The present invention relates to a dispersion composition containing an azo dye compound containing a fluorosulphonyl group for colouring synthetic textile materials and to a process for preparing such dispersion compositions containing azo dye compounds.
GB-A-856,348 relates to water insoluble monoazo dyestuffs and discloses one specific dye containing a 4-fIuorosulphonylnaphth-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.
US-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 dispersion composition comprising:
a dye compound dispersed in an aqueous medium and present in an amount of from 1 to 30% by weight of dye compound and aqueous medium, a dispersing agent present in an amount of 10 to 200% by weight of the dye compound and optionally additionally comprising ingredients selected from conventional components such as dispersing agents, wetting agents and defoamers, which dye compound
is free from water solubilizing groups and is of Formula (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 -S02F group or carries a substituent to which at least one -SO2F group is attached and wherein, 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.
Different compounds of Formula (1) may be mixed or the compounds of Formula (1) may be mixed with dyes which do not contain an -S02F group. The mixtures may be simple physical mixtures or may be mixed crystals formed for example by co-crystallisation. Such 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 -S02F groups in a dye molecule generally improves the properties of that dye and confers surprisingly good wet-fastness and light-fastness properties.
A synthetic textile material or fibre blend thereof may be coloured by a process which comprises applying to the synthetic textile material a dispersion composition according to a first embodiment of the invention in which the above requirement (a) is satisfied, which dispersion composition comprises an azo dye 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 in which at least one of A and D carries directly at least, one -S02F 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.
Azo dyes containing both an -S02F 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 form of filaments, loose fibres, yarn, woven or knitted fibres.
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, -C02H, -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 125°C to 140°C for from 10 to 120 minutes and under a pressure of from 1 to 2 bar; a sequestrant may optionally be added;
ii) continuous dyeing at a pH of from 4 to 6.5, at a temperature of from 190°C to 225°C 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 160°C to 185°C for 4 to 15 minutes for high temperature steaming, or at a temperature of from 190°C to 225°C for 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 120°C to 140°C 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 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 95°C to 100°C using a carrier such as methylnaphthalene, diphenylamme or 2-phenylphenol; sequesterants 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 85°C for acetate or at a temperature of 90°C for triacetate and nylon for from 15 to 90 minutes; sequesterants may optionally be added.
In all 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 present compounds generally provide coloured textile material which shows good fastness to washing, light and heat.
The heterocyclic group 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 carbocyclic group represented by A or D may be phenyl or naphthyl.
For the avoidance of doubt optionally substituted isoquinolinyl represented by A includes structures of the
formula:
(Formula Removed)
in which m is from 1 to 4 and m is preferably 3.
A and D each independently is preferably tnienyl, phenyl, naphthyl, thiazolyl, isothiazolyl, pyridonyi or quinolinyl, more preferably thien-2-ylf phenyl, naphth-1-yi, naphth-2-yl, thiazol-2-yl, iscthiazol-5-yl, pyriC1-4-one-5-yl or quinolinyl. A is especially preferably thien-2-yl or phenyl and D is especially"* preferably phenyl or naphth-1-yl.
Examples of suitable substituencs for A and D are cyano, hydroxy, nitro, fluoro, chloro, bromo, iodo, fluorosulphonyl, trifluoromethyl, alkyl, alkoxy, aryl, aryloxy, fluorosulphonylaryl, flurosulphonylaryloxy, -COalkyl, -COOalkyl, -OCOalkyl, -COaryl, -COOaryl, -OCOaryl, -NHCOalkyl, -NHCOaryl, -NHS02alkyl, -NHS02aryl, -Salkyl, -Saryl, -S02alkyl, -S02aryl, -SCN or -NRXR2 in which R1 and R2 each independently is -H, alkyl, aryl, or cycloalkyl. All the alkyl, alkoxy, aryl, aryloxy parts of the above substituents for A, D, R1 and R2 may optionally be substituted by -OH, -CN, -F, -Cl, -Br, -I, -S02F, alkoxy, alkenyl, phenyl, phenylS02F, aryloxy, aryloxyS02F, -N(alkyl)2, -OCOalkyl, -OCOalkylCl, -COOalkyl, -COOalkylOH, -COOalkyiCN, -COOalkylCOalkyl, -COOalkylphenyl, -OCO phenyl, -COphenylS02F, -OCOphenylN02, -OCOphenylalkyl, -OCOphenylalkoxy, -COOphenyl, -OCO(fluorosulphonylphenyl), -OalkylCN, -COOalkylOalkyl, -COOalkylOphenyl, -OCOalkylOphenyl, -COOalkylOalkylOalkyl, -OCOalkylCOOalkyl, -OalkylCOOalkyl, -OalkylCOOalkylOalkyl, -OalkylCOOalkylCOOalkyl, -OalkylOCOalkylOalkyl, -COOalkylOCOalkyl, -COOalkylCOOalkyl,
(Formula Removed)
n which L is -H or alkyi.
In all of the suitable substituents for A and D each alkyi is preferably C1-ic-alkyl, each alkoxy is preferably C1-io-aikoxy, each alkenyi is preferably C2_8-alkenyl, each of which may be straight or branched chain, each aryl is preferably phenyl or naphthyl and each heterocyclic groSp may be any of the groups described above for A and D and each alkyi, alkoxy, alkenyi, aryl, heterocyclic or phenyl group may carry an -S02F substituent. R1 and R2 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 group of Formula -N (R1") -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, alkyleneNHalkylene or -NR20-Z- or -0-Z- in which Z is optionally substituted alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkyleneNHalkylene or a direct link and R20 is -H, optionally substituted alkyi, aryl or alkylaryl,
W is -C02R21, -0C0R21, -OH or -CN in which R21 is optionally substituted alkyi, aryl, alkylaryl, alkylOalkyl or alkylOH,
R19 is -H or optionally substituted alkyi.
Where X, Z, R19, R20 or R21 is or contains alkyi it is preferably C1-8-alkyl, more preferably C1-6-alkyl, each of which may be straight or branched chain or cyclic alkyi. Where X or Z is alkenyi it is preferably C2-8-alkenyl which may be straight or branched chain or cyclic alkenyi. Where X, Z, R20 or R21 is aryl it is preferably phenyl or naphthyl, • more preferably phenyl. Where X or Z
is heterocyclic it may be selected frcn any of the heterocyclic groups defined above for A. Where X, Z or R2~ is alkylOalkyl.it is preferably C:-,--alkyIOCi_£-aikyl, each alkyl of which may be straight or branched chain and the alkylalkyl group may be cyclic ether. Where X cr Z is alkylnalkyi it is preferably C1-6alkylNHC1-6-alkyl in which each alkyl may be straight or branched chain and the alkylNHalkyi group may be a cyclic amine. Where R° or R^1 is alkylaryl it is preferably C:-6-alkylaryl, more preferably C1-6-alkylphenyl and especially benzyl or ethylphenyl . Where R21 is alkylOH it is preferably C1-6-alkylOH.
