Reactions of Atomic Carbon with Acid Chlorides

1his thesis is the flfst report of reactions of atomic calbon with acid chlorides. Carbon is known to react with phosgene to afford dichlorocarbene. We report a similar reaction with carbon and acid ch~lorides, generating alkylchlorocarbenes. We examine both the nature of the carbene products generated through deoxygenation and the general reacliviry ofcarbon with the acid chlorides. We report two ways in which carbon reacts with acid chlorides. First, as expected from prior work with phosgene, carbon deoxygenates the carbonyl group yielding alkylchlorcarbenes, which rearrange as expected. Second, carbon abstracts the chlorine, and generates the acyl radical, which, in the case of pivaloyl chloride and isobutyryl chloride. decarbonylates and a free radical chain reaction mechanism generates the alkyl halide. The reaction of isobutyryl chloride and carbon demonstrates that both the deoxygenation and chlorine abstraction mechanisms compete, as there is a 2: I ratio of the two processes, respectively.