ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Rearrangement of N -(3-pyridyl)nitramine

Grzegorz P. Spaleniak, Zdzisław Daszkiewicz, and Janusz B. Kyzioł

Institute of Chemistry, University of Opole, 45-052 Opole, Oleska 48, Poland

E-mail: grzegorz.spaleniak@uni.opole.pl

Received: 21 September 2007  Revised: 6 June 2008  Accepted: 9 June 2008

Abstract: Contrary to other N-(pyridyl)nitramines, the title compound cannot be rearranged to 3-amino-2-nitropyridine or other isomers. Hypothetical products of its transformation under influence of concentrated sulphuric acid, viz. 3-hydroxypyridine, 3,3′-azoxypyridine and 3,3′-azopyridine, were obtained from 3-nitro- and 3-aminopyridine in oxidation and reduction reactions. N-(3-Pyridyl)nitramine was prepared and rearranged in concentrated sulphuric acid. 3-Hydroxypyridine and 3,3′-azoxypyridine were isolated from the reaction mixture, other products were identified by the HPLC and GCMS methods. The results indicate that N-(3-pyridyl)hydroxylamine is an intermediate formed from N-(3-pyridyl)nitramine under the influence of concentrated sulphuric acid. The reaction path, leading to the final products, is discussed in context of the mechanism of nitramine rearrangement.

Keywords: nitramine rearrangement - nitro-to-nitrito transformation - azopyridines - azoxypyridines

Full paper is available at www.springerlink.com.

DOI: 10.2478/s11696-008-0099-7

Chemical Papers 63 (3) 313–322 (2009)