The present invention relates to a process for preparing a disazo dye compound. The said disazo dye compound contains a fluorosulphonyl goup, which dye compound is useful for colouring synthetic textile materials.
The present invention is a divisional. out of IP-19100l (formerly 113/DEL/95)
Disazo dyes including water solubilizing groups are disclosed in FR-A-1307200 and US-A-3131021. Disazo dyes including ice colour coupling components are disclosed is US-A-2427995. JP-A-54-050021 discloses a disazo dye in the context of reactive disperse dyes for cellulose.
The parent invention related to a dispersion composition comprising:
i) 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, ii) a dispersing agent present in an amiount of 10 to 200% by
weight of the dye compound and
iii) 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) :
A-N=N-D-N=N-E (1)
wherein,
each of A, D and E independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A, D and E carries directly at least one -SO2F group or carries a substitutent to which at least one -SO2F group is attached, and wherein, in the formula (1), each of A, D and E is such as to provide a dye compound selected from compounds of the formulae 2, 3 and 4 as given below:
(Formula Removed)
in which;
R1 and R2 each independently is -H, C1-6-alkyl or
C1-6-alkyl substituted by -OH, -CN, -F, -CI, -Br, -SO2F, phenyl, phenylS02F, -OCOC1-6-alkyl, -COOC1-6-alkyl, -COOC1-6-alkoxyC1-6-alkoxy, C1-6-alkoxy, C1-6-alkoxyC1-6-alkoxy, -OCC1-6-alkyl, -OCC1-6-alkoxyC1-6-alkoxy, -OCO(3-fluorosulphonylphenyl), -OCO(4-fluorosulphonylphenyl) , -OCOphenyl or -OCOC2-4-alkenyl; R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy; R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or -NHCOC1-6-
alkyl;
R5,R6,R7,R8,R9 and R10 each independently is -H,
C1-6-alkyl, C1-6-alkoxy or -SO2F; and R11,R12,R13,R14 and R15 each independently, is -H, -CN, -NO2, -SO2F, C1-6-alkyl, C1-6-alkoxy, -C0C1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3, -NR1R2, -CONR1R2 or -S02NR1R2 in which R1 and R2 are as hereinbefore defined;
(Formula Removed)

in which:
R1 and R2 each independently is -H, C1-6-alkyl or
C1-6-alkyl substituted by -OH, -CN, -F, -CI, -Br, -SO2F, phenyl, phenylS02F, -0C0C1-6-alkyl, -COOC1-6-alkyl, -COOC1-6-alkoxyC1-6-alkoxy, C1-6-alkoxy, C1-6-alkoxyC1-6-alkoxy, -0CC1-6-alkyl, -OCC1-6-alkoxyC1-6-alkoxy, -OCO(3-fluorosulphonylphenyl), -OCO(4-fluorosulphonylphenyl), -OCOphenyl or -OCOC2-4-alkenyl; R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy; R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or -NHCOC1-6-
alkyl; R5 and R6 each independently is -H, C1-6-alkyl, C1-6-alkoxy
or -SO2F; R11,R12,R13,R14,and R15 each independently is -H, -CN, -NO2, -SO2F, C1-6-alkyl, C1-6-alkoxy, -C0C1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3, -NR1R2, -CONR1R2 or -S02NR1R2 in which R1 and R2 are as hereinbefore defined; R16 is -H, -CN, -SO2F, -COOC1-6-alkyl, -COC1-6-alkyl or -CONR-1R2 in which R1 and R2 are as hereinbefore defined; and R17 is -H, -CN, -SO2F or C1-6-alkyl; and
(Formula Removed)
in which:
R3 is -H, -SO2F, Ci.5-alkyl or C1-6-alkoxy;
R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or -NHCOC1-6^ alkyl;
R5, R6, R7, R8, R9 and R10 each independently is -H, C1-6-alkyl, C1-6-alkoxy or -SO2F; and
R11, R12, R13, R14 and R15 each independently is -H, -CN, -N02,-S02F, C1-6-alkyl, C1-6-alkoxy, COC1-6-alkyI, -COOC1-6-alkyl, F, -CI, -Br, CF3, NR1R2, -CONRIR2 or -SO2NRIR2 in which R1 and R2 are as hereinbefore defined.
