Lezcano-González Inés, Boronat Mercedes, Blasco Teresa
Instituto de Tecnología Química, Avda. de los Naranjos s/n, 46022 Valencia, Spain.
Solid State Nucl Magn Reson. 2009 Apr;35(2):120-9. doi: 10.1016/j.ssnmr.2009.02.001. Epub 2009 Feb 20.
In the last years, 'in situ' solid-state NMR has been applied to investigate the Beckmann rearrangement of oximes into amides using zeolites and mesoporous materials of different structure containing Brønsted acids or silanol groups as active sites. DFT methods have been applied to model the geometry of the complexes resulting from adsorption of reactants, reaction intermediates and products on clusters representing the zeolite centers, and their (15)N and (13)C NMR chemical shift calculated theoretically. This article reviews the results reported in the bibliography on the Beckmann rearrangement of various oximes (acetophenone oxime, cyclohexanone oxime and cyclododecanone oxime) mainly using 'in situ'(15)N NMR spectroscopy and theoretical calculations, and are compared with those obtained by 'in situ' infrared spectroscopy. The combination of experiment and theory has been shown to be very useful for the interpretation of the NMR spectra and the identification of the species present at different reaction temperatures.
在过去几年中，“原位”固态核磁共振已被用于研究肟在沸石和具有不同结构的介孔材料（含有布朗斯特酸或硅醇基团作为活性位点）作用下重排为酰胺的反应。密度泛函理论（DFT）方法已被用于模拟反应物、反应中间体和产物吸附在代表沸石中心的簇上所形成配合物的几何结构，并从理论上计算它们的（15）N和（13）C核磁共振化学位移。本文综述了文献中报道的主要使用“原位”（15）N核磁共振光谱和理论计算对各种肟（苯乙酮肟、环己酮肟和环十二酮肟）进行贝克曼重排的结果，并与通过“原位”红外光谱获得的结果进行了比较。实验与理论相结合已被证明对解释核磁共振光谱以及识别不同反应温度下存在的物种非常有用。
