Potential energy profiles for unimolecular reactions of isolated organic ions: CH3CH2CHNHCH3 and (CH3)2CNHCH3

Abstract

The slow unimolecular reactions of metastable CH₃CH₂CHNHCH₃ and (CH₃)₂CNHCH₃ ions are reported and discussed. Details of the mechanisms of these reactions are elucidated by ²H-labelling studies. Loss of C₃H₆ from these C₄H₁₀N⁺ ions is shown to occur after irreversib le isomerisation to CH₃CH₂CH₂NHCH₂ and related structures. The behaviour of CH₃CH₂CHNHCH₃ and (CH₃)₂CNHCH₃ is compared with that of the lower homologues [CH₃CH₂CHNH₂, (CH₃)₂CNH₂, and CH₃CHNHCH₃] and contrasted with that of the oxonium ion analogues CH₃CH₂CHOCH₃ and (CH₃)₂COCH₃.