According to the present invention there is provided a process for preparing a disazo dye compound which is free from water solubilizing groups and is of Formula (1):
A-N=N-D-N=N-E (1)
wherein each of A, D and E independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A, D and E 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 or propionic acid or a mixture thereof and at a temperature of from -5°C to +50C to form a diazotised amine;
(2) coupling the diazotised amine with a first coupling
component of the formula (11)
X-D-NH2 (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 first coupling component of the formula (11) in an alkanol such as methanol at a temperature of from 0 to 5°C to form a monoazo compound of the formula (12)

A-N=N-D-NH2 (12)
wherein each of A and D is as defined above;
(3) diazotising the monoazo compound in an acidic medium such as acetic or sulphuric acid or mixture thereof using a nitrosating agent to form a diazotised monoazo compound;
(4) coupling the diazotised monoazo compound with a second coupling component of the formula (13)
E—X (13)
wherein each of E and X is as defined above,
by reacting the diazotised monoazo compound (12) with the second coupling component (13) in an aqueous medium, preferably whilst maintaining the pH at about 3 to form a disazo dye; and at least when each of A in the amine of the formula (10), D in the first coupling component of the formula (11) and E in the second coupling component of the formula (13) is free from an -SO2F group or a group to which at least one -SO2F is attached, introducing at least one fluorosulphonyl group into a compound of Formula (I) or into a component providing a group A, D or E therein, by a conventional process,
and wherein, in the formula (1), each of A, D and E is such as to provide dye compound selected from compounds of the formulae:
(Formula Removed)

in which:
R1 and R2 each independently is -H, C1-6-alkyl or C1-6-alkyl substituted by-OH, -CN, -F, -CI, -Br, -SO2F, phenyl, phenylS02F, -OCOC1-6-alkyl, -COOC1-6-alkyl, -COOC1-6-alkoxyC1-6-alkoxy, C1-6-alkoxy, C1-6-alkoxyC1-6-alkoxy, -OCC1-6-alkyl, -OCC1-6-alkoxyC1-6-alkoxy, -OCO (3-fluorosulphonylphenyl), -OCO (4-fluorosulphonylphenyl), -OCOphenyl or -OCOC2-4-alkenyl;
R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy;
RMs -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or-NHCOCi.6-alkyl;
R5, R6, R7, R8, R9 and R10 each independently is -H, C1-6-alkyl, C1-6-alkoxy or-S02F; and
R11, R12, R13, R14 and R15 each independently is -H, -CN, -NO2, -SO2F, C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3,
-NR1R2, -CONR1R2 or -SO2NRIR2 in which Ri and R2 are as hereinbefore defined;
(Formula Removed)
in which:
R1 and R2 each independently is -H, C1-6-alkyl or
C1-6-alkyl substituted by -OH, -CN, -F, -CI, -Br, -SO2F, phenyl, phenylSOaF, -OCOC1-6-alkyl, -COOC1-6-alkyl, -COOC1-6-alkoxyC1-6-alkoxy, C1-6~alkoxy, C1-6-alkoxyC1-6-alkoxy, -OCC1-6-alkyl, -OCC1-6-alkoxyC1-6alkoxy, -OCO(3~fluorosulphonylphenyl), -OCO(4-fluorosulphonylphenyl), -OCOphenyl or -OCOC2-4-alkenyl;
R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy;
R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or -NHCOC1-6-alkyl;
R5 and R6 each independently is -H, C1-6-alkyl, C1-6-alkoxy or -SO2F;
R11, R12, R13, R14 and R15 each independently is -H, -CN, -NO2, -SO2F, C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3, -NR1R2 -CONR1R2 or -SOsNR1R2 in which R1 and R2 are as hereinbefore defined;
R16 is -H, -CN, -SO2F, -COOC1-6-alkyl, -COC1-6-alkyl or -CONR1R2 in which R1 and R2 are as hereinbefore defined; and
R17 is -H, -CN, -SO2F or C1-6-alky1; and
(Formula Removed)
in which:
R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy;
R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or -NHCOC1-6-
alkyl; R5,R6,R7, R8, R8, R9 and R10 each independently is -H,
C1-6-alkyl, C1-6-alkoxy or -SO2F; and R11, R12, R13, R14 and R15 each independently is -H, -CN, -NO2, -SO2F, C1-6-alkyl, C1-6-alkoxy, -COC1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3, -NR1R2, -CONR1R2 or -S02NR1R2 in which R1 and R2-are as hereinbefore defined except for 4-(2'-methoxyphenyla-zo-4'-(4'-fluorosulphonylphenyl azo))phenol. A synthetic textile material or fibre blend thereof may be coloured by a process which comprises applying to the synthetic textile material a compound of Formula (1); prepared as described above.
The presence of one or more -SO2F groups in a dye molecule so prepared generally improves the properties of that dye and confers surprisingly good wet-fastness and light-fastness properties.
Different dye compounds of Formula (1) may be mixed or the dye 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. Such mixtures
generally show improvement in dyeing properties. Crystalline modifications of the dye 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 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, such as polyhexamethylene adipamide or polyethylene terephthalate more preferably aromatic polyester 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 dye compounds of Formula (1) are thus free from water solubilizing groups such as -SO2H, -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. For example, the dyes of Formula (1) in the form of an aqueous dispersion may be applied by dyeing, padding or printing processes using the conditions and additives
conventionally used in carrying out such processes. 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, 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 85°C for acetate or at a temperature of 90°C for
triacetate and nylon for from 15 to 90 minutes;
sequestrants 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 dye compounds of Formula (1) preferably carry a total of from one to three -SO2F groups, more preferably from one to two -SO2F groups and especially one -SO2F group.
