Collect. Czech. Chem. Commun. 1983, 48, 3027-3032

On the comparison of the theoretical and experimental data for the kinetics of the Cope rearrangement of 1,5-hexadiene

Zdeněk Slanina

The J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, 121 38 Prague 2


The Cope rearrangement of 1,5-hexadiene is treated as a process passing through an intermediate; this feature was verified by recent quantum-chemical studies. Relationships are derived between the characteristics of the both partial activation processes involved and the experimental data (which characterize the overall process). It is shown that proper consideration of the kinetic consequences of the existence of the intermediate might help to eliminate the recently reported large difference between the MINDO/3 activation entropy and the experimental entropy for the boat pathway for the Cope rearrangement.