3-溴-1,1,1-三氟-2-丙醇辅助二氧化碳与烯丙基缩水甘油醚偶联反应研究
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陕西省科技统筹创新工程项目


3-Bromo-1,1,1-trifluoro-2-propanol Assisted Coupling Reaction of CO2 and Allyl Glycidyl Ether
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Shaanxi science and technology innovation project (No.2015KTCL01-12)

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    摘要:

    以烯丙基缩水甘油醚(AGE)、CO2为原料,以3-溴-1,1,1-三氟-2-丙醇(BTFP)为活化剂,以四丁基溴化铵(TBAB)为有机分子催化剂,经偶联反应合成4-烯丙氧甲基-1,3-二氧环戊-2-酮(AGC)。对四丁基季铵盐和活化剂种类进行了筛选,考察了反应温度、活化剂用量、反应压力、反应时间对产物收率的影响,并提出了可能的反应机理。采用GC-MS、FTIR、NMR对目标产物进行了表征。结果表明:BTFP用量为AGE物质的量的2%,TBAB用量为AGE物质的量的2%,无需任何反应溶剂,90 ℃、0.5 MPa CO2压力下反应18h,AGC收率可达96.5%。

    Abstract:

    4-Allyloxymethyl-1,3-dioxolan-2-one (AGC) was prepared by the coupling reaction of allyl glycidyl ether (AGE) and CO2 using 3-bromo-1,1,1-trifluoro-2-propanol (BTFP) as activator. The coupling reaction was catalyzed by TBAB organocatalyst. Many kinds of quaternary ammonium salts and activators were screened. The effects of reaction temperature, activator amount, carbon dioxide pressure and reaction time on the yield of the product were investigated. A possible reaction mechanism was proposed. The product was analyzed by gas chromatography coupled with mass spectrometry (GC-MS), infrared spectroscopy (FTIR) and - nuclear magnetic resonance spectroscopy (1H-NMR, 13C-NMR). The results demonstrated that the yield of the corresponding cyclic carbonate could reach 96.5% when BTFP was 2 mol% of AGE, n-butylammonium bromide (TBAB) was 2 mol% of AGE at 0. 5 MPa CO2, 90 ℃ for 18 h under a solvent-free condition.

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马辉,谷玉杰,王博,赵波,毛伟,吕剑.3-溴-1,1,1-三氟-2-丙醇辅助二氧化碳与烯丙基缩水甘油醚偶联反应研究[J].精细化工,2018,35(6):0

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  • 收稿日期:2017-03-25
  • 最后修改日期:2017-08-13
  • 录用日期:2017-09-25
  • 在线发布日期: 2018-02-28
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