The Borderline between Reactivity and Pre-reactivity of Binary Mixtures of Gaseous Carboxylic Acids and Alcohols.

By mixing primary and secondary alcohols with carboxylic acids just before the supersonic expansion within pulsed Fourier transform microwave experiments, only the rotational spectrum of the ester was observed. However, when formic acid was mixed with tertiary alcohols, adducts were formed and their rotational spectra could be easily measured. Quantum mechanical calculations were performed to interpret the experimental evidence.