118. Reaction monitoring by Benchtop NMR spectroscopy using a novel stationary flow reactor setup

Anne Friebel, Erik von Harbou, Kerstin Münnemann, and Hans Hasse, Industrial & Engineering Chemistry Research, (2019) DOI: 10.1021/acs.iecr.9b03048

A flow reactor setup for non-invasive monitoring of reactions using a compact medium field nuclear magnetic resonance (NMR) spectrometer is presented, in which a tubular flow reactor is inserted into the bore of the NMR spectrometer and operated at stationary conditions. To monitor the composition change of reaction mixture in the flow reactor, the entire reactor is moved to different longitudinal positions in the bore. As the flow is stationary, the composition of the reaction mixture does not change with time at a fixed reactor position. Thus, also time-consuming 2D NMR techniques can be applied to elucidate unknown products. As quantitative information is obtained directly from the NMR spectrum without calibration, the method is also appropriate for quantifying substances that are unstable as pure components. As test cases, two esterification reactions, the formation of methyl formate (MF) and the formation of methyl acetate (MA) from the pure alcohols and acids, were investigated using this technique. In addition, three 2D NMR pulse sequences (H-H-COSY, HETCOR, and HMBC) were applied in flow. The comparison of the results of the present work to literature data shows that the new method gives reliable results.