Patent GB-630459-A (GB)
Title: A new process for the manufacture of dyestuffs and intermediates
IPC: C09B9/00
Filed: 1947-07-11
Abstract: Alkali metal (e.g. sodium and potassium) and ammonium salts of chlorosulphonic acid are obtained by (1) reacting the corresponding solid chloride with gaseous or solid sulphur trioxide at 50-100 DEG C., or (2) treating a suspension of the chloride in an inert diluent, e.g. acetonitrile, with sulphur trioxide or chlorsulphonic acid or an ester thereof.ALSO:Leuco-sulphuric esters of vat dyes (see Group IV (c)) and anthraquinone intermediates and salts thereof are made by treating the vat dye or anthraquinone intermediate and a metal, or a metal salt of the corresponding leuco compound, or a complex compound comprising the metal salt of the corresponding leuco compound, with a salt of chlorsulphonic acid in an anhydrous inert medium and substantially in the absence of a free organic base.  Salts of chlorsulphonic acids specified are the alkali metal and ammonium salts (see Group III), the alkylammonium and arylammonium salts, and the quaternary ammonium and ternary sulphonium salts, and these salts may be formed in situ.  The process may be carried in one stage using the dye or intermediate, a metal, and the already formed chlorsulphonic salt in an inert medium, or by a two-stage process, by reacting the dye or intermediate in the medium with a metal in presence of a quaternary ammonium salt, giving the metal salt of the leuco body, and subsequently adding chlorsulphonic acid or an ester thereof.  The products may be mixed with sodium carbonate or dextrin. In examples: (1) 2 - chloro - 3 - acetylaminoanthraquinone is reacted with iron powder and the reaction product from methyl-triethylammonium methosulphate and methyl chlorsulphonate; (2) diethyl sulphide-sulphur trioxide addition product is reacted with methyltriethylammonium chloride, followed by addition of anthraquinone and iron powder; (3) methyltriethylammonium chlorsulphonate is reacted with anthraquinone and iron powder.  The quaternary ammonium and ternary sulphonium chlorosulphonates may be made by (1) reacting chlorosulphonic acid or an ester of chlorosulphonic acid with a quaternary ammonium or ternary sulphonium salt of a different acid; (2) reacting a quaternary ammonium or ternary sulphonium sulphate or alkosulphate with sulphuryl chloride; (3) reacting a quaternary ammonium or ternary sulphonium chloride with sulphur trioxide.  Examples are: (1) methyltriethylammonium chlorosulphonate which may be made by reacting methyltriethylammonium chloride with methyl chlorosulphonate in acetone, or by reacting triethylamine with dimethylsulphate in acetonitrile and adding chlorosulphonic acid or by reacting methyltriethylammonium methosulphate with sulphuryl chloride, or by reacting methyltriethylammonium methosulphate with methyl chlorosulphonate or by reacting triethylamine with at least one molecular proportion of methyl chlorosulphonate in acetone.  (2) tetraethylammonium chlorosulphonate which may be made by reacting tetraethylammonium bromide with methyl chlorosulphonate; (3) tetramethylammonium chlorosulphonate which may be made by reacting tetramethylammonium sulphate with sulphuryl chloride; (4) methyldiethylsulphonium chlorosulphonate which may be made by reacting diethylsulphide with methyl chlorosulphonate.ALSO:Leuco-sulphuric esters of vat dyes and anthraquinone intermediates and salts thereof are made by treating the vat dye or anthraquinone intermediate and a metal, or a metal salt of the corresponding leuco compound, or a complex compound comprising the metal salt of the corresponding leuco compound, with a salt of chlorsulphonic acid in an anhydrous inert medium and substantially in the absence of a free organic base.  Salts of chlorsulphonic acids specified are the alkali metal and ammonium salts, the alkylammonium and arylammonium salts, and the quaternary ammonium and ternary sulphonium salts, and these salts may be formed in situ (see Groups III and IV (b)).  The process may be carried in one stage using the dye or intermediate, a metal, and the already formed chlorsulphonic salt in an inert medium, or by a two-stage process, by reacting the dye or intermediate in the medium with a metal in presence of a quaternary ammonium salt, giving the metal salt of the leuco body, and subsequently adding chlorsulphonic acid or an ester thereof.  