Carmeli Mira, Rozen Shlomo
School of Chemistry, Tel-Aviv University, Tel-Aviv 69978, Israel.
J Org Chem. 2006 Jun 9;71(12):4585-9. doi: 10.1021/jo060440u.
The HOF.CH3CN complex, readily prepared by passing F2 through aqueous acetonitrile, is an exceptionally efficient oxygen transfer agent. It is unique in its capacity to oxidize various azides into the corresponding nitro derivatives. This method requires short reactions times and room temperature or below, and the desired nitro compounds were usually isolated in very good yields. The respective nitroso derivatives are believed to be the intermediates in this reaction. Functional groups such as aromatic rings, ketones, nitriles, halides, alcohols, and esters are tolerated. Sulfides react with HOF.CH3CN usually at the same rate as azides. Amines and olefins, however, react faster, so they have to be protected first. Nitro derivatives with various oxygen isotopes can be made using the labeled H18OF.CH3CN. In the case of chiral azides the stereochemistry around the nitrogen-bonded carbons is retained.
通过让F₂通过乙腈水溶液很容易制备出的HOF·CH₃CN配合物，是一种极其高效的氧转移剂。它在将各种叠氮化物氧化成相应硝基衍生物的能力方面很独特。该方法反应时间短，在室温或室温以下进行，所需的硝基化合物通常以非常高的产率分离出来。据信相应的亚硝基衍生物是该反应的中间体。诸如芳环、酮、腈、卤化物、醇和酯等官能团都能耐受。硫化物与HOF·CH₃CN的反应速率通常与叠氮化物相同。然而，胺和烯烃反应更快，所以必须先进行保护。使用标记的H¹⁸OF·CH₃CN可以制备出含有各种氧同位素的硝基衍生物。在手性叠氮化物的情况下，与氮相连的碳原子周围的立体化学得以保留。
