高等学校化学学报

高等学校化学学报 ›› 1998, Vol. 19 ›› Issue (S1): 178.

• Organic Synthesis Chemistry • 上一篇    下一篇

Synthesis and Complexation of Phosphorus- and Selenium-Containing Macrocycles

Jinliang Li, Changqiu Zhao, Yongmei Wang, Jiben Meng   

  1. Department of Chemistry, Nankai University, Tianjin 300071
  • 出版日期:1998-12-31 发布日期:1998-12-31

Synthesis and Complexation of Phosphorus- and Selenium-Containing Macrocycles

Jinliang Li, Changqiu Zhao, Yongmei Wang, Jiben Meng   

  1. Department of Chemistry, Nankai University, Tianjin 300071
  • Online:1998-12-31 Published:1998-12-31

PDF (PC)

摘要： A facile synthesis method for SePSe-containing macrocycles was developed. The macrocycles were obtained by one-pot reaction. The powder selenium was reduced by potassium borohydride in absolute alcohol to produce potassium diselenide,which reacted with bis(o-bromomethylphenyl)phenylphosphine oxide 1 to give the intermediate, 1-phenyl-2,3:8,9-dibenzo-5,6-diselena-1-phosphacyclononadiene 1-oxide 2, and its oligomer. Without isolation, the mixture was treated with potassium borohydride and sodium hydroxide to produce diselenide anion, then allowed to react with alkyl dibromide to give SePSe-containing macrocycles (shown as Scheme 1). A medium-sized eight-membered heterocycle, l-phenyl-2,3:7,8-dibenzo-5-selena-1-phosphacyclooctadiene 1-oxide 4 was obtained surprisingly. The formation of heterocycle 4 was due to the presence of potassium selenide when selenium was reduced by potassium borohydride. The attempts to isolate the intermediate 2 were totally unsuccessful. When the alkyl dibromide was the 1,2-dibromoethane, the expected macrocycle was not obtained, with deposition of red selenium and extrusion of ethylene. The similar case was reported by Pinto B. M. in 1989.

Abstract: A facile synthesis method for SePSe-containing macrocycles was developed. The macrocycles were obtained by one-pot reaction. The powder selenium was reduced by potassium borohydride in absolute alcohol to produce potassium diselenide,which reacted with bis(o-bromomethylphenyl)phenylphosphine oxide 1 to give the intermediate, 1-phenyl-2,3:8,9-dibenzo-5,6-diselena-1-phosphacyclononadiene 1-oxide 2, and its oligomer. Without isolation, the mixture was treated with potassium borohydride and sodium hydroxide to produce diselenide anion, then allowed to react with alkyl dibromide to give SePSe-containing macrocycles (shown as Scheme 1). A medium-sized eight-membered heterocycle, l-phenyl-2,3:7,8-dibenzo-5-selena-1-phosphacyclooctadiene 1-oxide 4 was obtained surprisingly. The formation of heterocycle 4 was due to the presence of potassium selenide when selenium was reduced by potassium borohydride. The attempts to isolate the intermediate 2 were totally unsuccessful. When the alkyl dibromide was the 1,2-dibromoethane, the expected macrocycle was not obtained, with deposition of red selenium and extrusion of ethylene. The similar case was reported by Pinto B. M. in 1989.

TrendMD: