化学学报 ›› 1965, Vol. 31 ›› Issue (1): 42-49. 上一篇    下一篇

论文

双[1,3-二苯基-2-咪唑烷叉]和几种卤代烷的自由基型反应

蒋锡夔, 张俊逸, 石宇   

  1. 中国科学院化学研究所
  • 投稿日期:1963-12-30 发布日期:2013-06-03

FREE RADICAL REACTIONS OF BIS [1, 3-DIPHENYL-2-IMIDA-ZOLIDINYLIDENE] WITH VARIOUS HALOALKANES

S. HSI-KWEI JIANG, CHANG CHUN-YI, SHI YU   

  1. Institute of Chemistry, Academia Sinica
  • Received:1963-12-30 Published:2013-06-03

在促进自由基型反应的条件(紫外光照射、无溶剂、室温振荡48小时)下,双[1,3-二苯基-2-咪唑烷叉](Ⅰ)与过量四氯化碳反应后生成较复杂产物(转化率约24%),自其中可分离检定二氯化物Ⅲe(约39%),一氯化物Ⅳ(约15%)及少量六氯乙烷.双体Ⅰ与1-氯丁烷反应(转化率约11%),亦可得二氯化物Ⅲe(约52%).同样,自过量1-溴丙烷可得二溴化物Ⅲd(产率约59%,反应转化率约29%),自过量碘乙烷可得二碘化物Ⅲb(产率约70%,反应转化率约41%).在离子型或异裂性的反应条件(室温、乙腈溶液、无引发自由基因素)下,各卤素与双体Ⅰ迅速反应,并以100%转化率及高产率形成其相应二卤化物Ⅲ.计:二氯化物Ⅲe,产率98%;二溴化物Ⅲd,产率90%;二碘化物Ⅲb,产率90%.新化合物Ⅲe及Ⅲd的结构通过几近定量的化学转化、紫外吸收光谱的对比、不同方法合成同一产物的熔点及混合烷点的对比以及元素分析得到证明.本工作说明,双体Ⅰ的反应方式不仅限于作为亲核卡宾Ⅱ的来源.双体Ⅰ本身是活泼分子,既能参与离子型反应,也能参与自由基型反应.

Structures of the two new compounds Ⅲd and Ⅲe were identified by their almost quantitative conversion to the known diperchlorate Ⅲa, by the determination of melting points and mixed melting points with samples prepared by a different route (vide infra), by the analogy of their ultraviolet spectra (Fig.1) as well as that of the diiodide Ⅲb, and by halogen elemental analyses.In addition to the dichloride Ⅲe, the reaction with carbon tetrachloride also yielded some 1,3-diphenylimidazolinium chloride (Ⅳ, ca.15%) and hexachloroethane.