The optional substituents for any of the groups represented by X, Z, R19, R^° or R':1 may be selected from any of the optional substituents listed for A, D, R" or R2.
Preferred substituents for A and D are cyano, nitro, chloro, bromo, f luorosulphonyl, C1-6-aikyl, C1-6-alkoxy, -COC1-s-alkyl, -NHCOCx-e-alkyl, -0C0C,-;-alkyl, -C00C1-6-alkyl, phenoxy, 4-S02Fphenoxy, RI9N-Y-X-W in which R1', Y, X and W are as herein before defined, and -NRXR2 in which R1 and R2 each independently is -H, C:-£-alkyl, C1-6-alkyl substituted by -OH, -CN, -CI, phenyl, -0C0C1-6-alkyl, -COOCx-6-alkyl,
(Formula Removed)
-C1-4-alkyl ( 4-f luorosulphonylphenyl) , -OCO ( 3-fluorosulphonylphenyl), -OCO(4-fluorosulphonylphenyl), -C2-4-alkenyl, -COOC1-6-alkylOC1-6-alkyl, -OC1-6-alkylCN, -OC1-6-alkylOCOCj-e-alkylOC1-6-alkyl, -COOalkylOCOalkyl and
-COOalkylCOOaikyl or where R1 and Pt together with the -H atom to which they are attached form a morphoiinc or piperidino ring.
The compounds of Formula (1) preferably carry a total of from one to three -SO?F groups, more preferably one or two -SO2F groups and especially one -SO2F group.
The compounds of Formula (1) more preferably carry one -SO2F group and one ester group.
Compounds of Formula (1) present in the above dispersion compositions are novel.
In these compounds, each of A and D independently is an optionally substituted heterocyclic or carbocyclic group, ar least one of A and D carries directly at least one -S02F 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, present in a dispersion composition according to a first embodiment of the invention, 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, 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 pyriC1-4-one-5-yl.
D is preferably phenyl.
Preferred compounds of Formula (1) 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-1-yl.
The optional substituents for A and D are any of those defined for A and D above.
Preferred sub-groups of compounds of Formula (1) present in dispersion compositions in accordance with the invention are those of Formulae (3), (4), (7) and (5), defined successively below.
Formula (3) is:
(Formula Removed)
wherein:
R1 and R2 each independently is -H or optionally substituted C1-6alkyl or optionally substituted aryl;
R3, R4, R5 and Rc each independently is -H, -F, -CI, -Br, -I, -S02F or C1-6-alkyl, C1-6-alkoxy, C1-4alkanoylamino, -NHS02alkyl or Ophenyl, each of which may be optionally substituted;
R7, R8 and R? each independently is -H, C1-6_alkyl, -N02, -COOC1-6-alkyl, -OCOalkyl, -CI, -F, -Br, -I, -COC1-6-alkyl, -CN, formyl, protected formyl or -S02F provided that at least one of R1 to R9 is -S02F or carries a substituent to which at least one -S02F group is attached and provided that R' and R9 are not both -S02F.
Where R7, R8 and R5 is or contains alkyl the alkyl may be optionally substituted.
Protected formyl groups include for example oxazolidone, imidazoline, thiazclidine, bisulphite, cyanohydrin, hydrazone and oxime.
The compounds of Formula (3) are novel and accordingly dispersions thereof are a further aspect of the present invention.
The optional substituents for groups represented by R1 to R9 may be selected from any of the substituents described above for A and D. The optional substituents for R1 to R9 are preferably -CN, -OH, -OCOC1-6-alkyl, -COOC1-6-alkyl, phenyl, -OCOphenyl, -OCOphenylS02F, phenylS02F, -OphenylS02F, -C02phenylS02F, -COOC1-6-alkylOCOC1-6-alkyl and -COOC1-6-alkylCOOC1-6-alkyl.
Preferred compounds of Formula (3) are those in which R1 and R2 each independently is -CH3, -C2H5, -C2H4CN, -C2H4OH, -CH(CH3) CH2CH3, -C4Hg, -CH2(4-
fluorosulphonylphenyl) , -C2H4 (4-fluorosulphonylphenyl), -C3H7 (4-f luorosulphonylphenyl) , RJ, R4, R5 and R6 each independently is -H, -CI, -CH3, -OCH3, -NHCOCH3, -NHCOC2H5, -NHS02CH3 or -S02F and R7, R8 and R9 each independently is -H, -N02, -CN, -COCH3, -COOC2H5, -S02F or -CH3 provided that both R7 and R9 are not -S02F.
Especially preferred compounds of Formula (3) are those in which
R1 and R2 each independently is -C2H4CN, -C2H5 or (4-f luorosulphonylphenyl) C1-6-alkyl;
R3 is -H, OCH3, -CH3 or -S02F;
R4 and R5 each independently is -H, -CI or -S02F;
R6 is -H, -NHCOCH3, -NHCOC2H5, -CH3 or -S02F;
R7 is -N02, -COCH3, -COOC2H5 or -S02F;
R8 is -H, -S02F or -Cl; and
R9 is -N02, -S02F or -CHO.
formula is 4 wherein:
(Formula Removed)
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, CI, Br, I, -S02F or C1-6alkyl, C1-6alkoxy, C1-4alkanoylamino, NHS02alkyl or -Ophenyl, each of which is optionally substituted; and
R10 to R14 each independently is -H, alkoxy, alkyl, -N02, -S02F, -F, -Cl, -Br, -I or -CN;
provided that when R10 is S02F, R12 is not -N02 and R11, Ri3 and Rl4 are not all -H.
In such a compound, Rlz maybe -S02F, in which case each of R10, Rn, R13 and R14 independently may be H, alkoxy, alkyl, -N02, -S02F, -F, -Cl, -Br, -I or -CN.
Where a group represented by R10 to R14 is alkyl it is preferably C1-10-alkyl, more preferably C1-6-alkyl. Where a group represented by R10 to R14 is alkoxy it is preferably C1-10-alkoxy, more preferably C1-6-alkoxy.
