Title of Invention	PHTHALIMIDYL AZO DYES, AND THE PROCESS FOR PREPARING THE SAME
Abstract	The present invention relates to dyes of formula wherein R is hydrogen or bromine, R<sub>1</sub> is hydrogen, methyl or -NHC0-C<sub>1</sub>-C<sub>4</sub>alkyl, R<sub>2</sub> isC<sub>1</sub>-C<sub>4</sub>alkyl substituted byC<sub>1</sub>-C<sub>4</sub>alkoxy and R<sub>3</sub> has, independently of R<sub>2</sub>, any of the meanings of R<sub>2</sub>, and to the process for the preparation thereof

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Phthalimidvl azo dves. process for the preparation thereof and the use thereof The present invention relates to disperse dyes having an N-methyi-phthalimide-diazo component and an aniline coupling component, to processes for the preparation of such dyes and to the use thereof in dyeing or printing semi-synthetic and especially synthetic hydrophobic fibre materials, especially textile materials. Disperse azo dyes having an N-alkyl-phthalimide-diazo component and an aniline coupling component have been known for a long time and are used in dyeing hydrophobic fibre materials. It has, however, been found that the dyeings or prints obtained using the currently known dyes do not in all cases satisfy today's requirements, especially in respect of fastness to washing and fastness to perspiration. There is therefore a need for new dyes that especially have good washing fastness properties. It has now been found, surprisingly, that the dyes according to the invention meet the criteria given above to a considerable degree. The present invention accordingly relates to disperse dyes that yield dyeings having a high degree of fastness to washing and to perspiration and that, in addition, have good build-up characteristics both in the exhaust and thermosol processes and in textile printing. The dyes are also suitable for discharge printing. R3 has, independently of R2, any of the meanings of R2. R1 is preferably "NHC0-C1-C4alkyl. C1-C4Alkyl in the radical ~NHC0-C1-C4alkyi is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, especially methyl. R2 and R3 as C1-C4alkyl are, each independently of the other, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. R2 and R3 preferably have the same meaning. R2 and R3 are especially ethyl. C1-C4Alkoxy as substituent of C1-C4alkyl in R2 and R3 is, for example, methoxy, ethoxy or propoxy, especially methoxy. The dyes are prepared, for example, by nitration of a phthalimide of formula (50) in the acid range, as described, for example, on page 459 in Organic Synthesis, Collective Volume 2, (a Revised Edition of Annual Volumes X-XIX), J.Wiley & Sons, followed by alkylation of the resulting nitro compound, for example in accordance with a method described in Journal of Organic Chemistry 32 (1967) on page 1923, paragraph 3, and, for example after reductive treatment described in Bull. Soc. Chim. de France 1957 on page 569, conversion into an intermediate of formula (51). Using generally known methods, the intermediate of formula (51) is mono- or di-halogenated and the resulting compound is then, in an acid medium, diazotised and coupled to a compound of formula (52) wherein R1, R2 and R3 have the definitions and preferred meanings given above. The halogenation is carried out, for example, by reacting the compound of formula (51) first with sodium acetate in acetic acid and then with bromine in the same medium to form the corresponding mono- or di-bromo compound. The diazotisation of the compound of formula (51) is likewise carried out in a manner known perse, for example with sodium nitrite in an acidic, for example hydrochloric-acid-containing or sulfuric-acid-containing. aqueous medium. The diazotisation may, however, also be carried out using other diazotisation agents, e.g. with nitrosylsulfuric acid. In the diazotisation, an additional acid may be,present in the reaction medium, e.g. phosphoR1c acid, sulfuR1c acid, acetic acid, propionic acid, hydrochloR1c acid or mixtures of such acids, e.g. mixtures of propionic acid and acetic acid. The diazotisation is advantageously carR1ed out at temperatures of from -10 to 30°C, for example from -10°C to room temperature. The coupling of the diazotised compound of formula (51) to the coupling component of formula (52) is likewise effected in known manner, for example in an acidic, aqueous or aqueous-organic medium, advantageously at temperatures of from -10 to 30°C, especially below 10°C. Examples of acids used are hydrochloR1c acid, acetic acid, propionic acid, sulfuR1c acid and phosphoR1c acid. The diazo components of formula (51) and the coupling components of formula (52) are known or can be prepared in a manner known perse. The present invention relates also to dye mixtures compR1sing at least one azo dye of formula (1) and at least one azo dye of formula wherein R1 is hydrogen, methyl or -NHC0-C1-C4alkyl, R2 is C1-C4alkyl. it being possible for the alk^y chain, from C2 upwards, optionally to be interrupted by an oxygen atom, and R3 has, independently of R2, any of the meanings of R2. Preference is given to dye mixtures that compR1se at least one azo dye of formula (1) and tre azo dyes of formulae Special preference is given to dye mixtures that compR1se the azo dyes of formulae (2), (5) and (6). The azo dyes of formulae (1). (5) and (6) can be prepared analogously to known compounds using generally known methods. The azo dyes of formula (4) used in accordance with the invention are prepared, for example, by nitration of a phthalimide of formula (50) in the acid range, as descR1bed, for example, on page 459 in Organic Synthesis, Collective Volume 2, (a Revised Edition of Annual Volumes X-XIX). J.Wiley & Sons, followed by alkylation of the resulting nitro compound, for example in accordance with a method descR1bed in Journal of Organic Chemistry 32 (1967) on page 1923, paragraph 3, and, for example after reductive treatment descR1bed on page 569 in Bull. Soc. Chim. de France 1957, conversion into an intermediate of formula Using generally known methods, the intermediate of formula (53) is dihalogenated and then in an acid medium, diazotised and coupled to a compound of formula wherein R1, R2 and R3 have the definitions and preferred meanings given above. The reaction to form the final dyes is carR1ed out by replacement of the two bromine atoms by cyano groups using methods known perse, for example using CuCN or mixtures of CuCN and an alkali metal cyanide in a solvent, for example dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-vinylpyrrolidone. sulfolane or pyR1dine. The halogenation is carR1ed out. for example, by reacting the compound of formula (53) first with sodium acetate in acetic acid and then with bromine in the same medium to form the corresponding di-bromo compound. The diazotisation of the compound of formula (53) is likewise carR1ed out in a manner known perse, for example with sodium nitR1te in an acidic, for example hydrochloR1c-acid-containing or sulfuR1c-acid-containing, aqueous medium. The diazotisation may, however, also be carR1ed out using other diazotisation agents, e.g. with nitrosylsulfuR1c acid. In the diazotisation, an additional acid may be present in the reaction medium, e.g. phosphoR1c add, sulfuR1c acid, acetic acid, propionic add, hydrochloR1c acid or mixtures of such acids, e.g. mixtures of propionic acid and acetic add. The diazotisation is advantageously carR1ed out at temperatures of from -10 to 30°C, for example from -10°C to room temperature. The coupling of the diazotised compound of formula (53) to the coupling component of formula (54) is likewise effected in known manner, for example in an acidic, aqueous or aqueous-organic medium, advantageously at temperatures of from -10 to 30°C. especially beiow 10°C. Examples of acids used are hydrochloR1c acid, acetic acid, propionic acid, sulfuR1c acid and phosphoR1c acid. The diazo components of formula (53) and the coupling components of formula (54) are known or can be prepared in a manner known perse. The dye mixtures according to the invention compR1sing the azo dyes defined hereinbefore can be prepared, for example, by simply mixing the individual dyes, for example by mixing the azo dyes of formulae (2), (5) and (6). The amounts of the individual dyes in the dye mixtures according to the invention can vary within a wide range, for example from from 30 to 55 parts by weight, especially from 34 to 50 parts by weight, of the azo dye of formula (1) to from 45 to 70 parts by weight, especially from 50 to 66 parts by weight, of the azo dye of formula (4), based on 100 parts by weight of the dye mixture according to the invention. The dye mixtures according to the invention preferably contain from 34 to 50 % by weight of the azo dye of fomiula (2), from 25 to 33 % by weight of the azo dye of formula (5) and from 25 to 33 % by weight of the azo dye of formula (6), based on 100 % by weight of the dye mixture according to the invention. The dyes and dye mixtures according to the invention may be used for dyeing or pR1nting semi-synthetic and especially synthetic hydrophobic fibre mateR1als, especially textile mateR1als. Textile mateR1als composed of blend fabR1cs that compR1se such semi-synthetic or synthetic hydrophobic fibre mateR1als can