tert-Butylation of α,β-Unsaturated Nitriles by tert-Butylmercury Halides in the Presence of Iodide Ion

Glen A. Russell*, Ping Chen, C. F. Yao, B. H. Kim

*此作品的通信作者

研究成果: 雜誌貢獻期刊論文同行評審

23 引文 斯高帕斯(Scopus)

摘要

Iodide ion promotes the free radical addition of t-BuHgI to acrylonitrile to form t-BuCH2CH (CN)HgI. A facile reaction of the adduct 1-cyanoalkyl radical with t-BuHgI2-is indicated. Further promotion is observed in the presence of NH4I or PTSA/KI in a reaction now leading directly to t-BuCH2CH2CN. Protonation of the intermediate adduct radical followed by electron transfer from t-BuHgI2-is postulated. With fumaronitrile reaction of the adduct, radical [t-BuCH (CN)C·HCN] with t-BuHgI can be promoted by the addition of acids or bases. In the presence of NH4I or PTSA/KI, the reductive alkylation product is formed, while in the presence of DABCO, oxidative alkylation occurs to yield t-BuC (CN)=CHCN and t-BuC (CN)=C (CN)Bu-t. Protonation of [t-BuCH (CN)C·HCN] increases the ease of reduction while deprotonation yields an easily oxidized radical anion.

原文英語
頁(從 - 到)5967-5972
頁數6
期刊Journal of the American Chemical Society
117
發行號22
DOIs
出版狀態已發佈 - 1995 6月
對外發佈

ASJC Scopus subject areas

  • 催化
  • 化學 (全部)
  • 生物化學
  • 膠體和表面化學

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