The products may be mixed with sodium carbonate or dextrin.  In examples: (1) methyltriethylammonium metho-sulphate is reacted with methyl chlorsulphonate, and then with dimethoxydibenzanthrone and iron powder; (2) 2 - chloro - 3 - acetylaminoanthraquinone replaces the dye in (1); (3) diethyl sulphide-sulphur trioxide addition product is reacted with methyltriethylammonium chloride, followed by addition of anthraquinone and iron powder; (4) methyltriethylammonium chlorsulphonate is reacted with anthraquinone and iron powder; (5) and (6) tetraethyl- and tetramethyl-ammonium chlorsulphonate are reacted with 4 : 10-dichloroanthanthrone and iron powder; (7) methyl triethylammonium chloride is reacted with 1 : 4 - dibenzoylaminoanthraquinone, methyl chlorsulphonate and zinc dust; (8) and (9) methyltriethylammonium chloride is reacted with 3 : 31-dichlorindanthrone, methyl chlorsulphonate and zinc dust; (10) the last example is repeated but using 3.31-dichlorodianthraquinoneazine prepared by nitric acid oxidation of the dihydroazine; (11) tetraethylammonium chlorosulphonate is reacted with thioindigo and iron powder; (12) and (13) potassium chlorosulphonate is reacted with iron powder and anthraquinone and dimethoxydibenzanthrone respectively; (14) methyltriethylammonium chlorosulphonate is reacted with iron powder and the azo compound obtained by coupling diazotized 1-aminoanthraquinone with o-chloroacetoacetanilide; (15) methyl chlorosulphonate is added to a mixture of methyltriethylammonium chloride, 3 : 31-dichloroindanthrone and zinc dust; (16) the last example is repeated but using the green azine of 3 : 31-dichloroindanthrone prepared by bichromate oxidation of 3 : 31 - dichloroindanthrone.  In the above examples, acetone and acetonitrile are used as inert media.  Other starting p  materials specified are thioindigo, indigo, 5 : 51-7 : 71-tetrabromoindigo, 6 : 61-diethoxythioindigo, 6 : 61-dichloro-4 : 41-dimethylthioindigo, 5 : 51 - dichloro - 7 : 71 - dimethylthioindigo, 5 : 61 - dichloro - 7 : 41 - dimethylthioindigo, 61 - chloro - 7 : 41 - dimethylthioindigo, 2 : 1 : 21 : 11 - bis - naphthathioindigo, N : N1-dihydrodianthraquinoneazine, dianthraquinoneazine, 3 : 31 - dichloro - N : N1 - dihydrodianthraquinoneazine, 3 : 31 - dichlorodianthraquinoneazine, flavanthrone, pyranthrone, dibromopyranthrone, dibenzanthrone, dimethoxydibenzanthrone, dichloroisodibenzanthrone, ethylenedioxydibenzanthrone, tetrachlorodibenzanthrone, dibenzpyrenequinone, dibromodibenzpyrenequinone, anthraquinone - 1 : 2 : 5 : 6 - diphenylthiazole, dichloroanthanthrone, dibromoanthanthrone, anthraquinone - 1 - azo - p - chloroacetoacetic anilide, trichloro - 31 : 41 - phthaloylacrodine, the condensation products of 6-amino-31 : 41-phthaloylacridone with 2-p-bromophenyl-anthraquinone-21 : 31 - oxazole and with 2 - p - bromobenzoylaminoanthraquinone, the condensation product of 6 - p - bromobenzoylamino - 31 : 41 - phthaloylacridone with 6-amino-11 : 21-phthaloyl-51 : 61-benzcarbazole, 51 : 511 - dibenzoylamino - 1 : 11 : 5 : 111 - trianthrimide - 2 : 21 : 6 : 211-dicarbazole, 4 : 41 : 411-tribenzoylamino-1 : 11 : 8 : 111-trianthrimide - 2 : 21 : 7 : 211 - dicarbazole, 4 : 51 : 511 - tribenzoylamino - 1 : 11 : 8 : 111 - trianthrimide-2 : 21 : 7 : 211 - dicarbazole, 51 : 511-dibenzoylamino - 1 : 11 : 4 : 111 - trianthrimide - 2 : 21 : 3 : 211-dicarbazole, 2-(1-amino-2-anthraquinonyl)anthraquinone-21 : 31-oxazole, 4 : 41 - and 5 : 51 - dibenzoylaminoterephthal - 1 : 11 - dianthraquinonylamide, 4 : 51 - dibenzoylamino - amino - 1 : 11-dianthrimide-2 : 21-carbazole, 5-benzoylamino - 1 : 11 - dianthrimide - 2 : 21 - carbazole, 5 : 51-dibenzoylamino-1 : 11-dianthrimide-2 : 21 - carbazole, 1 : 11 : 5 : 111 - trianthrimide - 2 : 21 : 6 : 211 - dicarbazole, 1 : 11 : 4 : 111 - trianthrimide - 2 : 21 : 3 : 211 - dicarbazole, and the vat dyestuff obtained by coupling diazotized 1 - aminoanthraquinone with o - chloroacetoacetanilide.  Specifications 245,587, 271,533, 274,156, [all in Class 2 (iii)], and 610,117 are referred to.