Isotopic exchanges in the treatment of cyclobutane with tritiated or deuterated trifluoromethanesulfonic acid or with tritiated sulfuric acid

Abstract

When cyclobutane (1) is shaken at 0 °C with [3H]CF3SO3H (2-t) or with (2H)CF3SO3H (2-d), incorporation of T or D into the hydrocarbon layer readily occurred. All eight H atoms of 1 can be involved in the exchange since polydeuterated species including octadeuterated hydrocarbons were observed by mass spectrometry. In an experiment with 1 and 2-t, quenching of the acid layer with H2O gave a mixture of cyclobutanol, cyclopropylcarbinol, and allylcarbinol in the ratio of 61:37:2, respectively, as estimated by isotopic dilution, while vpc analysis of the hydrocarbon layer showed the presence of 1, methylcyclopropane, and 1-butene in the ratio of 66:30:4. The results are explained by a carbocationic chain mechanism, involving the formation of equilibrating bicyclobutonium ions. Similar but slower incorporation of T into the hydrocarbon layer was observed when 1 was treated with [3H]H2SO4.