Compounds of Formula (4) are preferably those in which R1 and R2 each independently is -CH3, -C2H5, -C3H7, -C4H9, -C5H11, -C6H13, -CH (CH3) CH2CH3, -CH2phenyl, -C2H4phenyl, -C3H6phenyl, -C2H4CN, -C2H4OH, C2H4OCH3, -C2H4COOCH3, -C4H8COCH3, -C2H4COCH3, -C2H4OCOCH3, -C3HsOCOCH3, -C4H8OCOCH3, -C2H4OCOphenyl, -C2H4OCOphenyl (S02F) , -C2H4COOC2H4OCH3, -C2H4OC2H4COOC2H4OCH3, allyl, -C2H40phenyl,
-C2H40 (f luorosulphonylphenyl) , -CH:CH (CN) (OC2H4), Chalky lphenylS02F,
(Formula Removed) -COOC1-6alkylOCOC1-6alkyl or -COOC1-6-alkylCOOC1-6-alkyl ;
R3 is -H, -OCH3 or -Cl;
R4 is -H, -CH3, -NHCOCH3, -NHCOC2H5, -NHCOCH (CH3) 2, -NHC0C3H6C1, -NHCOC (CH3)3, -OCH3, -OC4H5, -F, -CI, Br, -I :r -NHS02C1-6-alkyl;
R5 is -H, OCH3, -OC2H5 or -CI;
R6 is -H, -CH3, -OCH3, -F, -Ci, Br, -I or -NHS02C1-6-alkyi;
R10 is -H, -OCH3, -N02, -CI, -Br or -CN;
R11 is -H;
R12 is -S02F or -N02;
R13 is -H, -OCH3, -S02F, -Cl, -Br or -N02; and
R14 is -H, -OCH3, -Cl, -Br or -CN, provided that at least one of RJ or R3 is -H and that at least one of R4 cr R6 is -H.
More preferably compounds of Formula (4) are those in which R1 and R2 each independently is -C2H5, -C4H9, -CH(CH3)CH2CH3, -C2H4OCOCH3, -C4H8OCOCH3, -C2H4OCOphenyl, -CH2phenyl, C1-6-alkylphenylS02F, C1-6-alkyl0phenylS02F,
(Formula Removed) -COOC1-6-alkylOCOC1-6alkyl or -CO0C1-6-alkylCOOC1-6-alkyl ; R4 is -H, -CH3 or -NHCOCH3; R3, R5, R6 and R11 are -H; R10 and R13 each independently is -H, -Cl, -Br or
-N02;
R12 is -S02F; and
R14 is -H, -CI or -Br.
An especially preferred compound of Formula (4) is that in which R1 is -C2H5; R2 is -C2H4OCOphenyl; R4 is -CH3; R10 and R13 are both -CI; R12 is -S02F; and R3, R5, R6, R11 and R14 are all -H.
Formula (7) is:
(Formula Removed) in which
R1 and R2 each independently is optionally substituted C1-6-alkyl;
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, alkylene-NH-alkylene, -NR20-Z-, -COOZ or -O-Z in which Z is alkylene, alkenylene, arylene, heterocyclic, alkyleneOalkylene, alkylene-NH-alkylene or a direct link and R20 is -H, alkyl, aryl or alkylaryl, W is -C02R21, or -OH in which R21 is alkyl, aryl, aikylaryl, alkylOalkyl or alkylOH, and R19 is -H or alkyl;
R5 is -H, C1-6~alkoxy or -Ophenyl;
R10 is -N02 or CI; and
R13 and R14 each independently is -H or -Cl .
In the dyes of Formula (7)
R1 and R2 each independently is preferably C1-6-alkyl or C1-6-alkyl substituted by phenyl or -COOC1-6-alkyl, and
more preferably is ethyl, propyl, butyl, 1-methylpropyi, hexyl, benzyl, ethylphenyl or propylphenyl.
R4 is preferably a group of Formula -N (R~~) -Y-X-W m which
R19 is preferably -H or C1-6-alkyl, mere preferably -H; Y is preferably a direct link or C = 0, more preferably C = 0;
X is preferably a direct link, C1-8-alkylene, C2-9 alkenylene, any of the carbocyciic or heterocyclic groups defined above for A, C1-6-alkyiOC1-6-alkyl, -NR20-Z-, -C00Z or -0-Z- in which R20 is preferably -H, C1-6-alkyl, phenyl or benzyl; and
Z is preferably a direct link or C1-6-alkylene, C2-8 alkenylene, phenyl, benzyl or any of the heterocyclic groups defined above for A.
X is more preferably a direct link, CH2, C2H4, CH2C(CH3)2, cyclohexyl, CH = CH, phenyl, -NR20-Z-, -COCZ or -0-Z- in which
R20 is preferably -H, Z is preferably a direct link, C1-6alkyl or benzyl.
W is -C02R21, -0C0R21 or -OH in which R21 is C1-6-alkyl, phenyl, chlorobenzyl, C1-6-alkoxybenzyl, benzyl, C1-6-alkylOC1-6-alkyl or C1-6-alkyl0H 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-S02F group are generally more stable and build up better on polyester textile material than do the corresponding 2-S02F dyes.
Formula (5) is:
(Formula Removed) wherein:
R1 and R2 each independently is H or optionally substituted C1-6 alkyl;
R3 is optionally substituted C1-6alkyl or C1-6aikoxy;
R4 is optionally substituted C1-6alkyl or C1-6alkoxy;
R10 is optionally substituted C1-6alkyl, NO2 or CI; and
R15 to R18 each independently is -H, -F, -CI, ~Br, -I, -S02F, -N02, -CN, -NR1R2, OH or optionally substituted -C1-6-alkyl or -C1-6-alkoxy;
R12 is N02 or -S02F;
R11 is H; and
R13 and R14 each independently is H or C1.
The optional substituents for any of the groups represented by R15 to R16 may be selected from any of optional substituents described above for A, D, R1 and R2
Compositions in accordance with the invention, comprising dispersions of azo dye compounds of Formula (1) typically comprise from 1% to 30% of a compound of Formulae (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 conventionally used in dyeing applications such as dispersing agents for example lignosulphonates, naphthalene sulphonic acid/formaldehyde condensates or
phenol/crescl/sulphanilic acid/formaldehyde condensates, surfactants, wetting agents such as alkyl aryl ethoxylates which may be sulphonated or phosphated, inorganic salts, de-fearners 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 Formulae (1). Wetting agents may be used at from 0% to 20% on the weight of the compound (1). The dispersions may be prepared by bead milling the compound of Formula (1) with glass beads or sand in an aqueous medium.
The compounds of Formula (1) may be 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 D-X in which A and D are as hereinbefore defined and X is a group displaceable by a diazotised amine. Typically the 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 -10°C to 10°C. 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 0°C to 10CC. After coupling the compound of Formula (1) may be recovered from the reaction mixture by any convenient means such as by filtration.
