Reactions of atomic carbon with acyl chlorides

Reactions of arc-generated carbon atoms with acyl chlorides proceed by two distinct mechanistic pathways depending on the nature of the alkyl group in the substrate. Acetyl chloride affords vinyl chloride from the putative chloromethylcarbene produced by deoxygenation, whereas pivaloyl chloride gives t-butyl chloride as the predominant product via a chain reaction from the initially generated pivaloyl radical. When the alkyl group is isopropyl, both pathways are implicated.