Title of Invention

"PROCESS FOR THE PREPARATION OF AN AZO DYE COMPOUND"

Abstract

A process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1): wherein: A and D each independently is an optionally substituted heterocyclic or carbocyclic group and at least one of A or D carries directly at least one -SO2F group or carries a substituent to which at least one -S02F group is attached except for 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, provided that one of A or D is not 3,5-difluorosulphonylthien-2-yl, optionally substituted l-phenyl-pyrazol-4-yl-5-one or or that one of A or D does not carry an -NCH2CH(OH) CH2C1, -NCOCH2C1 or -NCH2CH2S02F substituent. The presence of one or more -S02F groups in a dye molecule generally improves the properties of that dye and confers surprisingly good wet fastness and light fastness properties.

Full Text

The present invention relates to a process for the preparation of an azo dye compound containing a fluorosuiphonyl group, which azo dye compound is useful for colouring synthetic textile materials. GB-A—856,343 relates to water insoluble monoazo dyestuffs and discloses one specific dye containing a 4— fluorosulphonylnaphth-1-yl group which is excluded from the present claims. GB—A—819, 664 relates to water insoluble monoazo dyestuffs and discloses two specific dyes both of which are excluded from the present claims. EIJS—A—2,576,037 relates to the coloration of cellulose acetate with certain —SO2F containing azo dyes. Such dyes, particularly those which also contain -NC2H4OH groups or derivatives thereof are dye bath unstable and as such are unsuitable for coloration of polyester textile materials. According to the present invention there is provided a process for preparing an azo dye compound which is free from water solubilising groups and is of Formula (1) A-N=N- D (1) wherein A and D each independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A and D carries directly at least one -SO2F group or carries a substituent to which at least one -SO2F group is attached which process comprises: (1) diazotising an amine of the formula (10) A—NH2 (10) wnerein A is as defined above, by reaction of the said amine with a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite in an acid medium such as acetic, propionic or hydrochloric acid at a temperature of from -100C to +100C to form a diazotised amine; (2) coupling the diazotised amine with a coupling component of the formula (11) D—X (11) wherein X is a group displaceable by the diiazotised amine and D is as defined above, by adding the diazotised amine to a mixture of the coupling component of the formula (11) in an alkanol such as methanol at a temperature of from 0 to 100C to form a monoazo compound; and at least when both A in the amine of the formula (10) and D in the coupling component of the formula (11) are free from an -SO2F' group or a group to which at least one -SO2F' group is attached, (3) forming a chlorosulphonyl derivative of at least one of the said monoazo compound, the amine of the formula (10) and the coupling component of the formula (11) free from —SO2F, (i) with chlorosulphonic acid to form the chlorosulphonyl derivative thereof, which reaction is optionally carried out in the presence of dimethylformamide and thionylchloride at a temperature of 30 to 1400C, but, where the said compound free from —SO2F has an amino group therein, which reaction is carried out after protecting the amino group of the said amine if necessary, or (ii) firstly, with oleum or sulphuric acid to sulphonate the said compound free from ~SO2I~ and then optionally with an inorganic salt— or ester—forming compound to form the inorganic salt or ester of the suiphonic acid derivative and then reacting one of the sulphonic acid derivative, inorganic salt and ester thereof with thionylchlobide, optionally in the presence of a chlorophosphorus compound such as phosphorous oxychloride or phosphorous pentachloride in an organic liquid such as an aromatic hydrocarbon at a temperature of from 200C to 1100C; and (4) reacting the said chlorosulphonyl derivative with potassium chloride in a boiling aqueous medium to obtain at least one of the amine of the ~ormula (10) and the coupling component of the formula (11) having an -SO2F group to be subjected to at least one of the above diazotising and coupling steps (1) and (2) or to provide the said monoazo compound with an -SO2F group, thereby to obtain the said azo dye compound of the formula (1); and wherein at least one of the following requirements is satisfied: (a) in the formula (1), at least one of A and D carries directly at least one ester group or carries a substituent to which at least one ester group is attached; and (b) in the formula(l), each of A and D is such as to provide a dye compound selected from compounds of the formulae wherein: wherein: R' and R2 each independently is H or optionally substituted C16-alkyl or optionally substituted aryl; K3, R4, R5 and K6 each independently is H, F, Cl, Br, I, —SO2F or C16 alkyl, C16—alkoxy, C,4alkanoylamino, —NHSO2alkyl or —Ophenyl, each of which may be optionally substituted; R7, K8 and K9 each independently is H, C16—alkyl, NO2, —COOC,6—alkyl, —OCOalkyl, Cl, F, Br, I, -COC,~—alky1, —eN, formyl, protected formyl or —SO2F provided that at least one of K1 to K9 is -SO2F or carries a substituent to which at least one -SO2F group is attached and provided that K7 and K9 are not both -SO2F; wherein: 1 2 R and K each independently is H or optionally substituted C,6—alkyl or optionally substituted aryl; 3 4 5 6 R , R , R and R each independently is H, F, Cl, Br, I, —SO2F or C,6—alkyl, C,6—alkoxyl, C,4—alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; K12 is —SO2F; and K'0, K", K'3 and K'4 each independently is H, alkoxy, alkyl, NO2, —SO2F, F, Cl, Br, I or —CN; in which R1 and K2 each independently is optionally substituted C,6—alkyl; K4 is alkyl or a group of Formula -N(R'9)—Y—X-W in which Y is a direct link or C = 0, X is a direct link, alkylene, alkenylene, arylene, heterocyclic, 20 alkyleneoalkylene, alkyleneNHalkylene, —N(R )—Z—, —COOZ or —OZ- in which Z is alkylene, alkenylene, arylene, heterocyclic, alkyleneoalkylene, alkyleneNHalkylene or a direct link and 20 is —H~ alkyl, aryl or alkylaryl, W is 21 21 21 -CO2R , —OCOK or —OH in which K is alkyl, aryl, alkylaryl, alkyloalkyl or alkylOH, and K'9 is H or alkyl; K5 is H, C16-alkoxy or -Ophenyl; R'0 is NO2 or Cl; and K'3 and K'4 each independently is H or Cl; and wherein 1 2 R and K each independently is H or optionally substituted C,6—alkyl; K3 is optionally substituted C,6-alkyl or C,6—alkoxy; K4 is optionally substituted C~6-alkyl or C~6—alkoxy; K'0 is optionally substituted C16—alkyl, NO2 or Cl; K'5 to K'8 each independently is H, C16-alkyl, C,6— 12 alkoxy, F, Cl, Br, I, —SO2F, NO2, -eN or NK K ; 12 K is NO2 or -SO2F; R" is H; and K13 and R'4 each independently is H or Cl except for: 4- (4—fluorosulphonylphenylazo) —N,N—dimethylaniline, 4—(4—fluorosulphonylphenylazo) —N,N—diethylaniline, 4- (4—fluorosulphonylphenylazo) —N-ethyl—N— acetoxyethylaniline, 4— (4—fluorosulphonylphenylazo) —3— (trifluoromethylcarbonylamino) -N-ethyl-N- (2-methoxyethyl) aniline, 4- (4—fluorosulphonylphenylazo) -3-(trifluoromethylcarbonylamino) —N—ethyl—N- (2— cyanoethyl) aniline, 4- (4-fluorosulphonylphenylazo)—2,5-dimethyl—Nethyli N— (2—methoxyethyl) aniline, 4- (4-fluorosulphonylphenylazo) —2,5—dimethyl—N—ethyl-N- (2-cyanoethyl)aniline, 4- (4-fluorosulphonylphenylazo) -N-ethyl-N- (2-fluorosulphonylethyl) aniline, 4- (4-fluorosulphonylphenylazO) —N,N-di (2-fluorosulphonylethyl) aniline and 4- (4—fluorosulphonylphenylaZO) —N-ethyl-N (((2-methoxy) -2-ethoxy) ethyl) aniline; and (c) in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formulae When at least one of the amine of the formula (10) and the coupling component of the formula (11) carries an -SO2F group, the process comprises the preliminary step of (i) reacting at least one of the amine of the formula (10) and the coupling component of the formula (11), after protecting the amino group of the said amine if necessary, with chlorosulphonic acid, optionally in the presence of dimethylformamide and thionylchloride at a temperature of 30 to 1400C to obtain the corresponding chlorosulphdnyl derivative thereof and reacting the said chlorosulphonyl derivative with potassium chloride in a boiling aqueous medium to obtain at least one of the amine of the formula (10) and the coupling component of the formula (11) having an —SO2F group substituted directly thereon or attached to a substitueht thereof; or (ii) sulphonating at least one of the amine of the formula (10) and the coupling component of the formula (11) by reaction thereof with oleum or sulphuric acid to give the corresponding sulphonic acid derivative; optionally forming an inorganic salt or ester of the suiphonic acid derivative; reacting one of the sulphonic acid derivative, inorganic salt and ester thereof, for conversion thereof to the corresponding chlorosulphonyl derivative, with thionylchloride, optionally in the presence of a chlorophosphorus compound such as phosphorus oxychloride on phosphorus pentachloride in an organic liquid such as an aromatic hydrocarbon at a temperature of from 200C to 1100C; and reacting the said chlorosulphonyl derivative with potassium chloride in a boiling aqueous medium to obtain at least one of the amine of the formula (10) and the coupling componen.t of the formula (11) having an -SO2F group substituted directly thereon or attached to a substituent thereof. A synthetic textile material or fibre blend thereof may be coloured by a process which comprises applying to the synthetic textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1), prepared as described above. Different compounds of Formula (1) may be mixed or the compounds of Formula (1) may be mixed with dyes which do not contain an —SO2F group. The mixtures may be simple physical mixtures or may be mixed crystals formed for example by co-crystallisation. Sdch mixtures generally show improvement in dyeing properties. Crystalline modifications of compounds of Formula (1) exist and it is intended that the present definition includes such crystalline modifications which may be formed by heat treatment. The presence of one or more —SO2F groups in a dye molecule generally improves the properties of that dye and confers surprisingly good wet-fastness and lightfastness properties. One such process for manufacturing a coloured synthetic textile material or fibre blend thereof comprises applying to the synthetic textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1) ~.4herein A and D each independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A and D carries directly at least one -SO2F group or carries a substituent to which at least one -SO2F group is attached and at least one of A and D carries directly at least one ester group or carries a substituent to which at least one ester group is attached, in accordance with requirement (a) a~bove. Azo dyes containing both an -SO2F and an ester group have improved performances in wash fastness properties over azo dyes carrying only an -SO2F group. The synthetic textile material may be selected from secondary cellulose acetate, cellulose triacetate, polyamide, polyacrylonitrile and aromatic