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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >'Solventless' continuous flow homogeneous hydroformylation of 1-octene
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'Solventless' continuous flow homogeneous hydroformylation of 1-octene

机译：1-辛烯的“无溶剂”连续流均相加氢甲酰化

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The hydroformylation of 1-octene under continuous flow conditions is described. The system involves dissolving the catalyst, made in situ from [ Rh(acac)(CO)(2)] (acacH = 2,4- pentanedione) and [RMIM][TPPMS] ( RMIM = 1-propyl (Pr), 1-pentyl (Pn) or 1-octyl (O)-3-methyl imidazolium, TPPMS = Ph2P(3-C6H4SO3)), in a mixture of nonanal and 1-octene and passing the substrate, 1-octene, together with CO and H-2 through the system dissolved in supercritical CO2 (scCO(2)). [PrMIM][TPPMS] is poorly soluble in the medium so heavy rhodium leaching (as complexes not containing phosphine) occurs in the early part of the reaction. [PnMIM][ PPMS] affords good rates at relatively low catalyst loadings and relatively low overall pressure (125 bar) with rhodium losses < 1 ppm, but the catalyst precipitates at higher catalyst loadings, leading to lower reaction rates. [OMIM][ TPPMS] is the most soluble ligand and promotes high reaction rates, although preliminary experiments suggested that rhodium leaching was high at 5-10 ppm. Optimisation aimed at balancing flows so that the level within the reactor remained constant involved a reactor set up based around a reactor fitted with a sight glass and sparging stirrer with the CO2 being fed by a cooled head HPLC pump, 1-octene by a standard HPLC pump and CO/H-2 through a mass flow controller. The pressure was controlled by a back pressure regulator. Using this set up, [OMIM][ TPPMS] as the ligand and a total pressure of 140 bar, it was possible to control the level within the reactor and obtain a turnover frequency of ca. 180 h(-1). Rhodium losses in the optimised system were 100 ppb. Transport studies showed that 1-octene is preferentially transported over the aldehydes at all pressures, although the difference in mol fraction in the mobile phase was less at lower pressures. Nonanal in the mobile phase suppresses the extraction of 1-octene to some extent, so it is better to operate at high conversion and low pressure to optimise the extraction of the products relative to the substrate. CO and H2 in the mobile phase also suppress the extraction effciency by as much as 80%.
机译：描述了在连续流动条件下1-辛烯的加氢甲酰化。该系统涉及溶解由[Rh（acac）（CO）（2）]（acacH = 2,4- pentanedione）和[RMIM] [TPPMS]（RMIM = 1-propyl（Pr），1 -戊基（Pn）或1-辛基（O）-3-甲基咪唑，TPPMS = Ph2P（3-C6H4SO3）），在壬醛和1-辛烯的混合物中，并通过底物1-辛烯与CO和H-2通过系统溶解在超临界CO2（scCO（2））中。 [PrMIM] [TPPMS]在介质中的溶解度很差，因此在反应的早期会发生大量的铑浸出（因为不含膦的复合物）。 [PnMIM] [PPMS]在相对较低的催化剂负载量和相对较低的总压力（125 bar）且铑损失<1 ppm的情况下提供了良好的速率，但是催化剂在较高的催化剂负载量下会沉淀，导致较低的反应速率。 [OMIM] [TPPMS]是最易溶的配体，可促进高反应速率，尽管初步实验表明铑的浸出率高达5-10 ppm。旨在平衡流量的优化，以使反应器内的液位保持恒定，这是基于一个装有观察镜和鼓泡搅拌器的反应器而建立的，该反应器的CO2由冷却头HPLC泵进料，1-辛烯由标准HPLC进料泵和CO / H-2通过质量流量控制器。压力由背压调节器控制。使用[OMIM] [TPPMS]作为配体，总压力为140 bar，可以控制反应器内的液位，并获得约20的周转频率。 180小时（-1）。优化系统中的铑损失为100 ppb。迁移研究表明，尽管在较低压力下流动相中摩尔分数的差异较小，但在所有压力下1-辛烯均比醛优先迁移。流动相中的壬醛在一定程度上抑制了1-辛烯的萃取，因此最好在高转化率和低压下操作，以相对于底物优化产物的萃取。流动相中的CO和H2也会抑制提取效率高达80％。

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