As indicated above, a sub-group of dye compounds of Formula (1), prepared by a process embodying the invention, is that of dye compounds of Formula (2):
(Formula Removed)
in which:
R and R each independently is -H, C1-8alkyl or
C1-6-alkyl substituted by -OH, -CN, -F, -CI,
-Br, -SO2F, phenyl, phenylS02F, -OCOC1-6-alkyl,
-COOC1-6alkyl, -COOC1-6-alkoxyC1-6-alkoxy,
C1-6-alkoxy, C1-6-alkoxyC1-6-alkoxy,
-OCC1-6-alkyl, -OCC1-6-alkoxyC1-6-alkoxy,
-OCO(3-fluorosulphonylphenyl),
-OCO(4-fluorosulphonylphenyl), -OCOphenyl or
-OCOC2-.4-alkenyl; R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy; R4 is -H, -SO2F, C1-6-alkyl, d-g-alkoxy or -NHCOC1-6-
alkyl; R5,R6,R7, R8,R9 and R10 each independently is -H,
C1-6^alkyl, C1-6~alkoxy or -SO2F; and R11, R12, R13, R14 and R15 each independently is -H, -CN,
-NO2, -SO2F, C1-6-alkyl, C1-6-alkoxy,
-C0C1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3,
-NR1R2, -CONR^R' or -SO2NR1R2 in which R1 and R2
are as hereinbefore defined. In compounds of Formula (2) R7, R8,R9, and R10 each independently is preferably -H, C1-6-alkyl or C1-6-alkoxy.
A further sub-group of dye compounds of Formula (1), prepared by a process embodying the invention, is that of dye compounds of Formula (3):
(Formula Removed)
in which:
R1,R2,R3,^
R4, R5,R6,R11, R12, R13, R14 and R15 are as hereinbefore
defined for compounds of Formula (2); and R16 is -H, -CN, -SO2F, -COOC1-6-alkyl, -COC1-6-alkyl or
-CONR-1R2 in which R1 and R2 are as hereinbefore
defined; and R17 is -H, -CN, -SO2F or C1-6-alkyl.
In compounds of Formula (3) R16 is preferably -H, -CN, -COOC1-6-alkyl, -COC1-6-alkyI or -CONR1R2 and R17 is preferably -H, -CN or C1-6-alkyl.
A further subgroup of dye compounds of Formula (1), prepared by a process embodying the invention, is that of dye compounds of Formula (4):
(Formula Removed)
in which R3 to R15 are as hereinbefore defined, except for 4-(2'-methoxyphenylazo-4'-{4''-fluorosulphonylphenylazo)) phenol, which may alternatively be named as l-(4'-hydroxyphenylazo)-2-methoxy-4-(4''-fluorosulphonylphenylazo)benzene.
In a further preferred process embodiment of the present invention the dye compounds of Formulae (1), (2), (3) and (4) so prepared carry directly at least one -SO2F group or carry a substituent to which at least one -SO2F group is attached and carry at least one ester group or carry a substituent to which at least one ester group is attached. Such dyes with both -SO2F and ester groups show improved dyeing properties, particularly wet-fastness and light-fastness.
Compositions containing dye compounds prepared by a process embodying the invention and comprising dispersions of the dye compounds of Formulae (1), (2), (3) and (4) as hereinbefore defined in aqueous media are
novel. The compositions typically comprise from 1% to 30% of a compound of Formula (1), (2) or (3) and are preferably buffered at a pH from 2 to 7, more preferably at a pH from 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/cresol/sulphanilic acid/formaldehyde condensates, surfactants, wetting agents such as alkyl aryl 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 dye compound of Formula (1). Wetting agents may be used at from 0% to 20% on the weight of the dye compound of Formula (1). The dispersions may be prepared by bead milling the dye compound of Formula (1) with glass beads or sand in an aqueous medium.
A number of compounds of Formula (1) used in the above coloration process are novel except for 1-(4-hydroxyphenylazo)-2-methoxy-4-(4-fluorosulphonylphenylazo)benzene;
1- (2-chloro-4-nitrophenylazo)-5-methyl-2-fluorosulphonyl-4-(2-hydroxy-3-(carbonyl(n-phenyl)amino)naphth-1-ylazo)benzene;
1-(2-methyl-5-fluorosulphonylphenylazo)-3-ethoxy-4-(2-hydroxy-3-(carbonyl(N-phenyl)amino)naphth-1-ylazo)benzene;
1-(3-fluorosulphonylphenylazo)-2,5-dimethoxy-4- (2-hydroxy-3-(carbonyl(N-naphth-1-yl)amino)naphth-1-ylazo)benzene; and
1-(2-methyl-5-fluorosulphonylphenylazo)-4-(2-hydroxy-3-(carbonyl(N-phenyl)amino)naphth-1-ylazo)naphthalene.
The compounds of Formula (1) may be prepared by usual methods for the preparation of disazo compounds such as by diazotisation of an amine A-NH2 and coupling onto a component X-D-NH2 in which A and D are as hereinbefore defined and X is a group displaceable by a diazotised amine, followed by diazotisation of the resultant monoazo compound A-N=N-D-NH2 and coupling onto a component E-X in which E and X are as hereinbefore defined.
Typically the amine A-NH2 may be diazotised in an acidic medium such as acetic or propionic acid or mixtures thereof using a nitrosating agent such as nitrosyl sulphuric acid at a temperature from -5°C to 5°C. The diazotised amine may be coupled onto the component X-D-NH2 in an alkanol such as methanol and water at a temperature of from 0°C to 5°C. The monoazo compound A-N=N-D-NH2 may be recovered from the reaction mixture by filtration. The compound A-N=N-D-NH2 may be diazotised in an acidic medium such as acetic or sulphuric acid or mixtures thereof using a nitrosating agent as described above and coupled onto a component E-X in aqueous medium preferably whilst maintaining the pH at about 3. The A-N=N-D-N=N-E product may be recovered from the reaction mixture by filtration and may be purified by slurrying in an alkanol such as methanol and refiltering.