polyester. The synthetic textile material is preferably polyamide or aromatic polyester, more preferably aromatic polyester such as polyhexamethylene adipamide or polyethylene terephthalate and especially polyethylene terephthalate. Fibre blends may comprise mixtures of different synthetic textile materials or mixtures of synthetic and natural textile materials. Preferred fibre blends are those of polyester cellulose such as polyester-cotton. The textile materials or blends thereof may be in the fbrm of filaments, loose fibres, yarn, woven or knitted fibres. Another such process for colouring a polyester textile material or fibre blend thereof comprises applying to the polyester textile material a compound or mixture thereof, which is free from water solubilising groups, of Formula (1) in which A and D are each independently in an optionally substituted phenyl group and one of A and D carries a 4-SO2F group, except for 4- (4-fluorosulphonylphenylazo) —N,N—dimethylaniline, provided that one of A and D does not carry an -NHCH2CH (OH) CH2Cl, -NCOCH2Cl or -NCH2CH2SO2F substituent. The dye compounds of Formula (1) preferably have low solubility in water, typically less than 1% preferably less than 0.5% and especially less than 0.2% solubility in water. The dyes of Formula (1) are thus free from water solubilising groups such as —SO3H, —CO2H, —PO3H and quaternary amino. The dye compounds of Formula (1), optionally in conjunction with other disperse dyes may be applied to the synthetic textile materials or fibre blends thereof by methods which are conventionally employed in dyeing disperse dyes to such materials and fibre blends. The process conditions may be selected from the following i) exhaust dyeing at a pH of from 4 to 6.5, at a temperature of from 1250C to 1400C for from 10 to 120 minutes and under a pressure of from 1 to 2 bar; a sequestrant may be optionally added; ii) continuous dyeing at a pH of from 4 to 6.5, at a temperature of from 1900C to 2250C for from 15 seconds to 5 minutes; a migration inhibitor may optionally be added; iii) printing direct at a pH of from 4 to 6.5, at a temperature of from 1600C to 1850C for 4 to 15 minutes for high temperature steaming, or at a temperature of from 1900C to 2250C for 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 1200C to 1400C and 1 to 2 bar for 10 to 45 minutes for pressure steaming; wetting agents and thickeners (such as alginates) •of from 5 to 100% by weight of the dye may be optionally be added; iv) discharge printing (by padding the dye. onto the textile material, drying and overprinting) at a pH of from 4 to 6.5; migration inhibitors and thickeners may optionally be added; v) carrier dyeing at a pH of from 4 to 6.5, at a temperature of from 950C to 1000C using a carrier such as methylnaphthalene, diphenylamine or 2-phenylphenol; sequestrants may optionally be added; and vi) atmospheric dyeing of acetate, triacetate and nylon at a pH of from 4 to 6.5, at a temperature of 850C for acetate or at a temperature of 900C for triacetate and nylon for from 15 to 90 minutes; sequestrants may optionally be added. In all of the above processes the dye compound of Formula (1) is applied as a dispersion comprising from 0.001% to 4% of the compound in aqueous medium. The azo dye compounds produced by a process of the present invention generally provide coloured textile material which shows good fastness to washing, light and heat. In such compounds, then provided that requirements (a) - (c) defined above are satisfied, the heterocyclic groups represented by A and D may be selected from thienyl, thiazolyl, isothiazolyl, ~pyrazolyl, imidazolyl, pyridyl, pyridonyl, 1,2,4— and 1,3,4—thiadiazolyl, furanyl, pyrrolyl, pyridazyl, pyrimidyl, pyrazinyl, benzothiazolyl, benzoisothiazolyl, quinolinyl, isoquinolinyl, indolyl, pyridothiazolyl, pyridoisothiazolyl, 1,2,3—triazolyl and 1,2,4—triazolyl. The carboxylic groups represented by A and D may be phenyl or naphthyl. For the avoidance of doubt optionally substituted isoquinolinyl represented by A includes structures of the formula: in which m is from 1 to 4 and m is preferably 3. A and D each independently is preferably thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl, pyridonyl or quinolinyl, morepreferably thien-2-yl, phenyl, naphth-lyl, naphth—2—yl, thiazolyl-2—yl, isothiazol-5—yl, pyrid— 4—one-5—yl or quinolinyl. A is especially preferably thien-2-yl or phenyl and D is especially preferably phenyl or naphth-l-yl. Examples of suitable substituents for A and D are cyano, hydroxy, nitro, fluoro, chioro, bromo, lodo, fluorosulphonyl, trifluoromethyl, alkyl, alkoxy, aryl, aryloxy, fluorosulphonylaryl, fluorosulphonylaryloxy, -COalkyl, —COOalkyl, -OCQalkyl, -COaryl, -COOaryl, -OCOaryl, -NHCOalkyl, -NHCOalkyl, -NHCOaryl, -NHSO2alkyl, —NHSO2aryl, —Salkyl, -Saryl, —SO2alkyl, —SO2aryl, -SCN or 12' -NR R in which K' and R2 each independently is -H, alkyl, aryl or cycloalkyl. All the alkyl, alkoxy, aryl, aryloxy parts of the above substituents for A, D, K' and R2 may optionally be substituted by -OH, -CN, -F, -Br, —I, -SO2F, alkoxy, alkenyl, phenyl, phenylSO2F, aryloxy, aryloxySO2F, —N(alkyl)2, —OCOalkyl, -OCOalkylCl, -COOalkyl, -COOalkylOH, —COOalkylCN, -COOalkylCOalkyl, -COOalkylphenyl, -OCO phenyl, -CophenylSO2F, -OCOphenylNO2, -OCOphenylalkyl, -OCOphenylalkoxy, -COOphenyl, -OCO(fluorosulphonylphenyl), -CalkylCN, -COOalkylOalkyl, -COOalkylOphenyl, -OCOalkylOphenyl, 5 -COOalkylOalkylOalkyl, —OCOalkylCOOalkyl, —OalkylCOOalkyl, -OalkylCOOalkylOalkyl, -OalkylCOOalkylCOOalkyl, -OalkylOCOalkylOalkyl, -COOalkylOCOalkyl, -COOalkylCOOalkyl, in which L is -H or alkyl. In all of the suitable substituents for A and D each 15 alkyl is preferably Cli,o—alkyl, each alkoxy is preferably C,10-alkoxy, each alkenyl is preferably C28—alkenyl, each of which may be straight or branched chain, each aryl is preferably phenyl or naphthyl and each heterocyclic group may be any of the groups described above for A and D and 20 each alkyl, alkoxy, alkenyl, aryl, heterocyclic or phenyl 1 2 group may carry an -SO2F substituent. R and K together with the -N atom to which they are attached may form a 5— or 6— membered ring such as morpholino or piperidino. A further suitable substituent for A and D is a 25 group of Formula -N(R'9)-Y-X-W in which Y is a direct link or C = 0, X is a direct link, optionally substituted alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, 20 alkyleneNHalkylene or -NR -Z- or -O-Z- in which Z is 30 optionally substituted alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene or a 20 direct link and K is —H~ optionally substituted alkyl, aryl or alkylaryl, 21 21 - 1. W is -CO2K , -OCOR , -OH or -CN in which R2 is optionally substituted alkyl, aryl, alkylaryl, 5 alkylOalkyl or alkylOH, K'9 is —H or optionally substituted alkyl. Where X, Z, K'9, K20 or R21 is or contains alkyl it is preferably C>8-alkyl, more preferablyC,5alkyl, each of which may be straight or branched chain or cyclic alkyl. 10 Where X or Z is alkenyl it is preferable C28—alkenyl which may be straight or branched chain or cyclic 20 21 alkenyl. Where X, Z, R or K is aryl is preferably phenyl or naphthyl, more preferably phenyl. Where X or Z is heterocyclic it may be selected from any of the 21 15 heterocyclic groups defined above for A. Where X, Z or R is alkylOalkyl it is preferably C,8—alkylOC>8—alkyl, each alkyl of which may be straight or branched chain and the alkylOalkyl group may be cyclic ether. Where X or Z is alkylNHalkyl it is preferably C16-alkylNHC,6-alkyl in 20 which each alkyl may be straight or branched chain and 20 the alkyiNHalkyl group may be a cyclic amine. Where K or 21C,6—alkylaryl K is alkylaryl it is preferably more preferably C,6-alkylphenyl and especially benzyl or 21 ethylphenyl. Where R is alkylOH it is preferably 25 C,6—alkylOH. The optional substituents for any of the groups represented by X, Z, K'9, R20 or K2' may be selected from any of the optional substituents listed for A, D, K' or 2 K. 30 Preferred substituents for A and 0 are cyano, nitro, chloro, bromo, fluorosulphonyl, C,~6—alkyl, C,8-alkoxy, -COC,6—al kyl, —NHCOC16—alkyl, -OCOC,6-alkyl, -COOC1~-alkyl, phenoxy, 4-SO2Fphenoxy, K N-Y-X-W in which K1 ~, Y, X and W are as herein before defined and -NK'K' in which K3 and K2 each independently is -H, C16—alkyl, C16—alkyl substituted by -OH, —CN, Cl, phenyl, 5 —0C0C16—alkyl, -COOC1..8-alkyl, -COOC1~-aikyi -C00016-alkyi —C,4—alkyl (4-fluorosulphonylphenyl), 10 -OCO(3-fluorosulphonylphenyl), -OCO (4-fluorosulphonylphenyl), C24-alkenyl, -COOC,6-alkyl, -0C16-alkylCN, -OC,6—alkylOCOC16-alkylOC1~8-alkyl, -COOalkylOCOalkyl and -COOalkylCOOalkyl or where K1 and K2 together with the -N 15 atom to which they are attached form a morpholino or piperidino ring. The compounds of Formula (1) preferably carry a total of from one to three —SO2F groups, more preferably one or two -SO2F groups and especially one -SO2F group. 20 The compounds of Formula (1) more preferably carry one -SO2F group and one ester group. Compounds of Formula (1) prepared by the above process which satisfy the above requirements (a) - (c) are novel. 25 In particular, compounds of the formula (1), which satisfy the above requirement (a) are novel compounds. In these compounds, each of A and D independently is an optionally substituted heterocyclic or carbocyclic group, at least one of A and D carries directly at least one 30 -SO2F group or carries a substituent to which at least one -SO2F group is attached and at least one of A and D carries directly at least one ester group or carries a substituent to which at least one ester group is attached. In such an azo dye compound, prepared by a process of the invention and in which requirement (a), as defined 5 above is satisfied, A and D each independently may be any of the heterocyclic groups defined for A above. A and D each independently may be any of the carbocyclic groups defined for A and D above. A and D each independently is preferably thienyl, 10 phenyl, naphthyl, thiazolyl, isothiazolyl or pyridonyl, more preferably thienyl, phenyl, thiazolyl, isothiazolyl or pyridonyl and especially thien-2-yl, phenyl, thiazol— 2—yl, isothiazol-5—yl or pyrid-4-one-5—yl. D is preferably phenyl. 