ISSN:
0030-4921
Keywords:
Chemistry
;
Analytical Chemistry and Spectroscopy
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The barriers to rotation about the C—N bond in eighteen substituted N,N-dimethylbenzamides have been determined by complete line shape analysis of the NMR spectra of the N,N-dimethyl protons. The barriers have been correlated with the substituent constants σ and σ+. It has been shown that polar solvents increase the barrier in N,N-dimethylbenzamide.Acid catalysis of rotation about the amide C—N bond in N-(p-N,N-dimethylcarboxamidobenzyl)-pyridinium bromide has been investigated. 18O exchange studies show that catalysis is due to N-protonation rather than the formation of a tetrahedral intermediate. The rate of rotation is a function of the Hammett acidity function, H0, and the water activity, and it is shown that proton exchange between the N- and O-protonated species involves the intermediacy of a water molecule.The differences in chemical shifts for the non-equivalent N, N-dimethyl groups of the benzamides are also a function of the substituents. Possible explanations of this phenomenon are discussed.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/mrc.1270010204
