Infrared Fingerprints of nN → σ*NH Hyperconjugation in Hydrazides

An earlier study demonstrated that hyperconjugation operates in hydrazides by analyzing the N-H stretching mode in gas phase infrared (IR) spectroscopy, and then observing two very distinct bands corresponding to isolated isomers experiencing or not the n(N) -> sigma*(N-H) electron delocalization. The present work reports a chemical method to obtain insight on the hyperconjugation in hydraiide derivatives from solution IR spectroscopy. The analogous amides did not show a v(N-H) red-shifted band, as the electron donor orbital in the above hyperconjugative interaction does not exist. In addition, the effect of electron withdrawing groups bonded to a nitrogen atom, namely the trifluoroacetyl and the methanesulfonyl groups, was analyzed on the conformational isomerism and on the ability to induce a stronger hyperconjugation in the resulting compounds.