Some Rearrangements of Free Alkyl Radicals and Alkyl Cations in Solutions

The results of studies of rearrangement reactions by the author and his co-workers during the last 20 years are described. A rearrangement of the n-propyl free radical in solutions as a result of the hydrogen 1,3-shift has been discovered and its characteristic features have been investigated (using carbon-14, deuterium, and tritium). The reaction involving the formation of organomercury compounds from mercury salts of carboxylic acids and peroxides has been studied and a mechanism has been proposed for it. New skeletal rearrangements in the thermal decomposition of cycloalkyl peroxides in benzene and bromoform have been discovered. It has been shown by the method of double 13C NMR that some of the reactions involve the formation of species which manifest properties intermediate between those of free radicals and carbonium ions. The mechanism of the thermolysis of peroxides is considered. The skeletal rearrangements and hydride shifts in the deamination and solvolysis of alicyclic compounds have been studied and a number of rearrangements with 1,2-migration of the halogen and in particular the isomerisation of acyloxybromopropanes in organic solvents, which takes place particularly readily, have been observed. The bibliography includes 103 references.