Patent GB-420149-A (GB)
Title: Improvements in the manufacture and production of dyestuffs for animal fibres
IPC: C09B1/26
Filed: 1933-03-17
Abstract: Anthraquinone dyes of the general formula <FORM:0420149/IV/1> (wherein A is an anthraquinone radicle, n1 a whole number above zero, n2 a whole number from 1 to 4, n3 is 1 or 2, X is a sulphonic acid group, Y is a group --N.R1R2 attached to an a -position of the anthraquinone radicle and Z is a group --CONR3R4 attached to a b -position of the anthraquinone radicle, R1, R3, R4 being hydrogen, alkyl, cycloalkyl, aralkyl, oxyalkyl, aryl or aryl substituted by alkyl, cycloalkyl, halogen, hydroxy, alkoxy, amino, acylamino, R2 being hydrogen, alkyl, cycloalkyl or aralkyl) are prepared (1) by sulphonating an a -aminoanthraquinone containing at least one carboxylic acid amide group in a b -position; (2) by partially saponifying a b -cyano-a -aminoanthraquinone containing at least one sulphonic acid group to give a b -carboxylic acid amide product; (3) by treating an a -aminoanthraquinone containing at least one sulphonic acid group and one or two b -carbonic acid halide groups with ammonia, or primary or secondary amines; (4) by reducing an a -nitroanthraquinone containing at least one carboxylic acid amide in a b -position and at least one sulphonic acid group (5) by treating an a -nitro-, a -hydroxy-, or an a -halogen-anthraquinone containing a b -carboxylic acid amide group and a sulphonic acid group with ammonia or primary or secondary amines; (6) by reacting an a -sulphoanthraquinone containing at least one b -carboxylic acid amide group and at least one further sulphonic acid group with ammonia or primary or secondary amines; (7) by a modification of the processes (5) and (6) whereby an a -nitro-a -hydroxy-, a -sulpho- or a -halogen-anthraquinone containing at least one p-carboxylic acid amide group is reacted with primary or secondary amines containing at least one sulphonic acid group; (8) by a modification of the process (3) whereby an a -aminoanthraquinone-b -carboxylic acid halide is reacted with an amine containing at least one sulphonic acid group. The following preparations are described in examples: (1) 1-nitroanthraquinone-2-carboxylic acid chloride treated with aqueous ammonia under pressure and brominated to give 1-amino-4-bromoanthraquinone-2-carboxylic acid amide; this is reacted with p-toluidine, p-aminodiphenyl, p-phenylenediamine followed by sulphonation in each case (dyes wool blue shades in each case); (2) 1 - methylamino - 4 - bromanthra - quinone-2-carboxylic acid methylamide (prepared from 1-nitroanthraquinone-2-carboxylic acid chloride and methylamine with subsequent bromination) reacted with aniline, p-toluidine, p-aminodiphenyl and p-phenylenediamine followed by sulphonation in each case (dyes wool green to blue shades); (3) 1-amino-4-bromoanthraquinone-2-carboxylic acid methyl amide (from 1-nitroanthraquinone-2-carboxylic acid methyl amide and aqueous ammonia followed by bromination) reacted with p-toluidine, p-aminodiphenyl, p-phenylenediamine followed by sulphonation in each case (dyes wool blue to green shades); (4) 1-methylamino 4-bromanthraquinone-2-carboxylic acid amide (from 1-nitroanthraquinone-2-carboxylic acid amide and methylamine followed by bromination) reacted with aniline, p-toluidine, p-aminodiphenyl, p-phenylenediamine followed by sulphonation in each case (dyes wool blue to green), and with metanilic acid (dyes wool reddish-blue); (5) 1-cyclohexylamino-4-bromoanthraquinone-2-carboxylic acid amide and cyclohexylamine followed by bromination) reacted with p-toluidine and sulphonated (dyes wool blue-green); (6) 1-methylamino-4-bromanthraquinone - 2 - carboxylic acid cyclohexylamide (from 1 - nitroanthraquinone - 2 - carboxylic acid chloride and cyclohexylamine, followed by reaction with methylamine and bromination) reacted with p-toluidine and sulphonated (blue-green on wool); (7) 1-amino-4-bromanthraquinone-2-carboxylic acid cyclohexylamide (prepared as in (6) using aqueous ammonia in place of methylamine) reacted with p-toluidine and sulphonated (blue on wool); (8) 1-oxyethylamino-4-bromoanthraquinone-2-carboxylic acid cyclohexylamide (from 1-nitroanthraquinone-2-carboxylic acid cyclohexylamide and ethanolamine followed by bromination) reacted with p-toluidine and sulphonated (blue on wool); (9) 1-oxyethylamino-4-bromanthraquinone-2-carboxylic acid oxyethylamide reacted with aniline, p - toluidine and p - aminodiphenyl followed by sulphonation (blue to green shades); (10) 1-amino-4-bromanthraquinone-2-carboxylic acid chloride reacted with methyltaurine (orange-red on wool) and this product further reacted with p-toluidine (green-blue on wool and cyclohexylamine (reddish-blue on wool); (11) 1,4 - diaminoanthraquinone - 2- carboxylic acid amide (prepared by brominating 1-aminoanthraquinone-2-carboxylic acid amide, reacting with p-toluenesulphonamide and saponifying) is sulphonated (reddish-blue on wool); (12) 1,4 - dichloroanthraquinone - 2 - carboxylic acid amide is condensed with p-toluidine and sulphonated (yellowish-green); (13) 1-nitroanthraquinone-2-carboxylic acid chloride reacted with aniline and sulphonated (red shades on chrome-mordanted wool); (14) 1,5-dinitroanthraquinone - 2,6 - dicarboxylic acid chloride reacted with ammonia, brominated and finally condensed with p-toluidine and sulphonated (greenish-blue); (15) 1-nitroanthraquinone-2-carboxylic acid chloride reacted with methyltaurine and then with methylamine, the product brominated and condensed with benzidine (yellowish-green); (16) 1-nitroanthraquinone-2-carboxylic acid amide reacted with p-toluidine and sulphonated (red shades), and with taurine (red shades); (17) 1-nitroanthraquinone-6-carboxylic acid amide reacted with p-toluidine and sulphonated (bluish-red); (18) 1-nitroanthraquinone-2-carboxylic acid methylamide reacted with p-toluidine and sulphonated (reddish-orange); (19) 1-nitroanthraquinone-2-carboxylic acid chloride reacted with methyltaurine and product reacted with ammonia, methylamine and cyclohexylamine (orange to red shades); (20) 1-nitroanthraquinone-2-carboxylic acid N-methylanilide (prepared from 1-nitroanthraquinone-2-carboxylic acid chloride and methylaniline) reacted with methylamine and sulphonated (dyes bluish-red; this product is brominated (violet-red) and reacted with p-aminodiphenyl (bluish-green shades); (21) 1-amino-2-carboxylic acid chloride reacted with methyltaurine (orange shades); (22) 1-methylamino - 2 - cyano - 4 - (p - aminophenylamino) - anthraquinone (prepared by reacting 1-methylamino - 2 - bromoanthraquinone with cuprous cyanide, brominating this product and reacting with p-phenylenediamine) is sulphonated and the resulting reaction mixture cautiously diluted with water while maintaining a temperature of 50--55 DEG  C.; the cyano group is thus saponified to the carboxylic acid amide group; (23) 1-chloranthraquinone-2-carboxylic acid methyltauride (action of methyltaurine on the corresponding acid chloride) is boiled with sodium disulphide and the 1-mercapto derivative oxidized by peroxide to a 1-sulphonic acid derivative; this product is condensed with methylamine and cyclohexylamine (dyes red shades). Specification 350,928 is referred to.