydroxy-6-(2,5-dicyano-3,4,6-trifluorophenyl)amino naphthalene-3- sulphonic acid (0.1 M) in water. The mixture was stirred at pH 5, 0°C for 16 hours, allowed to warm to room temperature and filtered. Brine (10% w/v) was added to the stirred filtrate and the resultant precipitate was dissolved in the minimum quantity of water and brine (29% w/v) was added. The resultant precipitate was collected and dried to give the title product (14.6g, M.I. 1050)having a λmax at 511 nm. Dyeing The title product was applied to cotton by exhaust dyeing and was found to have excellent build up and fastness. Examples 3 to 8 Following similar methods to those described in Examples 1 and 2 the following dyes may also be prepared: Example 3 wherein CuPc is copper phthalocyanine, x + y = 4 and each of x and y independently is fc 1. Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 The method of Example 1 was repeated except that in place of 1- benzoylamino-8-hydroxynaphthalene-1 ,3-disulphonic acid there was used 1-amino-2-(2,5- disulphophenyl azo)-8-hydroxynaphthalene-3,6-disulphonic acid.

Claims: CLAIMS 1. A dye having at least one 2,4,5-trifluoro-3,6-dicyanophenyl group. 2. A dye according to claim 1 wherein the 2,4,5-trifluoro-3,6-dicyanophenyl group is attached to an amine group in the dye. 3. A dye according to any one of the preceding claims containing a group of the Formula (1 ): (1) arylene group; and R 1 is H or alkyl. 4. A dye according to any one of the preceding claims of the formula D-(NR 1 -Z) n wherein Z is 2,4,5-trifluoro-3,6-dicyanophenyl; n is 1 , 2 or 3; D is the residue of an azo, anthraquinone, phthalocyanine, triphenodioxazine or formazan chromophore; and R 1 is H or alkyl. 5. A water-soluble dye according to claim 4 wherein D is the residue of an azo chromophore selected from monoazo and disazo chromophores. 6. A monoazo dye according to claim 1 of the Formula (2) or salt thereof: wherein : X is H or sulpho; is an aryl or heteroaryl group; R 1 is H or alkyl; and Z is 2,4,5-trifluoro-3,6-dicyanophenyl. A disazo dye according to claim 1 of the Formula (5) or salt thereof: L-N=N-A-N=N-B-NR 1 Z (5) wherein: A and B are each independently optionally substituted phenylene or naphthylene; L is an aryl or heteroaryl group; R 1 is H or alkyl; and Z is 2,4,5-trifluoro-3,6-dicyanophenyl. 8. A compound of the Formula (10): wherein: R 1 is H or C,^-alkyl; R 2 is H, C -alkyl, C lJt -alkanoyl or optionally substituted benzoyi; and B is optionally substituted phenylene or naphthylene. 9. A process for the coloration of a substrate comprising applying thereto a dye according to any one of claims 1 to 7. 10. A process according to claim 9 wherein the substrate is a cellulosic textile material.

Inventors: TAYLOR JOHN ANTHONY, TAYLOR, JOHN, ANTHONY
Applicants: TAYLOR JOHN ANTHONY, ZENECA LTD, TAYLOR, JOHN, ANTHONY, ZENECA LIMITED
Application year: 1996
Main classification: C09B62
IPC codes: C07C255, C09B62, D06P1, D06P3