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在微反应器中利用电渗流产生浓度梯度以实现立体选择性化学合成。

The generation of concentration gradients using electroosmotic flow in micro reactors allowing stereoselective chemical synthesis.

作者信息

Skelton V, Greenway G M, Haswell S J, Styring P, Morgan D O, Warrington B H, Wong S Y

机构信息

Department of Chemistry, Faculty of Science and the Environment, University of Hull, Cottingham Road, Hull, UK HU6 7RX.

出版信息

Analyst. 2001 Jan;126(1):11-3. doi: 10.1039/b006727j.

Abstract

The stereoselective control of chemical reactions has been achieved by applying electrical fields in a micro reactor generating controlled concentration gradients of the reagent streams. The chemistry based upon well-established Wittig synthesis was carried out in a micro reactor device fabricated in borosilicate glass using photolithographic and wet etching techniques. The selectivity of the cis (Z) to trans (E) isomeric ratio in the product synthesised was controlled by varying the applied voltages to the reagent reservoirs within the micro reactor. This subsequently altered the relative reagent concentrations within the device resulting in Z/E ratios in the range 0.57-5.21. By comparison, a traditional batch method based on the same reaction length, concentration, solvent and stoichiometry (i.e., 1.0:1.5:1.0 reagent ratios) gave a Z/E in the range 2.8-3.0. However, when the stoichiometric ratios were varied up to ten times as much, the Z/E ratios varied in accordance to the micro reactor i.e., when the aldehyde is in excess, the Z isomer predominates whereas when the aldehyde is in low concentrations, the E isomer is the more favourable form. Thus indicating that localised concentration gradients generated by careful flow control due to the diffusion limited non-turbulent mixing regime within a micro reactor, leads to the observed stereo selectivity for the cis and trans isomers.

摘要

通过在微反应器中施加电场来控制试剂流的浓度梯度,实现了化学反应的立体选择性控制。基于成熟的维蒂希合成的化学反应,是在一个由硼硅酸盐玻璃制成的微反应器装置中进行的,该装置采用了光刻和湿法蚀刻技术。通过改变施加到微反应器内试剂储存器的电压,来控制合成产物中顺式(Z)与反式(E)异构体比例的选择性。这随后改变了装置内试剂的相对浓度,导致Z/E比在0.57 - 5.21范围内。相比之下,基于相同反应长度、浓度、溶剂和化学计量比(即1.0:1.5:1.0的试剂比例)的传统间歇法,得到的Z/E比在2.8 - 3.0范围内。然而,当化学计量比变化高达十倍时,Z/E比根据微反应器而变化,即当醛过量时,Z异构体占主导,而当醛浓度较低时,E异构体是更有利的形式。因此表明,由于微反应器内扩散受限的非湍流混合机制,通过精确的流量控制产生的局部浓度梯度,导致了观察到的顺式和反式异构体的立体选择性。

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