An Experimental and Theoretical Investigation of the Mechanism of Deoxygenation of Carbonyl Compounds by Atomic Carbon

Article abstract of DOI:10.1021/ja00400a052

The reactions of atomic carbon with butanal and butanone have been studied by both MNDO calculations and experiment.The calculations indicate the preferred path to involve addition of carbon across the C=O bond to form an oxiranylidene which rearranges to ketene.Since the ketene is formed with enough excess energy to undergo dissociation to carbon monoxide and a carbene, it should be detectable only under conditions where the excess energy is rapidly dissipated.While no ketene was observed when the reactions were carried out in the gas phase, a ketene intermediate was trapped by addition of water following the reaction of arc-generated carbon atoms with frozen butanal.