Flurosulphonyl 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 Formula (1), A-NH2, the NH2 being protected as necessary, or D-X, in which A, and D are as hereinbefore defined, with chlorosuiphonic acid optionally in the presence of dimethylformamide and thionylchloride at a temperature of from 30°C to 140°C gives the chlorosulphonyl derivative. 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 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 thionylchloride optionally in the presence of a chlorophosphorus compound such as phosphorus oxychloride or phosphorus pentachloride in an organic liquid such as an aromatic hydrocarbon at a temperature of from 20°C to 110°C. Similarly a sulphonate ester may be converted to the corresponding chlorosulphonyl derivative. The chlorosulphonyl derivative may then be converted to the fluorosulphonyl 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 provides for a dispersion composition comprising:
a dye compound dispersed in an aqueous medium and present in an amount of from 1 to 30% by weight of dye compound and aqueous medium, a dispersing agent of the kind such as herein described present in an amount of 10 to 200% by weight of the dye compound and optionally additionally comprising ingredients selected from conventional components such as wetting agents and defoamers, which dye compound 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 -S02F group or carries a substituent to which at least one -S02F group is attached and wherein, 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.
The present invention also provides for a process for the preparation of a dispersion composition, comprising mixing homogenously a dye compound of formula (1) , in an amount of from 1 to 30% by weight of the composition, a dispersing agent in an amount of 10 to 2 00% by weight of the dye compound and conventional components such as wetting agents and defoamers in an aqueous medium in a manner such as herein described, to obtain a dispersion composition in the form of a homogenous mixture.
The invention is further illustrated by the following Examples.
Example 1
Preparation of 4- (2,5-dichloro-4-
fluorosulphonylphenylazo)-3-methyl-N-ethyl-N-(2-
benzoyloxyethyl)aniline
i) Preparation of 2,5-dichloro-4-chlorosulphonylaniline
2,5-Dichloroaniline (32.4 parts) was added portionwise to chlorosulphonic acid (93 parts) at 35°C. The mixture was stirred at 120°C for 3hrs and then cooled to 70°C. Dimethyl formamide (1.6 parts) and thionyl chloride (15 parts) were added, maintaining the temperature at 65-70°C and the mixture stirred at 70°C 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).
ii) Preparation of 2,5-dichloro-4-fluorosulphonylaniline A mixture of 2,5-dichloro-4-chlorosulphonylanxline (44.2
parts), potassium, fluoride (3= parrs) and water 130 parts) was stirred under reflux for 5 hours. The reection. mixture was cooled to ambient temperature and drowned into water (30C parts). The cream precipitate was isolated by filtration, washed with water ar.d dried under vacuum to yield; 2 , 5-dichloro-4 -fluorosulphonylanline (37.2 parts), i ii ; Preparation of 3-methyl-N-ethyl-N- (2 benzoyloxyethyl) aniline
Benzoylchloride (3.2g) was added to e mixture of N-ethyl-N-hydrcxyet'nyl-3-methylaniline (2.1g) ir. acetone :25cm3! and pyridine (I0M) and stirred at reflux for 1 hour. The reaction mixture was cooled and used directly in iv) below.
i v) Preparation of 4- (2,5-dichloro-4-flucrcsuiphoylphenylazo) -3-methyl -N-ethyl-N-(2-benzoyloxyethyl)aniline
Nitrosyl sulphuric acid (3cm3 of 40%' was added to a mixture of 2,5-dichIoro-4-fluorosulphonylaniline (2g) in acetic/prcpicnic acid (86:14, 25cm3) at 0°C to 5°C. The mixture was stirred at 0°C to 5°C for 2 hours before adding the reaction mixture from lii) above in methanol (100cm3) at 0°C to 5°C. The precipitated solid was collected by filtration, washed with water, slurried with methanol, collected by filtration and washed with methanol to give 4 -(2,5-dichloro-4-fluorosulphonylphenylazo)-3-methyl-N-ethyl-N- (2-benzoyloxyethyl) aniline (2.1g) when applied to polyester materials from aqueous dispersion gives bluish-red shades with excellent wet and light fastness properties.
The following examples of dyes of Formula:
(Formula & table Removed)
Example 8 7 (Process outside the invention but included by way
of explanation)
Preparation of 4 - (2,6-dibromo-4-fluorosulohonvlphenvlazo)-3 -acetarnido-
N,N-diethylaniline
i) Preparation of 2,6-dibromo-4-fluorosulohonvlaniline
To a solution of 4-aminobenzenesulphonyl fluoride (10 parts)
in acetic acid (100 parts), stirring at 0-5°C, was added gradually a
solution of bromine (18 parts) in acetic acid (50 parts); keeping the
temperature below 5°C. 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 product was
isolated by filtration, washed with cold water and dried at 50°C to
yield,- 2 , 6-dibromo-4-f luorosulphonylaniline (17.5 parts),
ii) Preparation of 4-(2,6-dibromo-4-fluorosulphonylphenylazo)-3-
acetamido-N,N-diethylaniline
A mixture of 2,6-dibromo-4-fluorosulphonylaniline (2.7 parts) and acetic/propionic acid mixture (15 parts, 86/14 vol/vol) was stirred and heated until a complete solution was formed. The solution was set stirring at 0-5°C, and nitrosyl sulphuric acid soln (5 parts) was added dropwise. The mixture was stirred at this temperature for a further 3 0min.
The diazo solution was aided slowly to a mixture of 3-N,N-diethylamincacetanilide (1.7 parts), methanol 50 parts! and sulthamic acid (0.5 parts); stirring at G-5°C. After stirring for Ihr at this temperature, water (50 parts) was added and the mixture was stirred a further 3 0min at ambient temperature. The product was isciated by filtraticn, washed with water end methanol and tnen dried at 50°C to yield; 4- (2,6-dibromo-4-fluorcsulphonyiphenylazo) -3-acetamidc-N,N-diethylanilme (1.8 parts) max=480nm.
When applied tc polyester materials from an aqueous dispersion, the dye gives dull orange shades with excellent light fastness and excellent fastness to wet treatments. The following examples of dyes of Formula:
were prepared by the procedure of Example 87;
(Formula & table Removed)
Example 106
Preparation of 4-(2,6-dicvano-4-fluorosulphonvlohenvlazo) -3-acetamido-
N.N-diacetaxybutylamino aniline
The dye m Example 103 (3.0g) was stirred in DMF (3 0cm:) and
CuCN (l.Og) at 90°C 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 dichloromethane, filtered and
the filtrate evaporated to give a blue dye (Amax 608nm).
