Abstract

AbstractA marked temperature dependence of the 13C and 15N chemical shifts of 3‐hydroxypyridine in D2O (pD = 7.0) was observed. This dependence is explained in terms of thermally induced equilibrium shifts between the neutral form and the zwitterionic form of 3‐hydroxypyridine. A method was developed to characterize the thermodynamics of the equilibria that are rapid on the NMR time scale, using the observed average 13C and 15N chemical shifts at different temperatures. This method was applied to the thermodynamics of the tautomerization equilibria of 3‐hydroxypyridine. The equilibrium constants and the standard enthalpy change of the tautomerization equilibrium obtained by 13C and 15N methods agree very well with the results obtained by other spectroscopic methods.

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