Wv. Doering et Dc. Zhao, GAS-PHASE ADDITION OF [C-13]METHYLENE TO ETHENE - REARRANGEMENT OF CHEMICALLY EXCITED PROPENE, Journal of the American Chemical Society, 117(12), 1995, pp. 3432-3437
Reaction of ethene with singlet [C-13]methylene, generated photochemic
ally from [C-13]diazomethane at four pressures in the range 35-800 Tor
r, reveals rearrangement of excited [3-C-13]propene (3), the product o
f insertion, to [1-C-13]propene (1) and [2-C-13]propene (2). This prev
iously unrecognized reaction is formulated as the reverse of the therm
al rearrangement of cyclopropane to propene, well known in both therma
l and chemically excited modes. The origin of a small excess of 1 over
2 is discussed. Mercury sensitization does not alter the observations
at 820 Ton.