Example 114 (Process outside the invention but included by way of explanation)
x) Preparation of 2-nitro-4-fluorosulohonylaniline
N-acetyl sulphanilyl chloride (100a) was dissolved in concentrated sulphuric acid (515 cm3), cooled to 4°C and a mixture of concentrated nitric acid (38.6 cm3) and concentrated sulphuric acid (42.9 cm3) added dropwise maintaining the temperature at 4-6°C. After l 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 yellow solid was refluxed for 3 hours in water (20 cm3) , p-dioxane (20 cm3) and KF (19.4g) then drowned onto ice and the precipitate collected. This precipitate was refluxed in absolute ethanol (35 cm3) and concentrated hydrochloric acid (35 cm3) for 1 hour then drowned onto ice, filtered and suction dried. Recrystallisation from ethanol yielded 8.7g of the required compound.
ii) 2-Nitro-4-fluorosulphonyl aniline (0.01 mol) was dispersed in a mixture of acetic:propionic acid (86:14; 25cm3), cooled to 0-5°C and nitrosyl sulphuric acid (0.01 mol) added portionwise at 0-5°C. The reaction mixture was stirred for 10 minutes at 0-5°C then added dropwise to a mixture of the 3-(N,N-diethylamino) acetanilide (O.Olmol), methanol (5'Ocm3) and ice (50g) . The resultant precipitate was filtered, washed with water and then methanol and oven dried at 50°C. The dry dye has a Amax of 54lnm and gives good fastness to washing, light and heat. The following examples of dyes of Formula:
were prepared by the procedure of Example 114:
(Formula & table Removed)
Example 139 (Process outside the invention but included by way of explanation)
i) Preparation of 2-nitro-fluorosulphenyl - 6 - chloroaniline.
2 -Nitro-4 - f lucrosulphonylaniiine (lOg) was dispersed in 30% KC1 (S3.Sg), cooled ;c 0-5°C and sodium chlorate (2g) dissolved in water (3.6g) added drepwise ensuring maintaining the temperature at 0-5°C. After 30 minutes reaction mixture drowned onto ice and precipitate collected, washed with water and suction dried to yield 8.5g of 2-Nitro-4 -fluorosulphony1 - 6-chlorcaniline.
ii) 2 -Nitro-4-flucrcsulphony1 - 6 -chlorcanilme (7.66mmol) was
dispersed in a mixture of acetic :prcpiomc acid (8S-.14; 25cm3) , cooled zo 0-5°C and nicrcsyl sulphuric acid (7.85= nmci; added portionwise at 0-5°C. The reaction mxcure was stirred for 10 nmutes at 0-5°C then added dropwise to a mixture of the 3 - (N,N-diethyiamino) acetanilide (7.86 mmol), methanol (50cm3) and ice (SOg). The resultant precipitate was filtered washed with water and then methanol and oven dried at 50°C. The dry dye has a max of 550nm and gives good fastness to washing, liahc and heat.
were prepared by the procedure of example 225:
The following examples cf dyes of Formula:
(Formula & table Removed)
Example 157 (Process outside the invention but included by way of explanation)
P2 Deration of 4 - (2 -nitro-4-f lucrosulphcnyl -6 -bromoohenylazo) -3-
aac tamido N N-diethylamline
1) 2 -Nitro-4 -flucrosulphonylaniline 5g) was dissolved in
glacial acetic acid (50 cm3) and bromine (4.4c' added. Reaction mix
warmed to 75°C for 2 hours then drowned cntc ice, filtered, washed with
water and suction dried. Yield 6.5g cf yellow solid,
ii: 2-Nitro-4-fluorosulphonyl-6-bromcaniiine (C.01 mol) was
dispersed m a mixture of acetic:propicnic acid (66:14; 25cm3) , cooled to 0-5°C and nitrosyl sulphuric acid (0.01 mcl; added porcionwise at 0-5°C. The reaction mixture was stirred for 10 -inutes at 0-5°C then added dropwise to a mixture of the 3 -(N,N-diethylamino) acetanilide (0.01 mol), methanol (50cm3) and ice (50g). The resultant precipitate was filtered washed with water and then methanol and even dried at 50°C. The dry dye has a Amax of 550nm and gives coed fastness to washing, light and heat. The following dyes of Formula.-
were prepared by the procedure of Example 157:
(Formula & table Removed)
Example 162 (Process outside the invention but included by way
of explanation)
Preparation of 4-(2-nitro-4-fluorosulohonvl-6-cvanophenvlazo)-3-acetamido-N,N-diethylanilihe
Dye Example 157 (2.0g) was stirred at 90°C with CuCN (0.42g)
and DMF (20cm3) for 3 hours. The.reaction mix was drowned onto ice
(50g) and the precipitate collected, washed with water and suction
dried. The filter cake was slurried in dichloromethane, filtered and
the filtrate evaporated to give a solid dye (Amax 603nm) which gives
good fastness to heat, washing and light.
The following dyes of Formula:
were prepared by the procedure of Example 162:
(Formula & table Removed)
Example 166
Preparation of 4-(3-carboethoxy-5-nitrathien-2-ylazo)-3-methyl-N-ethyl
N- (3-fluorosulphonylbenzoyloxy)ethyl aniline
4- (3-carboethoxy-5-nitrothienyl~2-ylazo)-3-methyl-N-ethyl
N-hydroxyethyl aniline (5mmol) was disolved in chloroform (20cm3) ,
potassium carbonate (0.7g) and 3-fluorosulphonylbenzoylchloride (1.2g)
were added and the mixture refluxed for 2 hours. The reaction mixture
was filtered and the filtrate evaporated to leave the solid dye, max
5 8 3 nm.
The following examples of dyes of Formula:
were prepared by the crocedure of Example 166:

(Formula & table Removed)
Example 172 (Process outside the invention but included by way of explanation)
Preparation of 4 - (3-carboethcxy-5-nitrothien_-2-ylazo) -3-methyl-N-ethyl-N- (4-fluorosulphonylphenyl)methyl aniline
2-Amino-3-carboethoxy-5-nitrothiophene (0.01 mol) was
dispersed in a mixture of acetic propionic acid (86:14, 2 5cm3), cooled
to 0-5°C and nitrcsylsulphuric acid (0.01 mol) added portionwise at 0-
5°C. The reaction mixture was stirred for 10 minutes at 0-5°C then
added dropwise to a mixture of the N-ethyl-N-(4 -fluorosulphonylbenzyl)-
3-toluidme (0.01 mol), methanol (50cm3) and ice (50g). The resultant
Drecmitate was filtered washed with water and then methanol and oven
dried at 50°C. The dry dye has a Amax of 580nm and gives good fastness
to washing, light and heat.
The N-ethyl-N-(4-fluorosulphonylbenzyl)-3-toluidine was prepared as follows:
N-Ethyl-3-toluidine (O.Olmol), potassium carbonate (O.Olmol), DMF (50cm3) and 4-fluorosulphonylbenzyl bromide (0.2mol) were stirred at 100°C for 24 hours. The reaction mix was filtered, drowned onto Lee and extracted with dichloromethane to give an impure product (22g). No further purification was required.