15 Preferred compounds of Formula (1) in which the above requirement (a) is satisfied are those in which A is phenyl and D is phenyl; A is thien—2-yl and D is phenyl; and A is phenyl and D is naphth-l-yl. The optional substituents for A and D are any of 20 those defined for. A and D above. A preferred sub-group of compounds of Formula (1) prepared by a process embodying the invention in which, in Formula (1), the above requirement (a) is satisfied are those of Formulae (3), (4), (7) and (5), defined 25 successively below. wherein: K1 and K2 each independently is -H or optionally substituted C16—alkyl or optionally substituted aryl; 3 4 5 6 K , K , K and K each independently is -H, —F, —Cl, 5 -Br, -I, -SO2F or C,6-alkyl, Cli6—alkoxy, C14alkanoylamino, —NHSO2alkyl or Ophenyl, each of which may be optionally substituted; K7, K8 and K9 each independently is —H, C1.6—alkyl, -NO2, —COOC,6—alkyl, -OCOalkyl, -Cl, —F, -Br, -I, -C0C16-10 alkyl, —CN, formyl, protected formyl or -SO2F provided that at least one of K1 to K9 is —SO2F or carries a substituent to which at least one -SO2F group is attached and provided that K7 and K9 are not both -SO2F. Where K7, K8 and K9 is or contains alkyl the alkyl 15 may be optionally substituted. Protected formyl groups include for example oxazolidone, imidazoline, thiazolidine, bisulphite, cyanohydrin, hydrazone and oxime. The compounds of Formula (3) are novel and 20 accordingly processes for preparing them are a further aspect of the present invention. The optional substituents for groups represented by K' to ~ may be selected from any of the substituents described above for A and D. The optional substituents 25 for K' to K9 are preferably -CN, -OH, —OCOC,6—alkyl, -COOC,6-al kyl, phenyl, -OCOphenyl, -OCOphenylSO2F, phenylSO2F, -OphenylSO2F, -CO2phenylSO2F, -COOC,~6-alkylOCOC1~6-alkyl and ~COOC16-alkylCOOCi~o-alkyl. Preferred compounds of Formula (3) are those in 30 which K' and K2 each independently is -CH3, —C2H5, -C2H4CN, -C2H4OH, -CH (CH3) CH2CH3, —C4H9, -CR2 (4- fluorosulphonylphenyl), -C2H4 (4-fluorosulphonylphenyl), 3 4 5 6 —C3H7(4—fluorosulphonylphenyl), K, K, K and K each independently is -H, -Cl, -CH3, -OCH3, -NHCOCH3, —NHCOC2H5, 7 8 9 -NHSO2CH3 or -SO2F and K , R and K each independently is -H, —NO2, -CN, —COCH3, -COOC2H5, -SO2F or -CH3 provided 5 that both K7 and K9 are not -SO2F. Especially preferred compounds of Formula (3) are those in which 1 2 K and K each independently is -C2H4CN, —C2H5 or (4— fluorosulphonylphenyl) C16—alkyl; - 10 K3 is —H, OCH3, -CH3 or —SO2F; R4 and K5 each independently is -H, -Cl or —SO2F; K8 is —H, -NHCOCH3, -NHCOC2H5, —CH3 or -SO2F; K7 is -NO2, -COCH3, —COOC2H5 or -SO2F; 8 K is -H, -SO2F or -Cl; and 15 K9 is —NO2, —SO2F or —CHO. Formula (4) is: R'1 R10 R4 R3 / \ - / ~ R12 N-N — >R2 (4) 20 R13 R14 R6 wherein: 1 2 K and K each independently is H or optionally substituted C,6—alkyl or optionally substituted aryl; 3 4 5 6 25 K , K , K and K each independently is H, F, Cl, Br, I, —SO2F or C,6alkyl, C,6alkoxy, C14alkanoylamino, NHSO2alkyl or -Ophenyl, each of which is optionally substituted; and K'0 to K14 each in dependently is -H, alkoxy, alkyl, 30 —NO2, —SO2F, —F, -Cl, —Br, —I or —CN; 10 12 11 13 provided that when K is SO2F, K is not -NO2 and K , K and K'4 are not all -H. Where a group represented by R~c to K'4 is alkyl it is preferably C,,o—alkyl, more preferably C,6—alkyl. Where a group represented by R10 to K'4 is alkoxy it is preferably C,,o—alkoxy more preferably C,6-alkoxy. 5 Compounds of Formula (4) are preferably those in which K1 and K2 each independently is -CH3, -C2H5, -C3H7, -C4H9, -C5H,1, -C6H,3, -CH (CH3) CH2CH3, -CH2phenyl, -C2H4phenyl, -C3H6phenyl, -C2H4CN, —C2H4OH, C2H4OCH3, -C2H4COOCH3, -C4H8COCH3, -C2H4COCH3, -C2H4OCOCH3, -C3H6OCOCH3, 10 -C4H8OCOCH3, -C2H4OCOphenyl, -C2H4OCOphenyl (SO2F), -C2H4COOC2H4OCH3, -C2H4OC2H4COOC2H4OCH3, a 1 lyl, -C2H4Ophenyl, -C2H40(fiuorosulphonylphenyl), —CH2CH(CN) (0C2H4), C,6-alkylphenylSO2F, 15 -COOC1~-aIkyI o -COOC1~-aikyi -COOC,6-alkylOCOC,6-alkyl or -COOC,6-alkylCOOC,6-alkyl; R3 is -H, -OCH3 or -Cl; 20 K4 is —H, -CH3, -NHCOCH3, -NHCOC2H5, -NHCOCH (CH3) 2, -NHCOC3H6Cl, -NHCOC(CH3)3, -OCH3, -0C4H9, -F, -Cl, Br, -I or -NHS02C16—al kyl; R5 is -H, OCH3, -0C2H5 or -Cl; 6 K is —H, —CH3, -OCH3, -F, —Cl, Br, -T or -NHSO2C,6— 25 alkyl; K'0 is -H, -OCH3, -NO2, —Cl, -Br or -CN; R" is —H; 12 K is -SO2F or -NO2; K'3 is —H, —OCH3, —SO2F, —Cl, -Br or —NO2; and 30 K'4 is -H, -OCH3, —Cl, -Br or —CN, provided that at 4 least one of K' or R~ is —H and that at least one of K or 6 R is -H. More preferably compounds of Formula (4) are those in which R' and K2 each independently is -C2H5, —C4H9, -CH (CH3) CH2CH3, -C2H4OCOCH3, -C4H8OCOCH3, -C2H4OCOphenyl, -CH2phenyl, C1>6-al kylphenylSO2F, C,6-al kylOphenylSO2F, 5 -CoOC1~-aikyi -COOC1~-aikyi —COOC,6-alkylOCOC~~6-alkyl or -COOC,6-alkylCOOC,-6—alkyl; 10 K4 is -H, —CH3 or -NHCOCH3; •R3, K5, K8 and K" are-H; K'0 and K'3 each independently is -H, —Cl, -Br or -NO2; 12 K is -SO2F; and 15 K'4 is —H, -Cl or —Br. An especially preferred compound of Formula (4) is that in which K' is -C2H5; K2 is -C2H4OCOphenyl; R4 is 1 12 3 5 -CH3; K 0 and R13 are both -Cl; K is -SO2F; and K , K 6 11 14 —H. K, K andR are all 20 Formula (7) is: in which 1 2 K and P each independently is optionally 30 substituted C16—alkyl; K4 is alkyl or a group of Formula -N(R'9)-Y-XW in which Y is a direct link or C = 0, X is a direct link, alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkylene-NH-alk,ylene, -NR -Z-, -COOZ or —O—Z in which Z is alkylene, alkenylene, arylene, heterocyclic, alkylencOal kylene, al kylene-NH-al kylene or 5 a direct link and K is —H, alkyl, aryl or alkylaryl, W 21 ' 21 is —OH or —CO2R , in which R is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and K'9 is —H or alkyl; K5 is —H, C,6—alkoxy or —Ophenyl; R'0 is —NO2 or Cl; and 10 K'3 and K'4 each independently is -H or -Cl. In the dyes of Formula (7) 1 2 K and K each independently is preferably C,8-alkyl or C,6—alkyl substituted by phenyl or —C00C16—alkyl, and more preferably is ethyl, propyl,-butyl, l-methylpropyl, 15 hexyl, benzyl, ethylphenyl or propylphenyl. K4 is preferably a group of Formula -N(R'9)-Y-X-W in which K19 is preferably -H or C,6—alkyl, more preferably -H; Y is preferably a direct link or C = 0, more 20 preferably C = 0; X is preferably a direct link, C18-alkylene, C28-alkenylene, any of the carbocyclic or heterocyclic groups defined above for A, C16—alkylOC,~s-alkyl, -NK20-Z -, —COOZ or -O—Z— in which K20 is preferably -H, C16-alkyl, phenyl 25 or benzyl; and Z is preferably a direct link or C16—alkylene, C28— alkenylene, phenyl, benzyl or any of the heterocyclic groups defined above for A. X is more preferably a direct link, CH2, C2H4, 30 CH2C(CH3)2, cyclohexyl, CH = CH, phenyl, —NK20—Z-, -COOZ or -0-Z- in which >R2 R15 20 R is preferably —H, Z is preferably a direct lick, C,8alkyl or benzyl. W is ~CO2R2l, OCOR2' or —OH in which K2' is C>8-alkyl, phenyl, chlorobenzyl, C,6—alkoxybenzyl, benzyl, C1-6- 5 alkylOC,6—alkyl or C,6—alkylOH more preferably ethyl, methyl, butyl or 1,3-dimethylbutyl. Dyes in which both A and D are phenyl and in which one of A and D carries a 4-SO2F group are generally more stable and build up better on polyester textile material 10 than do the corresponding 2-SO2F dyes. Formula (5) is:(5) 15 wherein: 1 2 20 K and K each independently is H or optionally substituted C16 alkyl; K' is optionally substituted C16alkyl or C1~6alkoxy; K4 is optionally substituted C,6alkyl or C16alkoxy; K'0 is optionally substituted C,6alkyl, NO2 or Cl; 25 and 15 18 K to K each independently is —H, -F, -Cl, -Br, —I, -SO2F, -NO2, -CN, —NR1R2, OH or optiqnally substituted —C,6—alkyl or —C,6—alkoxy; 12 R is NO2 or —SO2F; 30 K1' is H; and 13 14 K and K each independently is H or Cl. The optional substituents for any of the groups represented by K'~ to K'8 may be sel ected from any of optional substituents described above for A, D, K' and R~. Azo dye compounds prepared by a process of the 5 invention and in which, in Formula (1), requirement (b) is satisfied, are also novel compounds. Such azo dye compounds are selected from compounds of formulae (3), (4), (5) and (7) as defined with reference to requirement (b) above. These compounds differ from the corresponding 10 compounds of formulae (3), (4), (5) and (7) defined with reference to requirement (a) in that (i) such compounds need not necessarily contain an ester group as defined in requirement. (a); (ii) for compounds of the formula (7) , in the groups 15 —N (K'9) —Y—X—W, W may be additionally -0C0R21, in which K2' is as defined above; and (iii) for compounds of the formula (4), K is -SO2F and K'0, K", K'3 and K'4 each independently is H, alkoxy, 20 alkyl, NO2, —SO2F, F, Cl, Br, I or —CN. Azo dye compounds prepared by a process of the invention, in which, in Formula (1), requirement (c) is satisfied, are also novel compounds of the respective formulae (267), (268), (269), (273), (275), (276), (277) 25 and (278), as defined with reference to requirement (c) above. Compositions comprising dispersions of the compounds of Formula (1) prepared by the process of the present invention may be formulated. The compositions typically comprise from 1% to 30% of the compound of Formula (1) in an aqueous medium. The compositions are preferably buffered at pH 2 to 7 more preferably at pH 4 to 6. These dispersions may further comprise ingredients 5 conventionally used in dyeing applications such as dispersing agents for example lignosulphonates, naphthalene sulphonic acid/formaldehyde condensates or phenol/cresol/sulphani lic acid/formaldehyde condensates, surfactants, wetting agents such as alkyl aryl 10 ethoxylates which may be sulphonated or phosphated, inorganic salts, de—foamers such as mineral oil or nonanol, organic liquids and buffers. Dispersing agents may be present at from 10% to 200% on the weight of the compound of Formula (1) . Wetting agents may be used at 15 from 0% to 20% on the weight of the compound (1) . The dispersions may be preparedby bead milling the compound of Formula (1) with glass beads or sand in an aqueous medium. In accordance with the invention, the compounds of 20 Formula (1) are obtained by usual methods -for the preparation of azo compounds such as by diazotisation of an amine of Formula A-NH2 and coupling onto a component DX in which A and D are as hereinbefore defined and X is a group displaceable by a diazotised amine. Typically the 25 amine, A—NH2 may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from —100C to 100C. Coupling onto the component D-X may be achieved by adding the diazotised amine to a mixture of D—X in an alkanol such as methanol at a temperature from 0CC to 100C. After coupling the compound of Formula (1) may be recovered from the reaction mixture by any convenient 5 means such as by filtration. Fluorosulphonyl groups may be introduced into the compounds of Formula (1) or into the A and D components prior to coupling by methods generally available in the literature. For example reaction of the compound of 10 Formula (1), A—NH2, the NH2 being protected as necessary, or D-X, in which A, and D are as hereinbefore defined, with chlorosulphonic acid optionally in the presence of dimethylformamide and thionylchloride at a temperature of from 300C to 1400C gives the chlorosulphonyl derivative. 