Reactivities of Stable Rotamers XXXVII : Thermolyses and Photolyses of 2(1H)-Thioxo-1-pyridyl 3-(1,4-Dimethyl-9-triptycyl)-3-methylbutanoate Rotamers

• Published in: Bulletin of the Chemical Society of Japan 1996-01, Vol.69 (1), p.177-187
• Main Authors: Toyota, Shinji, Oki, Michinori
• Format: Article
• Language: English
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.69.177

By decomposition of the title compounds, 2-(1,4-dimethyl-9-triptycyl)-2-methylpropyl radical rotamers were generated. In thermolysis the ap-isomer gave, as a main product, a cyclic compound which was formed by attack of the radical on the benzene ring in proximity, whereas extensive rearrangement took place to produce 1-substituted methyl derivatives in the case of sc. In photolysis, various out-of-cage products were found from both rotamers including dimers of radicals. The results are attributed to formation of high concentration of the radicals in photolyses. The product distributions are also affected by the phase, i. e. solution, melts, or solid, as well as temperature. Solid state photolyses afforded 2-pyridyl thioethers as almost exclusive products, suggesting that recombination of radicals in the cage is important under the conditions where movement of the radicals is restricted.