Fujimoto Keisuke, Takimoto Satoshi, Masuda Shota, Inuzuka Toshiyasu, Sanada Kazutaka, Sakamoto Masami, Takahashi Masaki
Department of Applied Chemistry, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Naka-ku, Hamamatsu, 432-8561, Japan.
Division of Instrumental Analysis, Life Science Research Center, Gifu University, 1-1 Yanagido, Gifu, 501-1193, Japan.
Chemistry. 2021 Jun 21;27(35):8951-8955. doi: 10.1002/chem.202100944. Epub 2021 May 17.
5,11-Diazadibenzo[hi,qr]tetracene was synthesized as a new nitrogen-substituted polycyclic heteroaromatic compound by Pd-catalyzed cycloisomerization of an alkyne precursor followed by oxidative cyclization with bis(trifluoroacetoxy)iodobenzene. The substitution of imine-type nitrogen atoms significantly enhanced its electron-accepting character and facilitated the direct nucleophilic addition of arylamines under strongly basic conditions to afford the desired amino-substituted products. The introduction of amino groups induced a remarkable red-shift in their absorption spectra; the tetrasubstituted product exhibited intense near-infrared absorbing property. Furthermore, the π-electronic system, which includes a redox-active 1,4-diazabutadiene moiety, underwent reversible interconversion to its corresponding reduced form upon reduction with NaBH and aerobic oxidation.
通过炔烃前体的钯催化环异构化反应，随后用双（三氟乙酰氧基）碘苯进行氧化环化反应，合成了5,11-二氮杂二苯并[hi,qr]四并苯作为一种新型的氮取代多环杂芳族化合物。亚胺型氮原子的取代显著增强了其吸电子特性，并促进了在强碱性条件下芳胺的直接亲核加成反应，从而得到所需的氨基取代产物。氨基的引入导致其吸收光谱发生显著红移；四取代产物表现出强烈的近红外吸收特性。此外，包含氧化还原活性1,4-二氮丁二烯部分的π电子体系在用硼氢化钠还原并进行有氧氧化后，会可逆地转化为其相应的还原形式。