15 The chlorosulphonyl derivative may be reacted in boiling aqueous media with potassium fluoride to give the fluorosulphonyl derivative. Alternatively the compound of Formula (1), A-NH2 or D—X may be sulphonated with sulphuric acid or oleum to 20 give the sulphonic acid derivative which may be converted to the chlorosulphonyl derivative by reaction, either of the free acid or an inorganic salt thereof, with thionyichioride optionally in the presence of a chlorophosphorus compound such as phosphorus oxychloride 25 or phosphorus pentachloride in an organic liquid such as an aromatic hydrocarbon at a temperature of from 200C to 1100C. Similarly a sulphonate ester may be converted to the corresponding chlorosulphonyl derivative. The chlorosulphonyl derivative may then be converted to the fluorosuiphonyl derivative as described above. The compounds of Formulae (1) are useful for the coloration of synthetic textile materials particularly polyester textile materials and fibre blends thereof to which they impart colours which have excellent wet and light fastness properties. Therefore, the present invention relates to a process for preparing an azo dye compound which is free from water solubilizing groups and is of Formula (1): A-N=N-D (1) wherein A and D each independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A and D carries directly at least one -SO2F group or carries a substituent to which at least one -SO2F group is attached which process comprises: (1) diazotising an amine of the formula (10) A-NH2 (10) wherein A is as defined above, by reaction of the said amine with a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite in an acid medium such as acetic, propionic or hydrochloric and at a temperature of from -100C to + 100C to form a diazotised amine; (2) coupling the diazotised amine with a coupling component of the formula (11) D-X (11) wherein X is a group displaceable by the diazotised amine and D is as defined above, by adding the diazotised amine to a mixture of the coupling component of the formula (11) in an alkanol such as methanol at a temperature of from 0 to 100C to form a monoazo compound of the formula (1) and wherein at least one of the following requirements is satisfied: (a) in the formula (1), at least one of A and D carries directly at least one ester group or R8 carries a substituent to which at least one ester group is attached; and (b) in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formulae: (3) ~R2 wherein: R' and R2 each independently is H or optionally substituted C,6-alkyl or optionally substituted aryl; K3, K4, K5 and R6 each independently is H, F, Cl, Br, I, -SO2F or C,~ alkyl, C~6-alkoxy, C14alkanoylamino, -NHSO2alkyl or - Ophenyl, each of which may be optionally substituted; K7, R8 and R9 each independently is H, C,~— alkyl, NO2, -COOC,6-alkyl, -OCOalkyl, Cl, F, Br, I, -COC,6-alkyl,-CN, formyl, protected formyl or -SO2F provided that at least one of R' to K9 is -SO2F or carries a substituent to which at least one -SO2F group is attached and provided that R7 and K9 are not both -SO2F; wherein: K' and K2 each independently is H or optionally substituted C16-alkyl or optionally substituted aryl; 3 4 5 6 R , R , R and R each independently is H, F, Cl, Br, I, -SO2F or C, 6~alkyl, C,6-alkoxyl, C,.4- alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; 12 R is -SO2F; and R'0, K", K'3 and K'4 each independently is H alkoxy, alkyl, NO2, -SO2F, F, Cl, Br, I or -CN; in which 1 2 K and R each independently is optionally substituted C,6alkyl; K4 is alkyl or a group of Formula -N(R'9)-Y-X-w in which Y is a direct link or C = 0, X is a direct link, alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene, -N(R20)-Z-, -COOZ or -OZ in which Z is alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene or a direct link and R20 is -H, alkyl, aryl, or alkylaryl, W is -C02R21, -21 OCOR or -OH in which R2' is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and K'9 is H or alkyl; R5 is H, C,6-alkoxy or -Ophenyl; R'0 is NO2 or Cl; and R16 R" and R'4 each independently is H or Cl; and Rl2 wherein R' and R2 each independently is H or optionally substituted C,6-alkyl; 3 K is optionally substituted C16-alkyl or C,6-alkoxy; R4 is optionally substituted C,6-alkyl or C,6-alkoxy; R'0 is optionally substituted C,~6-alkyl, NO2 or Cl; K'5 to K'8 each independently is H, C16-alkyl, C,6-alkoxy, F, Cl, Br, I, -SO2F, NO2, -CN or NR K R'2 is NO2 or -SO2F; R" is H; and K'3 and R'4 each independently is H or Cl except for: 4- (4-f luorosulphonylphenylazo) -N,Ndimethylaniline, 4- (4-f luorosulphonylphenylazo) -N,Ndiethyl aniline, 4- (4-f luorosulphonylphenylazo) -N-ethyl-Nacetoxyethylaniline, 4- (4-fluorosulphonylphenylazo) -3- (trifluoromethylcarbonylamino) -N-ethyl-N- (2-methoxyethyl) aniline, 4- (4-f luorosulphonylphenylazo) -3-(trifluoromethylcarbonylamino) -N-ethyl-N- (2-cyanoethyl) anl me, The invention is further illustrated by the following Examples. 1') Example 1 Preparation of 4-(2,5—dichloro-4— fluorosulphonylphenylazo) —3-methyl-N-ethyl—N— (2-benzoyloxyethyl) aniline 1; i) Preparation of 2,5-dichloro—4-chlorosulphonylaniline 2,5—Dichloroaniline (32.4 parts) was added portionwise to chlorosulphonic acid (93 parts) at 350C. The mixture was stirred at 1200C for 3hrs and then cooled 2) to 700C. Dimethyl formamide (1.6 parts) and thionyl chloride (15 parts) were added, maintaining the temperature at 65-700C and the mixture stirred at 700C for 24 hours. The reaction mixture was cooled to ambient temperature and poured with caution onto stirred ice (1000 parts) producing a cream precipitate. The product was isolated by filtration, washed acid—free with ice/water and dried under vacuum to yield 2,5-dichloro-4-chlorosulphonylaniline (44.2 parts) 33 ii) Preparation of ~,5~dichloro—4-fluorQ5ulphOnylaniline A mixture of ~,5~dichioro—4- mixture of 2,5-C cr9cr uo~-osulrhonvlani~ine i3~~ ~c- ac-etic,"pror'icnio arid 15 (5614, '~' c 50K- The TfiXtUtC was szirreo at 9~C to ?0C for 2 hours beforC ~~1uo roe react~cn mixture from iii) above in metnanol (.1G0cm~ at 00C to 50C The orec~r~tateO soiio was oo~eored by filtration wae.hed with water, darned with methanol, collected by filtration and wasneci with methanol to give 4-(2,5-diohloro-4- 20 fluorosulchonvlvhenvlazo)-3-methvi-N-ethvi-N- L-beazovJoxvet)7vlK-nilin~ (2lg) when arplied to polyester materials from earienus d~spers~on Gives bluish-red shades with exoelient wet ann light fastness properties. The following examples of dyes of Formula: i) PreDaraticin of 2,6~dibromo~4~fluOroSulflhOnVlaniline To a solution of '1~aminobenzeneSU1PhonY1 fluoride (10 parts) in acetio aoid (100 parts), stirring at 0-~0C was added gradual lya solution of bromine (18 parts) in acetic acid (50 parts) keeping the temperature below 50C The temperature was allowed to warm to ambient and the mixture was stirred at this temperature for a further lhr. The reaction mass was drowned into water (500 parts) . the produot was isolated by filtration, washed with cold water and dried at 500C to yield,- 2,6~dibromo~4~fluoro5ulphOnYlaniline (17.5 oartsY ii) Preoaration of 4- (2,6~dibromo4fluOrOsulOhonvlPhenvlazo~3 acetamido~N,N-diethVlaniline A mixture of 2,6~dibromo~4~fluoro5u2PhcnYlaniline (2.7 parts) and aceticiprcpioiiic acid mixture (15 parts. 86/14 vol/vol) was stirred and heated until a complete solution -was formed. The solution was set stirring at 0-50C, and nitrosyl sulpnuric acid soln (5 parts) was added dropwise The mixture was stirred at this temperature for a further 30mm. Br 40 The diazo solut ion was added el c~i~: tc a rrri~~UrC r-~iZ 11 o ethyl amincacetani I ide (1 7 p-arts) , methamml (50 part ~c-m ulchanic acid (05 parts); stirring at 0~5cC. dter stirrinq i~r 1n'- t tnrs ernoerature, water (50 carts) was added and the mixture wa~ ~t irred a further 30mm at ambient t ermerature - The crc-duct was - ~ ~t ~d by filtration, washed with water and methanol and then orie~ ot CQC5 tc wield; 4- (2,6-djbromo~'1~flucr-csuichcnvicm-. -,'la-zc- ao~amidoC Nu~ethyJaniline (1.5 oarts) ),max—-15t'nm. 9;hem applied tc polyester matc: cals frcm an amuec-us misoersion, the dye gives dull orange ~ha~ with excel I emt iuht fastness and excellent fastness to wet treatments The followino examoles of dyes of Formula: were prepared by the procedure of Example 8 ____ ____ '2frlir7Jano-4-fluorO5ulOhoflVO-hCn7iaZ'~) - ~-oc'~-amido CC-,) Ie"ifl'"mi '~Lr of. -~- 2, 6-clibromo--1-fluorosulphonylmheliyliazo- 3- lanirime (Example 101) (1 5 carts) cuorous cwan~OC ' The react ion mixture was diluted with ~ - - 0mm and the product was iso~ateo by filtration to - --1- flucrosulohonvlphenviazP)->aOCtan~(iC>H.N 1-ersion, th~ ~ nives bcight blue shades with excellent lioht fastness ano excellent fastness to wet treatments. Exammi e 105 Hrec-arat ~on c- - C? 6-dicvano-4- fluorosuichonvlohenvlaxo) -3- acetamido ~ 1-1-ni - n - nutyl ani line Tne uve in Example 102 (LOg) was stirred in UME (30cm3) and CuCN (ThOu) at 90CC for'2 hours The reaction mix was drowned onto iOC and the precipitate collected, washed with water and dried under suction. The filter cake was dissolved in dichioromethane. filtered and the filtrate evaporated to give a blue dye C..max 611mm) - Example 306 Preoarat~cn of '1- (2,6~di~,ano~4~fluoro5ulphonVlPhenVlaZo(-3OcCtamido- N N-diacetoxvbutvlamrno aniline The dye in Example 103 WOo) was stirred in OME (30cm3) and CuCN (1.Og) at 9t'0C for 2 hours. The reaction mix was drowned onto ice and the precipitate collected, washed with water and dried under suction. The filter cake was dissolved in dichloromethame. filtered and the filtrate evaporated to give a blue dye (Xmax 608mm). Example 107 Preparation of 4- (?.6~dichloro~4~fluorosulPhOnV½henVlaZo)N.N-di-n-butvl aniline i)Preparation of 2,6~diohloro~4~ohlOro5ulOhonVlamiline The procedure of Example lii) was repeated except that in place of the 32.4 parts -of 2.5-dichloraniline, 32A parts of 2,6-dichloroanilifle were used, to yield 2.6-diohloro-4-chlorosulphOfiYlaniline (42.6 partsY ii)PreparatiOn of 2,6~dichloro~4~fluorOsUlPhonVlanilime The procedure of Example Iii) was repeated except that in place of the 442 parts of 2,5~dichlorc~4~chlorosulPhonYlaniline. 42.6 -parts of ?,6~dichioro~4~chlOro5ulPhOnYlanilime were used, to yield 2,6-dichloro~4~fluorosulPhonYlaniline (360 parts). iii)Preoaration of 4- (?.6~diohlOrc~4fluorpsulphonVlphenYlazoK-N,Ndifl butylanil me A mixture of 2.6~diohlorn~4~flUorO5ulPhomYlOniline (2.0 Ohenac-oliod to Thciyester mat e~i~l~ ~r-o an aqueous niscersion, the nwe otwes dull yellow brown snaucs with excellent fastness to lioht and wet treat mont 5 - The followino exa'r In-s c-f d-,--es of Fc-rmtila: Examole 111 Precaration of ~ diethvlaniline The procedure of Example 87ii) was repeated except that in place of the 2.7 parts of 2,6~dibromo~4~fluorosulphOflYlanilifle 2~O carts of 2-bromo-4-fluoro5ulphOnylaTiil~r1e were used The product. 4- (2-bromo~4~fluorosulDhonylphenViaZOY3-aoetamidol-~ N-diethylhnlline (1.6 ca'--~) ).max=S2nm, when applied to polyester materials from an aoiieous discersiom gives bright mm red shades with excellent fastness to light and wet treatments. The crocedure of Example 5~ti wa~ repeated except t hat in place of the z . / parts of 2, E--dibrcmo ~ lea '-suiphcnx'lani lime; 2.0 parts of 2-nitro-5-c-hloro-4-fluorosulcnon--1aciline were used. The product, 4-(i-nrtro-5-chlcro-4-flucrcRulC-h'~'\tmhCnVlaZo-~-acetam1(io-N,N-diethvlaniline (2.6 Parts) ~max~5C~nrrI wl-'-n acoliod to cotwestor materials from an aqueous niscersion cii va-s bluish red shades with excellent fastness to light and wet treatmemts. Examole 114 - i) Preparation of 2-nitro-'~-fluorc-sulchomvlaniline N-acetvl sulphanilyl chloride (10cg~ was dissolved in concentrated sulphuric acid (515 cmi), cooled to 4'C and a mixture of concentrated nitria acid (38.6 cm3) and concentrated sulphuric acid (42P cm3) added droowise maintaining the temperature at 4-6'C. After 1 hour the reaction mix was drowned onto ice and the precipitate collected, extracted into dichloromethane and evaporated to a yellow solid (92g) -31g of this veflow solid was ref luxed for 3 hours ~n wa~r 17fl c-mi , dioxane (20 cm3) and KE (l9Ag) then drowned onto ice and the precipitate collected. This precipitate was refluxed in absolute ethanol (35 cm3) and concentrated hydrochloric acid (35 cmi) for 1 hour then drowned onto ice, filtered and suotion dried. Peorystallisation from ethanol yielded 8J7g of the recuired compouna. ii) 2-Nitro--fluorosulphonyl aniline (0.01 mol) was dispersed in a mixture of aoeoic:propionic acid (86:14; 25cm3). cooled to 0-5CC and nitrosyl sulphuric aoii~ (0.01 mall added portionwise at 0-50C. The reaction mixture was stirred for 10 minutes at 0-50C then added dropwise to a mixture of the 3- (N,N-diethylamino) acetanilide (0.Olmol), methanol (50cm3) and ice (SOg) - The resultant precipitate was filtered, washed with water and them methanol and oven dried at 5005. The dry dye has a ).max of 54mm and gives good fastness to washing, light and heat. The following examples of dyes of Formula: we-ce crocared by the procedure of Examote 114: i, Prem. C-tcm of 2-—it'r--~--flucrosu]chonvl-6-chloroaniline 2-r-)icro--fiuorcsultthonylaniline (lOg) was dispersed in 30~ PCI (6 (c-.) cooled to 0-5'-C and sodium chlorate (2g) dissolved in water (Il- -~ ouc u droowi se ensuring ma~ ntaining the temperature at 0- '-0 ' r — 'r it cc reaction mtxeure tirowned onto ice and orecicit are ecliectec, w-~'----- th water and suction dried ~c -.