The 4-fluorosulphonylbenzylbromide was prepared as follows: Tosyl chloride (50g), bromine (43g) and carbon tetrachloride (500mls) were stirred at reflux while shining a UV lamp (365nm) onto the reaction. Once the solution became colourless the reaction was stopped and the solvent removed by evaporation. 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 (500g) and the precipitate collected, washed with water and dried in vacuo. Yield 34g of pale yellow crystals which by GLC is 54% required material, 17% starting material and 12% dibrominated species.
Example 174
Preparation of 4-(3-carboethoxy-5-nitrothien-2-ylazo)-N-ethyl-N-(4 -
fluorosulphonylohenyl) propyl aniline
2-Ammo-3-carboethoxy-5-nitrothicphene (O.Olmol) was
dispersed in a mixture of acetic:prcpionic acid (86:14; 25cm3}, cooled
to 0-5°C and nitrosyl sulphuric acid (O.Olmol; added portionwise at 0-
5°C. The reaction mixture was stirred for 10 minutes at 0-5°C then
added dropwise to a mixture of the N-(4-fluorosulphonylphenylpropyl)-N-
ethylaniline (O.Olmol), methanol (50cm3) and ice (50g). The resultant
precipitate was filtered washed with water and then methanol and oven
dried at 50°C. The dry dye has a max of 593nm and gives good fastness
to washing, light and heat.
The N-ethyl-N-(4-fluorosulphonylphenylpropyl)aniline was
prepared as follows:
N-Ethylaniline (O.Olmol), potassium carbonate (O.Olmol), DMF (50cm3) and 4-fluorosulphonylphenylpropyl bromide (0.2mol) were stirred at 100°C 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 required.
The 4-fluorosulphonylphenylprcpylbromide was prepared as
follows:
Phenylpropyl bromide (19.9g) was dissolved in chloroform (500mls) and chlorosulphonic acid (116g) added dropwise. Stirred for 12 hours at 4 0C then drowned onto ice (10kg) . 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 15g. This solid was dissolved in p-dioxane (50mls) and
KF (l0g) and refluxed for three nours After cooling to ambient the reaction mixture was drowned onto ice 1400g), extracted with dichloromethane (3x200mls), dried ever magnesium sulphate and evaporated to a brown oil. Yield 9g.
Example 175
Preparation of 4- ( 3 -carboetnoxy-5-nitrothier.-2 -ylazo) -N- (2-cyanoethyl) -
N- {4-fluorosuiohonylonenyl) ethylamline
2 -Amino-3-carbcethoxy-5-nitrothicphene (0 . 01mol: was
dispersed in a mixture of acetic propionic ecid (86:14; 25cm3), coded
to 0-5°C and nitrosyl sulphuric acid (C.Olmol; added porticnwise at 0-
5°C. The reaction mixture was stirred for 10 minutes at 0-5°C then
added dropwise to a mixture of the N- (2-cyanoethyl) -N- (4-fluorosulphcnyl
phenylethyl)aniline (O.Olmol), methanol (50cm3 and ice (50g). The
resultant precipitate was filtered washed with water and then methanol
and oven dried at 50°C. The dry dye has a A max cf 547nm and gives good
fastness to washing, light and heat.
The N- (2-cyanoethyl) -N- ( 4 - f luorosulphcnyiphenylethyl) aniline was prepared as follows:
N-(2-cyanoethyl)aniline (O.Olmol), potassium carbonate (O.Oimol), DM? (50cm3) and 4 -f luorosulphonylphenylethylbromide (O.mol) were stirred at 100°C 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 required.
The 4-fluorosulphonylphenylethyibromide was prepared as
follows:
Phenylethyl bromide (36.5g) was dissolved in chloroform (500mls) 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 magnesium sulphate and evaporated to a pale yellow oil that crystallised on standing. Yield 40.8g. This solid was dissolved in p-dioxane (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 (3x200mls) , dried over magnesium sulphate and evaporated to a brown oil. Yield 33.7g.
The following examples of dives of Formula:
(Formula Removed)
were prepared using the procedure of Example 172, the
fluorosulphonylphenylalkyl bromides were prepared as described in
examples 172, 174 and 175 as appropriate.
(Table Removed)
Example 194
Preparation of 4-(2,4-dinitrophenylazo)-3-methyl-N-ethyl-N-(4-(3-
fluorosulohonylbenzoyloxyl)n-butyl) aniline
2,4-Dinitroaniline (O.Olmol) was dispersed in a mixture of
acetic: propionic acid (86:14; 25cm3), cooled to 0-5°C and nitrosyl
sulphuric acid (O.Olmol) added portionwise at 0-5°C. The reaction
mixture was stirred for 10 minutes at 0-5°C then added dropwise to a
mixture of the N-ethyl-N-hydroxybutyl-3-toluidine (O.Olmol), methanol
(50cm3) and ice (50g). The resultant precipitate was filtered washed
with water and then methanol and oven dried at 50°C. The hydroxy dye (5
mmol) was dissolved in chloroform (20 cm3), potassium carbonate (0.7g)
and m-(sulphonylfluoride) benzoyl chloride (1.2g) and refluxed for 2
hours. The reaction mix was filtered and the filtrate evaporated to
yield a solid violet dye which gives good fastness to washing, light and
heat.
Example 195
Preparation of 4-(2,4-dinitro-S-bromophenvlazo)-3-acetamido-N-n-propyl-
N- (3-fluorosulphonylbenzoyloxy)ethyl aniline
2,4-Dinitro-6-bromoaniline (O.Olmol) was dispersed in a —mixture of acetic propionic 86:14)25 ml coolded to 0. 5°C and
mitrosyl sulpnuric acid 10 .01 ml calcrocform 20 cml was dissolved in
caloroform 20 cml potassium carbonaste (0. 7g ) and m- (sulphonylfluoride)
benicyl colcride (1,2g) and refluxed for 2 hours the reaction ,mix was
flacered and the filtrate evaporated to yield a solid dye (lmax) 552 nm)
which gives good fastness to washing
Example 195 (Process outside the invention put included by way of explanation)
Preparation of 4- ( 2 -chloro-5 -fluorosulpronylphnnylazo)-N-ethyl-N- benzyl aniline
3-Amino-4-chlorc benzene sulcnrr.yi fluoride (2 pares) was
stirred in acecic/prcpiomc acid 96/14 vcl/vol (25 pares) and cooled to 0-S°C. Nitrosyl sulphuric acid solution (2.S parts) was added dropwise at Q-5°C and stirred under these conditions for 2 hours. The diazo solution was then added to a mixture of N-ethyi-N-benzyl^aniline (2.7 parts), methanol (100 parts) and suiphamic acid (1 part) stirring at 0-5°C. After stirring under these conditions for 30 mms, ice/water (100 parts) was added and the mixture stirred for a furtner 1 hour. The product was isolated by filtration, washed witr. water and pulled dry. The damp solid was then slurried in methanol (100 parts) and re-filtered. Dried at 50°C to yield 4 - (2-chicrc-5-flucrosulphonyl phenyl azo)-N-ethyl-N-benzyl aniline (2.3 parts).