Fluorosulphonyl groups may be introduced into the dye compounds of Formula (1) or into the A, D and E components prior to coupling by methods generally available in the literature. For example reaction of the dye 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 chlorosulphonic acid optionally in the presence of dimethylformamide and thionylchloride at a temperature of from 30°C to 100°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 dye 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. The chlorosulphonyl derivative may then be converted to the fluorosulphonyl derivative as described above.
The dye compound of Formula (1) is useful for the coloration of synthetic textile materials particularly polyester textile materials and fibre blends thereof to which they impart colours which are excellent in wet and light fastness properties.
The invention is further illustrated by the following Examples.
Example 1
4-Aminobenzenesulphonyl fluoride (4 parts) was stirred in acetic/propionic acid 86/14 vol/vol (250 parts) at 0-5°C. While maintaining the temperature below
10°C, 40% nitrosyl sulphuric acid (4.8 parts) was added carefully and stirred for 1.5 hours before adding slowly to 2-amino-3-cyanothiophene (4.2 parts) in methanol (625 parts) and ice/water (840 parts). The pH was maintained at 3 by the addition of sodium acetate and 50% sodium hydroxide solution. After stirring at 0-5°C for a further 2 hours filtration yielded 3.3 parts of 2-amino-3-cyano-5-(4'-sulphonylfluorophenylazo)thiophene.
2-Amino-3-cyano-5-(4'-sulphonylfluorophenylazo) thiophene (12.5 parts) was stirred in glacial acetic acid (830 parts) at 15°C while 50% sulphuric acid (375 parts) was added slowly. On cooling further to 0-5°C, 40% nitrosyl sulphuric acid (18 parts) was added carefully and the reaction stirred for 2 hours before adding slowly, while maintaining the pH at 3 by the addition of 50% sodium hydroxide solution, to a mixture of N,N-bis-(acetoxyethyl)-aniline (15 parts) in ice/water (960 parts), sulphamic acid (10 parts) and saturated sodium acetate solution (50 parts). The product was isolated by filtration, washed with water and pulled dry. The damp solid was then slurried in methanol (100 parts), refiltered and dried overnight to yield
4-(3-cyano-5-(4'-sulphonylfluorophenylazo)-2-thiophene-azo)-N,N-bis-(acetoxyethyl)-aniline (4 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades.
Example 2
The procedure for Example 1 was repeated except that in place of 15 parts of N,N-bis-(acetoxyethyl)-aniline; 15 parts of N-(2-cyanoethyl)-N-(2-methoxy-carbonylethyl)-m-toluidine were used to yield 4-(3-cyano-5-(4'-
sulphonylfluorophenylazo)-2-thiophene-azo)-N-(2-cyanoethyl)-N-(2-methoxy-carbonylethyl)-m-toluidine (3.8 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades.
Example 3
The procedure for Example 1 was repeated except that in place of 15 parts of N,N-bis-(acetoxyethyl)-aniline; 15 parts N,N-bis-(2-cyanoethyl)-aniline were used to yield the product 4-(3-cyano-5-(4'-sulphonylfluoro-phenyl azo)-2-thiophene-azo)-N,N-bis-(2-cyanoethyl)-aniline (2.2 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. X^ax 575nm.
Example 4
The procedure for Example 1 was repeated except that in place of 15 parts of N,N-bis-(acetoxyethyl)-aniline; 15 parts of N-ethyl-N-(2-carboxyethyl)-aniline were used to yield the product 4-(3-cyano-5-(4'-
sulphonylfluorophenylazo)-2-thiophene-azo)-N-ethyl-N-(2-carboxyethyl)-aniline (2.4 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades. max 637 nm.
Example 5
The procedure for Example 1 was repeated except that in place of 15 parts of N,N-bis-(acetoxyethyl)-aniline; 15 parts of N,N-diethyl m-acetanilide were used to yield the product 4-(3-cyano-5-(4'-sulphonylfluorophenylazo)-2-thiophene-azo)-N,N-diethyl m-acetanilide (6.5 parts) which V7hen applied to polyester materials from an aqueous dispersion gave blue shades.
Example 6
3-Aminobenzenesulphonyl fluoride hydrochloride hydrate (4 parts) was stirred in acetic/propionic acid 86/14 vol/vol (250 parts) at 0-5°C. While maintaining the temperature below 10°C, 40% nitrosyl sulphuric acid (4.8 parts) was added carefully and stirred for 1.5 hours before adding slowly to 2-amino-3-cyanothiophene (4.2 parts) in methanol (625 parts), ice/water (840 parts). The pH was maintained at 3 by the addition of sodium acetate and 50% sodium hydroxide solution. After stirring at 0-5°C for a further 2 hours filtration yielded 3.3 parts of 2-amino~3-cyano-5-(3'-sulphonyl fluoro-phenylazo)-thiophene.
