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Synthesis of 6‑Amino- and 6‑Arylazoazulenes via Nucleophilic Aromatic Substitution and Their Reactivity and Properties

The nucleophilic aromatic substitution (SNAr) reaction of diethyl 6-bromoazulene-1,3-dicarboxylate (1) with a variety of amines afforded the corresponding 6-aminoazulene derivatives 2a–2j in good-to-excellent yields. 6-Aminoazulene derivatives 3a–3f without the 1,3-diethoxycarbonyl functions were ob...

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Bibliographic Details
Published in:Journal of organic chemistry 2019-02, Vol.84 (3), p.1257-1275
Main Authors: Shoji, Taku, Sugiyama, Shuhei, Takeuchi, Mutsumi, Ohta, Akira, Sekiguchi, Ryuta, Ito, Shunji, Yatsu, Tomoaki, Okujima, Tetsuo, Yasunami, Masafumi
Format: Article
Language:English
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Summary:The nucleophilic aromatic substitution (SNAr) reaction of diethyl 6-bromoazulene-1,3-dicarboxylate (1) with a variety of amines afforded the corresponding 6-aminoazulene derivatives 2a–2j in good-to-excellent yields. 6-Aminoazulene derivatives 3a–3f without the 1,3-diethoxycarbonyl functions were obtained by the deesterification of 2a–2f with 100% H3PO4. The reactivity of 6-aminoazulenes toward the bromination, SNAr, and palladium-catalyzed cross-coupling reactions was also clarified. 6-Arylazoazulenes 13a–13c were also prepared via the SNAr reaction of 1 with arylhydrazines, followed by oxidation with Pb­(OAc)4 in the presence of N2H4. The structural, optical, and electrochemical properties of the 6-amino- and 6-arylazoazulenes were revealed by single-crystal X-ray structure analysis, UV/vis spectroscopy, voltammetry analysis, spectroelectrochemistry, and theoretical calculations.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.8b02648