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有机化学
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有机化学 ›› 2009, Vol. 29 ›› Issue (11): 1843-1848. 上一篇    下一篇

研究简报

N,N-二丁基甲酰胺的制备—二正丁胺存在下二氧化碳催化氢化反应的研究

马润芝 李云庆 周宏勇 王家喜*   

  1. (河北工业大学化工学院 天津 300130)
  • 收稿日期:2009-02-07 修回日期:2009-04-28 发布日期:2009-06-30

Preparation of N,N-Dibutylformylamide—Hydrogenation of Carbon Dioxide in Presence of Dibutylamine

Ma, Runzhi     Li, Yunqing       Zhou, Hongyong       Wang, Jiaxi*   

  1. (School of Chemical Engineering, Hebei University of Technology, Tianjin 300130)
  • Received:2009-02-07 Revised:2009-04-28 Published:2009-06-30

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研究了在二正丁胺存在下RuCl3/DPPE催化二氧化碳氢化反应, 探讨了N,N-二正丁基甲酰胺的制备新途径, 考察了温度、溶剂、二氧化碳及氢气压力等对催化氢化反应的影响, 产物的结构及量用核磁共振波谱、气相色谱分析测定. 反应的催化效率随温度的升高(120 ℃)先上升后降低; 在4 MPa二氧化碳压力下催化效率随氢气的压力升高而升高; 在4 MPa氢气压力下, 催化效率随二氧化碳压力的升高(6 MPa)先升高后降低, 在10 MPa氢气压力下, 催化效率随二氧化碳的压力升高而升高. 二氧化碳压力的非线性效应可能是由于二丁胺与二氧化碳反应, 导致二丁胺对甲酸的稳定化效应随二丁胺的量的变化而变化的结果, 该假设得到对照实验的验证.

关键词: 二氧化碳, RuCl3/DPPE, 催化氢, N, N-二正丁基甲酰胺, 甲酰化

The catalytic hydrogenation of carbon dioxide in the presence of dibutylamine promoted by RuCl3/DPPE has been studied, and the new preparation pathway of N,N-dibutylformylamide has been explored. The effects of temperature, solvent, and the initial pressure of carbon dioxide and hydrogen on the catalytic reaction have been investigated. The turnover number of the reaction was measured by GC and the structure of products was characterized by NMR. The TON (turnover number, mole of product per mole of catalyst) increased with temperature until 120 ℃, then declined. At 4 MPa pressure of CO2, the TON increased with pressure of H2, while at 4 MPa pressure of H2, the TON increased with pressure of CO2 until the pressure of CO2 was up to 6 MPa, then declined. However, at 10 MPa pressure of H2, the TON increased with pressure of CO2. The nonlinear effect of the pressure of CO2 may be due to the reduced stability of dibutylamine to formic acid caused by competition reactions between CO2 and formic acid with dibutylamine. This assumption has been confirmed by the contrast reactions.

Key words: carbon dioxide, RuCl3/DPPE, catalytic hydrogenation, N,N-dibutylformamide, formylation