Metyrapone [2-methyl-1,2-di(3-pyridyl)propan-2-one, 1] undergoes effic
ient a-cleavage via the n(o) pi triplet. The fate of the resulting ac
yl and alkyl radicals has been determined by transient studies as well
as through the isolation of the final products, quantum yield measure
ments and trapping studies. Processes previously documented for carboc
yclic analogues of 1, such as disproportionation and coupling of the a
lkyl radicals nd recombination to the starting compound are here accom
panied by another major process, viz. coupling with attack of the acyl
radical on the pyridine ring, which eventually leads mainly to a poly
meric material.