Patent GB-347193-A (GB)
Title: Process for the manufacture of substitution products of carbazole sulphonic acids
Filed: 1930-01-23
Abstract: Substituted carbazole sulphonic acids are made by diazotizing aminocarbazole sulphonic acids or their substitution products and replacing the diazo group in known manner by an anion, such as OH, Cl, Br, I, CN, SH or -S-S-.  The products are intermediates for the manufacture of dyestuffs and pharmaceutical products.  In examples: (1) 1-oxycarbazole-3 : 6 : 8-trisulphonic acid is obtained by diazotizing 1-aminocarbazole-3 : 6 : 8-trisulphonic acid and boiling the diazo compound with copper sulphate and dilute sulphuric acid; (2) 3-oxycarbazole-1 : 6 : 8-trisulphonic acid is similarly obtained from 3-aminocarbazole-1 : 6 : 8-trisulphonic acid (made by nitrating and reducing carbazole tetrasulphonic acid); (3) 1-oxy-8-iodo-carbazole-3 : 6-disulphonic acid is made by diazotizing 1-oxy-8-aminocarbazole-3 : 6-disulphonic acid and treating the diazo compound with potassium iodide and copper powder; (4) 1-iodocarbazole-3 : 6 : 8-trisulphonic acid is similarly obtained from 1 - aminocarbazole - 3 : 6 : 8 - trisulphonic acid; (5) 1 : 11-dicarbazole-disulphide-3 : 31-6 : 61-: 81-hexasulphonic acid is made by diazotizing 1-amino-carbazole-3 : 6 : 8-trisulphonic acid, treating the diazo compound with potassium xanthogenate and saponifying the xanthogenic ester thus obtained with potassium hydroxide, and, (5) 1-chlor-, 1-brom-, and 1-cyanocarbazole-3 : 6 : 8-trisulphonic acids are obtained from 1-aminocarbazole-3 : 6 : 8-trisulphonic acid by the Sandmeyer reaction.  The Specification as open to inspection under Sect. 91 (3) (a) refers also to thiocyano, mercapto, hydrazino, arsinic and stibinic acid groups as anions which may replace the diazo group, and states that the following substituted carbazole sulphonic acids may be prepared by the process of the invention :-1-oxycarbazole-2 : 6 : 8- and 4 : 6 : 8-trisulphonic acids, 1-oxycarbazole-3 : 6-disulphonic acid, 1-oxycarbazole-3- and -6-sulphonic acids, 2-oxycarbazole-3 : 6 : 8-, -1 : 6 : 8- and -1 : 4 : 8 trisulphonic acids, 2-oxycarbazole-3 : 6-disulphonic acid, 2-oxycarbazole-6-sulphonic acid, 3-oxycarbazole-1 : 5 : 8-, -1 : 5 : 7-, -2 : 3 : 8-, and -2 : 5 : 7-trisulphonic acids, 3-oxycarbazole-6 : 8- and -5 : 7-disulphonic acids, 3-oxycarbazole-6- and -8-sulphonic acids, 1 : 8 - dioxycarbazole-3 : 6 - disulphonic acid (from 1-amino-8-oxycarbazole-3 : 6-disulphonic acid), 2 : 7-dioxycarbazole-3 : 6-disulphonic acid, 3 : 6-dioxycarbazole-1 : 8-disulphonic acid, 2 : 7-dioxycarbazole-8-sulphonic acid, 3 : 6-dioxycarbazole-1-sulphonic acid, 2-oxy-8-iodocarbazole-3 : 6- and -3 : 7-disulphonic acids, 3-oxy-1-iodocarbazole-6 : 8-disulphonic acid, 1-oxy-3 : 6-diiodocarbazole - 8 - sulphonic acid, 1 - mercaptocarbazole-3 : 6 : 8-trisulphonic acid, 1-mercaptocarbazole-3- and -6-sulphonic acids, 2-mercaptocarbazole-3 : 6 : 8-trisulphonic acid, 2-mercaptocarbazole-6 : 8-disulphonic acid, 3-mercaptocarbazole-1 : 6 : 8-trisulphonic acid, 1-chlorcarbazole-2 : 6 : 8- and -4 : 6 : 8-trisulphonic acids, 1-chlorcarbazole-3 : 6-disulphonic acid, 1-chlorcarbazole-3- and -6-sulphonic acid, 2-oxy-8-chlorcarbazole-3 : 6-disulphonic acid, 3-oxy-1-chlorcarbazole-6 : 8-disulphonic acid, 2-oxy-8-chlorcarbazole-3 : 7-disulphonic acid, 1 - oxy - 3 : 6 - dichlorcarbazole - 8-sulphonic acid, 2-chlorcarbazole-3 : 6 : 8-, 1 : 6 : 8-, and 1 : 4 : 8-trisulphonic acids, 2-chlorcarbazole-3 : 6-disulphonic acid, 2-chlorcarbazole-6-sulphonic acid, 2-bromocarbazole-1 : 6 : 8-trisulphonic acid, 3-bromcarbazole-1 : 5 : 7-, -2 : 3 : 8-, and -2 : 5 : 7-trisulphonic acids, 3-bromcarbazole-6 : 8- and -5 : 7-disulphonic acids, 3-bromcarbazole-6- and -8-sulphonic acids, 2-oxy-8-bromcarbazole-3 : 6- and -3 : 7-disulphonic acids, 3-oxy-1-bromcarbazole-6 : 8-disulphonic acid, 1-oxy-3 : 6-dibromcarbazole-8-sulphonic acid, 2 : 7-diiodocarbazole-3 : 6-disulphonic acid, 3 : 6-diiodocarbazole-1 : 8-disulphonic acid, 2 : 7-diiodocarbazole-8-sulphonic acid, 3 : 6-diiodocarbazole-1-sulphonic acid, 2-cyanocarbazole-1 : 6 : 8-, 1- : 4 : 8-, and -3 : 6 : 8-trisulphonic acids, 2-cyanocarbazole-3 : 6-disulphonic acid, 2-cyanocarbazole-6-sulphonic acid, 1-cyano-8-oxy (or chlor)-carbazole-3 : 6-disulphonic acid, 3-cyanocarbazole-1 : 6 : 8-, -1 : 5 : 8-, 1 : 5 : 7-, -2 : 3 : 8-, and -2 : 5 : 7-trisulphonic acids, 3-cyanocarbazole-6 : 8- and -5 : 7-disulphonic acids, 3-cyanocarbazole-6- and -8-sulphonic acids, 3-cyano-8-oxy-carbazole-1 : 6-disulphonic acid, 1-hydrazinocarbazole-3 : 6 : 8-, -2 : 6 : 8-, and -4 : 6 : 8-trisulphonic acids, 1-hydrazinocarbazole-3 : 6-disulphonic acid, 1-hydrazinocarbazole-3- and -6-sulphonic acids, 2-hydrazinocarbazole-3 : 6 : 8-, 1 : 6 : 8- and -1 : 4 : 8-trisulphonic acids, 2-hydrazinocarbazole-3 : 6-disulphonic acid, 2-hydrazinocarbazole-6-sulphonic acid, 3 : 6 : 8-trisulphocarbazole-1-arsinic acid, 3-6-disulphocarbazole-1 : 8-diarsinic and -1-arsinic acids, 1-oxy-3 : 6-disulphocarbazole-1-arsinic and stibinic acids, 3-sulphocarbazole-6-arsinic and stibinic acids, 2 : 6 : 8-trisulphocarbazole-1-stibinic acid, and 3 : 6-disulphocarbazole-1 : 8-distibinic and -1-stibinic acids.  This subject-matter does not appear in the Specification as accepted.