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Nucleophilic Aromatic Substitution of Hydrogen in the Reaction of tert ‐Alkylamines with Nitrosobenzenes – Synthesis and NMR Study of N ‐( tert ‐Alkyl)‐ ortho ‐nitrosoanilines
Author(s) -
Lipilin Dmitriy L.,
Churakov Aleksandr M.,
Ioffe Sema L.,
Strelenko Yuri A.,
Tartakovsky Vladimir A.
Publication year - 1999
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199901)1999:1<29::aid-ejoc29>3.0.co;2-m
Subject(s) - chemistry , alkyl , nucleophilic substitution , nitroso , nitro , medicinal chemistry , yield (engineering) , nucleophile , nucleophilic aromatic substitution , oxidizing agent , stereochemistry , organic chemistry , catalysis , materials science , metallurgy
The reaction of primary amines bearing tertiary alkyl groups (e.g. R–NH 2 ; R = t Bu, 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. MnO 2 ) increases the yield of products. 1 H‐, 13 C‐, 14 N‐ and 15 N‐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.