The Decomposition of Benzoyl Hypochlorite in the Presence of Metal Ions

Abstract

The decomposition of benzoyl hypochlorite, the intermediate in the Hunsdiecker reaction between chlorine and silver benzoate, is accelerated by light and by azobisisobutyronitrile (AIBN), but not by transition metal ions. The molar yield of the chlorobenzene produced in the decomposition increases as the temperature of the reaction mixture is raised, but is independent of whether or not the reaction is promoted by light or AIBN. It is suggested that this variation in the yield is a result of the readier decarboxylation at higher temperatures of the benzoyloxy radicals which are believed to be intermediates in the decomposition process. No such pronounced effect of temperature on the yield of halides from aliphatic silver carboxylates has been observed, presumably because aliphatic acyloxy radicals decarboxylate readily even at low temperatures.

Novel chlorination of the adamantyl system by silver salts in carbon tetrachloride

“…The reactivity trend being described here for acetyl hypobromite parallels that of benzoyl hypochlorite, which gave in benzene a moderate yield of phenyl benzoate at 3°b ut little at reflux. 18 Since acetic acid and bromine chloride should be produced in equimolar quantities (Chart II), lower acetic acid yields reflect lower bromine chloride production and hence at elevated temperatures the major part of the propagation effort would have to be effected by the acetyl hypobromite decomposition products and the trichloromethyl radicals. Propagation by these less potent and thus more discriminating hydrogen abstractors,19 as expected, causes an increase in the l-:2-chloroadamantane ratio (Table II).…”