Graduate School of Science and Technology , Shinshu University , Matsumoto 390-8621 , Japan.
Graduate School of Science and Technology , Hirosaki University , Hirosaki 036-8561 , Japan.
J Org Chem. 2019 Feb 1;84(3):1257-1275. doi: 10.1021/acs.joc.8b02648. Epub 2019 Jan 15.
The nucleophilic aromatic substitution (SAr) 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% HPO. The reactivity of 6-aminoazulenes toward the bromination, SAr, and palladium-catalyzed cross-coupling reactions was also clarified. 6-Arylazoazulenes 13a-13c were also prepared via the SAr reaction of 1 with arylhydrazines, followed by oxidation with Pb(OAc) in the presence of NH. 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.
二乙酯基 6-溴位蓝花素-1,3-二羧酸酯（1）与各种胺的亲核芳香取代（SAr）反应以良好至优异的收率得到相应的 6-氨基位蓝花素衍生物 2a-2j。通过用 100% HPO 对 2a-2f 进行脱酯化反应，得到没有 1,3-二乙氧羰基功能的 6-氨基位蓝花素衍生物 3a-3f。6-氨基位蓝花素对溴化、SAr 和钯催化交叉偶联反应的反应性也得到了阐明。6-芳基偶氮位蓝花素 13a-13c 也通过 1 与芳肼的 SAr 反应，然后在 NH 存在下用 Pb(OAc) 氧化制备。6-氨基-和 6-芳基偶氮位蓝花素的结构、光学和电化学性质通过单晶 X 射线结构分析、紫外/可见光谱、伏安法分析、光谱电化学和理论计算揭示。
