ON THE OXIDATION OF BRIDGED 1-NAPHTHYLAMINE AND ANILINE DERIVATIVES -FORMATION OF SUBSTITUTED QUINOLINE AND BENZO[C,D]INDOLE DERIVATIVES

The bridged aniline or 1-naphthylamine derivatives 8-10 react with nit rous acid in the presence of perchloric acid to give the bridged diphe noquinone diiminium salts 12.2 HClO4, 17.2 HClO4, 19.2 HClO4 and 23. T he same products are obtained from these substrates upon their reactio n with hydrogen peroxide. Upon treatment of the bridged diphenoquinone diiminium salts 12.2 HClO4 and 23 with base, a disproportionation rea ction occurs resulting in the formation of the corresponding benzidine derivatives 13 and 26 and, following a multistep process, the quinoli ne derivatives 15 and 25 are obtained. Analogously, the 1,2-dihydroben zo[c,d]indole hydroperchlorate 10 . HClO4 is transformed into the brid ged benzidine derivative 21 and the bis(benzo[c,d]indol-6-yl) hydroper chlorate 20 . HClO4. Furthermore, as a result of an oxidation process initiated by the protonated species of the corresponding indaminium sa lts, condensation of N,N-dimethyl-4-nitrosoaniline (27) with the bridg ed aniline or naphthylamine derivatives 8a-8c leads to the N'-(6-quino lyl)-substituted N, N-dimethylbenzoquinone bis(iminium) salts 29a-28c rather than the corresponding indaminium salts 28a-28c.