Premium
Benzo‐1,2,3,4‐tetrazine 1,3‐Dioxides: Synthesis and NMR Study
Author(s) -
Churakov Aleksandr M.,
Smirnov Oleg Yu.,
Ioffe Sema L.,
Strelenko Yuri A.,
Tartakovsky Vladimir A.
Publication year - 2002
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 - 10.1002/1099-0690(200207)2002:14<2342::aid-ejoc2342>3.0.co;2-h
Subject(s) - azoxy , chemistry , tetrazine , ring (chemistry) , medicinal chemistry , nitro , nitrogen atom , nitrogen , combinatorial chemistry , organic chemistry , alkyl
Benzo‐1,2,3,4‐tetrazine 1,3‐dioxides (BTDOs) represent fairly stable high‐nitrogen systems, incorporating two head‐to‐tail linked azoxy groups. The synthetic pathway to these heterocycles suggested the use of the tert ‐butyl‐ NNO ‐azoxy group as a building block, allowing the first azoxy group to be incorporated into the ring. The second azoxy group was added with the help of the oxodiazonium ion (−N=N=O + ) or its synthetic equivalent. This could be generated by two new methods. The first of these involved treatment of N ‐nitroamines with nitrating agents, and the second treatment of diazonium salts with peracids in the presence of a base. The proposed key stage in the tetrazine 1,3‐bis( N ‐oxide) ring formation is the reaction between the oxodiazonium ion and the distal nitrogen atom of the tert ‐butyl‐ NNO ‐azoxy group, followed by elimination of the tert ‐butyl cation. The syntheses of bromo‐BTDOs 3b−f and nitro‐BTDOs 4a−c are described. The BTDOs were characterized by NMR, including 14 N and 15 N experiments. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)