~ield 5.So c-f 2- tIltic ct usuim c-hI c-roam i I inc - I ?ttCt 4-fluorcsulohcnx'1-E---ohloroaniline (7SSmmolt ~Z u~soerseo in - 'r-'x .rc c; ac-ettc-:orc-cicnic ac-id (56:14; 25cm~), cooled cc 0- S'-C and nr~~~; sulphuric- ac-ia (L86 mmcl) added portionwise at 0-I-'-C. The reaction rrixture was stirred for 10 minutes at 0~5~C then atioco ntoowi'-C- tm a mixture of the 3- (N,N-diethvlaminc) ac-etaniline (756 mmcl), methanol (SOc-mi and ice (BOg) - The resultant precipitate was filtered washed with water and then methanol and oven dried at 500C The dry dye has a Amax ci 550mm and pives good fastness to washing, ioht and heat - 'the followH,o examples of dyes of Formula: NO2 P4 FO2S were prepared by the procedure of Example 139: Example 156 Precaration of 4- (5-ohlcro-4-flucrosulphcnvl-2-nitrOohenvlaZo)-3- aceoamido-6-methoxv-N . N-dibutvlani I Pie k-Nitro-m-chloroacetaniiide t~umy was added cautiously to chlorosulphon~c- ac-ic (40cm3) then heated at 1200C for 2 hours. The reaction mix was cooled to 5005 and drowned onto ice. The precipitate was filtered, washed with a little water ana suction dried. This solid was dispersed in water (20 cm3) , p-dioxane (20 cm3) and KF (lOg) - After refluxinci for ~ incurs the reaction m:x was crowned into water, the precipitate filtered and suction dried This solid was refluxed in water (50 cm3) and 36% 1151 (50 cm3) for 2 hour, drowned onto ice and the precipitate collected. Yield 3.5g. - ii) ~-Nitrc-4-f2uorcsulphPnvl-5-c-hlOrcaniline ('>86 mmcl) was disoersed in a mixtuce of aceoic:crcpicnic acid (86:14; 25cm3), cooled to 0-SOC and nitrcsvl su3pir~r~c ac-id '>56 mmcl) added portionwise at 0-50C The reaction mixture was stirrec for 10 minutes at 0-50C then added droc-wise to a mixture of the 3-(N,N-diburvlanino)-4-methoxvacetanilide (7.86 mmcl). methanol (50cm3) and ice (SOg) - The resultant precipitate was filtered washed with water and then methanol and oven tiried at 500K- The 'dry dye has a Amax Of 604nm and aives good Br tc-c tneos to wasbino 3 iuht antI (teat - Examole 157 Prenaration of 4- (2~nitro-4~fluorrcuiic1 C- i ErCTCOFCnvtazc~ -j-acetamido-N, N-diethvlanil me I) 2-Nitro-'i-fluoro-sulphcnyh- ii K-' dissolved in Glacial acetic ac-id (SO cm~ and orc a -~- ' - -- Peact :cn mix warmed to 750C for 2 hours th -rca, .~shcu .-;~th water anti suction dried. Yield El n r ii) 2-Nitro~4~fluoCoe~lphcn-,Ci - "C F' - - - C r I was (iisoerseo in a mixture of ac-etic:ocootr---i- C- ~ ) in c-pc--led to Q~5Oc and nitrosyl sulphuric acid I r owise at 0-W'C The reaction mixture was st ic-c-eu C tnen added droowise to a mixture of the ~- N -T ~- C~dViJine (0.01 mol) , methanol (50cm3) and ice (St-n) - The resultant crec-icitare was filtered washed with water and then nethanci ac-ct c-yen OrAeo at SOCC The dry dye has a Amax of SSOnm and gives 0cc-u tastiness to washino, lioht and heat. The following dyes of Formula: were prepared by the procedure of Examole 157: Example 162 Prenaration of 4-(2-nitro-4-fluorosulphonvl-6-cvanoohenvlazo)-3-acetamido-N.N-diethvlaniline Dye Example 157 (2Oa) was stirred at 90CC with CuCN (042g) and PMF (20cm3) for 3 hours. The reaction mix was drowned onto ice (SOg) and the precipitate collected, washed with water and suction dried. The filter cake was slurried in dichlorcmetT-iane, filtered and the filtrate evaporated to oive a solid dye Omax 603nm which gives pond fastness to heat, washino and linho. The following dyes of Formula: Examo-le 166 Preoaraoion of ~- (3-oarboethox\'-5-nitrothien-2-vlazo)-3-methvl-N-eehvl N- iS-fluorosu'chonylbenzovloxy)ethvl aniline 4- (3-carboethoxy- 5-nioroohienyl-2-ylazo) -3-methyl - N- ethyl N-hydroxvethvl aniline )Smmol) was disolved in chloroform (20cm3 potassium carbonate (0.7g) and 3-fluorosulrhonylbenzoylchloride (>2g) were anoen and the mixture refluxed for 2 bours. The reaction mixture was filtered and the filtrate evaporated to leave the solid dye, Amax = 558pm. The following examples of dyes of Formula: - C4H,O-CCK3-SO-Fshenvl) - C~HOCC(3-SC2Fchenvl) - C~H4OCO (S - EC-Ephenyl - CZTI~OCO (3- SO,Fphenvl) - C~11~ OCC(3-SO2Fphenvl) ~ers crepared by the oroceoure of Example 166: Example 272 Preparation of '~- ~ N- bi-fluorosulnhonylOhenvl (methyl aniline ~-Amino-3-carboethoxy-5-nitrothiophene (0.01 mol) was dispersed in a mixture of aceoic:propionio acid (86:14, 25cm3), cooled to 0-5C and nitrcsmlsulphurio acid (0.01 mol) added portionwise at 0-50Q The reaction mixture was- stirred for 10 minutes at 0-50C then added dropwise to a mixture of the N-ethyl-N- (4-fluorosulphonylbenzyl)-3-toluidine (002 mol) . methanol (50cm3) and ice (50gb The resultant or ec- i pitate was filtered washed with water and then methanol and oven dried at 50CC. The dry dye has a Amax of SSOnm and oives qood fastness to washing, light and heat The N-ethyl-ZN- (4-fluorosulphonylbenzyl)-3-toluidifle was prepared as follows: N-Ethyl-3-toluidine (0.Olmol). potassium carbonate (0.Olmol), OMP (50cm3) and i-fluorosulphonylbenzyl bromide (0.2mol) were stirred at 10005 for 24 hours. The reaction mix was filtered, drowned onto ice and extracted with dichloromethane to give an impure product (229) . No 30 further purification was required. The 4-fluorOsulphOflylbenZylbrOinide was prepared as follows: Tosyl chloride (SOg) , bromine (43g) and carbon tetrachloride (SOOmIs) were stirred at reflux while shining a uv lamp (365mm) onto the reaction Once the solution beoame colourless the reaction was stopped and the solvent removed by evasoration. The resultant oil was refluxed in water (200mls) and potassium fluoride (47g) for three hours After three hours the reaction mix was drowned onto ice (SOOg) and the precipitate collected, washed with water and dried in vaouo. Yield 34q cif pale yellow crystals which by GLC is 54% reniiired material. 27% startino material and 12% dibrominated species. N-Erhyianiline (0 t2m'A c-ct assiurr cartonate (K- t'lmc-l ,CMK(500m3) and -fluerosu:chomvlhenzx': o-rc-mtde 02tr:cll were stirred at 100CC for 24 hours. The reaction nix wa-s filtered, drowned c-nrc- it~e and extracted with dichlcromerhano to piPe an tnpure product (2t;c--) - No further pt]rif~cation was recuired Example 174 Preparation of 4~(3~c-arhoethrxv~r~nitrcthien-2-VlaZcJ-H-CthVl-N-('1-fluorcsulohpnvl.ohen\'l orcoytaniline 2-Amino-3-carbc-ethoxv-5-inltrothicoheine (0.Olmtl) was dispersed in a mixture of ac-etic:prcpionic acid (86:24; 25cm3), cooled to 0-~0C and nitrosyl sulphuric ac-id (0.Olmol) added pc-rtronwise at 0-~0C The reaction mixture was stirred for 20 minutes aT C-~0C then added droowise to a mixture of the N~(4~fluorosuiphcnylphenylpropyl)-N-ethylaniline (0.Olmol) , methanol (50cm3) and ice (SOg) - The resultant precipitate was filtered washed with water and then methanol and oven cried at 500C. The dry dye has a Amax of 693mm ano nives 0000 fastness to washing, light and heat. The N-ethyl-N- (4~fluocosulPhonylphenylprcPyl)aniline was prepared as follows: 35 N-Ethvlanil2ine (0.O2rnol). potassium carbonate (002mo1). DMF (50cm3) and -fluorosulnhonylphenylprOpyi bromide (0.2mol) were stirred at 10005 for 24 hours. The reaction mix was filtered,drowned onto- ice and extracted with dichloromethane to give an impure product (25g) - No further purification was reouireoThe 4~fluorO5ulPhOnylphenylpropylbromide was prepared as follows: Phenvlproovl c-romioe 25.901 was dissolved in chloroform (SOOmIs) and ohlorosulphonic ac-id (226q) added droowise. stirred for 12 hcurs at 40C then drowned onto ice lOkg) - The white precipitate was collected, redissolved in dichloromethane, washed with water, dried over magnesium sulphate and evaporated to a pale yellow oil that crystallised on standing. Yield 15n This solid was dissolved in p-dioxane (SOmIs) and (2 So) and refluxed for I:erc-e- houre After ocolimo to araici en: reaotton mixture was cii-c-:wneo onto ice- 40t)ut , extracted with di chioromethane (3x200nls) dcied om~-'c reaunesium eulohat e a-'- - - ':acorateiJ to a orow nre of the N- ~z ~-amcath:'l ~ -N- (I 'c-='-'sult'honyl phenyieth-.vl)aniline (002mo1), methanol (50cm and ice (SOY -The resultant precipitate was filtered washed with water anu teem methanol ama oven dried at 5005. The dry dye has a ).ma;~ c-f ci no anu u~ves opoc-. fastness to washing, light aiid heat The N- (2-cyanoeth~l)-N- (-fluorosulphonxdc--henvleohyP aniline was prepared as follows: 20 N- (2-oyanoethvl)aniline (OOlmol), potassium carbonate. (0.01mc-2,~ , ONE (50cm3) and 4-fluorosulphonylplienylethv2brom~de (0.mol) were stirrc-u at 20005 for 2 hours. The reaction mix was filtered, drowned onto toe ama extracted with dichloromethane to oive am rmpure product (25o) - rIo further purification was reouired The '4- fluorosulphonvlphenc'leohylhromide was preo-arec as follows: Phenylethyl bromide (365g) was dissolved in chloroform (5c-Omls; and chlorosulphonic acid (233g) added dropwise. Stirred for 12 hours at ambient then drowned onto ice (10kg) . The white precipitate was collected, redissolved in dichloromethane, washed with water, dried over maunesium sulphate and evaporated to a pale yellow oil that crystallised on standing. Yield 40.8g. This solid was dissolved in p-d~oxane ~200mls) and KF (24.7g) and refluxed for three hours. After cooling to ambient the reaction mixture was drowned onto ice (700g) , extracted with dichloromethane (3x200m1s) . dried over magnesium sulphate and evaporated to a brown oil. Yield 33.7g. Example 176 Preparation of 4- (~ ~-dinitrothien-2-vlazo) -N-ethyl-fl- (4-fluorosulohonvlchenvl T methyl aniline 2-Amino-3,5-drnitrothioohene (002m01) was dispersed in a mixture of acetio:propionic ac-id (66:14; 25cm3), cooled to O~5eC and nitrosyl sulphuric- acid (OOlmol) added porrionwise at 0-5'-C. The reaction mixture was stirred for 10 minutes at 0~5oC then added droowise to a mixture of the N-ethyl-N- (4~fluorosulphonvlbCinZyl)aniliIie (OOlmol), methanol (50cm3) and ice (SOg) - The ½sulrant precipitate - "—- wa'- rre-A fcr 10 minutes at 0-S"C the'- - ~cu e C-' C- LTC I. CcVj 2.