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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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Published in: | Journal of organic chemistry 2019-02, Vol.84 (3), p.1257-1275 |
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Main Authors: | , , , , , , , , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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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. |
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ISSN: | 0022-3263 1520-6904 |
DOI: | 10.1021/acs.joc.8b02648 |