2-Amino-3-cyano-5-(3'-sulphonylfluoro-phenylazo)-thiophene (12.5 parts) was stirred in glacial acetic acid (830 parts) at 15°C while 50% sulphuric acid (375 parts) was added slowly. On cooling further to 0-5°C, 40% nitrosyl sulphuric acid !(18 parts) was added carefully and the reaction stirred for 2 hours before adding slowly, while maintaining the pH at 3 by the addition of 50% sodium hydroxide solution, to a mixture of N,N-diethylaniline (15 parts) stirred in ice/water (960 parts), sulphamic acid (10 parts) and saturated sodium acetate solution (50 parts). The diazo (12.5 parts) was then added slowly. The product was isolated by filtration, washed with water and pulled dry. The damp solid was then slurried in methanol (100 parts), refiltered then washed with water to yield 4-(3-cyano-5-(3'-sulphonylfluorophenylazo)-2-thiophene-azo)-N,N-diethyl aniline (1.7 parts). When applied to polyester
materials from an aqueous dispersion, the dye qave blue shades.
Example 7
The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl aniline; 15 parts of N-ethyl-N-(2-cyanoethyl) aniline were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluorophenylazo)-2-thiophene-azo)-N-ethyl-N-(2-cyanoethyl) aniline (7 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades.
Example 8
The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl aniline; 15 parts of N-(2-cyanoethyl)-N-(acetoxyethyl)aniline were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluorophenylazo)-2-thiophene-azo)-N-(2-cyanoethyl)-N-(acetoxyethyl)aniline (2 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades max 585 nm.
Example 9
The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl aniline; 15 parts of N-octyl-N-(sec)butyl-aniline were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluorophenylazo)-2-thiophene-azo)-N-octyl-N-(sec)butyl-aniline (1.5 parts) which when applied to polyester materials from an aqueous dispersion gave blue/green shades.
Example 10
The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl aniline; 15 parts of N,N-diethyl m-acetanilide were used to yield the product 4- (3-cyano-5-(3'-sulphonylfluorophenylazo)-2-thiophene-azo)-N, N-diethyl m--acetanilide (3 parts) which when applied to polyester materials from an aqueous dispersion gave blue/green shades.
Example 11
The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl aniline; 15 parts of N-butyl-N-secbutyl m-acetanilide were used to yield the product 4- (3--cyano-5- (3 ' -sulphonylf luorophenylazo) -2-thiophene-azo)-N-butyl-N-sec-butyl m-acetanilide (8.5 parts) which when applied to polyester materials from an aqueous dispersion gave blue/green shades.
Example 12
The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethyl aniline; 15 parts of N-ethyl-N-benzyl-aniline were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluoro-phenylazo)-2-thiophene-azo)-N-ethyl-N-benzyl-aniline (2.3 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades.
Example 13
The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethylaniline; 15 parts of N-ethyl-N-2-isopropenoxycarbonylethylaniline were used to yield the product 4-(3-cyano-5-(3'-sulphonylfluorophenylazo)-2-thiophene~azo)N-ethyl-N-2-
iso-propenoxycarbonyl~ethyl-aniline (2 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades.
Example 14
3-Amino-4-methoxybenzene3ulphonylfluoride (4 parts) was stirred in acetic/propionic acid 86/14 vol/vol (250 parts) at 0-5°C. While maintaining the temperature below 10°C, 40% nitrosyl sulphuric acid (4.8 parts) was added carefully and stirred for 1.5 hours before adding slowly to 2-amino-3-cyanothiophene (4.2 parts) in methanol (625 parts) ice/water (840 parts). The pH was maintained at 3 by the addition of sodium acetate and 50% sodium hydroxide solution. After stirring at 0-5°C for a further 2 hours filtration yielded 3.2 parts of 2-amino-3-cyano-5-(2'methoxy-5'-sulphonylfluoro-phenylazo)-thiophene.
2-Amino-3-cyano-5-(2'-methoxy-5'-sulphonylfluoro-phenylazo)-thiophene (12.5 parts) was stirred in glacial acetic acid (830 parts) at 15°C while 50% sulphuric acid (375 parts) was added slowly. On cooling further to 0-5°C, 40% nitrosyl sulphuric acid (18 parts) was added carefully and the reaction stirred for 2 hours before adding slowly, while maintaining the pH at 3 by the addition of 50% sodium hydroxide solution, to a mixture of N-(2-cyanoethyl)-N-acetoxyethylaniline (15 parts) stirred in ice/water (960 parts), sulphamic acid (10 parts) and saturated sodium acetate solution (50 parts). The product was isolated by filtration, washed with water and pulled dry. The damp solid was then slurried in methanol (100 parts), refiltered then washed with water to yield 4-(3-cyano-5-(2'-methoxy-5'-sulphonylfluoro-phenyl-azo)-2-thiophene-azo)-N-(2-cyanoethyl)-N-
acetoxyethyl aniline (3 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades.
Example 15
The procedure for Example 14 was repeated except that in place of 15 parts of N-(2-cyanoethyl)-N-acetoxyethyl aniline; 15 parts of N-butyl-N-(2-cyanoethyl) aniline were used to yield the product 4-(3-cyano-5-(2'-methoxy-5'-sulphonylfluorophehylazo)-2-thiophene-azo)-N-butyl-N-(2-cyanoethyl)aniline (6 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades.