also be dyed or pR1nted using the dyes or dye mixtures according to the invention. Semi-synthetic fibre mateR1als that come into consideration are, especially, cellulose 21/2-acetate and cellulose tR1acetate. Synthetic hydrophobic fibre mateR1als consist especially of linear, aromatic polyesters, for example those of terephthalic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane; of polycarbonates, e.g. those of a,a-dimethyl-4,4-dihydroxy-diphenylmethane and phosgene, and of fibres based on polyvinyl chloR1de and on polyamide. The application of the dyes and dye mixtures according to the invention to the fibre mateR1als is effected in accordance with known dyeing methods. For example, polyester fibre mateR1als are dyed in the exhaust process from an aqueous dispersion in the presence of customary anionic or non-ionic dispersants and, optionally, customary swelling agents (carR1ers) at temperatures of from 80 to 140°C. Cellulose 21/2-acetate is dyed preferably at from 65 to 85°C and cellulose tR1acetate at temperatures of from 65 to 115°C. The dyes and dye mixtures according to the invention will not colour wool and cotton present at the same time in the dyebath or will colour such mateR1als only slightly (very good reservation) so that they can also be used satisfactoR1ly in the dyeing of polyester/wool and polyester/cellulosic fibre blend fabR1cs. The dyes and dye mixtures according to the invention are suitable for dyeing in accordance with the thermosol process, in the exhaust process and for pR1nting processes. In such processes, the said fibre mateR1als can be in a vaR1ety of processing forms, e.g. in the form of fibres, yams or nonwoven, woven or knitted fabR1cs. It is advantageous to convert the dyes or dye mixtures according to the invention into a dye preparation pR1or to use. For this purpose, the dye is ground so that its partide size is on average from 0.1 to 10 microns. GR1nding can be carR1ed out in the presence of dispersants. For example, the dR1ed dye is ground together with a dispersant or kneaded into a paste form together with a dispersant and then dR1ed in vacuo or by atomisation. After adding water, the resulting preparations can be used to prepare pR1nting pastes and dyebaths. For pR1nting, the customary thickeners will be used, e.g. modified or unmodified natural products, for example alginates, BR1tish gum, gum arabic, crystal gum, locust bean flour, tragacanth. carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof, or polyvinyl alcohols. The dyes and dye mixtures according to the invention impart to the said mateR1als, especially to polyester mateR1als, level colour shades having very good in-use fastness properties such as, especially, good fastness to light, fastness to heat setting, fastness to pleating, fastness to chloR1ne, and wet fastness, e.g. fastness to water, to perspiration and to washing; the finished dyeings are further characteR1sed by very good fastness to rubbing. Special emphasis should be given to the good fastness properties of the dyeings obtained with respect to perspiration and, especially, to washing. The dyes and dye mixtures according to the invention can also be used satisfactoR1ly in producing mixed shades together with other dyes. Furthermore, the dyes and dye mixtures according to the Invention are also well suited to dyeing hydrophobic fibre mateR1als from supercR1tical CO2. The present invention relates to the above-mentioned use of the dyes and dye mixtures according to the invention as well as to a process for the dyeing or pR1nting of semi-synthetic or synthetic hydrophobic fibre mateR1als, especially textile mateR1als, in which process a dye according to the invention is applied to the said mateR1als or incorporated into them. The said hydrophobic fibre mateR1als are preferably textile polyester mateR1als. Further substrates that can be treated by the process according to the invention and preferred process conditions can be found above in the more detailed descR1ption of the use of the dyes according to the invention. The invention relates also to hydrophobic fibre mateR1als, preferably polyester textile mateR1als, dyed or pR1nted by the said process. The dyes according to the invention are, in addition, suitable for modern reproduction processes, e.g. thermotransfer pR1nting. The Examples that follow serve to illustrate the invention. Parts therein are parts by weight and percentages are percentages by weight, unless otherwise indicated. Temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as between grams and cubic centimetres. Example 1: 26.25 g of glacial acetic acid are introduced into a