Nucleophilic Aromatic Substitution of Hydrogen in the Reaction of tert-Alkylamines with Nitrosobenzenes – Synthesis and NMR Study of N-(tert-Alkyl)-ortho-nitrosoanilines
✍ Scribed by Dmitriy L. Lipilin; Aleksandr M. Churakov; Sema L. Ioffe; Yuri A. Strelenko; Vladimir A. Tartakovsky
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- English
- Weight
- 161 KB
- Volume
- 1999
- Category
- Article
- ISSN
- 1434-193X
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✦ Synopsis
Nucleophilic aromatic substitution / Oxidative nucleophilic substitution of hydrogen
The reaction of primary amines bearing tertiary alkyl groups substituted to afford N,NЈ-di(tert-alkyl)-4-nitro-2-nitroso-1,3phenylenediamines 8a,b. The addition of oxidizing agents (e.g. R-NH 2 ; R = tBu, 1-adamantyl) with nitrosobenzenes has been found to proceed by oxidative nucleophilic aromatic (e.g. MnO 2 ) increases the yield of products. 1 H-, 13 C-, 14 Nand 15 N-NMR studies have confirmed the structures of the substitution of hydrogen, thereby affording N-(tert-alkyl)ortho-and -para-nitrosoanilines. The replacement of compounds under investigation. In ortho-nitrosoanilines, the rotamer with the nitroso group syn to the amino group is hydrogen proceeds more rapidly than the replacement of ortho-or para-nitro or -bromo substituents. With p-favored. nitronitrosobenzene, both ortho-hydrogen atoms are the nitroso group to afford N-(tert-butyl)-o-nitrosoaniline [a]