Electron-Rich Hexasubstituted Benzene Derivatives and Their Oxidized Cation Radicals, Dications with Potential Triplet Ground States, and Polycations

Five new benzene derivatives have been synthesized carrying electron-releasing substituents. The derivative of hexaaminobenzene with six ethano bridges connecting all the nitrogens can be reversibly oxidized all the way to a tetracation; the dication is a (ground-state) triplet species. Two derivatives of l, 3, 5-trihydroxy-2, 4, 6-triaminobenzene were also prepared, as well as two derivatives of 1, 3, 5-triaminobenzene-2, 4, 6-trithiol. In these cases three ethano bridges connected heteroatoms. Cation radicals could be prepared in all cases, and with one of the oxygen compounds a triplet-state dication was also prepared. The synthetic procedures involved an unusual “zipper” cyclization in the hexaaza series.