A. A. Tomashevskii, V. Sokolov, A. A. Potekhin
Feb 1, 2003
Citations
0
Influential Citations
15
Citations
Journal
Russian Journal of Organic Chemistry
Abstract
Abstract(α-Chloroalkyl)thiiranes react with sodium phenolates at heating in water-alcohol mixtures furnishing phenoxymethylthiiranes, 3-phenoxythietanes (resulting from thiirane-thietane rearrangement), or their mixture. The increased polarity of solvent favors the thiirane-thietane rearrangement. 2,2-Dimethyl-3-(chloromethyl)thiirane forms an exclusion for it does not afford (phenoxymethyl)thiirane even in anhydrous ethanol. Diastereomeric erythro- and threo-(1-chloroethyl)thiiranes react stereospecifically giving 2-methyl-3-phenoxymethylthiiranes or 2-methyl-3-phenoxythietanes of trans- and cis-configuration respectively. Specific features of these reactions are discussed from the viewpoint of solvent polarity effect on the competition between formal chlorine substitution along “recyclization” mechanism or through thiirane-thietane rearrangement.