Orientational Dependance of Vicinal and Geminal13C–1H Coupling
作者:
J. A. Schwarcz,
A. S. Perlin,
期刊:
Canadian Journal of Chemistry
(NRC Available online 1972)
卷期:
Volume 50,
issue 22
页码: 3667-3676
ISSN:0008-4042
年代: 1972
DOI:10.1139/v72-581
出版商: NRC Research Press
数据来源: NRC
摘要:
The effect of changes in the relative orientation of vicinal and geminal13C and1H nuclei, and in the disposition of adjacent substituents, on coupling between these nuclei has been examined with a variety of13C-labelled carbohydrates. Compounds synthesized for this purpose include derivatives ofD-glucose-1- and -6-13C andL-idose-6-13C, and related lactones, and the measurements have been made with p.m.r. spectra of these compounds. Vicinal13C-1H coupling, both through C—C and C—O bonds shows an orientational dependance analogous to that for protons:i.e., dihedral angles of 60–100° are associated with smaller coupling (0–3 Hz) than angles of 140–180° (4.5–5.5 Hz); sp2carbon produces splittings of almost twice these values. The observed spacing is smaller when an oxygen atom is in the plane of the coupling pathway than when out of plane, both for vicinal and geminal13C–1H interactions, and the presence of an extra oxygen also may have a notable impact on the geminal interaction. A study of rotational isomerism in these compounds indicates that the characteristics of coupling between13C and1H nuclei may fruitfully be compared with those of H–H coupling in the analysis of such dynamic systems.
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