The Influence of the Size and Structure of a Spectator Alkyl Group on the Relative Rates of Alkyl Radical Elimination from Ionised Tertiary Amines

The relative rates of alkyl radical elimination by α-cleavage of ionised amines of general structure, CH3CH2CH2(CH3CH2)CHN(CH3)R+• or CH3CH2CH2CH2(CH3CH2CH2)CHN(CH3)R+•, where R = n-CnH2n + 1 (n = 1–10, 12 or 14), iso-C5H11, CH2CH(CH3)C2H5, neo-C5H11 or CH2CH2C(CH3)3, are reported. The size of the spectator alkyl group, R, affects the ratio of ethyl and propyl radical loss from metastable ionised amines containing a 3-hexyl group; the slight …