Gas-phase rearrangements of deprotonated ketoximes, ketoxime ethers, and aldoximes. A negative-ion beckmann rearrangement
Abstract
Evidence is presented which indicates that the pronounced loss of water from deprotonated ketoximes involves specific proton transfer followed by a negative-ion Beckmann rearrangement. For example, Me2CNO–→–CH2(Me)CNOH[graphic omitted][(CH2CNMe)–OH]→ CH2CNCH2–+ H2O. Deprotonated aldoximes, e.g. MeCHNO–, fragment in this way, but also undergo the competing process MeCHNO–→ MeNOH →[(MeCN)–OH]→–CH2CN + H2O. Other rearrangements occur when proton transfer to oxygen does not occur; e.g. Ph2CNO– [graphic omitted] PhNOPh → PhO–+ PhCN.