When applied to polyester materials from an aqueous dispersion, the dye gave yellow shades. A.max 4=3nm. The following examples of dyes of Formula:
(Formula Removed)
were prepared by the procedure of Example 196: (Table Removed) Example 208
Preparation of 4-(2-chIoro-4-fluorosulphonvlphenvlazo)~3-acetamido-N, N-
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-
acetoxyethyl) aminoacetanilide were used to yield the product, 4- (2-
chlcro-4-fluorosulphonyl phenylazo) -3-acetamido-N,N-bis (2-acetoxyethyl)
aniline (1.2 parts) . When applied to polyester materials from an
aqueous dispersion, the dye gave orange shades- Amax 4 94nm.
Example 20 9 (Process outside the invention but included by way of explanation)
Preparation of 4- (2-methoxv-5-fluorosulphonylphenylazo) -3-methyl-N-ethyl -W-benzyl aniline
3-Amino-4-methoxy benzene sulphonylfluoride (1 part) was stirred in acetic/propionic acid 86/14 vol/vol (15 parts) and cooled to
0-5cC. Nitrosyi sulphuric acid solution (1-5 parts) was drcpwise and stirred at 0-5°C for 2 hours. The diazc solution was then added to a stirred mixture of N-ethyl-N-benzyl-m-toluidine (1.3 parts), methanol (50 parts), sulp.namic acid (0.5 parts! and sodium acetate (5 parts) stirring in ice/water at C-5°C. After stirring for 2 hours under tnese conditions, the dye was filtered off and washed well with water. The damp solid was slurried m water and re-filtered. The dye was then-stirred in methanol at room temperature for 1 hour, filtered, and dried at 50°C to yield the.product, 4 -(2-mechoxy- 5 - fluorosulphonyi phenylazoj-3-methyl-N-ethyl-N-benzyl aniline (1.5 carts'. When applied to polyester materials from an aqueous dispersion, the dye gave yellow shades. Amax 450. The following examples of dyes of Formula:

(Formula Removed)
were prepared by the procedure of Example 203.-
(Table Removed)
Example 214 (Process outside the invention but included by way of explanation)
Preparation of 4-(4-chloro-5-fluorosulphonvlohenvlazo)-N,N-bis (2-cyanoethvl) aniline
i) 2-Chloro-5-nitro benzene sulphonic acid (484 parts) was
charged to a flask then quickly added thionyl chloride (1190 parts) and dimethyl formamide (12 parts). The resultant slurry was heated to 6 0°C and stirred at 60-65°C for a total of 5 hours. The mixture was cooled to room temperature then poured onto ice/water. The precipitated solid was filtered off and washed with cold water before drying in vac oven to yield the product 2-chloro-5-nitro benzene sulphonylchloride (3 95 parts).
ii) 2-Chloro-5-nitro benzene sulphonylchloride (40 parts) was stirred in p-dioxane (48 parts) at room temperature. Potassium fluoride
(10 carts) dissolved m water (35 parts; was added, and the mixture heated to 7C°C. Stirred at ?0°C for 4 hours then cooled to room temperature and poured onto ice/water. Allowed to stand for 2 days tne: filtered off the precipitate and dried in air to yield the product 2-chloro-5-nitro benzene sulpnonylfluoride (3S parts).
iii) The 2-chloro- 5-r.itro benzene sulphonylf luoride (2.4 parts) was stirred in glacial acetic acid (25 parts with iron powder '2 parts) . Heated to reflux and stirred at reflux for 2.5 hours, then cooled to room temperature, poured onto ice/water and allowed tc stand at room temperature overnight. The resultant precipitate was filtered off and dried in air to yield the product 2-chlorc-5-amino benzene sulphonylfluoride (0.8 parts).
iv) 2-Chloro-5-amino benzene sulphonylfluoride (2.1 parts* was
were prepared by the procedure of Example 21<
stirred in acetic/prcpionic acid 86/14 vol/vol (25 parts) and cooled to 0-5°C. Nitrcsyl sulphuric acid solution (2.c parts! was added and stirred at 0-5°C for 3 hours. The diazo solution was then added to a mixture of N,N-bis(2-cyanoethyl) aniline (2.1 parts), methanol (75 parts) and sulphamic acid (1 part) stirring m ice/water (75 parts) at 0-5°C. Stirred under these conditions for l 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-fiuorosulphonyl phenylazo)-N,N-bis(2-cyanoethyl) aniline (3.6 parts). The dye, when applied to polyester material from an aqueous dispersion, gave yellow shades. Imax 4l4nm. The followinc Examples of dves of Formula:
(Table & formula Removed)
General Method for the Preparation of Dye Examples 222 - 23 8
i) Preparation of 2-nitro-4-fluorosulp'nonylaniiine
N-acetyl sulphanilyl chloride (lOOg) was dissolved in concentrated sulphuric acid (515 cm3), cooled to 4°C and a mixture of concentrated nitric acid (38.6 cm3) and concentrated sulphuric acid
(42.9 cm3) added dropwise 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 yellow solid was refluxed for 3 hours in water
(20 cm3) , p-dioxane (20 cm3) and KF (19.4g) then drowned onto ice and the precipitate collected. This precipitate was refluxed in absolute ethanol (35 cm3) and concentrated hydrochloric acid (35 cm3) for 1 hour then drowned onto ice, filtered and suction dried. Recrystallisation from ethanol yielded 8 . 7g of the required compound.
ii) Preparation of 2-nitro-4-fluorosulohcnvl-6-chloroaniline
2-Nitro-5-chloracetanilide (lOg) was added cautiously to chlorosulphonic acid (40cm3) then heated at 120°C for 2 hours. The reaction mix was cooled to 50°C and drowned onto ice. The 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 refluxing 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% HC1 (50cm3) for 1 hour, drowned onto ice and the precipitate collected. Yield 3.5g.
