68558-73-6Relevant academic research and scientific papers
The Insertion and Extrusion of Heterosulfur Bridges. XIV. Synthesis of Nitrotriphenylenothiophenes
Klemm, L. H.,Hall, Eliot,Cousins, Lisa,Klopfenstein, C. E.
, p. 1749 - 1756 (2007/10/02)
Sulfur bridging to form triphenylenothiophene (2) in ca. 46percent yield has been effected at 540 deg C 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 (80percent), while reductive acetylation of 3 produces 1,4-diacetoxytriphenylene.Treatment of 2 with nitric acid in acetic anhydride at 65 deg C gives a mixture of 1-nitro (30percent), 3-nitro (47percent), and 1,7-ditnitro(11percent) 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 Hueckel molecular orbital calculations on reactivity and with substitution in analogous polycyclic, condensed aromatic compounds.
