The reorientation of t-butyl groups in butylated hydroxytoluene: A deuterium nuclear magnetic resonance spectral and relaxation time study

Abstract

Deuterium nuclear magnetic resonance (NMR) spectra and spin–lattice relaxation times were determined in order to study the dynamics of t-butyl groups in butylated hydroxytoluene. The results are consistent with a model first proposed by Beckmann et al. [J. Magn. Reson. 36, 199 (1979)], where there is an inequivalence between the methyl groups within each t-butyl group. While two methyl groups reorient rapidly relative to the whole t-butyl rotation, the remaining methyl group is more restricted in its motion, reorienting at a rate comparable to that of the t-butyl group itself. The spin–lattice relaxation data show two T1 minima, the high temperature minimum (40 °C) corresponding to the combined t-butyl and ‘‘slow’’ methyl rotations, and the low temperature minimum corresponding to ‘‘fast’’ methyl group rotation. Using an explicitly defined T1 fitting function, the T1 data yield activation energies of 2.2 and 6.0 kcal/mol for the fast methyl and t-butyl rotations, respectively, both in agreement with Beckmann’s values obtained from proton T1 experiments. It was also possible to simulate the low temperature deuterium NMR spectra from T=−160 °C to T=−80 °C using the aforementioned dynamical inequivalence between the t-butyl methyl groups. While the fast methyl group rotation was in the motional narrowing region for T>−160 °C, it was possible, from the simulations, to determine the t-butyl exchange rates to within 10%. The jump rates are remarkably close to the values predicted from the T1 results. Above −80 °C, the spectra could not be simulated, implying that a third motion must be present to further alter the high temperature line shapes. The effective axial asymmetry of the T>−20° spectra indicates that the additional motion involves a two site exchange.