| Autor: |
Oshima, Takumi, Nishioka, Ryoji, Nagai, Toshikazu |
| Zdroj: |
Bulletin of the Chemical Society of Japan; March 1982, Vol. 55 Issue: 3 p904-908, 5p |
| Abstrakt: |
A stereochemical study was made of the reaction of phenyldiazomethane(1) with chloranil(2) at 20 °C in 28 aprotic solvents. The products were trans-spirooxetane(4) and cis-transmixtures of stilbene(3) (ca.2–5 times cis-rich). The molar ratios of cis-3to the sum of the trans-3and 4tended to increase, whereas the 4to trans-3ratios decrease with the increase in the solvent basicity and polarity. These effects of solvents on the product distributions were interpreted in terms of the effects of the solvent basicity and polarity on the stereoselective formation of the diazonium betaine intermediate and on the conformational isomerism. Moderately successful linear-free-energy(LFE) relationships were established for these product ratios with the aid of the combination of the empirical solvent basicity parameter, Dπ, and the Kirkwood function, f(ε), or ETvalues as the solvent polarity parameters. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
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