Title of Invention

A PROCESS FOR THE PREPARATION OF A MONAZO DYE FREE FROM WATER SOLUBILIZING GROUPS

Abstract

A process for the, preparation of a monoazo dye free from water solubilizing groups having the formula wherein Q is -Br or -CI; R1 and R2 each independently is H or is selected from the group consisting of C1-6-alkyl and aryl groups, each of which may be unsubstituted or substituted by one or more nonionic substituents; and R3, R4, R5 and R6 each independently is H, F, CI, Br, I, -SOzF or an organic moiety selected from the group consisting of C1-6-alkyl, C1-6-alkoxy, C1-4 alkanoylamino, -NHSO2 alkyl, -NHCOC1-4 alkyl and Ophenyl moieties, each organic moiety being unsubstituted or substituted by one or more nonionic substituents comprises diazotizing 6-bromo-2,5-dichloro-4- fluorosulphonylaniline or 2,3,6-trichloro-4-fluorosulphonylaniline and coupling the resulting diazo compound with an aromatic amine of the formula 3 wherein R1 to R6 are as herein described above. Resulting monoazo dye is recovered in a known manner.

Full Text

This invention relates to azo dyes and more particularly to water-insoluble monoazo dyes containing the fluorosulphonyl group, to a method for their preparation and to their use for colouring synthetic textile and other materials. Our International patent application published as WO 95/20014 describes azo compounds which contain at least one fluorosulphonyl group and are free from water-solubilising groups. The use of these compounds for colouring synthetic textile materials and for the mass coloration of plastics is also described. It has now been found that certain dyes falling within the general class described in WO 95/20014 but not specifically disclosed therein exhibit advantageous properties when applied as disperse dyes to synthetic textile materials. Thus, according to the invention, there are provided monoazo dyes which are free from water-solubilising groups and have the formula: R1 and R2 each independently is H or is selected from the group consisting of C^-alkyl and aryl groups, each of which may be unsubstituted or substituted by one or more nonionic substituents; and R3, R\ R5 and R6 each independently is H, F, CI, Br, I, -S02F or an organic moiety selected from the group consisting of C^-alkyl, C^-alkoxy, CM alkanoylamino, -NHS02alkyl, -NHCOC1-4alkyl and -Ophenyl moieties, each organic moiety being unsubstituted or substituted by one or more nonionic substituents. Water solubilising groups which must be absent from the dyes of Formula 1 particularly include -S03H, -CQ,H, -PQ H and quaternary ammonium groups and salts thereof. When either or both of R1 and R2 represents a C3-6alkyi group, the alkyl group can be linear or branched, and when branched, the branching may form a secondary or tertiary group. One or two points of branching may be present. The C-N bond can be formed between the N atom and any carbon in R1 or R2. When either or both of R1 and R2 represents an aryl group, the aryl group may be a phenyl or naphthyl group, which may be substituted at any position relative to the bond to the N atom. When either or both of R1 and R2 represents a phenyl group, any substituents are preferably present ortho and/or para to the phenyl- N bond. In certain embodiments, R1 and R2 may be fused to form, together with the N atom, an aromatic or conjugated heterocyclic group, particularly one comprising a 5 or 6 membered ring, or a saturated heterocyclic group, particularly one comprising a 5, 6 or 7 membered ring. such as nitrosylsulphuric acid, sodium nitrite or methyl nitrite at a temperature from -10°C to 10°C. Coupling with the aromatic amine of Formula 3 may be achieved by adding the diazotised 6-bromo-2,5-dichloro-4-fluorosulphonylaniline or diazotised 2,3,6-trichloro-4-fluorosuiphonylaniline to the amine of Formula 3 in an alkanol such as methanol at a temperature from 0°C to 10°C. After coupling, the compound of Formula 1 may be recovered from the reaction mixture by any convenient means such as by filtration. The 6-bromo-2,5-dichloro-4-fluorosulphonylaniline and 2,3,6-trichloro-4-fluorosulphonylaniline, respectively, may be obtained by bromination or chlorination of 2,5-dichloro-4-fluorosulphonylaniline. The azo compounds of Formula 1 are useful as disperse dyes and are valuable for colouring synthetic textile materials and fibre blends containing such materials. 