Patil Vilas Venunath, Shankarling Ganapati Subray
Department of Dyestuff Technology, Institute of Chemical Technology, N. P. Marg, Matunga, Mumbai 400019, India.
J Org Chem. 2015 Aug 21;80(16):7876-83. doi: 10.1021/acs.joc.5b00582. Epub 2015 Aug 3.
Unusual regio- and chemoselective oxidation of aromatic amines hindered with ortho substituents (except -NH2, -NHCH3, and -OH) to the corresponding nitro compounds is described by use of nonanebis(peroxoic acid). The mechanistic investigation for selective oxidation of amines ortho-substituted with -NH2 or -OH showed the involvement of H-bonding between the ortho hydrogen of the adjacent -XH group (where X = NH, NR, or O) and an oxygen atom from the diperoxy acid. Various mono- and diamines are oxidized into corresponding mononitro derivatives in high yield and purity without employing any protection strategies. The protocol was also found to successful on the gram scale.
描述了使用壬二酸双（过氧酸）将被邻位取代基（-NH2、-NHCH3和-OH除外）阻碍的芳香胺选择性地区域选择性和化学选择性氧化为相应的硝基化合物。对被-NH2或-OH邻位取代的胺进行选择性氧化的机理研究表明，相邻-XH基团（其中X = NH、NR或O）的邻位氢与二过氧酸中的一个氧原子之间存在氢键作用。无需采用任何保护策略，各种单胺和二胺均可高产率、高纯度地氧化为相应的单硝基衍生物。该方法在克级规模上也被证明是成功的。