- (4-flucrosulp~honvlphenviorn ~ nt (tAi2 mo-I) , methanol (S0c'n~ and ice (SOoT - The resultant crec:p-ttate was filtered washed with water and rh~n inethonol and omen dried at S The dry dye has a Amax of El-i 7inm and gives aood fastness to- wasni ng, light and hear Examole 178 Pcenarat~on of '1-Vt 5-otnirrcthien-2-vlazo-N-(2-cvanoeohvl)-N-c'i-fiuorosulohcnviohenyl) ethyl aniline ~-Amino-3,5-dinitrothicPhene (O.Olmol) was dispersed in a Irixture of aoeoic:o-ropionio acid (66:14; 25cm~), cooled to 0-SOC and nitrosyl sulphuric acid (0.01 mol) added port ic-inwise at 0-~'-C The reaction mixture was stirred for 10 minutes at 0~5oC then added drcpwK-e to a mixture of the N- (2-cyanoethyl) , N- (4-fluorosulphonvlphenylethvl) aniline (0.Olmc-l), methanol (50cm3) and ice (5OgV The resultant precipitate was filtered. washed with water and methanol and oven dried at 5005. The dry dye has a Amax of 580mm and gives good fastness to washing, light and heat. - 30 The followino examples of dyes of Formula: were prepared using the procedure of Example 172, the fluo-rosulchonvlphenylalkyl bromides were prepared as described in examples 275 as aporooriate. P Exatnole 190 Preparation of '1- ~ - seobutvl-N- 4-fluorosulohonvlohenvl (methyl aniline 2,-Pinitroaniline (OOimol) was dispersed in a mixture of acetio:propionic acid (86:2-1; 2Scmj, cooled to 0-50C,and nitrosyl sulphuric acid (O.Olmol) added cortionwise at 0-50C The reaction mixture was stirred for 10 minutes at O~5oC then added drcpwise to a mixture of the 3- (N- (4-fluorosulo-hon lbenzyl)-N-seo butvlamino)-4-methoxvacetanilide (OOlmol). methanol (50cm3) ahd ice (SOg). The resultant preciVitate was filtered washed with water and then methanol and oven dried at 500C. The dr-v dye has a Xmax of 575nm and gives good fastness to washing, lioht and heat 30 The 3- (N- (4-fluorosulphonylbenzyl)-N-seo-butvlamino) -4-methoxyacetanilide was prepared as follows: 3- (N-sec--butvl)amino-4-methOxvacetani lide, potassium carbonate (0.Olmoll, DMF (50cm3) and '1-fluorosulphonylbenzyl bromide (0.2mol( were stirred at 2000C for 24 hours. The reaction mix was filtered, drowned 35 onto ice and exrracted~with dichloromethane to aive an impure product (220X 1-Ic ~uCther purification was reouireo. Example 291 Preparation of 4~(2A~dinitro~6-tromormhenvlazO)-3-aOCtamidOVtmethO~JN 40 sec-butvl-N- i-fluorosulphonvlphenvl (methyl aniline ~,-P~n~trO-6-brotflOAinilinC (OOlmol) was dispersed in a acetic:propionic acid (86:14; 25cm3), cooled to 0~5oC and mixture of fast ness to- washi mu, i luLt arirt heat - Example 202 5reuarat~on Of 4rnLUi-d~ ri t -c~ 5- ovatto-che mvl as' -: - ac-ct amino-:- -met hox-~r-T-Isec-buryl -N- 1-f luormsui ohooxI ohen-;l m:etmt: amiThe d~-.'e I rcm Example ~53 - ___mr~ol -.~as di ssc'l -:ed in DM1-' (30cm3) and CuCH (02n) and stirred at CC-' C Ic: 1 hour - The reaction tnix was drowned onto ice and the pt-cc-imitate fileered The dried filter cake was sitirried in dichloromnerhane , filtered and the filtrate evaporated to a sotlid dye with Amax p-f C-.l2nm Example 253 Preoaration of - ~ butyl -N- ('1.fluorosulohoinvlphenvl)n~prcovl aniline The method of Example 292 was used except that 2, ~2-dinitro-6-chloroaniline (0.02 mall was used in place c-f the 2,4-dinitro-El-bromoaniline and 3- (N- (4-fluoc-osuit:homy~pnenyi (prc-ovl-N-n-butvl-6-methoxy)toludine(0.02 nol) was used in place of the 3- (N- (4-fluorosulohonylbenzyl~ -N-seobutyl-4-mc'choxvac-ctanlide. The dye has a Amax of 586 Snm and oives good fastness to washino, liqht and heat. Examole 194 Preoaration of 4-(2.-dinitroohenylaxn(-3-methvl-N-ethvl-N-(4-(3-30 fluorosulohonvlbenzoyloxvl)n-butyl T aniline 2,4-Pinitroaniline (0.OImol) was dispersed in a mixture of acetic: propionic acid (86:24; 25cmi), cooled to 0-~0C and nitrosyl sulphuric acid '(0. 02mph added portionwise at 0-50C. The reaction mixture was stirred far 10 minutes at 0~5OC then added dropwise to a 35 - mixture of the N-erh"l-N-hydroxvbutyl-3-toluidiine (0.OImol), methanol (50cm3) and ice (SOg) - The resultant precipitate was filtered washed with water and then methanol and oven dried at 500C. The hydroxy dye (S mmol) was dissolved in chloroform (20 cm3), potassium carbonate (0.7g) and m-(sulphonylfluoride) benzoyl chloride (Th2q) and refluxed for 2 40 hours. The reaction mix was filtered and the filtrate evaporated to yield a solid violet di~e which aives nc-pd fastness to washing, light and heat. Example 295 Preparation of '1- (2.4-dinitro-6-bromoc-henvlaro)-3-acetamido-N-n-propvl- N- (3-fluprosulphonvlbenzovloxv)ethvl aniline L.4-Dinitro-6-brc-mpaniline (OOlmol) was dispersed in a iyr~~rC-- C- acetic:pro-cronic acid (56:2'> 25cm'), cc-c led to C-t'-j -~~trosv2 sulohuri p acid (0. OImoI added pc-rc icawi se at El;- S'-C - The reaction mixture was stirred for 20 minutes at O-5'-C then aotleo o-.Fpw~-e to a mixture of the 3- (N-procvl-N-hvdroxvethvl) acetanilide (CA-2:r,-'2) metnanol (50cm3) and ice (5Cc-) - The resultant orecimitat e was f~ 0. cd -~-.~ed with water and then methanol and oven d~ '2'm'-'~~ (Sminol I was dissolved in chloroform 20cm') - ~umn rart-onat e - 7g1' and m- (sulo-honvlfluoride( benzovl chIc: and ref½--"—-d to: 2 hours. The reaction mix was filtered ann i e f'ltraoe e-~'ap-t'raten to- yield a sc-lid dye (Amax 552mm) which Gives pC-'~c ' ness to xasri:nn, hoSt and heat. Fxampie 296 (-'remaration of 4- (2-chloro-S-f1uorpsu2ohomv2ohenvlrz~-- (2-ethyl-N- henzvl 1 - me 3-Amino-4 -chioro benzene suiphonvl fluoride (2 carts' was strrred in acetic/Propionic acid 8~/2'1 vol/vol (2'-- paC-rs) and cooled to t-50C. Nitrosyl sulphuric acid solution ('>5 carts) was added urcc-w3se at 0~5OC and stirred under these conditions for 2 hours. The diazo solution was then added to a mixture of N-ethyl-N-benzvl aniline ('>7 parts), methanol (100 parts) and suinhamic acid (2 carti stirrtnn at 0-50C After stirring under these conditions fc-f 30 nuns, ice/water (100 parts) was added and the mixture stirred for a further I hour. The product was isolated by filtration, washed with water and pulled dry. The damp solid was then slurried in methanol (200 parts) and re-filtered. Pried at 50CC to yield 4-(2-chloro-5-fluorosulphonvl phenyl azot-N-ethyl-N-benzyl aniline (2.3 parts). When applied to polyester materials from an anuec-us dispersion, the dye gave yellow shades. Amax 463nm The following examples of dyes of Formula: CI P4 P1 /\N N~N P2 FO2S were prepared by the procedure of Example 256: aniline -Chloro-4-amiino benzene sulphonylfiuc-ride (I part) was stirren tn acet~c!orooibnic acid 86/14 vol/vol (15 parts) and cooled to 0-~'-C. Nitrosyl sulphuric acid solution (1.9 parts) was added droowrse then strrren at 0-5'-C for 2 Tiours. The diazo dolution was then added to a stirred mixture of N-ethyl-N-benzyl-aniline (2.0 parts), methanol (50 parts), sulphamic acid (05 parts) and sodium acetate (5 parts) with ice,'water (100 parts) at 0~5OC. After stirring under the-se conditions for 2 (tour, the dye was filtered off and washed well with water. The damp solid was slurried in methanol (100 parts) and re-filtered. Dried at 50CC to yield the product 4-(2-chloro-'1-fluorosulphc-nyl phen~lazo) -N ,.tC.~ TAb be - ~'-'~½e ~i.n pa ....en applied ~- "-=t~' from an aqueous dispersion the dye gave orange shades. Amax 483mm 30 Example 208 Preparation of 4-(2-chlorO-4-fluc-rc-5ulphonV2PhCinVlaZO)-3-aoetatnAdo-NJ~ bis)2-acetoxvethvl) aniline The procedure of Example 207 was repeated except that in place of 2 parts of N- ethyl-N-benzyl aniline; 2 parts of N,N-bis(2-acetoiovethvl( an-inoacetanilide were used to yield the product. '1-(2-chloro-4-fluorosulphonyl phenylazo) -3-acetamido-N,N-bis(2-acetoxveth;'l) aniline (1.2 parts). When applied to polyester materials from an acuec-us dispersion, the dye gave orange shades. Amax 49'1nm Example 205' Prec-aration of 4- ~ -N-benzvl aniline 25 - nn (2.5 carts) was droc-wrse ann 'azc solution was then added to a I 'C' mi—'-'V-~ o I~ ~h-'l ¾ '-err" m-toIuiotne (13 parts), methanol 5( te-.~~C-j ~~~rnomiC- ~FiC~ ~C on'- '-) and sodiurri acetate (5 parts) S C-~ -'-e 'wet'- . t r sttrrtnn for 2 hours tinder these - i~- em oU and washed well with water - The Gamin' ( V fed io water ann '-- t1cen. tine u-vs was then 1 at room oemc-eratu hour, filtered, and dried at cr'"icc' '1- 2 - me' '-C' '-lucrcsulr-hoa'1 phenvi arc-) - .--inr, ( ~i t n H ~o' a'-- tine ci - - c-er- -.,m to - "'~ applied c-c-i -"' '- inn - - ,-I '- from alt am'jeops a ~o~' '-in, tne aye nave yellow charles. Amax 45~. 'lbs f c:i 2 owinG examnl es of dyes of Fcrmnul a Ri -N N P2 FO-)S were prepared by the procedure of, Example 205: Examole 214 Preparation of 4- ('1-chloro-5-fluorosulphonvlphenvlazo)-N,N-bis (2-cvanoethvl ( aniline i) 2-Chloro-5-nitro benzene sulphonic acid (484 parts) was charged to a flask then quickly added 'chionyl chloride (2190 parts) and dimeth'vl formamide (12 parts) - The resultant slurry was heated to 60CC and stirred at 60~65OC for a total of 5 hourS. The mixture was cc-c-led to room temperature then poured onto ice/water. The precipitated solid was filtered off and washed with cold water before drying in yap oven to yield the product 2-chloro-5-nitro benzene sulpho-nylohloride (395 parts) - ii) 2-Chloro-5-nitro henrene sulphonylchloride (40 parts) was stirred in o-dioxane (48 parts) at room temperature. Potassium fluoride (20 parts) dissolved in water (35 Parts) was added, mid the mixture heated to 70'C. Stirred at 70'C for 4 hours then cooled to room temperature and poured onto ke/water. Allowed to stand for 2 days then filtered off the precipitate and dried in ai: to yield the product 2- 5 chloro-S-nitro tenzcne sulphcnylfluoride (36 parts). iii) The 2-chlore.-5-nitro benzene sulphcnylfluoride 12.4 parts) was stirred in glacial ace:ir acid (25 parts; with iron powder (2 parts). Heated to refl:.x and stirred at reflux for 2.5 hours, then cooled to room temperature. poured onto ice/water and allowed to stand at room temperature overnight. The resultant preeipi:ate was filtered off and dried in air to yield the product 2-chloro-5-amino benzene suiphonylfluoride (0.8 parts). iv) 2-Chloro-5-amino bentene suiphonylfluoride (2.3 parts) was stirred in acetic/prcpionic acid 86/34 vol/vol (25 parts) and cooled to 0-SC. Nitrosyl sulphuric acid solution (3.8 parts) was added and stirred at 0-5C for 3 hours. The diazo solution was then added to a mixture of R.N-bis(2-cyanoethyl) aniline (2.1 parts), methanol (75 parts) and suiphamic 'acid (I part) stirring in ice/water (75 parts) at 0-5C. Stirred under these conditions for 3 hour then allowed to stand at room temperature overnight before filtering off the dye. The solid was dried overnight to yield the product 4-(4-chloro-5-fluorosulphonyl phenylazo)-N,N-bist2-cyatioethyl) aniline (3.6 parts). The dye, when applied to polyester scene] from an aqueous dispersion, gave yellow shades. Amex 414mm. The following Examples of dyes Of Formula: were prepared by the procedure of Example 214: ExamDle 220 Preuaration of ~- ~ 1~ N-diethviarn~no~ an~iine 2-Chlorosulphonyl-5-chlorothiophenE- (Th3.