NMR spectra, MO calculations of spin–spin coupling constants and conformational analysis of substituted 1,3‐dioxolanes
作者:
Rois Benassi,
Luisa Schenetti,
Ferdinando Taddei,
Luigi Villa,
Vincenzo Ferri,
期刊:
Organic Magnetic Resonance
(WILEY Available online 1980)
卷期:
Volume 13,
issue 1
页码: 17-25
ISSN:0030-4921
年代: 1980
DOI:10.1002/mrc.1270130105
出版商: John Wiley&Sons Limited
数据来源: WILEY
摘要:
AbstractThe NMR spectra of a number of 2,4‐disubstituted 1,3‐dioxolanes have been recorded and the proton chemical shifts and coupling constants derived from complete spectral analysis. Vicinal coupling constants were found to be dependent on the substituent at C‐4 and this effect is more pronounced forJ(trans)of the C‐4‐C‐5 fragment. These coupling constants also indicate a homogeneous behaviour within a series with either acisortransconfiguration, although thecisbehaviour differs from that oftransisomers. This has been interpreted in terms of definite ring conformations in substituted derivatives, while the unsubstituted 1,3‐dioxolane undergoes free pesudorotation. Calculations of coupling constants were performed by semi‐empirical MO methods, both for unsubstituted 1,3‐dioxolane and for C‐4 substituted derivatives in a large number of conformations, in order to compare calculated and experimental values; the correct order ofJ(cis)andJ(trans)for 1,3‐dioxolane is obtained only by employing energies fromab‐initioMO calculations averaged over the pseudorotation circuit. For the C‐4 substituted compounds calculated coupling constants were employed in a ‘trial and error’ process for the identification of the preferred conformations of these compounds; a set of two torsional angles for each compound was derived which allows a tentative description of the geometry of each molecule. A criticism of these geometries is given according to the evidence available on the structure
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