Hydrogen rearrangements in ionized alkanoic acids. An ion lifetime study

摘要: Abstract Single and double hydrogen rearrangements involving β-bond cleavage have been studied in ionized butanoic, pentanoic hexanoic acids specifically deuterium labelled at the hydroxy group all carbon atoms of side chains. The reactions range 6×10 −11 -10 −5 s after ionization using field kinetic technique. At short ion lifetimes ( r −10 s) n -butanoic acid shows exclusively a single rearrangement which involves γ-hydrogen is followed by cleavage. longer t >10 −8 this preceded exchange between hydroxylic β- γ-hydrogens as found previously. In -pentanoic -hexanoic acids, transfer with competes effectively long lifetimes. again predominantly atom, those from γ- δ-positions. extensive observed even on picosecond time scale leads to participation ϵ- (for acid) positions reactions, although δ-hydrogens are involved longest (∼ 10 s).