Patent GB-756879-A (GB)
Title: Anthraquinone dyestuffs
Filed: 1953-12-28
Abstract: Bromo-, chloro- and iodo-benzene-sulphonamides are prepared by reacting the corresponding 2-, 3- or 4-halobenzenesulphonyl chlorides with dimethylamine, methylamine, diethanolamine, ethanolamine and 2,21-iminobispropionitrile.  2-, 3- or 4-Halo-N,N-bis{2-[2-(2-hydroxyethoxy) ethoxy]ethyl}benzene-sulphonamides are prepared by reacting 2-, 3- or 4-halo-N - (2 - hydroxy - ethyl) benzenesulphonamides with ethylene oxide.  3,4-Dihalo-N,N-bis-(2-hydroxy - ethyl) benzenesulphonamides are prepared by chlorosulphonating the corresponding dihalobenzenes and treating the resulting sulphonyl chlorides with diethanolamine, ethanolamine, dimethylamine, methylamine, 2,21-iminobispropionitrile and b -methylaminopropionitrile.  2 - Chloro - 3,5 - dinitrobenzene - sulphonamides are prepared by treating 2-chloro - 3,5 - dinitrobenzenesulphonylchloride with diethanolamine, ethanolamine, dimethylamine, methylamine and 2,2-iminobispropionitrile.  N,N - Bis-[bis-(2 - hydroxyethyl)] - 4 - bromo-m-benzenedisulphonamide is prepared by bis-chlorsulphonating bromobenzene and reacting the product with diethanolamine.  Other amines such as methylamine, dimethylamine and ethanolamine may be used to form similar products. Metanilamides are prepared by chlor-sulphonating nitrobenzene, nitrotoluenes, nitroxylenes in which the nitro group is not ortho to either methyl group, or chlornitrobenzenes, and reacting the sulphonyl chloride with ammonia or amines, e.g. as defined above. Sulphanilamides are prepared by chlorsulphonating acetanilides which may have nuclear substituents, and treating the sulphonyl chlorides with ammonia or amines as defined above and removing the acetyl group by hydrolysis.ALSO:The invention comprises compounds of the formula:-<FORM:0756879/IV(c)/1> wherein R3 R4 and R5 are selected from the group consisting of hydrogen, hydroxy, amnoalkylaminoarylamino and acylamino, R1 is selected from the group consisting of hydrogen, alkyl, hydroxy alkyl, hydroxyalkoxyalkyl, hydroxypolyalkoxyalkyl, cyanoalkyl and R2 from the same group excluding hydrogen or R1 and R2 when taken together may be the group <FORM:0756879/IV(c)/2> Y is selected from the group consisting of Cl, NO2 and <FORM:0756879/IV(c)/3> wherein R1 and R2 have the above definitions and n has a value of 0, 1 or 2 but wherein R3 does not represent an amino benzene sulphonamide group containing an alkyl group in either of the positions ortho to the amino linkage.  The above compounds may be produced by condensing an a -aminoanthraquinone with an appropriately substituted haloarylsulphonamide in the presence of an acid acceptor and a catalyst such as copper or cuprous or cupric salts, heating optionally in the presence of an organic diluent e.g. nitrobenzene, quinoline or pyridine (I) or condensing an a -halonthraquinone with an aminoaryl sulphonamide under similar conditions (II) or by reacting a 1, 4-dihydroxy-anthraquinone, e.g. quinizarin, 1, 4, 5-tri-hydroxy- or 1, 4, 5, 8-tetrahydroxyanthraquinone, as its leuco form or in the presence thereof, with amino-arylsulphonamides optionally in the presence of an organic solvent and boric acid (III) or by desulphonating an anthraquinone compound bearing in the 2-position, relative to an amino or hydroxy group, a sulphonic acid radical and in another a -position, e.g. the 4-position a radical <FORM:0756879/IV(c)/4> wherein R1, R2, Y and n are as defined above, e.g. by warming with glucose in an aqueous alkaline medium (IV) or by converting an a -anilinoanthraquinone to a sulphonyl halide with a halosulphonic acid, e.g. chloro- or bromosulphonic acid or by converting an a -anilino-anthraquinone sulphonic acid in which the sulphonic acid radical is attached to the anilino radical by treatment with a halogenating agent such as chlorosulphonic acid or phosphorus pentachloride to the corresponding sulphonyl halide and treating the sulphonyl halide with an appropriate amine optionally in the presence of water, organic solvents and an acid asceptor.  Many starting materials comprising a -amino- and substituted amino anthraquinones,  -halo and substituted a -haloanthraquinones, haloaryl- and aminoaryl sulphonamides and amines are listed.  The products include vat dyes and colours and may be employed in dyeing or colouring "Dacron".  "Orlon" (Registered Trade Marks), Dynel, Acrilan, cellulose acetate and nylon.  In examples, dyestuffs are produced when: p-Bromo-N, N-bis (2-hydroxyethyl) benzene sulphonamide is reacted with 1-amino-4-hydroxyanthraquinone (1); 1, 4-diaminoanthraquinone is reacted similarly to obtain a product substituted at both amino groups (2); p-bromo-N, N-bis (2-[2 (-2hydroxyethoxy)ethoxy]ethyl) benzene sulphonamide is reacted with 1, 4-diaminoanthraquinone (3); p-bromoN, N-dimethylbenzene sulphonamide is reacted with 1-amino-5-benzamidoanthraquinone (4); and with 1-amino-4-benzamido-anthraquinone (5); p-bromo-N(2-hydroxyethyl) benzenesulphonamide is reacted with 1-amino-4-hydroxyanthraquinone (6); 1-amino-4-methyl- and 1-amino-4-ethylamino anthraquinone are employed in processes similar to (1) (7), 4, 8-diaminoanthrarufin is reacted with p-bromo-N, N-bis 2[2-(2-hydroxyethoxy)ethoxy] ethyl benzenesulphonamide (8); p-bromo-N-[2-(2-hydroxyethoxy)ethyl] - N - (2-hydroxyethyl) benzene sulphonamide is employed in a similar process (9); 1-amino-anthraquinone is reacted with p-bromo-N, N-bis (2-hydroxyethyl) benzenesulphonamide, and with p - bromo - N (2 - hydroxyethyl) - and p-bromo-N, N-dimethyl benzene sulphonamides (10); 1-methylamino-4-bromoanthraquinone is reacted with N1, N1-bis-(2-hydroxyethyl) metanilamide (11); sodium 1-amino-4-(m-[bis(2-hydroxyethyl) sulphamyl]anilino)-2-anthraquinone-2-sulphonate prepared by reacting sodium-1-amino-4-bromoanthraquinone-2-sulphonate and N1, N1-bis (2-hydroxyethyl) metanilamide, is treated in water with glucose and potassium hydroxide; desulphonation of 1-amino -4- [m - (2-hydroxyethylsulphamyl) anilino]-2-anthraquinone sulphonic acid yields a similar product (12); 1-amino-4-[2-hydroxyethyl)amino] anthraquinone is reacted with p-bromo-N, N-bis (2-hydroxyethyl) benzenesulphonamide, p-bromo-N-(2-hydroxyethyl) benzensulphonamide and with p-bromo-N, N-dimethylbenzensulphonamide (13); 4, 8-diaminoanthrarufin is reacted with p-bromo-N, N-bis (2-hydroxyethly) benzene sulphonamide (14) quinizarin together-with leuco-quinizarin is reacted with N1, N1-bis (2-hydroxyethyl) metanilamide in the presence of boric acid and cyclohexanol, the latter is removed from the reaction mixture and sodium hydroxide is added to the product suspended in water, in similar processes N1-(2-hydroxyethyl) metanil-amide and N1, N1 - dimethyl- and N1 - ethylmetanil-amides are employed (15); in similar processes leucotetrahydroxyanthraquinone is reacted with N, N-bis (2-hydroxyethyl)-, N1-(2-hydroxyethyl)-, N1, N1-dimethyl- and N1-ethyl-metanilamides the residue obtained on removal of the cyclohexanol being heated with nitrobenzene and piperidine (16); 1-hydroxy-4-o-toluinoanthraquinone is converted with chlorsulphonic acid to the corresponding sulphonyl chloride which is then reacted with diethanolamine (17); 1-o-toluino-4, 5, 8-trihydroxy-anthraquinone, 1-p-anisidino 4-hydroxy anthraquinone, 1, 4-di-p-toluinoanthraquinone and 1-hydroxy-4-p-toluinoanthraquinone are similarly converted to the corresponding sulphonyl chlorides which are reacted with diethanolamine (18-21); 1, 5-di-p-toluinoanthraquinone is similarly converted to the sulphonyl chloride which is reacted with monoethanolamine (22); 1-aminoanthraquinone is reacted with p-bromo-N, N-bis (2-hydroxyethyl)-p-bromo-N (2-hydroxyethyl)- and p-bromo-N, N-dimethyl benzene sulphonamides (23); 6-chloro-1-p-toluinoanthraquinone and 1, 5-di-p-toluino-4, 8-dihydroxyanthraquinone are converted to sulphonyl chlorides which are reacted with diethanolamine (24, 25); p-(4-amino-1-anthraquinonylamino) -N-methylacetanilide is reacted with p-bromo-N, N-bis (2-hydroxyethyl) benzene sulphonamide (26); 1-amino-4-hydroxy anthraquinone is reacted with N, N1-bis [(bis(2-cyanoethyl)] -4- bromo-m-benzenedisulphonamide (27); 1-amino-4-hydroxy anthraquinone is reacted with N1-bis[(bis 2-cyanoethyl)] -4- bromo-m-benzenedisulphonamide (28); 1-amino-4-hydroxyanthraquinone is reacted with N, N-bis (2-hydroxy ethyl)-2-chloro-3, 5-dinitrobenzene sulphonamide (29) 1-amino-4-hydroxyanthraquinone is reacted with 3, 4-dichloro- N1, N1-bis (2-hydroxyethyl) benzene sulphonamide (30); and 1-hydroxy-4-o-toluinoanthraquinone is converted to the sulphonyl chloride which is reacted with morpholine.