POSITIVE HALOGEN COMPOUNDS .16. COMPARISON OF ALKOXY RADICALS FROM DIFFERENT SOURCES AND ROLE OF HALOGEN ATOMS IN HYPOHALITE REACTIONS

A comparison of the reactions of t-butoxy and other t-alkoxy radicals derived from hypochlorites, hypobromites, peroxalates, and hyponitriles indicates that chlorine atom chains may compete with alkoxy-radical chains in the reaction of hypochlorites with substrates containing benzylic hydrogen and in the decomposition of benzyldimethylcarbinyl hypochlorite. They are, however, eliminated by traces of olefin which act as chlorine atom traps, and greatly suppressed in mixed aliphatic-benzylic systems where chains propagate largely through alkyl radicals. Bromine atom chains with t-butyl hypobromite are also detectable, but less important. These chlorine atom chains account for several anomalies in hypochlorite chemistry reported previously, but we conclude that most of the data gathered on relative reactivities toward alkoxy radicals and on /3-scission processes were gathered under conditions where they were unimportant. © 1969, American Chemical Society. All rights reserved.