Several primary amines 2 have been oxidized with dimethyldioxirane (1) under a variety of conditions. Mixtures of dimeric nitrosoalkanes 4 and oximes 5 were typically obtained with solutions of the oxidant in excess. In several instances, nitrones 12 were found as byproducts in these reactions. In situ oxidations using oxone in buffered aqueous acetone solution also gave nitrosoalkanes 4 and oximes 3 as important products; in addition, oxaziridines 11 were obtained in significant amounts in biphasic procedures containing methylene chloride. The corresponding nitroalkanes 3 were not formed in major amounts in either oxidation procedure, unless large excesses of oxidant were used. These results are discussed in terms of the several competing processes which occur under the different reaction conditions.
Methyltrioxorhenium-Catalyzed Oxidation of Secondary and Primary Amines with Hydrogen Peroxide
作者:Shigekazu Yamazaki
DOI:10.1246/bcsj.70.877
日期:1997.4
The methyltrioxorhenium-catalyzed oxidation of secondaryamines and primaryamines with hydrogen peroxide has been carried out. The oxidation of secondaryamines afforded nitrones in good-to-excellent yield. Benzylamines were selectively oxidized to oximes, while general primary alkylamines possessing the α-C–H bond gave mixtures of oximes, nitroso dimers, and azoxy compounds.