62640-72-6Relevant academic research and scientific papers
Hydrothermal photochemistry as a mechanistic tool in organic geochemistry: The chemistry of dibenzyl ketone
Yang, Ziming,Lorance, Edward D.,Bockisch, Christiana,Williams, Lynda B.,Hartnett, Hilairy E.,Shock, Everett L.,Gould, Ian R.
, p. 7861 - 7871 (2015/03/18)
Hydrothermal organic transformations under geochemically relevant conditions can result in complex product mixtures that form via multiple reaction pathways. The hydrothermal decomposition reactions of the model ketone dibenzyl ketone form a mixture of reduction, dehydration, fragmentation, and coupling products that suggest simultaneous and competitive radical and ionic reaction pathways. Here we show how Norrish Type I photocleavage of dibenzyl ketone can be used to independently generate the benzyl radicals previously proposed as the primary intermediates for the pure hydrothermal reaction. Under hydrothermal conditions, the benzyl radicals undergo hydrogen atom abstraction from dibenzyl ketone and para-coupling reactions that are not observed under ambient conditions. The photochemical method allows the primary radical coupling products to be identified, and because these products are generated rapidly, the method also allows the kinetics of the subsequent dehydration and Paal-Knorr cyclization reactions to be measured. In this way, the radical and ionic thermal and hydrothermal reaction pathways can be studied separately.
Electrooxidative pinacol-type rearrangement of β-hydroxy sulfides. Efficient C-S cleavage mediated by chloride ion oxidation
Kimura, Makoto,Kobayashi, Kazutaka,Yamamoto, Yasushi,Sawaki, Yasuhiko
, p. 4303 - 4310 (2007/10/03)
Electrooxidation of α-phenyl substituted β-hydroxy sulfides in dichloromethane in the presence of chloride ions as the electrolyte results in a novel pinacol-type rearrangement to give 2-phenyl substituted ketones like 2-phenylcycloalkanone as the ring expansion product. The rearrangement is induced by an electrogenerated chloronium ion, which effects, instead of common C-C scission, a selective C-S cleavage of β-hydroxy sulfides.
