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Synthesis 2011(10): 1561-1568  
DOI: 10.1055/s-0030-1260000
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Reactions of Unsaturated Azides; Part 27: [¹] Synthesis of 1,4-Diazidobuta-1,3-dienes

Klaus Banert*a, Frank Köhlera, Antje Melzera, Ingolf Scharfa, Gerd Rheinwaldb, Tobias Rüfferb, Heinrich Langb
a Chemnitz University of Technology, Organic Chemistry, Straße der Nationen 62, 09111 Chemnitz, Germany
Fax: +49(371)53121229; e-Mail: klaus.banert@chemie.tu-chemnitz.de;
b Chemnitz University of Technology, Inorganic Chemistry, Straße der Nationen 62, 09111 Chemnitz, Germany
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Publication History

Received 28 February 2011
Publication Date:
15 April 2011 (online)

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Reactions of Unsaturated Azides; Part 27: Synthesis of 1,4-Diazidobuta-1,3-dienesSynthesis 2011; 2011(11): 1814-1814
DOI: 10.1055/s-0030-1260041

Abstract

Three different methods to prepare 1,4-diazidobuta-1,3-dienes are presented: nucleophilic substitution of electron-poor dichlorinated substrates, nucleophilic addition of hydrazoic acid at an electron-deficient diallene, and a sequence of prototropic isomerizations of propargyl sulfones followed by nucleophilic additions. In all cases, isolation and assignment of the diastereomeric products was possible, and some sequential reactions, such as reduction or 1,3-dipolar cycloaddition of the azido groups, were performed.

Key words

allenes - alkynes - azides - cycloaddition - dienes - isomerisation - nucleophilic addition - nucleophilic substitution

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11

The trans,trans structure of the higher-melting diastereoisomer of 7 was discussed,¹² and the crystal and molecular structure of dimethyl trans,trans-2,5-dichloro-muconate was determined by single-crystal X-ray diffraction techniques.¹³ In the latter case, however, neither the melting point nor other information on 7 including the method used to prepare this compound were given. Thus, the found (Z,Z)-configuration could not be assigned to the substances depicted in Scheme  [²] .