The decomposition of gaseous chloroformates. Part IV. Allylic and benzyl chloroformates

Abstract

The rates of conversion of some allylic and benzyl chloroformates into the allylic (or benzyl) chloride are reported. Reactions not previously observed for the gas phase are the S_Ni′ reactions which give the chlorides with allylic rearrangement and the reversible allylic isomerisation of the chloroformates. There are parallel heterogeneous processes which are more extensive at lower temperatures. The ready calculation of rate constants from the data, even when there are several reactions at once, is described and is characteristic of the stirred flow method used.