Rhodium-Catalyzed Hydroformylation in Supercritical Carbon Dioxide
Rhodium-Catalyzed Hydroformylation in Supercritical Carbon Dioxide
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DOI：
10.1021/ja980729w
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发表时间：
1998-12
影响因子：
15
通讯作者：
D. Koch;W. Leitner
中科院分区：
文献类型：
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作者：
D. Koch;W. Leitner
超临界二氧化碳 (scCO2) 是一种环境友好的反应介质，适用于高效铑催化加氢甲酰化反应。烯烃底物可以在 scCO2 中于 40−65 °C 下加氢甲酰化，以实际定量的产率得到相应的醛。通过在线GC监测详细分析了1-辛烯在scCO2中的加氢甲酰化反应过程。温度、合成气压力和[P]/Rh比等反应参数对反应速率和选择性的影响与在常规溶剂中观察到的效果非常相似。最大周转频率 1375、500 和 115 h-1 分别被确定为当前条件下未改性、膦改性和亚磷酸酯改性体系催化活性的下限。在其他条件相同的情况下，使用未改性的催化剂，scCO2 中的加氢甲酰化速率明显高于有机溶剂或液态 CO2 中的加氢甲酰化速率。改性催化体系
Supercritical carbon dioxide (scCO2) is an environmentally benign reaction medium for highly efficient rhodium-catalyzed hydroformylation reactions. Olefinic substrates can be hydroformylated in scCO2 at 40−65 °C to give the corresponding aldehydes in practically quantitative yields. The reaction course of the hydroformylation of 1-octene in scCO2 was analyzed in detail by online-GC monitoring. The influence of reaction parameters such as temperature, synthesis gas pressure, and [P]/Rh ratio on reaction rates and selectivities is grossly similar to the effects observed in conventional solvents. Maximum turnover frequencies of 1375, 500, and 115 h-1 were determined as lower limits for the catalytic activities under the present conditions for the unmodfied, phosphine-modified, and phosphite-modified systems, respectively. With unmodified catalysts, the hydroformylation rates are considerably higher in scCO2 than in organic solvents or liquid CO2 under otherwise identical conditions. Modified catalytic syste...