Imide‐ N ‐Oxyl Radicals in the Synthesis of Functionalized Azocompounds From Azines via Challenging Radical Addition to C═N─N═C Fragment

Imide‐ N ‐Oxyl Radicals in the Synthesis of Functionalized Azocompounds From Azines via Challenging Radical Addition to C═N─N═C Fragment Full article

Journal

European Journal of Organic Chemistry
ISSN: 1434-193X , E-ISSN: 1099-0690

Output data

Year: 2026, Article number : e70672, Pages count : DOI: 10.1002/ejoc.70672

Authors

Shevchenko Mikhail I. ¹ , Budnikov Alexander S. ¹ , Monin Fedor K. ^2,1 , Krylov Igor B. ¹ , Sokova Lyubov’ L. ¹ , Terent’ev Alexander O. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences Moscow Russian Federation
2	M. V. Lomonosov Moscow State University Moscow Russian Federation

Azines are easily available products of condensation between carbonyl compounds and hydrazine and at first glance look like perfect radical acceptors, azadienes. However, their free-radical chemistry is almost not developed due to relative inertness associated with the unusual behavior of the C═N─N═C fragment as a “conjugation stopper”. In the present work, the radical functionalization of azines by the addition of imide-N-oxyl radicals affording of bis-(imide-N-oxy) azocompounds is reported. The transformation proceeds through the generation of imide-N-oxyl radicals from N-hydroxyimides under room temperature and metal-free conditions. It is noteworthy that the addition of two equivalents of N-oxyl radicals occurs selectively, without the formation of products of hydrogen atom abstraction or other transformations of intermediate N, C-centered radicals (oxidation, dimerization, fragmentation, etc.). A broad range of ketazines and aldazines derived from aromatic and aliphatic carbonyl compounds are efficiently converted, demonstrating good functional-group tolerance. Notably, thermal decomposition of the NHPI-derived azo-ethers was found to generate phthalimide radicals. This work expands the radical chemistry of azines and provides a rare one-step approach to azo-ethers from readily accessible azines and N-hydroxyimides.

Shevchenko M.I. , Budnikov A.S. , Monin F.K. , Krylov I.B. , Sokova L.L. , Terent’ev A.O.
Imide‐ N ‐Oxyl Radicals in the Synthesis of Functionalized Azocompounds From Azines via Challenging Radical Addition to C═N─N═C Fragment
European Journal of Organic Chemistry. 2026. e70672 . DOI: 10.1002/ejoc.70672 OpenAlex

Submitted:	Mar 20, 2026
Published print:	Jul 15, 2026

≡ OpenAlex:

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