Chain process hypochlorite

The kinetics of formation and hydrolysis of /-C H OCl have been investigated (262). The chemistry of alkyl hypochlorites, /-C H OCl in particular, has been extensively explored (247). /-Butyl hypochlorite reacts with a variety of olefins via a photoinduced radical chain process to give good yields of aUyflc chlorides (263). Steroid alcohols can be oxidized and chlorinated with /-C H OCl to give good yields of ketosteroids and chlorosteroids (264) (see Steroids). /-Butyl hypochlorite is a more satisfactory reagent than HOCl for /V-chlorination of amines (265). Sulfides are oxidized in excellent yields to sulfoxides without concomitant formation of sulfones (266). 2-Amino-1, 4-quinones are rapidly chlorinated at room temperature chlorination occurs specifically at the position adjacent to the amino group (267). Anhydropenicillin is converted almost quantitatively to its 6-methoxy derivative by /-C H OCl in methanol (268). Reaction of unsaturated hydroperoxides with /-C H OCl provides monocyclic and bicycHc chloroalkyl 1,2-dioxolanes. 

Butyl hypochlorite, the most extensively studied member of the hypochlorite family, is moderately stable and can be distilled without decomposition however, it decomposes rapidly in bright sunlight to methyl chloride and acetone.42 The following chain process has been suggested44 for this decomposition. 

Answer The thermal homolysis of the weak oxygen-chlorine bond in r-butyl hypochlorite produces a r-butoxy radical that starts the chain. This radical will abstract a hydrogen atom from the benzylic methylene of 1-phenylpropane to give a resonance-delocalized benzylic radical, the most stable of all the possible alternatives. The propagation loop completes when the benzylic radical abstracts a chlorine atom from t-butyl hypochlorite and creates a r-butoxy radical to start the process over again. The products are 1-chloro-1-phenylpropane and r-butanol. 

The same fragmentation process is involved in the chain decomposition of alkyl hypochlorites ... 

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