化学
均分解
激进的
氯苯
光解
热分解
光化学
分解
药物化学
立体化学
有机化学
催化作用
作者
Urs Aeberhard,Reinhart Keese,Erich Stamm,Ulrich‐Christian Vögeli,W. Lau,Jay K. Kochi
标识
DOI:10.1002/hlca.19830660843
摘要
Malonylmethyl radical I [· CH2CH(COOEt)2] and its thioester analogue II [· CH2CH(COOEt) (COSEt)] were generated by standard photolytic and thermolytic methods from perester and bromo precursors. The structures of I and II were examined by ESR spectroscopy and found to exist in preferred conformations. However, no indication for their rearrangement by 1,2-shift of either an ethoxycarboxyl or (ethylthio)carbonyl group to the corresponding succinyl radicals III and IV, respectively, was found at temperatures below − 40°C. At higher temperatures of up to 140°C, the search for malonylmethyl → succinyl rearrangement was examined by thorough-product analysis of the perester decomposition. There is evidence for the rearrangement of the radical I to III by photolysis and of the radical II to IV by thermolysis at 130°C in chlorobenzene to only a small extent.
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