~ parts ~as &aaea tc fuming nitric acid (80 parts) allowina tc~ ~-xotherrn tc 350C. ~e~ec to 500C and stirred under these ccndjtion5 ~cz 2 bours Cooled to i-corn temperature then poured onto ice/water with ~iocrous st~rrmno. The white solid was filtered off and dried to v~e1c~ ~ne Drc.duct 2-chlorosulphonyl-4-nitro-5-chlcrothiophene (19 parts) 2—Ch1orasu1phony1-~-~n2tro-5-ch1orc~h2cphen~ (2O~ parts, x~ere stffred in p-dioxane (80 Darts) at room ternnerature. Pot~ss~um fluoride (52 parts) in water (20 parts) was added and the mixture beated to 500C Stirred under these conditions for 4 hours, then coclid and poured onto ice/water Ethyl acetate was then added to extract the product and separated Dried ovet magnessiurr sulphate then screenea and concentrated tc viejid the product 2-fluorosulphonyl-4-nitro-B-chloro thiophene (204 partsY iii) The 2-~iuorosu1phony1-4-natrC-5-chICTOthrnphefle (2O~ parts), was added to methanol (240 parts) with hexamine (22.5 parts). I~eated to ref lux and stirred under tlmse conditions fcr 4 hours Ceded to room temperature and poured onto 10% sulphuric acid sclution (2E0 parts) The product was extracted out with ethyl acetate, separated and dried over magnessium sulphate, then scr&ened and conc~ntrated to yieild the prcduct 2-i[lucrosulphonyl-4-niiro-2-aminOtbaCphefle (16 Parts). iv) L-F1uc.roslI1phony1-A-nitro-~-amiflCthiCphefle (42 parts) was added over 30 mins to a stirred so~uticn of acet~c/propicnic acid p6/14 vol/vol (60 parts~ with nitrosy2 sulphuric acid solution (10 parts) at O-50C Stirred under these conditions for hours. The diaze soiut~on ~as then added to a w~xture of 3—N,N-diethvl amnoacetaniiide (4.2 parts), water ~O parts). methanol (Th parts), and suiphamic ad6 U part) stirring in 5O~ sulphuric acid solution at O-50C Stirred under Lhese cond~t~ons for 45 mins then filtered off the dye and washed well yl -N. N- edurs of Example 220-ivi was repeaten except tnat inn c~e:n'vam~nc-acetanilide (1.4 parts of 3-meth-vl-P),t-I- - r '- o- ~cn-l '-e was used to yield 4- )3-nitro-5-fluorosulphonv]thien-on n~ti ~ I N-diethN'laininoainiline (0.3 parts) - When applied to e 1--C- C- r s- =~~l= from an anuec-us niscers~on the dye nave blue snanes. Amax 62 Sos - General Method for the Preparation of Dye Examples 222 - 238 i Preparation of 2-nitrn-4-fiuorosulohonvlaniline N-aoenvl sulphani lyl chloride (IQOg) was dissolved in concentrated sulphuric ac~u (515 cm3), cooled to 4~C and a innixture of concentrated nitric acid 535.6 cinn3) and concentrated sulpTiuric acid (42.9 cm3) added drcpwise maintaining the temperature at 4-.60C. After 2 nour the reaction mix was orowned onto ice and the precipitate -collected, extracted into dichloromethane and evaporated to a yellow solid (92~j. 31g of this yellow solid was refluxed for 3 hours in water (20 cm), p- dioxane (20 cm3) and KF (l9AgY then drowned onto ice and the crecipitate collected. This precipitate was refluxed in absolute ethanol (35 cm3) and concentrated hydrochloric acid (35 cm3) for 1 hour 3C then drowned onto ice, filtered and suction dried. Recrystallisation from ethanol yielded 5.7g of the required compound ii) Preparation of 2-nitro-4-fluorosulphonvl-6-ohlorOaniline 2-Nitro-5-chloraoetanilide (lOg) was added cautiously to chlc-rosuiphonic acid (40cm3) then heated at 22005 for 2 hours. The reaction mix was cooled to 50-(l and drowned onto ice. Th~ precipitate was filtered, washed with a little water and suction dried. This solid was dispersed in water (20cm3) . p-dioxane (20cm3) and KF (lOg) - After refiuxing for 2 hours the reaction mix was drowned into -water, the precipitate filtered and suction dried. This solid was refluxed in water (50cm3) and 36% lid (50cm3) for 2 hour, drowned onto ice and the precipitate collected. Yield 3.5g. 2-N½ro-4-fluorosulphonN'laniline (0.Olmol) (for dyes 222-230) or 2-nitro.6~chloro~4-fluc-rc-sulphonyl-aniline (0.Oimol) (for dyes 231-238) was dispersed in a mixture of acetic:propionio acid (86:24) (25m1) and cooled to 0-SOC and nitrosylsulphuric acid (0.Olmol) was then added portionwise a: ('—WC. from the cp'Oro1-riate- N ix nantnidc--6-nnethoxv)ainiline coup1 'nc. ( O,flOC'nOn wvni 25 ethx'1~n'cti'v1 ohio me (C 0-mm i-—n" p (0.Oimoi) in diobloromethane (SGml) was stirred arnd 0-caned unner nentle reflux for h and then allowed to cool and was then drowned c-ut into water. The resulting product was extracten ~ntc n:octoronenhaine. dried (Mg5O) and evaporated to dr-~--ness in' vacuc- to -yield the recruired coupler as a brown 20 oil. (ii) Preparation of Couniers for tx's Examotes ~25. 227, 225, 230 and 236 - 238 - Method 2: Dye Examples 225, 227, 228, 230 and 236 - 238 were prepared from the appropriate N,N-dialkyl- (3-ethvlsuccinamidc--6-methox (aniline coupling components which were prepared according to the following method. A mixture of 3- )N,N-dialkvlaminol --methoxyaniline (0.Olmol) and suocinic anhydride (0.Olmol) in anhvdrous toluene (SOmI) was stirred for l.5h and then evaporated to dryness in x-'aouo to give a brown gum. 30 The brown gum (the carhoxylic acid interned jate) was esterified by treatment with an appropriate alcohol (0.Imol) and cono. sulphuric acid (lml) at 100CC for lb and was then allowed to cool-. The mixture was drowned out into water and the product was extracted into ethyl acetate. dried (MgSO,) and evaporated to dryness in v-acuo to yield the repuired 35 coupler as a brown oil. Dye Examples 222 - 236 are sunmar~sed below: Dye Examples 239 - 246 were prepared usino the same general method as was used for the preparation of dye examples 222 - 238. The dyes, when applied to polyester as acruemus dispersions, nave qood fastness to washing light and heat. tee couplers for dye Examples 235, 2'> and 2-IC we-ri pt~-.. recin roe. 3-- 51, N- disthvlamino( -4-rnetlioxq'aniline acoordino to the Tnete-~~A usino ace-tv!saliocyl chloride (0.O2innol) in place of athvlsuccin-,:l chlorrue - Thu cc-uc-l er foc dye Example 2-21 was ore-oared from 9- (N - N - - - ')---mee)toxyaniline acoordino to the method I ustnn Cut —n in oCorman e (0. Olmol in place of eth:'lsucctnv~ chlccide - - inc co'-' C-~ iFt nyc Exa~no2 e 2-12 was prepared from 3- (I2,r-I-d~st(r,'lamino -line according to the method 2 usino etnvimalcm-vl ctiior:oe (C- - Olin'- ~ - , clace of ethylsucoinvl chloride. The coupler for dye Exanpie 2'13 was proc-aren troin 2- ~O (1-'-',C-in lr,'Jamino)--I-methox\'aniline according to the metnon _ ,'~'e male-ic anhmdride (0.Olmol) in place of suocinic anhvdride and ethanol as the eszerff-.inn alcohol. The- coupler for dye Example 244 was prettared '~-.'r- _ ~ (HFhyiainnino)-4-mechoxvaniline according to the method 2 usino 2,2- diinerhyisuco inic anhydride (OOlmol) in place of succinic anh-.vdrine ann t'ianol as the esterifying alcohol. The coupler for dye Example 245 was prepared fron 3- ()-I,N 2C- disthyiamino)-4-methoxvaniline according to the method I usino 4-innethoxvcarbon-vlohenylchlorofonnate (0.Olmol) in place of ethvlsuccinvl chlorine. SN's Examples 239 - 246 ~re summarised below Eya~rrl - Or~~ -'- -- S-dichicrc-'1-fluorosuiohonvlohenylaro(-'1,6- Th- p==edure of Example I was repeated except that in place of t"c s c-.rco on N,N-bis- (2-cyanoethyl)aniline; 1.5 parts of '1,6-niamin'-- , oroty' Coyrimidine were used. The product, 5-(2,5-dichloro-'I-f .ucrocut'-nonv -'1 nylazo) -4,6-'diamincmropylthioPvrimidine (3.4 parts) Amax='T2Onm, 'C-hen asp lied to polyester materials from an aqueous n~spersion gi-ves brinhr yellow shades with excellent fastness to lioht and wet treatments. Example 245 25 Preoacatnon of 4- (2.5-dichloro-4-fluorosulohonvlphenylaro)-3-chloro-N-ethyl ,N-menhvbchthalimi~doaniline The procedure of Example 1 was repeated except that in place of the 1.6 parts of N.N-bis- (2-cyanoethylYaniline; 2.6 parts of 3- chloro-N-ethyl,N-methylphthalimidoaniline were used. The product. 4- 30 (2,5-dichloro-4-fluorosulphonylphenylazo) -3-chloro-N-ethyl,N-metnvlc-hohalimidcaniline ('1.0 parts) Amax='1SSnm, when applied to polyester materials from an aqueous drspersion gives orange shades with excellent fastness no light and wet treatments. Example 249 Preparation of 4- (2.5-dichloro-4-fluorosulphonvlphenylazo)-3-methylmorohol inobenzene The procedure of Example 2 was repeated except that in place of the 2.6 parts of N,N-bis-(2-cvanoethyl)aniline; 2.5 parts of 3-methylmorpholinohenzene were used. The product, 4- (2,5-dichloro-'1-f luorosul ohonylphenylazo) -3-methylmorpholirtcbenrene (1.9 parts) Amax=48Cnm, when applied to polyester materials from an aqueous dispersion aives dull bluish red shades with excellent fastness to light anti wet treatments. parts) and ao~ i'--'t". -"c-ri'- ec~d mixture (20 parts, 86-24 vol/vol). 20 stirrino at 0 (' ~'- annen dropwise nitrosyl sulphuric coin soln (3.5 parts) - The mix~n re wa' 'rren at this temoerature for a further 15 nuns. Th~ di0ro ~c-iu 'c-in was coded to a mixture V N Ndieth'rlaniline (0.9 parts), methanol (50 parts) and sulphamic acid (0.5 25 parts); stirrino at 0.5'-C. After stirrino for 2 hours at this temperature, the product was isolated by filtration, washed with water and dried at SOC to yield; 'I- ('1,8~dif2uorosulphc-nylnaphthyl-2-aZo)-N,W diethvlaniline (1.8 parts) - When applied no polyester materials from an aqueous dispersion, the dye qives red shades with excellent fastness 30 to wet treatments. Amax of SOOnm. The following Examples of dyes of Formula: -very prepar-4-o:~~C-'t'—-~~laro'-N-t'thyThN-2- 'Ifluorosulphonvlphenoxv(eohylan 1icv~:- To a mixture of 2 c-'o'- ~-ninroaniline (I.S parts) and acetio/Propionic acid mixture (2~ pa te, 5(1/24 vol c-I). stirrino an - (I. 50C, was added dropwise nin~"' C-in 'p1turlc coin sc-tn (2.t carts'. The mixture was stirred at thi'- tom'-C-rature for a further 30 nuns. The diazo solution was aaded to a inrixture of N~ethvt N-?- (~-fluorosulphoinylphenoxyl)-ethvlaniline (3.0 parts), methanol (SC' c-arts) and sulphamic acid (0.5 parts) - ctp-rinn at 0.5'-C. After stirrino for 2 hours at this temperature, the product was iooated by filtra~i'-'n washed with water and dried at 50'-C to yield; 4- (2-oyano-4-nitrophenylaro)~-N-ethyl,N-2- (4-fluorosultthonylmhenoxy(ethylaniline (3.0 parts( . When applied to polyester materials from an anuec-us dispersion, the dye gives bluish red shades with excellent liuht 25 fastness and excellent fastness to wet treatments. Amex of SIOnn. Examole 258 Preparation of '1-(3-aoetvl-5-nitrothien-2-VIaZO(-N-ethl-N-2-(4- flucrpsuiphonvlphenyoxv( ethvlaniiine 30 The proceduTe of Example 257 was repeated except that in place of the 1.5 parts of 2-cyano-4-nitroaniline; 1.7 parts of 2-amino-3-acetvl-5-notrothiophene were used. The croduot 4-(3-acetvl-5-notrothienvl-2-azo)-N-ethyl.N-2- (4.fluorosulphonylpheno)oy)ethyianAline (2.0 parts) when applied to polyesnec materials from an aqueous dispersion gives reddish blue shades with excellent fastness to hobO and wet treatments. Amex of S9Onm. - Example 259 Preparation of 4~(2~chloro~4~nitroPhen.!iaro)-3-methvl-N-ethVl-)I-2-(4- fluorosulohonvlc-henoxv(ethvlainiliine - To chiorosulphonic acid (27.S parts) stirrino at CSC, was added gradually 3-methyl-4- (2-chlcro-'1-nitrophenylazo) -N- eth12 ,N- 2-phenox-'yeth'ilanihine (8.0 parts). Thion\'l chloride (S.4 parts) was added and the mixture was stirred at 0.5CC for 2 hours. The reaction mixture was drowned into ice/water (500 parts) , the product was isolated rat icc ann waco-en acm- tree vt th cc-Id water - The flit er o~lie was set stirring w'ith 2 -- lioxon' '½ carts, iiGO a solution of ccc assiuinr fluoride (2 .6 c-arts) inn n;at er (1 C carts: was added. The- mixture was heated at 60'-C for 3 hours, cooled tO- ambi eon ano the product was isolated by filtration to y~52d; --inret(tyi—'t- (2-chloro-'I-nitrcohen-vlaro)-N-ethvl,12-2- (-Iin _ oh'- no-I r'(ie-cox'.