摘要
本文以咔唑为原料,经碘化和N烷基化形成N-已基-3.6-二碘咔唑,再以丁炔醇为炔基化试剂发生Sonogashira偶联,碱促进下裂解生成N-己基-3,6-二乙炔基咔唑,总产率45%。同时,以类似的方法还合成了2,7-二乙炔基-9.9'-二己基咔唑,总产率为39%。并经1H NMR、13C NMR和HRMS确认了反应产物及其中间体的分子结构。
利用Tamao-Yamaguchi法合成了2,5-二溴-1,1-二甲基-3.4-二苯基噻咯,并通过解析1H和13C谱,确认了其结构。利用Sonogashira偶联反应合成了噻咯-二乙炔基咔唑PS-DyCz和噻咯-二乙炔基芴聚合物PS-DyF,总产率分别为37%和40%。聚合物PS-DyCz和PS-DyF分子量分别为Mn=4562 Da,Mw=12045 Da；Mn=14277 Da,Mw=38266 Da,聚合度分别为8,22。PS-DyCz和PS-DyF对热都很稳定,分解温度分别是319°C和341℃。PS-DyCz和PS-DyF的最大吸收峰分别为380、467 nm和391、418 nm;最大发射峰分别为542、569 nm和429、460 nm；基于紫外吸收边缘估算光学能带隙分别是2.25和2.70 eV。在B3LYP/6-31G*水平上的DFM计算表明HOMO轨道上电子确实主要分布在乙炔芳香环和噻咯环,而LUMO轨道上电子主要离域在噻咯环和乙炔基。
以对二溴苯为原料和三甲基硅基乙炔为炔基化试剂,经Sonogashira偶联并脱三甲基硅基合成了对二乙炔基苯。控制原料的摩尔比合成了单取代的芴和咔唑。利用硅胶催化法高效地合成了二溴咔唑,产率高达97%。通过四步合成了低能带隙的4,7-二噻吩苯并噻二唑,并用NBS单溴化得到4-(5-溴-2-噻吩)-7-(2-噻吩)-2,1,3-苯并噻二唑。以上化合物的结构均通过1H和13C谱确认了化学结构。
N-Hexyl-3,6-diiodocarbazole was prepared from carbazole by diiodonation reaction and N-alkylation reaction. Subsequently, N-Hexyl-3.6-diethynylcarbazole was synthesized by Sonogashira coupling with 3-methyl-1-butyn-3-ol and base-promoted cracking reaction with an overall yield of 45% based on carbazole. The synthetic procedure of 2,7-diethynyl-9,9'-dihexylfluorene is analogous to that described for N-Hexyl-3,6-diethynylcarbazole with an overall yield of 39% based on fluorene. Their chemical structures were confirmed by 1H NMR.13CNMR and HRMS.
2,5-dibromosilole was synthesized by Tamao-Yamaguchi's endo-endo intramolecular reductive cyclization, with diphenylethynylsilane as the starting material, and the results of 1H and 13C NMR spectra confirmed the molecular structure. Poly(silole-diethynylcarbazole) (PS-DyCz) and poly(silole-diethynylfluorene) (PS-DyF) were then successfully synthesized by Sonogashira coupling reaction in 37% and 40% yield, respectively. The molecuar weights are Mn=4562 Da, Mw=12045 Da for PS-DyCz, and Mn=14277 Da, Mw=38266 Da for PS-DyF. The degree of polymerization is 8 for PS-DyCz and 22 for PS-DyF, respectively. PS-DyCz and PS-DyF are thermally stable with decomposition temperatures of 319℃and 341℃, respectively. The maximum absorption and emission wavelength of PS-DyCz and PS-DyF are 380/467 nm,391/418 nm and 542/569 nm.429/460 nm. The optical band gaps are 2.25 eV for PS-DyCz and 2.70 eV for PS-DyF based on the absorption onset. DFT calculations were performed at B3LYP/6-31G* level, and the results suggest that the HOMOs are distributed over both acetenyl aromatics and Silole rings, but the LUMOs are mainly localized in the Silole ring and ethynyl spacer.
Finally,1,4-diethynylbenzene were synthesized by Sonogashira coupling with two steps. The monosubstituent fluorene/carbazole was synthesized by controlling the molar ratio of reactors. Dibomocarbazole was efficiently synthesized by silica gel catalyzation in 97% yield. 4,7-dithienyl-2,1,3-benzothiadiazole was synthesized through four steps, then monobrominated with NBS to give 4-(5-bromo-2-thienyl)-7-(2-thienyl)-2,1,3-benzothiadi-azole, their chemical structures were confirmed by 1H NMR and 13CNMR.
引文
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