Synthesis of monodisperse oligo(1,4-phenyleneethynylene-alt-1,4-triptycyleneethynylene)s.
Synthesis of monodisperse oligo(1,4-phenyleneethynylene-alt-1,4-triptycyleneethynylene)s.
复制标题
单分散低聚(1,4-亚苯基乙炔基-alt-1,4-三亚苯乙烯基)的合成。
作者：
D. Maag;T. Kottke;Miriam Schulte;A. Godt
本文报道了一种单分散的低聚对苯乙炔8a（n）的合成方法，该低聚对苯乙炔8a（n）的结构单元为2，5-二己基-1，4-苯撑和6，1,4-二叔丁基-1，4-三苯撑交替排列，炔端基为正交保护基。从6，1,4-二叔丁基-1-（2-三异丙基甲硅烷基乙炔基）-4-（2-三甲基甲硅烷基乙炔基）三蝶烯（5a）、1，4-二己基-2，5-二碘苯（10）和1，4-二己基-2-碘-5-（3-羟基丙-1-炔基）苯（9）开始，以炔基-芳基（Sonogashira-Hagihara）偶联为关键反应，通过部分发散-收敛路线合成了8个亚苯基亚乙炔基单元。起始化合物5a由三蝶烯醌通过以下顺序制备：加入2-三烷基甲硅烷基乙炔基锂，还原并伴随消除水，将苯酚转化为三氟甲磺酸酯，最后与三烷基甲硅烷基乙炔进行Pd/Cu催化的偶联。本文报道了一种类似的方法，通过严格的发散-收敛路线得到关键化合物6，14-二叔丁基-1-（3-羟基丁-1-炔基）-4-（2-三异丙基硅基乙炔基）三蝶烯（6）。低聚物8a（n）和相应的低聚物（2，5-二己基-1，4-亚苯基乙炔基）在稀溶液中的光学性质几乎相同，而它们对于固体、未稀释的化合物则显著不同。
The synthesis of monodisperse oligo(p-phenyleneethynylene)s 8a(n) with alternating 2,5-dihexyl-1,4-phenylene and 6,14-di-tert-butyl-1,4-triptycylene units and orthogonally protected alkyne end groups is reported. Starting from 6,14-di-tert-butyl-1-(2-triisopropylsilylethynyl)-4-(2-trimethylsilylethynyl)triptycene (5a), 1,4-dihexyl-2,5-diiodobenzene (10), and 1,4-dihexyl-2-iodo-5-(3-hydroxyprop-1-ynyl)benzene (9), oligomers with up to four repeating units, i.e., eight phenyleneethynylene units, were prepared through a partially divergent-convergent route with the alkynyl-aryl (Sonogashira-Hagihara) coupling as the key reaction. The starting compound 5a was prepared from triptycenequinone through a sequence of addition of 2-trialkylsilylethynyllithium, reduction and concomitant elimination of water, conversion of the phenol into a triflate, and finally Pd/Cu-catalyzed coupling with trialkylsilylethyne. A similar access to the key compound for a stringent divergent-convergent route, 6,14-di-tert-butyl-1-(3-hydroxybut-1-ynyl)-4-(2-triisopropylsilylethynyl)triptycene (6), is reported. The optical properties of the oligomers 8a(n) and the corresponding oligo(2,5-dihexyl-1,4-phenyleneethynylene)s in dilute solution are almost identical, whereas they differ significantly for the solid, undiluted compounds.