1-Oxo-1,3-dithiolanes - synthesis and stereochemistry
- 1-Oxo-1,3-dithiolane (4) and its cis- and trans-2-methyl (5,6), -4-methyl (7,8) and -5-methyl (9,10) derivatives were prepared by oxidizing the corresponding 1,3-dithiolanes (1-3) with NaIO(4) in water. The oxides were purified and their isomers separated using thin layer chromatography. The structural characterization was carried out with (1)H and (13)C NMR spectroscopy and molecular modelling. The sulfoxides 4-6 and 8-10 attain two S(1) type envelopes (sometimes slightly distorted) the S=O(ax) envelope greatly dominating. Cis-4-methyl-1-oxo-1,3-dithiolane is a special case exhibiting both two closely related S=O(ax) (30 and 27%) as well as S=O(eq) (21 and 22%) forms [S(1) and C(4) envelopes, respectively]. The relative energies of these conformations, the values of (1)H-(1)H coupling constants and (1)H and (13)C chemical shifts were estimated by computational methods and they support well the conclusions based on the experimental data.
Author details: | Kalevi Pihlaja, Jari Sinkkonen, Geza Stajer, Andreas KochORCiDGND, Erich KleinpeterORCiDGND |
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DOI: | https://doi.org/10.1002/mrc.2764 |
ISSN: | 0749-1581 |
Title of parent work (English): | Magnetic resonance in chemistry |
Publisher: | Wiley-Blackwell |
Place of publishing: | Malden |
Publication type: | Article |
Language: | English |
Year of first publication: | 2011 |
Publication year: | 2011 |
Release date: | 2017/03/26 |
Tag: | (1)H NMR; (13)C NMR; NMR; computational chemistry; conformational analysis; sulfur heterocycles |
Volume: | 49 |
Issue: | 7 |
Number of pages: | 7 |
First page: | 443 |
Last Page: | 449 |
Funding institution: | Academy of Finland; Finnish Cultural Foundation |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer review: | Referiert |