The exchange between the H atoms of cyclopentane (3) or cyclohexane (4) and the labeled acid protons of CF3SO3D (2-d), [3H]CF3SO3H (2-t), [3H]H2SO4 (1-t), or ZnCl2−[3H]HCl (5-t) has been investigated. Results from the treatment of 3 or 4 with 2-d at 0° or 20 °C, respectively, gave rise to polydeuterated cycloalkanes, indicating that all H atoms of 3 or 4 could be involved in the exchange. The rates of incorporation of the T-label into the hydrocarbon layer from the tritiated acids were found to be directly related to acid strength. After treatment of 3 or 4 with 2-t, quenching of the acid layer and analysis by isotope dilution showed the presence of cyclopentanol or cyclohexanol. A carbocationic chain mechanism for the exchange, as well as the mechanism for the formation of the cycloalkyl cation from the cycloalkane, are discussed.

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.