100354-41-4Relevant academic research and scientific papers
Some isotopic scrambling studies with singly or doubly labeled triphenylvinyl bromide
Lee, Choi Chuck,Fiakpui, Charles Y.
, p. 681 - 684 (2007/10/02)
The solvolysis of triphenyl14C>vinyl bromide (1-Br-2-14C) in 70percent HOAc - 30percent H2O or in 2,2,2-trifluoroethanol (TFE) carried out in the presence of an excess of p-CH3C6H4SNa gave the triphenylvynil p-tolyl thioether (1-STol) with a greatly decreased extent of scrambling of the 14C-label from C-2 to C-1 when compared with analogous reactions without the presence of the p-toluenethiolate anion.For example, the 1-STol product from the reaction of 1-Br-2-14C in 70percent HOAc - p-CH3C6H4SNa showed only 0.5-0.9percent scrambling, while previous studies on the reaction of 1-Br-2-14C in 70percent HOAc - NaOAc gave 14.7+/- 0.7percent scrambling.Previous work on the solvolysis of 1,2-diphenyl-2-2H5>phenyl13C>vinyl bromide (1-Br-2-13C-2-Ph-d5) in 70percent HOAc, as well as the present results from the solvolysis of 1-Br-2-13C-2-Ph-d5 in TFE - 2,6-lutidine, gave products derived from all 4 possible isotopomeric triphenylvinyl cations 3, 4, 5, and 6 arising from successive 1,2-phenyl shifts.On the other hand, solvolysis of 1-Br-2-13C-2-Ph-d5 in 70percent HOAc or TFE containing an excess of p-CH3C6H4SNa gave 1-STol in which the isotopically rearranged product was derived only from ion 5 arising from a 1,2-shift of the unlabeled phenyl group with no detectable amount of production derived from a 1,2-shift of the perdeuterophenyl group. These results are interpreted by the rapid trapping of the triphenylvinyl cation by the highly nucleophilic p-toluenethiolate anion.
