Journal of Organic Chemistry p. 5498 - 5502 (1991)
Update date:2022-08-16
Topics:
Baciocchi, Enrico
Rol, Cesare
Scamosci, Emanuela
Sebastiani, Giovanni V.
The anodic oxidation of a number of XC6H4CH2SC6H4Y has been investigated under a variety of conditions (AcOH/AcO(1-), AcOH/NO3(1-), AcOH/ClO4(1-), CH3CN/ClO4(1-) and the relative weight of the various reaction paths available to the intermediate radical cation (Cα-H deprotonation, C-S bond cleavage, attack on sulfur) evaluated via product analysis.It has been observed that in AcOH/AcO(1-) (presence of a strong base) the main reaction is Cα-H deprotonation, which is also favored when X is an electron-withdrawing substituent and depressed by electron-donating Y.The C-S bond cleavage reaction is particularly important in CH3CN/ClO4(1- ); its relative contribution is enhanced by an electron-donating X, which makes the benzyl carbocation more stable.The pathway leading to sulfoxides is favored in AcOH/NO3(1-) and, to a lesser extent, in AcOH/ClO4(1-).Formation of sulfoxide is also favored when Y is an electron-donating group.
View MoreDoi:10.1021/ja00461a007
(1977)Doi:10.1021/ja00778a068
(1972)Doi:10.1002/jms.1190300125
(1995)Doi:10.1002/chem.201504330
(2016)Doi:10.1016/0223-5234(96)88283-3
(1995)Doi:10.1016/S0040-4039(01)96356-7
(1971)