Example 16
3-7\minobenzene sulphonyl fluoride hydrochloride hydrate {4 parts) was stirred in acetic/propionic acid 86/14 vol/vol (250 parts) at 0-5°C. While maintaining the temperature below 10°C, 40% nitrosyl sulphuric acid (4.8 parts) was added carefully and stirred for 1.5 hours before adding slowly to 2-amino-3-ethoxycarbonyl-thiophene (4.2 parts) in methanol (625 parts), ice/water (840 parts). The pH was maintained at 3 by the addition of sodium acetate and 50% sodium hydroxide solution. After stirring at 0-5°C for a further 2 hours filtration yielded 3.3 parts of 2-amino-3-ethoxycarbonyl-5-(3'-sulphonylfluoro-phenylazo)thiophene.
2-Amino-3-ethoxycarbonyl-5-(3'-sulphonylfluoro-phenylazo)-thiophene (12.5 parts) was stirred in glacial acetic acid (830 parts) at 15°C while 50% sulphuric acid (375 parts) was added slowly. On cooling further to 0-5°C, 40% nitrosyl sulphuric acid (18 parts) was added
carefully and the reaction stirred for 2 hours before adding slowly, while maintaining the pH at 3 by the addition of 50% sodium hydroxide solution, to N-ethyl-N~ (2-cyanoethyl)-aniline (15 parts) stirred, in ice/water (960 parts), sulphamic acid (10 parts) and saturated sodium acetate solution (50 parts). The product was isolated by filtration, washed with water and pulled dry. The damp solid was then slurried in methanol (100 parts), refiltered then washed with water to yield 4-(3-ethoxycarbonyl-5-(3'-sulphonyl!luoro-phenyl-azo)-2-thiophene-azo)-N-ethyl-N-(2-cyanoethyl)-aniline (2.7 parts) which when applied to polyester materials from an aqueous dispersion gave blue shades.
Example 17
The procedure for Example 1 was repeated except that in place of 15 parts of N,N-bis-(acetoxyethyl)-aniline; 15 parts of N-ethyl-N-((4-sulphonylfluorophenyl)-propyl)-aniline was used to yield the product 4-(3-cyano-5-(4'-sulphonyl!luoro-phenylazo)-2-thiophene-azo)-N-ethyl-N-((4-sulphonylfluorophenyl)-propyl)-aniline (0.25 parts). When applied to polyester materials from an aqueous dispersion, the dye gave blue shades, max 649 nm.
Example 18
The procedure for Example 6 was repeated except that in place of 15 parts of N,N-diethylaniline; 15 parts of N-ethyl-N-((4-sulphonylfluorophenyl)-ethyl)-aniline was used to yield the product 4-(3-cyano-5-(3'-sulphonyl!luoro-phenylazo)-2-thiophene-azo)-N-ethyl-N-( (4-sulphonylfluorophenyl)-ethyl)-aniline (4 parts). When
applied to polyester materials from an aqueous dispersion, the dye gave blue shades, max 629 nm.
Example 19
The procedure for Example 14 was repeated except that in place of 15 parts of N-(2-cyanoethyl)-N-acetoxyethylaniline; 15 parts of N-ethyl-N-( (4-sulphonylfluorophenyl)-ethyl)-aniline was used to yield the product 4-(3-cyano-5-(2'-methoxy-5'-sulphonylfluoro-phenyl azo)-2-thiophene-azo)-N-ethyl-N- ( (4-sulphonylfluorophenyl)-ethyl)-aniline (1.6 parts). When applied to polyester materials from an aqueous dispersion, the dye gave blue shades, max 627 nm.
Example 20
The procedure for Example 16 was repeated except that in place of 4 parts of 3-aminobenzenesulphonyl fluoride hydrochloride hydrate; 4 parts of 4-nitroaniline was used and in place of 15 parts of N-ethyl-N-(2-cyanoethyl)-aniline; 15 parts of N-ethyl-N-((4-sulphonylfluorophenyl)-ethyl)-aniline was used. This yielded 4-(3-ethoxycarbonyl-5-(4'-nitro-phenyl-azo)-2-thiophene-azo)-N-ethyl-N-((4-sulphonylfluorophenyl)-ethyl)-aniline (1.9 parts), which when applied to polyester materials from an aqueous dispersion gave blue colours.
Example 21
Sulphanilyl fluoride (4 parts) was stirred in acetic/propionic acid 86/14 vol/vol (250 parts) at 0-5°C. While maintaining the temperature below 10°C, 40% nitrosyl
sulphuric acid (4.8 parts) was added carefully and stirred for 1.5 hours.
The diazo component was then added slowly to 2,5-dimethoxyaniline (4.1 parts) in methanol (625 parts) and ice/water (840 parts). The pH was maintained at 5-6 by the addition of sodium acetate. After stirring at 0-5°C for 2 hours the mixture was allowed to warm to room temperature before being filtered to yield 3.8 parts of 2,5-dimethoxy-4-(4'-sulphonylfluorophenyl-azo)-aniline.
2,5-Dimethoxy-4-(4'-sulphonylfluorophenyl-azo)-aniline (8 parts) was stirred in cone, sulphuric acid (750 parts). On cooling to 0-5°C, 40% nitrosyl sulphuric acid (12 parts) was added carefully and the reaction stirred for 1 hour before being allowed to warm to room temperature.