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 such as polyhexamethylene adipamide or aromatic polyester, especially polyethylene terephthalate. Fibre blends may comprise mixtures of different synthetic textile materials or mixtures of synthetic and natural textile materials. Preferred fibre blends include those of polyester-cellulose such as polyester-cotton. The textile materials or blends thereof may be in the form of filaments, loose fibres, yam or woven or knitted fabrics. The azo compounds of Formula 1 or mixtures thereof, optionally in conjunction with other disperse dyes, may be applied to the synthetic textile materials or fibre blends thereof by processes which are conventionally employed in applying disperse dyes to such materials and fibre blends. Suitable process conditions include 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 be optionally 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 tr from 4 to 15 minutes for high temperature steaming, or at a temperature of fom19Q€ to 225°C for from 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 from 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 on to 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 compound of Formula 1 or mixture thereof may suitably be applied as a dispersion comprising from 0.001% to 4% by weight of the azo compound or mixture thereof in aqueous medium. The dye dispersions may further comprise ingredients conventionally used in coloration applications such as dispersing agents, for example lignosulphonates, naphthalene sulphonic acid/formaldehyde condensates or phenol/cresol/sulphaniiic 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 azo compound of Formula 1. Wetting agents may be used at from 0% to 20% on the weight of the azo compound of Formula 1. Suitable 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 provide synthetic textile materials with yellow-brown colorations exhibiting good fastness to washing, light and heat. The azo compounds of Formula 1 are also useful for the mass coloration of plastics materials. The azo compound is generally incorporated by blending with granular or powdered plastics material by, for example, dry tumbling or high speed mixing followed by injection moulding on a screw machine or by conventional compounding/masterbatching techniques. The present dyes generally dissolve or disperse rapidly in hot plastics melts and provide bright colorations generally with good clarity and good light fastness. Plastics which may be coloured in this way include polystyrene, acrylics, styrene/acrylonitrile mixtures, acrylonitrile/butadiene/styrene mixtures, polycarbonate, polyether-suiphone, nylons, rigid PVC (uPVC) and polypropylene. The azo compounds of Formula 1 may also be used as colorants for the inks used in solvent-based ink-jet printing processes. These inks, typically based on ketones and/or alcohols, are useful for printing on to hydrophobic substrates such as plastics and metals. Accordingly, the present invention provides a process for the preparation of a monoazo dye which is free from water solubilizing groups of formula I wherein Q is -Br or -CI; R1 and R2 each independently is H or is selected from the group consisting of Ci-g-alkyl and aryl groups, each of which may be unsubstituted or substituted by one or more nonionic substituents; and R3, R4, R5 and R6 each independently is H, F, CI, Br, I, -S02F or an organic moiety selected from the group consisting of Ci.6-alkyl, Ci.6-alkoxy, CM alkanoylamino, -NHS02alkyl, -NHCOC,^ alkyl and -Ophenyl moieties, each organic moiety being unsubstituted or substituted by one or more nonionic substituents which comprises diazotizing 6-bromo-2,5-dichloro-4-fluorosulphonylaniline or 2,3,6-trichloro-4-fluorosulphonylaniline in a known manner and coupling the resulting diazo compound with an aromatic amine of the formula 3 wherein R1 to R6 are as defined herein above, and recovering the resulting monoazo dye in a manner known per se. The invention is illustrated but not limited by the following Examples in which all parts are by weight unless otherwise indicated. All X,max were measured in CH2C12. Example 1 To a solution of 2,5-dichloro-4-fluorosulphonylaniline (4.9 parts) in acetic acid (30 parts) stirring at ambient temperature, was added a solution of bromine (3.52 parts) in acetic acid (10 parts). The mixture was stirred for 2 hours at 70°C, cooled to ambient temperature and water (75 parts) was added. After stirring for 1 hour, the product was isolated by filtration and dried to yield; 6-bromo-2,5-dichloro-4-fluorosulphonylaniline (6.0 parts). To a mixture of 6-bromo-2,5-dichloro-4-fluorosulphonylaniline (2.6 parts) and acetic/propionic acid mixture (15 parts, 86/14 vol/vol), stirring at 0-5°C, was