ISSN:
1434-193X
Keywords:
Nitrosobenzenes
;
ortho-Nitrosoanilines
;
2-Nitroso-1,3-phenylenediamines
;
Nucleophilic aromatic substitution
;
Oxidative nucleophilic substitution of hydrogen
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
-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.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
Permalink