N-Ethyl-N-(4'-fluorosulphonylbenzyl)-aniline (14 parts) was stirred in ice/water (960 parts), sulphamic acid (10 parts) and methanol (1250 parts). The diazo (8 parts) was then added slowly while maintaining the pH at 5-6 by the addition of sodium acetate and sodium carbonate solution. The oil obtained was then taken up in the dichloromethane and purified by column chromatography to yield 0.1 parts of the product 4-(2',5'-dimethoxy-4-(4''-sulphonylfluorophenyl-azo)-phenylazo)-N-ethyl-N-(4'-fluorosulphonylbenzyl)-aniline, Amax 536 nm.
Example 22
The procedure for Example 21 was repeated except that in place of 14 parts of N-ethyl-N-(4'-fluorosulphonylbenzyl)-aniline; 14 parts of N,N-dibutyl-m-toluidine was used to yield the product 4-(2',5'-
dimethoxy-4-(4''-sulphonylfluorophenyl-azo)-phenylazo)-N,N-dibutyl-m-toluidine (0.27 parts).
Example 23
2-Methyl-4-)(4'-phenylazo-phenylazo)-phenol (3.2 parts) was carefully added to chlorosulphonic acid (376 parts), while stirring. Thionyl chloride (82 parts) was then added and the mixture heated at 90°C for 28 hours. The reaction mixture was then drowned out into ice/water very carefully and filtered. The solid was washed several times with water until the washings were neutral before drying to yield 5-(4 ' - ( 4 ' '-chlorosulphonyl-phenylazo)-phenylazo)-2-hydroxy-3-methyl-benzenesulphonyl chloride (3.1 parts).
5-(4'-(4' '-Chlorosulphonyl-phenylazo)-phenylazo)-2-hydroxy-3-methyl-benzenesulphonyl chloride (1.95 parts) was stirred in 1,4-dioxan (117.5 parts) before potassium fluoride (34 parts) dissolved in water (440 parts) was added over 2-3 minutes. After heating at 50-60°C for 2 hours the reaction mixture was cooled and filtered. The solid was washed with water and dried to yield 5-(4'-(4''-fluorosulphonyl-phenylazo)-phenylazo)-2-hydroxy-3-methyl-benzenesulphonyl fluoride (1.6 parts).
Example 2 4
The procedure for Example 23 was repeated except that the starting dye was 4-(4'-phenylazo-naphth-1-ylazo)-phenol (5.7 parts) and the treatment with chlorosulphonic acid was carried out at 75°C. The product (2.1 parts) was found to be a mixture of two compounds, 5- (4' '-(4'-fluorosulphonyl-phenylazo)-naphth-1-ylazo)-2-hydroxy-benzene sulphonyl fluoride and 5~(4''-(4'-
fluorosulphonyl-phenylazo)-naphth-1-ylazo)-2-hydroxy-benzene-1,3-disulphonyl fluoride.
Example 2 5
The procedure for Example 2 3 was repeated except that the starting dye was l-methyl-3-(4-phenylazo)-IH-quinolin-2-one (2.2 parts) and heating with chlorosulphonic acid was carried out for 2 hours. The product (0.6 parts) was found to be a mixture of 1-methyl-3-(4'-(4''-fluorosulphonyl-phenylazo)-phenylazo)-4-(lH-quinolin-2-onyl)-sulphonyl fluoride and l-methyl-3-(4-phenylazo-phenylazo)-4-(lH-quinolin-2-onyl)-sulphonyl fluoride.
Example 2 6
The procedure for Example 23 was repeated except that the starting dye was 4-(4'-(4''-nitro-phenylazo)-phenylazo)-phenol (11.5 parts) and that the dye was heated at 75-80°C with the chlorosulphonic acid. The product (5.5 parts) was found to be a mixture of two compounds, 2-hydroxy-5-( 4'-(4' '-nitro-phenylazo)-phenylazo)-benzenesulphonyl fluoride and 2-hydroxy-5-(4'-(4 ' '-nitro-phenylazo)-phenylazo)-benzene-1,3-disulphonyl fluoride.
Example 27
The procedure for Example 23 was repeated except that the starting dye was 2-methyl-4-(2',5'-dimethyl-4'-(4''-nitro-phenylazo)-phenylazo)-phenol (3.85 parts) and that the dye was heated for only 3 hours with chlorosulphonic acid. The product of the reactions was found to be 2-hydroxy-3-methyl-5-(2',5'-dimethyl-4'-(4''-
nitro-phenylazo)-phenylazo)-benzenesulphonyl fluoride (0.2 parts).
Example 28
The procedure for Example 23 was repeated except that the starting dye was 2-methyl-(3,3'-dichloro-4'-(4-hydroxy-3-methyl-phenylazo)-biphenyl-4-ylazo)-phenol (3.05 parts) and the dye was heated for only 3 hours. The product (2.95 parts) was found to be a mixture of two compounds, 5-(3,3'-dichloro-4'-(3-fluorosulphonyl-4-hydroxy-5-methyl-phenylazo)-biphenyl-4-ylazo)-2-hydroxy-3-methyl-benzenesulphonyl fluoride and 5-(3,3'-dichloro-4'-(3-methyl-4-hydroxy-phenylazo)-biphenyl-4-ylazo)-2-hydroxy-3-methyl-benzenesulphonyl fluoride.

