L. Klemm, E. Hall, L. Cousins
Nov 1, 1987
Citations
0
Influential Citations
14
Citations
Journal
Journal of Heterocyclic Chemistry
Abstract
Sulfur bridging to form triphenyleno[1,12-bcd]thiophene (2) in ca. 46% yield has been effected at 540° by direct addition of crystalline triphenylene (1) or dodecahydrotriphenylene (4) to a heterogeneous catalyst in a stream of hydrogen sulfide. Treatment of a reaction mixture of 1 and 2 with hydrogen peroxide-glacial acetic acid gives 2 sulfone 2d and 1,4-triphenylenoquinone (3). Reduction of 2d with lithium aluminum hydride in tetrahydrofuran leads back to 2 (80%), while reductive acetylation of 3 produces 1,4-diacetoxytriphenylene. Treatment of 2 with nitric acid in acetic anhydride at 65° gives a mixture of 1-nitro (30%), 3-nitro (47%), and 1,7-dinitro (11%) derivatives, separable by chromatography on alumina. Structures of these derivatives are assigned on the basis of ultraviolet-visible absorption and proton magnetic resonance spectra, as well as the chemical conversion 1-nitro-2 1,7-dinitro-2. The substitution pattern in 2 is correlated with Huckel molecular orbital calculations on reactivity and with substitution in analogous polycyclic, condensed aromatic compounds.