Pyrolysis of Alkyl Acetates. A Radical Pathway for the Formation of Minor Products

Article abstract of DOI:10.1021/jo00083a028

Decyl acetate and decene pyrolysis under the same reaction conditions show that the formation of the minor products during the pyrolysis of esters occurs by a parallel, and not a secondary, reaction.The radioactivity observed in the CO2 and CO produced during the pyrolysis of 1-hexyl acetate-1-14C and the radioactivity in the methane from the pyrolysis of 1-hexyl acetate-2-14C strongly suggested a radical reaction pathway for the formation of the minor products.Considering the above results together with the radioactivity data of gas samples from the pyrolysis of 1-decyl-1-14C acetate, 1-hexyl-1-14C acetate, and 1-heptadecyl-1-14C acetate leads to the conclusion that the mechanism of pyrolysis of esters may be viewed as a cyclo-D_ED_NA_N mechanism for the formation of the major alkene product and a radical mechanism for the formation of minor products.A useful synthetic procedure for the preparation of high carbon number alkenes (>10) also results from this study.