Heteroalicyclic Aminoalkanol. II. Reactions of DL-2-Piperidinemethanol involving the Formation of DL-1-Azabicyclo[4, 1, 0]heptane
作者:Tanezo Taguchi、Seiki Kasuga
DOI:10.1248/cpb.13.241
日期:——
DL-2-Piperidinemethanol (I) was converted to O-acyl, 2-isothioureido and oxazolidine derivatives to be subjected to reactions such as acyl migration, transguanylation and oxidation with bromine respectively. The xanthate (XIII) derived from the N-methyl derivative of I (XII) was thermally rearranged to the corresponding dithiolcarbonate (XIV). In particular, I was converted to DL-1-azabicyclo[4, 1, 0]heptane (XXIV) via DL-2-piperidinemethanol hydrogen sulfate (XXIII). XXIV was easily polymerizable and therefore, stabilized in the form of picrate for identification. Structural proof for XXIV was provided from results of reactions to which it was subjected. In conclusion, the reaction sequences of I and XII were similar to those of acyclic analogues as be theoretically expected.
DL-2-Piperidinemethanol (I) 被转化为 O-酰基、2-异硫脲基和噁唑烷衍生物,分别进行酰基迁移、反鸟苷酸化和溴氧化等反应。由 I 的 N-甲基衍生物(XII)衍生出的黄原酸酯(XIII)经热重排生成相应的二硫醇碳酸酯(XIV)。其中,I 通过 DL-2- 哌啶甲醇硫酸氢盐 (XXIII) 转化为 DL-1- 氮杂双环[4, 1, 0]庚烷 (XXIV)。XXIV 易于聚合,因此以吡啶甲酸盐的形式稳定下来以供鉴定。XXIV 的结构证明来自其所经历的反应结果。总之,I 和 XII 的反应顺序与理论上预期的无环类似物的反应顺序相似。