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Synthesis 2017; 49(15): 3471-3475
DOI: 10.1055/s-0036-1590685
paper
© Georg Thieme Verlag Stuttgart · New York

Solvent-Free Synthesis of Diazocine

Widukind Moormann
Otto Diels Institute for Organic Chemistry, University of Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany   Email: rherges@oc.uni-kiel.de
,
Daniel Langbehn
Otto Diels Institute for Organic Chemistry, University of Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany   Email: rherges@oc.uni-kiel.de
,
Rainer Herges*
Otto Diels Institute for Organic Chemistry, University of Kiel, Otto-Hahn-Platz 4, 24118 Kiel, Germany   Email: rherges@oc.uni-kiel.de
› Author AffiliationsThe authors gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft (DFG) within the Sonderforschungsbereich SFB677, ‘Function by Switching’.
Further Information

Publication History

Received: 17 May 2017

Accepted after revision: 29 June 2017

Publication Date:
11 July 2017 (online)

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Dedicated to Professor Herbert Mayr on the occasion of his 70th birthday

Abstract

A convenient two-step synthesis of diazocine starting from 2-nitrotoluene is described. The first step, the oxidative dimerization of 2-nitrotoluene, is improved to 95% yield. The second step, the reductive azo cyclization, is performed as a solvent-free reaction with lead powder in a ball mill (51% yield). As a reference, the previously described azo cyclization with Zn/Ba(OH)2 is investigated in detail. The results explain why in previous experiments the yields are low and extremely dependent on the reaction conditions. In view of potential applications in photopharmacology, we checked the stability under reducing conditions. Diazocine does not react with glutathione, indicating intracellular stability.

Key words

bridged azobenzene - diazocine - reductive azo-cyclization - solvent-free synthesis - oxidative C–C coupling - lead - azoxy - hydrazine - glutathione
 

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