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Conformational studies by nuclear magnetic resonance. VII—The direct observation of rotational isomers in some enamino carbonyl compounds and their thione derivatives by carbon magnetic resonance

✍ Scribed by Janusz Da̧browski; Krystyna Kamieńska-Trela; Lech Kozerski


Publisher
John Wiley and Sons
Year
1974
Tongue
English
Weight
348 KB
Volume
6
Category
Article
ISSN
0749-1581

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✦ Synopsis


Abstract

Carbon‐13 magnetic resonance spectra of the s‐cis and s‐trans rotamers of enamino ketones and thiones of the general formula
\documentclass{article}\pagestyle{empty}\begin{document}${\rm X =}\mathop {\rm C}\limits^{\rm 1} {\rm (}\mathop {\rm R}\limits^{\rm 1} {\rm)}\mathop {\rm C}\limits^{\rm 2} {\rm H =}\mathop {\rm C}\limits^{\rm 3} {\rm HN}\mathop {{\rm R}_{\rm 2}}\limits^{\rm 4}$\end{document} (where × = O or S and R‐1, R‐4 = alkyl) have been obtained. With dimethylaminoacrolein and its thione analogue, restricted rotation could only be observed in the latter. The chemical shift differences between rotamers and homologues are attributed to changes in conjugation and to induced bond polarisation, both these factors resulting from steric strain. In particular, nonplanar deformations of the s‐trans rotamers are deduced from their C‐2 chemical shift values.