laboratory reaction apparatus and, over the course of 3 minutes, 1.67 g of the compound of formula are introduced at room temperature. The resulting greenish suspension is stirred for 5 minutes and then, over the course of 7 minutes, 0.54 g of 98 % sulfuR1c acid is added; stirR1ng is carR1ed out for 10 minutes. Then, over the course of 20 minutes, with cooling at 15-20°C, 1.86 g of 40 % nitrosylsulfuR1c acid are added dropwise to the reaction mixture and stirR1ng is carR1ed out for 1 hour at that temperature. After the reaction is complete, the mixture is added dropwise, over the course of 10 minutes, to a mixture consisting of 6.30 g of glacial acetic acid, 0.58 g of 32 % hydrochloR1c acid, 11.00 g of ice-water and 5.00 g of a 31.1 7o aqueous solution of the compound of fomiula at a temperature of 0-5°C and is stirred for 120 minutes. Then, over the course of 10 minutes, 15.00 g of ice-water are added dropwise; the reaulting red suspension is filtered with suction, washed with deionised water and dR1ed. There are obtained 2,10 g of the dye of formula which dyes polyester a red-brown shade. Example 2: 1 part by weight of the dye of formula is ground in a sand mill, together with 17 parts by weight of water and 2 parts by weight of a commercially available dispersant of the dinaphthylmethanedisulfonate type, and converted into a 5 % aqueous dispersion. Using that formulation, a 1 % dyeing (based on the dye and the substrate) is produced on woven polyester fabR1c by the high-temperature exhaust process at 130°C and is cleaned reductively. The red-brown dyeing obtained in that manner has very good in-use fastness properties, especially excellent fastness to washing. The same good fastness properties can be achieved when woven polyester fabR1c is dyed in the thermosol process (10 g/litre of dye, liquor pick-up 50 %, fixing temperature 210°C). is ground in a sand mill, together with 17 parts by weight of water and 2 parts by weight of a commercially available dispersant of the dinaphthylmethanedisulfonate type, and converted into a 5 % aqueous dispersion. Using that formulation, a 1 % dyeing (based on the dye and the substrate) is produced on woven polyester fabR1c by the high-temperature exhaust process at 130°C and is cleaned reductively. The brown-black dyeing obtained in that manner has very good in-use fastness properties, especially excellent fastness to washing. The same good fastness properties can be achieved when woven polyester fabR1c is dyed in the themiosol process (10 g/litre of dye, liquor pick-up 50 %, fixing temperature 210°C). What is claimed is: wherein R is hydrogen or bromine, R1 is hydrogen, methyl or -NHC0-CrC4alkyl, R2 is C1-C4alkyl substituted by C1-C4alkoxy and R3 has, independently of R2, any of the meanings of R2. 2. A dye according to claim 1, wherein Ri is -NHCO-CrC4alkyl. 3. A dye according to claim 1 or claim 2, wherein R2 and R3 have the same meaning and are the radical -CH2CH2-OCH3. 6. A process for the preparation of a dye of formula (1) according to claim 1, in which process a phthalimide of formula is nitrated in the acid range, the resulting nitro compound is then alkylated and, by means of reductive treatment, converted into an intermediate of formula the intermediate of formula (51) is mono- or di-halogenated in an acid medium, and the resulting compound is then diazotised and is coupled to a compound of formula wherein R1, R2 and R3 are as defined for formula (1). 7. A dye mixture comprising at least one azo dye of formula (1) according to claim 1 and at least one azo dye of formula wherein Ri is hydrogen, methyl or -NHC0-C1-C4alkyl, R2 is CrC4alkyl, it being possible for the alkyl chain, from C2 upwards, optionally to be interrupted by an oxygen atom, and R3 has, independently of R2, any of the meanings of R2. 8. A process for dyeing or printing semi-synthetic or synthetic hydrophobic fibre materials, in which process a dye of formula (1) according to claim 1 or a dye mixture according to claim 7 is applied to the said materials or incorporated into them. 9. Use of a dye of formula (1) according to claim 1 in dyeing or printing semi-synthetic and especially synthetic hydrophobic fibre materials, especially textile materials. 10. A semi-synthetic or especially synthetic hydrophobic fibre material, especially a textile material, dyed or printed by the process according to claim 8. 11. A dye substantially as herein described and exemplified. 12. A process for dyeing or printing semi-synthetic or synthetic hydrophobic fibre materials substantially as herein described and exemplified.

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