使用 IBX/TBAF 作为硝化剂的硝基甲烷：在温和条件下从仲或叔胺合成亚硝胺。

Nitromethane with IBX/TBAF as a nitrosating agent: synthesis of nitrosamines from secondary or tertiary amines under mild conditions.

机构信息

Meyers Institute for Interdisciplinary Research in Organic and Medicinal Chemistry and Department of Chemistry and Biochemistry, Southern Illinois University, Carbondale, Illinois 62901, United States.

出版信息

J Org Chem. 2012 Jan 6;77(1):626-31. doi: 10.1021/jo202276x. Epub 2011 Dec 19.

DOI:10.1021/jo202276x

PMID:22148366

Abstract

Aliphatic or aromatic N,N-disubstituted nitrosamine was generated in fair to excellent yield from the reaction of a secondary or tertiary amine with o-iodoxybenzoic acid (IBX) or o-iodosylbenzoic acid (IBA)/R(4)NX (X = halide) and nitromethane. The product yield was strongly influenced by both the halide of R(4)NX and iodanes. IBX gave a higher yield than IBA, while the halides follow F(-) > Cl(-) > Br(-) ∼ I(-). Nitrous acid formed in situ from nitromethane and IBX (or IBA)/halides is likely responsible for the observed reaction.

摘要

脂肪族或芳香族 N,N-二取代亚硝胺可以由仲胺或叔胺与邻碘酰基苯甲酸（IBX）或邻碘代过氧苯甲酸（IBA）/R(4)NX（X = 卤素）和硝基甲烷反应生成，产率适中到很高。产物的产率受到 R(4)NX 和碘烷的卤素的强烈影响。IBX 的产率高于 IBA，而卤素则遵循 F(-) > Cl(-) > Br(-) ∼ I(-)。由硝基甲烷和 IBX（或 IBA）/卤化物原位形成的亚硝酸可能是导致观察到的反应的原因。