Gas-phase 200MHz 'H NMR spectra of nineteen primary and nine secondary aliphatic amines were obtained at total densities below 0.15 amagat at 148.6 OC. Theoretical predictions of 'H chemical shifts of ammonia and methylamine are compared with the gas-phase experimental values. The amino proton chemical shifts move downfield with increasing alkyl group size. For series of amines with similar structural geometry about the amino nitrogen, the 'H amino proton chemical shifts correlate reasonably well with gas-phase basicities as measured via ion cyclotron resonance spectroscopy ( r = 0.95 for a linear fit of chemical shift to the gas-phase basicity for the primary amines and r = 0.93 for the secondary amines). Gas-phase 'H NMR spectra for linear diamines, hydroxyamines, cyclic amines and substituted anilines were also obtained.
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