- et (cc I aniline (4. S marts) - The- croduoc when ac-plied to' ooi;'est or innat sri al '~ '(mi am an:isc:~,s nt sc:ers:cn cires mid red shades wi oh excellent a~ pC-'-~- - 1 oh' .cn wet treatments Amax of 520mm. tx~npls 260 T'et'aratic-n ~ L~ rosuIchonvlohenox~'(enhvlani2ine The procedure of Exainnple 257 was repeated except that in p-lice of the 2.5 marts of 2-cvano-'I--nioroanm~rne; 2.9 c-arts of 2-amino--El riocvanano-oeortn~arcle were used. The oroduct. -~- )6~thioc~yanatobenrohiarolyl~2~azo)-N-ethyi,N. .~ (A~fluorosulphonviphenoxy)ethylaniline (1.4 parts) when applied to 210 polyester materials from an aqueous dispersion give~ bluish rod shades with excellent fastness to light and wet treatments. Amax df 522mm. Example 261 Frenaration of 4- (2,6-dichloro-'1-nitroohenylazo(-N-eth-vl-N-2- (4-fiuorosuiohonvlphenoxv)ethlaniiine Theprooedure of Example 257 was repeated except than in place of the 1.5 parts of 2-ovano-4-nitroaniline; 2.9 parts of 2-amino-6-thiocyanatobenrthiarole were used. The product. 4- (6-thiocyanacobenrchiarolyl-2-azo)-N-ethyl.N-30 2- (4-fluorosul-chonylphenoxy)ethylaniline (1.4 parts) when applied to polyester materials from an aqueous dispersion gives bluish red shade with excellent fastness to light and wet treatments. Amax of 522nm. Example 262 Prenaration of 4- (6-'thioc-vanatobenzothiazol-2-vlaro)-3-methvl-N-eth-yl-N- 2- (4-fluorosuioho-nylohenoxv)ethylaniline The orocedure of Example 257 was repeated except that in place of the 3.0 parts of N-ethyl,N-2- (4-fluorosulphonylphenoxy)eohylaniline, 3.1 parts of N-ethyl,N-2- ('1-fluorosulphonvlphenoxy)ethyl-m-toluidine were used. The product. 3-methyl-4- (6-thiocyanatcbenzthiazolyl-2-azc)-N-ethyl,N-2- (4-fluorosulPhonvlphenoxy)ethylaniline (1.7 parts) when applied to polyester materials from an aqueous nispersion gives violet shades with excellent faotne~s to lioht and wet treatments. Amax pf 54 Onin. tiltamcle-s ,z ano Z(-~l u'-ec oracaren Oiy tWo croce-nure nescrib-ed for Example 239 hut 'isino the 3-nachthylamine to c-lar~ c-~ 13- (H,ti-dieth'iiamino)acecanilide are of Pormul a NO~ F()~S i —-N / RT I / N N ci — - Example 265 Preparation of J-n-butvl-5(2,5-dichloro-4-fluorosulohoinvlohenvlazo)-3-cvano-6-hvdroxv-4-meth'vl-2-cxo-111-ovridine The procedure of Example 2 was repeated except that in place of the 3.Og of 3-methyl-N-ethyl-N- (2-benroyloxyethyl)aniline, 2.8g of 1-n-butyl-3-cyano-6-hydroxy-4-methyl-2-oxo-IH-pyridine were used. The product 1-n-butyl-S(2,5-dichlorc--4-fluOrOsulphOnylphenylaZo)-3-OyainO-6- 25 h'vdroxv-4-met hyl-2-oxo-1H-pyridine (2.5g) when applied to polyester materials from aqueous dispersion gives greenish yellow shades with excellent wet and liuht fastness orooerties.Amax=435nm. Examole 266 Preoarat~on of 1-Phenyl-3-t-butvl-5-amiinO-4-(2.5-diOhlOrO-4- fluorosulphonylphenvlaro) ovrazole The procedure of Example 2 was repeated except that in place of the 3.Og of 3-methyl-N~ethyl~N-(2-beinZOylPxyethyl(ainiliine, i.5g of 1-' phenvl-3-t-butyl-5-aminopytazole were used. The product 1-phenyl-3-t- 35 butvl-5-amino-4- (2,5-dichloro-4-fluorosulphonylphCnylaZO) pyrarole (2.2g( when applied to polyester materials form aqueous dispersion gives greenish yellow shades with excellent wet and light fastness properties. Amax=442nm. The dyes of in he- ic-Il cvi no formulae- mmc.- Ce innane c-v the procedure of Example In by diarot~stno the aoprocrma~e amine ann coupling onto the appropriate r~upl ing coninnonen. - Examole 267 v-role 272 dyes of these Examples do not contain a fluorosuiphonyl group. WE CLAIM: 1. A process for preparing an azo dye compound which is free from water solubilizing groups and is of Formula (1): (Formula Removed ) wherein A and D each independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A and D carries directly at least one -SO2F group or carries a substituent to which at least one -SOaF group is attached which process comprises: (1) diazotising an amine of the formula (10) (Formula Removed ) wherein A is as defined above, by reaction of the said amine with a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite in an acid medium such as acetic, propionic or hydrochloric and at a temperature of from -10°C to + 10°C to form a diazotised amine; (2) coupling the diazotised amine with a coupling component of the formula (11) (Formula Removed ) wherein X is a group displaceable by the diazotised amine and D is as defined above, by adding the diazotised amine to a mixture of the coupling component of the formula (11) in an alkanol such as methanol at a temperature of from 0 to 10°C to form a monoazo compound of the formula (1); and wherein at least one of the following requirements is satisfied: (a) in the formula (1), at least one of A and D carries directly at least one ester group or carries a substituent to which at least one ester group is attached; and (b) in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formulae: (Formula Removed ) wherein: R1 and R2 each independently is H or optionally substituted C1-6-alkyl or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I, -SOaF or C1-6 alkyl, C1-6-alkoxy, C1-4alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; R7, R8 and R9 each independently is H, C1-6-alkyl, NO2, -COOC1-6-alkyl, -OCOalkyl, Cl, F, Br, I, -COC1-6-alkyl,-CN, formyl, protected formyl or -SOaF provided that at least one of R1 to R9 is -SO2F or carries a substituent to which at least one -SO2F group is attached and provided that R7 and R9 are not both -SO2F; (Formula Removed ) wherein: R1 and R2 each independently is H or optionally substituted C1-6-alkyl or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I, - SOaF or C1-6-alkyl, C1-6-alkoxyl, C1-4-alkanoylamino, -NHSOaalkyl or -Ophenyl, each of which may be optionally substituted; R12 is -SO2F; and R10, R11, R13 and R14 each independently is H alkoxy, alkyl, NO2, -SO2F, F, Cl, Br, I or -CN; FO,S (Formula Removed ) in which R1 and R2 each independently is optionally substituted C1-6alkyl; R4 is alkyl or a group of Formula -N(R19)-Y-X-W in which Y is a direct link or C = 0, X is a direct link, alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene, -N(R20)-Z-, -COOZ or -OZ- in which Z is alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene or a direct link and R20 is -H, alkyl, aryl, or alkylaryl, W is -CO2R21, - OCOR21 or -OH in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is H or alkyl; R5 is H, C1-6-alkoxy or -Ophenyl; R10 is NO2 or Cl; and R13 and R14 each independently is H or Cl; and (Formula Removed ) wherein R1 and R2 each independently is H or optionally substituted C1-6-alkyl; R3 is optionally substituted C1-6-alkyl or C1-6-alkoxy; R4 is optionally substituted C1-6-alkyl or C1-6-alkoxy; R10 is optionally substituted C1-6-alkyl, NO2 or Cl; R15 to R18 each independently is H, C1-6-alkyl, C1-6-alkoxy, F, Cl, Br, I, -SO2F, NO2) -CN or NR1R2; R12 is NO2 or -SO2F; R11 is H; and R13 and R14 each independently is H or Cl except for: 4-(4-fluorosulphonylphenylazo)-N,N-dimethylaniline, 4-(4-fluorosulphonylphenylazo)-N,N-diethylaniline, 4-(4-fluorosulphonylphenylazo)-N-ethyl-N- acetoxyethylaniline, 4-(4-fluorosulphonylphenylazo)-3- (trifluoromethylcarbonylamino)-N-ethyl-N-(2- methoxyethyl) aniline, 4-(4-fluorosulphonylphenylazo)-3- (trifluoromethylcarbonylamino)-N-ethyl-N-(2- cyanoethyl) anline, 4-(4-fluorosulphonylphenylazo)-2,5-dimethyl-N-ethyl-N- (2-methoxyethyl)aniline,4-(4-fluorosulphonylphenylazo)-2,5-dimethyl-N-ethyl-N- (2-cyanoethyl) aniline, 4-(4-fluorosulphonylphenylazo)-N-ethyl-N-(2- fluorosulphonylethyl) aniline, 4-(4-fluorosulphonylphenylazo)-N,N-di(2- fluorosulphonylethyl) aniline and 4-(4-fluorosulphonylphenylazo)-N-ethyl-N(((2-methoxy)-2- ethoxy)ethyl)aniline; and in the formula (1), each of A and D is such as to provide a dye compound selected from compounds of the formulae (Formula Removed ) 2. A process as claimed in claim 1, wherein requirement (a) is satisfied and in which A and D each independently is selected from thienyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyridonyl, 1,2,4-and 1,3,4-thiadiazolyl, furanyl, pyrrolyl, pyridazyl, pyrimidyl, pyrazinyl, benzothiazolyl, benzoisothiazolyl, quinolinyl, isoquinolinyl, indolyl, pyridothiazolyl, pyridoisothiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, phenyl and napthyl. 3. A process as claimed in claim 2, in which A and D each independently is selected from thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl, pyridonyl and quinolinyl. 4. A process as claimed in claim 3, in which A and D each independently is selected from thien-2-yl, phenyl, naphth-1-yl, naphth-2-yl, thiazol- 2-yl, isothiazol-5-yl, pyrid-4-one-5-yl and quinolinyl. 5. A process as claimed in claim 4, in which A is thien-2-yl or phenyl and D is phenyl or naphth-1-yl. 6. A process as claimed in claim 3, in which the compound of Formula (1) is of Formula (3): (Formula Removed ) wherein: R1 and R2 each independently is H or optionally substituted C1-6-alkyl or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I, -SO2F or C1-6- alkyl, C1-6-alkoxy, C1-4alkanoylamino, -NHSO2alkyl or -Ophenyl, each of which may be optionally substituted; R7, R8 and R9 each independently is H, C1-6-alkyl, NO2, -COOC1-6alkyl, -OCOalkyl, Cl, F, Br, I, -COC1-6-alkyl, -CN, formyl, protected formyl or SO2F provided that at least one of R1 to R9 is -SO2F or carries a substituent to which at least one -SO2F group is attached and provided that R7 and R9 are not both -SO2F. 7. A process as claimed in claim 3, wherein the compound of Formula (1) is of Formula (4): (Formula Removed ) wherein: R1 and R2 each independently is H or optionally substituted C1-6alkyl or optionally substituted aryl; R3, R4, R5 and R6 each independently is H, F, Cl, Br, I, -SO2F or Ci- ealkyl, C1-6alkoxy, C1-4-alkanoylamino, -NHSO2alkyl or -Ophenyl, each6 of which may be optionally substituted; and R10 to R14 each independently is H, alkoxy, alkyl, NO2, -SO2F, F, Cl, Br, I or -CN; provided that when R10 is SO2F, R12 is not NO2 and R11, R13 and R14 are not all H. 8. A process as claimed in claim 3, wherein the compound of Formula (1) is of Formula (7): (Formula Removed ) in which R1 and R2 each independently is optionally substituted C1-6alkyl R4 is alkyl or a group of Formula -N(R19)-Y-X-W in which Y is direct link or C=O, X is a direct link, alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene, -N(R20)-Z-, - COOZ or -O-Z- in which Z is alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene or a direct link and R20 is H, alkyl, aryl or alkyaryl, W is -CO2R21 or -OH in which R21 is alkyl, aryl, alkylaryl, alkylOalkyl or alkylOH, and R19 is H or alkyl; R5 is H, C1-6alkoxy or -Ophenyl; R10 is NO2 or Cl; and R13 and R14 each independently is H or Cl. 9. A process as claimed in claim 3, wherein the compound of Formula (1) is of Formula (5): (Formula Removed ) wherein: R1 and R2 each independently is H or optionally substituted C1-6-alkyl; R3 is optionally substituted C1-6-alkyl or C1-6-alkoxy; R4 is optionally substituted C1-6-alkyl or C1-6-alkoxy; R10 is optionally substituted C1-6-alkyl, NO2 or Cl; R15 to R18 each independently is H, C1-6-alkyl, C1-6-alkoxy, F, Cl, Br, I, -SO2F, -CN or NR1R2; R12 is N02 or -SO2F; R13 and R14 each independently is H or Cl. 10. A process for preparing an azo dye compound substantially as herein described with reference to and as illustrated in the foregoing examples.

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936-del-2002-abstract.pdf

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