27760-22-1Relevant academic research and scientific papers
The nucleofuge in the pyridinolysis of O-(4-nitrophenyl) S-aryl thio and dithiocarbonates
Castro, Enrique A.,Aliaga, Margarita E.,Gazitua, Marcela,Santos, Jose G.
, p. 994 - 997 (2012)
A kinetic investigation is undertaken on the pyridinolysis of S-phenyl O-(4-nitrophenyl) dithiocarbonate (1), S-(4-nitrophenyl) O-(4-nitrophenyl) dithiocarbonate (2) and S-phenyl O-(4-nitrophenyl) thiocarbonate (3) in aqueous ethanol. The Bronsted-type plots (log kN versus pKa) obtained are linear and are explained by a stepwise mechanism with the existence of a tetrahedral intermediate (T±) and its breakdown to products as the rate determining step. The high-performance liquid chromatography analysis of the products of these reactions and that for the reaction of S-(4-chlorophenyl) O-(4-nitrophenyl) dithiocarbonate (4) with 4-oxypyridine shows that 4-nitrophenoxide is the principal (or the sole) leaving group in these reactions. From the results obtained in the reaction of compound 2, it can be concluded that 4-nitrophenoxide is a better nucleofuge than 4-nitrobenzenethiolate from the same tetrahedral intermediate, although the former is three pKa units more basic than the latter. Reasons for this behaviour are given. Copyright
Novel Aryloxy Migrations in Substituted Diphenyldithiocarbonates Under Electron Impact Conditions
Ramana, D. V.,Mahalakshmi, P.,George, M.
, p. 459 - 462 (2007/10/02)
Unusual expulsion of 'SO' was observed from the molecular ions of substituted diphenyldithiocarbonates under electron impact conditions.An initial aryloxy migration to sulphur followed by further rearrangement is proposed for this process, based on the substituent effects.The diarylthioketone radical-cation structure assigned for the ion was confirmed through the collision-activated dissociation B/E linked-scan spectra.
