In:
Israel Journal of Chemistry, Wiley, Vol. 21, No. 2-3 ( 1981-01), p. 145-150
Abstract:
In order to study the stereochemistry of thiirane oxide decomposition, syn ‐ and anti ‐2,3‐dideuterothiirane‐1‐oxides and trans ‐2,3‐dideutero‐thiirane‐1‐oxide have been synthesized in three steps from cis ‐ and trans ‐dideuteroethylene via stereospecific formation of the corresponding oxiranes and thiiranes. The presence of the deuterium label was used so as not to perturb the course of the decomposition from that of the parent thiirane oxide. Pyrolysis of the labeled thiirane oxides in both gas and solution phase proceeded with greater than 90% retention of stereochemistry. Analyses were performed by comparison of the infrared spectra of the product mixtures with standard calibrated samples. Attempts to trap possible biradical intermediates with di(p‐anisyl)thioketone gave a low yield of products, possibly derived from addition to thiirane oxide. These results suggest a possible partial contribution of a biradical mechanism to the thiirane oxide decomposition. If bond rotation in the biradical is slow, this mechanism could be the sole mode of sulfur monoxide extrusion.
Type of Medium:
Online Resource
ISSN:
0021-2148
,
1869-5868
DOI:
10.1002/ijch.v21:2-3
DOI:
10.1002/ijch.198100031
Language:
English
Publisher:
Wiley
Publication Date:
1981
detail.hit.zdb_id:
2066481-3
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