チュガエフ反応則に反する転位とトランス脱離反応(第7報)Diethylthiopropanolの合成とそのS-Methyl Xanthateの熱処理について

概要

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In connection with previous studies which reported the rearrangement of xanthates to dithiolcarbonates by thermal treatment, propyl xanthates holding two ethylthio groups at β-position were examined for the same purpose. 1,3-Diethylthiopropyl S-methyl xanthate (8) underwent rearrangement to 2,3-diethylthiopropyl methyl dithiolcarbonate (10) by distillation and the same product (10) was also obtained by the analogous treatment of 2,3-diethylthiopropyl S-methyl xanthate (9) (Chart 3). This suggests that the reactions of 9 and 10 may pass through the same transition state, an ion pair, which has been well discussed previously. On the other hand, 2,2-diethylthiopropyl S-methyl xanthate (7) gave 1,2-diethylthiopropene (14) by thermal treatment (Chart 4). It is presumed that the product 14 resulted from a dithiolcarbonate which was intermediately formed by the rearrangement of the xanthate (7), although the dithiolcarbonate could not be isolated. For synthesis of the starting materials, thioketalization of pyruvic acid with ethanethiol was attempted in the cold yielding 2,2-diethylthiopropionic acid (4) which underwent rearrangement to 2,3-diethylthiopropionic acid (5) on heating. 4 was converted to 2,2-diethylthiopropanol (1) by reduction with LiAlH_4 (Chart 1).
公益社団法人日本薬学会の論文
1972-06-25