2-Nitro-4-fluorosulphonylaniline (O.Olmol) (for dyes 222-230) or 2-nitro-6-chloro-4-fluorosulphonyl-aniline (O.Olmol) (for dyes 231-238) was dispersed in a mixture of acetic:propionic acid (86:14) (25ml) and cooled to 0-5°C and nitrosylsulphuric acid (O.Olmol) was then added
portionwise at 0-5°C. The reaction mixture was stirred fcr 10 min. at 0-5°C and then added dropwise to a mixture cf the required coupler (O.Olmol), methanol (50ml) and ice (50g) maintaining the acidity between pK3 and pH5 by addition cf sodium acetate The resultant precipitate was filtered, washed with water and then methanol 1:1 water and dried in air. The dry dye, when applied to polyester as an aqueous dispersion, gave good fastness to washing, light and heat
(i) Preparation of Couplers for Dve Examples 222 - 224 22S , 229 and 231 - 23 5 - Method 1:
Dye Examples 222 - 224, 226, 225 and 231 - 235 were prepared
from the appropriate N, N-dialkyl-(3-ethyisuccinamido-6-methoxy)aniline
coupling components which were prepared according to the following
method. A mixture of 3- (N, N-dialkyl)-4-methcxyanilme (O.Olmol),
ethylsuccinyl chloride (O.Olmol) and pyridine (O.Olmol) in
dichlorcmethane (50ml) was stirred and heated under gentle reflux for 4h
and then allowed to cool and was then drowned out into water. The
resulting product was extracted into dichlcrorr.ethane, dried (MgS04) and
evaporated to dryness in vacuo to yield the required coupler as a brown
oil.
(ii) Preparation of Couplers for Dve Examples 225, 227, 228, 230 and 236 - 238 - Method 2:
Dye Examples 225, 227, 228, 230 and 235 - 238 were prepared
from the appropriate N,N-dialkyl-(3-ethylsuccinamido-6-methoxy) aniline
coupling components which were prepared according to the following
method. A mixture of 3-(N,N-dialkyiamino) -4-methoxyaniline (O.Olmol)
and succinic anhydride (O.Olmol) in anhydrous toluene (50ml) was stirred
for l.5h and then evaporated to dryness in vacuo to give a brown gum.
The brown gum (the carboxylic acid intermediate) was esterified by
treatment with an appropriate alcohol (O.lmol) and cone, sulphuric acid
(1ml) at 100°C for Ih 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 vacuo to yield the required
coupler as a brown oil.
Dye Examples 222 - 238 are summarised below:-
(Table & formula Removed)
Preparation of Dve Examples 23 9 - 245
Dye Examples 239 - 246 were prepared using the same general method as was used for the preparation of dye examples 222 - 238. The dyes, when applied to polyester as agueous dispersions, gave good fastness to washing light and heat.
The couplers for dye Examples 23 5, 24 0 and 24S were oreoarec from 3 - N , N-diechylamino) -4 -methoxyaniline according to the method 1 using acetylsalicoyl chloride (O.Olmol: m place of ethylsuooinyl chloride.
The coupler for dye Example 241 was prepared from 3-(N,N-diethylamino)-4-methoxyaniline according to the method 1 using cutylchlorcformate (O.Olmol) in place of ethylsuccinyi chloride. The coupler for dye Examcle 242 was prepared from 3 - (N, N-diethylamino-4-methoxyaniline according to the method 1 using ethylmalcnyl chloride (O.Olmol) in place of ethylsuccinyi chloride.
The coupler for dye Example 243 was prepared from 3-(N,N-diethylamino)-4-metnoxyaniiine according to the method 2 using maleic anhydride (O.Olmol) in place of succinic anhydride and ethanol as the esterifying alcohol.
The coupler for dye Example 244 was prepared from 3-(N,N-diethyiammo) - 4-methoxyaniline according to the method 2 using 2,2-dimethylsuccinic anhydride (O.Olmol) in place of succinic anhydride and ethanol as the esterifying alcohol.
The coupler for dye Example 245 was prepared from 3-(N,N-diethylammo)-4-methoxyaniline according to the method 1 using 4-methoxycarbonyiphenylchloroformate (O.Olmol) in place of ethylsuccinyi chloride. Dye Examples 239 - 246 are summarised below :-
(Table & formula Removed)

WE CLAIM:
1. A dispersion composition comprising:
a dye compound dispersed in an aqueous medium and present in an amount of from 1 to 30% by weight of dye compound and aqueous medium, a dispersing agent of the kind such as herein described present in an amount of 10 to 200% by weight of the dye compound and optionally additionally comprising ingredients selected from conventional components such as wetting agents and defoamers, which dye compound 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 carties directly at least one -SO2F group or carries a substituent to which at least one -SO2F group is attached and wherein, 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.
2. A dispersion composition as claimed in claim 1, wherein A and D each
independently is selected from thienyl, thiazolyl, isothiazolyl,
pyrazolyl, imidazolyl, pyridyl, pyridonyl, 1,2,4- and 1,3,4-thiadiazolyl,
furanyl, pyrralyl, pyridazyl, pyrimidyl, pyrazinyl, benzothiazolyl,
benzoisothiazolyl, quinolinyl, isoquinolinyl, indolyl, pyridothiazolyl, pyridoisotniazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, phenyl and napthyl.
3. A dispersion composition as claimed in claim 2, wherein A and D each independently is selected from thienyl, phenyl, naphthyl, thiazolyl, isothiazolyl, pyrodonyl and quinolinyl.
4. A dispersion composition as claimed in claim 3, wherein A and D each independently is selected from thien-2-yl, phenyl, naphtha-1-yl, naphtha-2-yl, thiazol-2-yl, isothiazol-5-yl, pyrid-4-one-5-yl and quinolinyl.
5. A dispersion composition as claimed in claim 4, wherein A is thien-2-yl or phenyl and D is phenyl or naphth-1 -yl.
6. A composition as claimed in any of the preceding claims, wherein the said dispersing agent is selected from the group consisting of lignosulphenates, naphthalene sulphonic acid formaldehyde condensates and phenol, cresol and sulphanilic acid formaldehyde condensates and surfactants.
7. A composition as claimed in any of the preceding claims, wherein the
said wetting agent comprises up to 20% of the weight of compound of
formula (1), and is selected from the group consisting of alkyl aryl
ethoxylates.
8.A composition as claimed in claim 7, wherein the ethoxylates are sulphonated or phosphated.
9.A composition as claimed in any of the preceding claims, wherein the defoamers are selected from the group consisting of mineral oil, nonanol, organic liquids and buffers.
10.A process for the preparation of a dispersion composition as claimed in claim 1, comprising mixing homogenously a dye compound of formula (1), as defined in claim 1, in an amount of from 1 to 30% by weight of the composition, a dispersing agent in an amount of 10 to 200% by weight of the dye compound and conventional components such as wetting agents and defoamers in an aqueous medium in a manner such as herein described, to obtain a dispersion composition in the form of a homogenous mixture.
11.A process as claimed in claim 10, wherein the said composition is prepared fey bead milling the dye compound of formula (1) with glass beads or sand in an aqueous medium.
12.A dispersion composition substantially as herein described with reference to and as illustrated in the foregoing examples.
13. A process lor the preparation of dispersion composition substantially as herein described with reference to and as illustrated in the foregoing examples.