Synthesis 2018; 50(17): 3520-3530
DOI: 10.1055/s-0037-1610173
paper
© Georg Thieme Verlag Stuttgart · New York

SN H Arylamination of 3-Nitropyridine: A Competitive Formation of 2-Arylamino-5-nitropyridines and 2-Arylamino-5-nitrosopyridines

Department of Chemistry, North Caucasus Federal University, Pushkin st. 1, Stavropol, 355009, Russia   Email: ivborovlev@rambler.ru
,
Oleg P. Demidov
Department of Chemistry, North Caucasus Federal University, Pushkin st. 1, Stavropol, 355009, Russia   Email: ivborovlev@rambler.ru
,
Gulminat A. Amangasieva
Department of Chemistry, North Caucasus Federal University, Pushkin st. 1, Stavropol, 355009, Russia   Email: ivborovlev@rambler.ru
,
Elena K. Avakyan
Department of Chemistry, North Caucasus Federal University, Pushkin st. 1, Stavropol, 355009, Russia   Email: ivborovlev@rambler.ru
,
Anastasia A. Borovleva
Department of Chemistry, North Caucasus Federal University, Pushkin st. 1, Stavropol, 355009, Russia   Email: ivborovlev@rambler.ru
,
Diana Yu. Pobedinskaya
Department of Chemistry, North Caucasus Federal University, Pushkin st. 1, Stavropol, 355009, Russia   Email: ivborovlev@rambler.ru
› Author Affiliations
This project received financial support from the Ministry of Education and Science of the Russian Federation in the framework of the State Assignment to the Higher Education Institutions № 4.6306.2017/8.9.
Further Information

Publication History

Received: 07 March 2018

Accepted after revision: 04 May 2018

Publication Date:
19 June 2018 (online)

Abstract

Arylamination of 3-nitropyridine via the nucleophilic substitution of hydrogen leads to a mixture of 2-arylamino-5-nitropyridines and novel 2-arylamino-5-nitrosopyridines, with the latter as the major product. The proposed mechanism includes the formation of σH-adducts and their further aromatization proceeding either through an oxidative pathway or intramolecular Red/Ox pathway of the SN H reaction. Moreover, we have shown that nitroso compounds can be selectively oxidized with m-chloroperbenzoic acid to give the corresponding nitro derivatives or their N-oxides, depending on the reaction temperature and the amount of oxidant.

Supporting Information

 
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