5670-74-6Relevant academic research and scientific papers
Nucleophilic aromatic substitution of hydrogen in the reaction of tert- alkylamines with nitrosobenzenes - Synthesis and NMR study of N-(tert-alkyl)- ortho-nitrosoanilines
Lipilin, Dmitriy L.,Churakov, Aleksandr M.,Ioffe, Sema L.,Strelenko, Yuri A.,Tartakovsky, Vladimir A.
, p. 29 - 35 (1999)
The reaction of primary amines bearing tertiary alkyl groups (e.g. R- NH2; R = tBu, 1-adamantyl) with nitrosobenzenes has been found to proceed by oxidative nucleophilic aromatic substitution of hydrogen, thereby affording N-(tert-alkyl)ortho- and -para-nitrosoanilines. The replacement of hydrogen proceeds more rapidly than the replacement of ortho- or para-nitro or -bromo substituents. With p-nitronitrosobenzene, both ortho-hydrogen atoms are substituted to afford N,N'-di(tert-alkyl)-4-nitro-2-nitroso-1,3- phenylenediamines 8a,b. The addition of oxidizing agents (e.g. MnO2) increases the yield of products. 1H-, 13C-, 14N- and 15N-NMR studies have confirmed the structures of the compounds under investigation. In ortho- nitrosoanilines, the rotamer with the nitroso group syn to the amino group is favored.
