Electron impact studies. Part 116. Mechanism of keten elimination from acetanilide and phenyl acetate radical ions
- 1 January 1977
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 13,p. 1670-1674
- https://doi.org/10.1039/p29770001670
Abstract
Ion cyclotron resonance studies show that the processes M+˙→(M – CH2CO)+˙ from both the acetanilide and phenyl acetate molecular ions occur through four-membered transition states; the non-decomposing product ions from these processes correspond to the aniline and phenol ion radicals respectively. Kinetic isotope effects (kH/kD) for H–D transfer from p-RC6H4·NH·CO·CH2·D increase (from 1.5 to 2.2 for decompositions in the first field-free region) with increasing σ+ values of R. Kinetic energy releases occurring during the metastable decompositions M+˙→(M – CH2CO)+˙ from p-RC6H4·NH·COMe increase with decreasing σ+. A similar study with p-substituted phenyl acetates shows kH/kD to be small (1.2–1.3) and insensitive to changes in the para-substituent. Kinetic energy release is also relatively insensitive to the nature of the substituent. These results are rationalised in terms of transition state geometries.Keywords
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