WE CLAIM:-
1. A process for preparing a disazo dye compound which is free from water solubilizing groups and is of Formula (1):
(Formula Removed)
wherein each of A, D and E independently is an optionally substituted heterocyclic or carbocyclic group in which at least one of A. D and E 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 or propionic acid or a mixture thereof and at a temperature of from -5°C to +5°C to form a diazotised amine;
(2) coupling the diazotised amine with a first coupling
component of the formula (11)
X-D-NH2 (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 first coupling component of the formula (11) in an alkanol such as methanol at a temperature of from 0 to 5°C to form a monoazo compound of the formula (12)
A-N=N-D-NH2 (12)
, wherein each of A and D is as defined above;
(3) diazotising the monoazo compound in an acidic medium
such as acetic or sulphuric acid or mixture thereof using a nitrosating
agent to form a diazotised monoazo compound;
(4) coupling the diazotised monoazo compound with a second
coupling component of the formula (13)
(Formula Removed)
wherein each of E and X is as defined above,
by reacting the diazotised monoazo compound (12) with the second
coupling component (13) in an aqueous medium,
preferably whilst maintaining the pH at about 3 to form a disazo dye; and
at least when each of A in the amine of the formula (10), D in the first
coupling component of the formula (11) and E in the second coupling
component of the formula (13) is free from an -SO2F group or a group to
which at least one -SO2F is attached, introducing at least one
fluorosulphonyl group into a compound of Formula (I) or into a
component providing a group A, D or E therein, by a conventional
process,
and wherein, in the formula (1), each of A, D and E is such as to provide
dye compound selected from compounds of the formulae:
(Formula Removed)
in which:
R1 and R2 each independently is -H, C1-6-alkyl or C1-6-alkyl substituted by-OH, -CN, -F, -CI, -Br, -SO2F, phenyl, phenylS02F, -OCOC1-6-alkyl,
-COOC1-6-alkyl, -COOC1-6-alkoxyC1-6-alkoxy,
C1-6-alkoxy, C1-6-alkoxyC1-6-alkoxy,
-OCCie-alkyl, -OCC1-6-alkoxyC1-6-alkoxy,
-OCO (3-fluorosulphonylphenyl),
-OCO (4-fluorosulphonylphenyl), -OCOphenyl or
-OCOC24-alkenyl;
R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy;
R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or-NHCOC1-6-alkyl;
R5, R6, R7, R8, R9 and 10 each independently is -H,
C1-6-alkyl, C1-6-alkoxy or -SO2F; and R11, R12, R13, R14 and R15 each independently is -H, -CN,
-NO2, -SO2F, C1-6-alkyl, C1-6-alkoxy,
-COC1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3,
-NR1R2, -CONR1R2 or -SO2NRIR2 in which Ri and R2 are as hereinbefore defined;
(Formula Removed)
in which:
R1 and R2 each independently is -H, C1-6-alkyl or C1-6-alkyl substituted by-OH, -CN, -F, -CI,
-Br, -SO2F, phenyl, phenylS02F, -OCOCO1-6-alkyl,
-COOC1-6-alkyl, -COOC1-6-alkoxyC1-6-alkoxy,
C1-6-alkoxy, C1-6-alkoxyC1-6-alkoxy, . ' -OCC1-6-alkyl, -OCC1-6-alkoxyC1-6-alkoxy,
-OCO (3-fluorosulphonylphenyl),
-OCO (4-fluorosulphonylphenyl), -OCOphenyl or -OCOC2-4-alkenyl;
R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy;
R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or-NHCOC1-6-alkyl;
R5 and R6 each independently is -H, C1-6-alkyl, C1-6-alkoxy or -SO2F;
R11, R12, R13, R14 and R15 each independently is -H, -CN,
-NO2, -SO2F, C1-6-alkyl, C1-6-alkoxy,
-COC1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3,
-NR1R2, -CONR1R2 or -SO2NRIR2 in which R1 and R2 are as
hereinbefore defined; RI6 is-H, -CN, -SO2F, -COOC1-6-alkyl, -COC1-6-alkyl
or -CONR1R2 in which R1 and R2 are as
hereinbefore defined; and
R17 is -H, -CN, -SO2F or C1-6-alkyl; and
(Formula Removed)
in which :
R3 is -H, -SO2F, C1-6-alkyl or C1-6-alkoxy;
R4 is -H, -SO2F, C1-6-alkyl, C1-6-alkoxy or -NHCOC1-6-alkyl;
R5, R6, R7, R8, R9 and R10 each independently is -H,
C1-6-alkyl, C1-6-alkoxy or -SO2F; and R11, R12, R13, R14 and R15 each independently is -H, -CN, -NO2, -SO2F, C1-6-alkyl, C1-6-alkoxy,
-COC1-6-alkyl, -COOC1-6-alkyl, F, -CI, -Br, -CF3, -NR1R2, -CONR1R2 or -SO2NRIR2 in which R1 and R2 are as hereinbefore defined except for 4-(2'-methoxyphenyla-zo-4'- (4' - fluorosulphonylphenylazo)) phenol.
2. A process as claimed in claim 1, wherein the compound of Formula (1) carries at least one ester group or carries a substituent to which at least one ester group is attached.
3. A process for preparing a disazo dye compound substantially as herein described with reference to the foregoing examples.