added dropwise nitrosylsulphuric acid solution (5 parts). The mixture was stirred at this temperature for a further 30 minutes. The diazo solution was added slowly to a mixture of N,N-diethylaniline (1.2 parts), methanol (20 parts), water (10 parts) and sulphamic acid (0.5 part), stirring at 0-5°C. After stirring for 3 hours at this temperature, the product was isolated by filtration, washed with water and dried to yield 4-(6-bromo-2,5-dichloro-4-fluorosulphonylphenylazo)-N,N-diethylaniline (1.3 parts). When applied to polyester materials from an aqueous dispersion, the dye gives yellow brown shades with excellent light fastness and excellent fastness to wet treatments. Amax = 452nm. Example 2 In place of N,N-diethylaniline (1.2 parts) in Example 1, there were used N-ethyl-N-(2-cyanoethyl)aniline (1.4 parts) to yield 4-(6-bromo-2,5-dichloro-4-fluorosulphonyl phenylazo)-N-ethyl-N(2-cyanoethyl)aniline (1.6 parts). When applied to polyester materials from an aqueous dispersion, the dye gives yellow brown shades with excellent light fastness and excellent fastness to wet treatments. Amax = 418nnr Example 3 In place of N,N-diethylaniline (1.2 parts) in Example 1, there were used N-ethyl-N-(2-ethoxycarbonylethyl)aniline (1.5 parts) to yield 4-(6-bromo-2,5-dichloro-4-fluorosulphonylphenylazo)-N-ethyl-N-(2-ethoxycarbonylethyl)aniline (1.4 parts). When applied to polyester materials from an aqueous dispersion, the dye gives yellow brown shades with excellent light fastness and excellent fastness to wet treatments. Amax = 436nm. Example 4 In place of N,N-diethylaniline (1.2 parts) in Example 1, there were used N-ethyl-N-(2-acetoxyethyl)aniline (1.4 parts) to yield 4-(6-bromo-2,5-dichloro-4-fluorosulphonylphenylazo)-N-ethyl-N-(2-acetoxyethyl)aniline (1.3 parts). When applied to polyester materials from an aqueous dispersion, the dye gives yellow brown shades with excellent light fastness and excellent fastness to wet treatments. Amax = 434nm. Example 5 In place of N,N-diethylaniline (1.2 parts) in Example 1, there were used N-ethyl-N-(2-phenoxyethyl)aniline (1.7 parts) to yield 4-(6-bromo-2,5-dichloro-4- fluorosulphonyl phenylazo)-N-ethyl-N-(2-phenoxyethyl)aniline (1.8 parts). When applied to polyester materials from an aqueous dispersion, the dye gives yellow brown shades with excellent light fastness and excellent fastness to wet treatments. Amax = 446nm. WE CLAIM: wherein Q is -Br or -CI; R and R each independently is H or is selected from the group consisting of Ci.6-alkyl and aryl groups, each of which may be unsubstituted or substituted by one or more nonionic substituents; and R3, R4, R5 and R6 each independently is H, F, CI, Br, I, -S02F or an organic moiety selected from the group consisting of Ci„6-alkyl, Ci-6-alkoxy, Ci_4 alkanoylamino, -NHS02alkyl, -NHCOC].4alkyl and -Ophenyl moieties, each organic moiety being unsubstituted or substituted by one or more nonionic substituents which comprises diazotizing 6-bromo-2,5-dichloro-4- fluorosulphonylaniline or 2,3,6-trichloro-4-fluorosulphonylaniline in a known manner and coupling the resulting diazo compound with an aromatic amine of 2. The process as claimed in claim 1 in the compound of formula I each of R1 and R independently is C1-6 alkyl which may be substituted or unsubstituted by one or more nonionic substitutents and each of R3, R4, R5 and R6 is H. 3. The process as claimed in claims 1 and 2, wherein each of R1 and R2 is ethyl which may be substituted or unsubstituted by one or more nonionic substituents. 4. The process as claimed in claim 3, wherein in the compound of formula I R1 is -C2H5 and R2 is -C2H4X and X is selected from -H, -CN, -COOC2H5, -OCOCH3and-OC6H5. 5. A process for colouring synthetic materials such as textiles or plastics comprising the step of applying or incorporating the monoazo dye prepared by claims 1 to 4 in a known manner. 6. A process for the preparation of a monoazo dye which is free from water solubilizing groups substantially as herein described.

Documents:

136-mas-1997 abstract duplicate.pdf

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136-mas-1997 abstract.pdf

136-mas-1997 claims duplicate.pdf

136-mas-1997 claims.pdf

136-mas-1997 correspondence others.pdf

136-mas-1997 correspondence po.pdf

136-mas-1997 description (complete) duplicate.pdf

136-mas-1997 description (complete).pdf

136-mas-1997 form-13.pdf

136-mas-1997 form-2.pdf

136-mas-1997 form-26.pdf

136-mas-1997 form-4.pdf

136-mas-1997 form-6.pdf

136-mas-1997 others.pdf

136-mas-1997 petition.pdf

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