化学学报 ›› 1981, Vol. 39 ›› Issue (4): 348-353. 上一篇    下一篇

研究简报

第五、六族元素的有机化合物在有机合成中应用的研究——Ⅸ.氰代亚甲基三苯基胂与酮的反应

黄耀曾, 邢宜德, 施莉兰, 林芳乐, 徐元耀   

  1. 中国科学院上海有机化学研究所
  • 投稿日期:1979-03-28 发布日期:2013-06-03

STUDIES ON THE APPLICATION OF ELEMENTO-CRGANIC COMPOUNDS OF FIFTH AND SIXTH GROUPS IN ORGANIC SYNTHESES Ⅸ. REACTIONS OF CYANOMETHYLENE TRIPHENYL ARSORANE WITH KETONES

HUANG YAO-ZENG(HUANG YAO-TSENG), KING YI-DE, SHI LI-LAN, LIN FANG-LE, XU YUAN-YAO   

  1. Shanghai Institute of Organic Chemistry, Academia Sinica
  • Received:1979-03-28 Published:2013-06-03

Trippett[1]曾报道氰代亚甲基三苯基膦不能与酮反应.作者之一及其同工作者曾报道甲氧羰基亚甲基三苯基胂与多种醛、酮反应,其反应性能比相应的膦试剂活泼.本文报道氰代亚甲基三苯基胂(2)的制备,以及它与一系列酮包括α,β-不饱和酮的反应(产物和产率列于表1),表明2的反应性能也较相应的膦试剂活泼.

In contrast to cyanomethylene triphenylphosphorane, the corresponding arsorane could react with a series of ketones giving the α,β-unsaturated nitrite in fair to good yields. The products and their yields are shown in Table 1. This result shows again that the arsonium glide is more reactive than the corresponding phosphonium glide. It is worthwhile to point out that this glide also could be obtained from the arsonium salt on treating with the weak base piperidine, and reacted with a-tetralone in situ under the mild conditions. The pure egocyclic olefinic product was obtained in 33% yield. When this glide reacted with 4-cholesten-3-one, the yield of the olefinio products was 87%.Their configurations were ascertained by 1H NMR spectra. Therefore in the above two cases, this arsonium glide seems to be superior than Horner-Wittig reagent.