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高等学校化学研究 ›› 2010, Vol. 26 ›› Issue (5): 768-772.

• Articles • 上一篇    下一篇

Synthesis of Di-substituted Proazaphosphatrane and Its Application in Carbon-carbon Double-bond Isomerization

WU Wei*, ZHANG Xiao-yun and KANG Shou-xing   

  1. Department of Chemistry, China University of Petroleum(East China), Qingdao 266555, P. R. China
  • 收稿日期:2009-10-06 修回日期:2010-01-22 出版日期:2010-09-25 发布日期:2010-11-26
  • 通讯作者: WU Wei. E-mail: wwu257@163.com
  • 基金资助:

    Supported by the Natural Science Foundation of Shandong Province, China(No.Y2007F05).

Synthesis of Di-substituted Proazaphosphatrane and Its Application in Carbon-carbon Double-bond Isomerization

WU Wei*, ZHANG Xiao-yun and KANG Shou-xing   

  1. Department of Chemistry, China University of Petroleum(East China), Qingdao 266555, P. R. China
  • Received:2009-10-06 Revised:2010-01-22 Online:2010-09-25 Published:2010-11-26
  • Contact: WU Wei. E-mail: wwu257@163.com
  • Supported by:

    Supported by the Natural Science Foundation of Shandong Province, China(No.Y2007F05).

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摘要： Diisopropyltren was synthesized from the reaction of tren with benzaldehyde in toluene, followed by  reducing the imine intermediate with NaBH4, and debenzylation catalyzed by 10% Pd/C in methanol. It was then converted to its corresponding azaphosphatrane via ring-closing reaction of HMPT and triflic acid. Deprotonation of azaphosphatrane with potassium t-butoxide afforded the target diisopropyl proazaphosphatrane 1d. A comparative study of compound 1d for isomerization of allylic system and methylene-interrupted diene system revealed that compound 1d is more efficient than its tri-substituted analoque(1b). In acetonitrile at 40 °C, allylaromatics were  selectively isomerized to 1-arylpropene generally in an isolated yield more than 95% with trans, cis molar ratios in a range of 87/13 to 96/4. Allyl phenylsulfide was converted to 1-phenylthiopropene(molar ratio of Z/E=54/46) in a yield of 93%―95%. Methylene-interrupted dienes were also isomerized in high yield.

关键词: Proazaphosphatrane, Isomerization, Nonionic strong base

Abstract: Diisopropyltren was synthesized from the reaction of tren with benzaldehyde in toluene, followed by  reducing the imine intermediate with NaBH4, and debenzylation catalyzed by 10% Pd/C in methanol. It was then converted to its corresponding azaphosphatrane via ring-closing reaction of HMPT and triflic acid. Deprotonation of azaphosphatrane with potassium t-butoxide afforded the target diisopropyl proazaphosphatrane 1d. A comparative study of compound 1d for isomerization of allylic system and methylene-interrupted diene system revealed that compound 1d is more efficient than its tri-substituted analoque(1b). In acetonitrile at 40 °C, allylaromatics were  selectively isomerized to 1-arylpropene generally in an isolated yield more than 95% with trans, cis molar ratios in a range of 87/13 to 96/4. Allyl phenylsulfide was converted to 1-phenylthiopropene(molar ratio of Z/E=54/46) in a yield of 93%―95%. Methylene-interrupted dienes were also isomerized in high yield.

Key words: Proazaphosphatrane, Isomerization, Nonionic strong base