含吡啶基四硫富瓦烯衍生物的合成、结构和电化学性质

发布时间：2018-03-12 14:45

本文选题：四硫富瓦烯　切入点：吡啶　出处：《高等学校化学学报》2017年02期 　论文类型：期刊论文

【摘要】：在乙酰乙酸乙酯和氧化亚铜共同催化下,二-(1,3-二硫环戊烯-2-硫酮-4,5-二硫)合锌酸四乙基铵盐分别与2-碘吡啶(1a)、3-碘吡啶(1b)和4-碘吡啶(1c)反应,制得硫酮化合物2,3-二(2-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2a)、2,3-二(3-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2b)和2,3-二(4-吡啶硫基)-1,3-二硫环戊烯-2-硫酮(2c).在醋酸汞催化下,硫酮化合物2a,2b和2c分别被氧化为2,3-二(2-吡啶硫基)-1,3-二硫环戊烯-2-酮(3a)、2,3-二(3-吡啶硫基)-1,3-二硫环戊烯-2-酮(3b)和2,3-二(4-吡啶硫基)-1,3-二硫环戊烯-2-酮(3c).以亚磷酸三乙酯为偶联剂,氧酮化合物3a,3b和3c分别发生自偶联反应生成2,3,6,7-四(2-吡啶硫基)四硫富瓦烯(4a)、2,3,6,7-四(3-吡啶硫基)四硫富瓦烯(4b)和2,3,6,7-四(4-吡啶硫基)四硫富瓦烯(4c).采用核磁共振波谱(NMR)、傅里叶变换红外光谱(FTIR)和质谱(MS)分析了所合成化合物的结构和组成,通过X射线衍射分析确认了吡啶基四硫富瓦烯衍生物4b和4c的晶体结构.循环伏安法研究结果表明,化合物4a,4b和4c呈现准可逆的两电子转移过程,结合量子化学计算,分析了不同位置取代的吡啶基对四硫富瓦烯电化学电势的影响.
[Abstract]:Under the catalysis of ethyl acetoacetate and cuprous oxide, the reaction of tetraethyl ammonium salt of zinc acid with 2-iodipyridine-3-iodopyridine (1b) and 4-iodopyridine (1c) was carried out by the reaction of dithiocyclopentene-2-thioketone (-4o) -5-dithioic acid (tetraethylammonium salt) with 2-iodopyridine (1a) and 3-iodopyridine (1b), respectively. In this paper, thioneone compounds 2o 3-dipyridine-2-pyridine thio -3- dithiocyclopentene-2-thiocarbazone 2b) and 2-dipyridine-2-pyridine-thiopentene-2-thiophenone were synthesized. Under the catalysis of mercuric acetate, the thioketone was prepared by the reaction of thiocarbazone and pyridine-2-pyridine-2-thiopentene-3-dithiopentene-2-thiocarbazone. In the presence of mercuric acetate, the thiopentene-2-thiophenone was used as the catalyst for the synthesis of thioketone and dithiopentene-2-thiocarbazone. Thioketone compounds 2a- 2b and 2c were oxidized to 2h3- dipyridine-2-pyridyl thiopentene-1-dithiopentene-3-dithiopentene-3-dithiopyridine-3-dithiopentene-3-dithiopentene-3-dithiopyranone (2c) and 23-di-4-pyridine-4-pyridyl thiopyclovalene-1-dithiopentene-3-dithiopentene-3-dithiophosphite (triethyl phosphite) as coupling agents, respectively. Oxygen ketone compounds 3afen 3b and 3c were self-coupled to form 2H3O3O6O6O7, Tetrathiolovarene (4aFV) 4b) tetrathiolovarene (4b) and 2O367- tetrapyridylpyridyl) tetrathiovarene (4cNMRs), respectively, by means of NMR spectroscopy, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, NMRs, and NMRs were used. The structure and composition of the synthesized compounds were analyzed by Fourier transform Infrared Spectroscopy (FTIR) and Mass Spectrometry (MS). The crystal structures of 4b and 4c derivatives of pyridyl tetrathiaflutene have been confirmed by X-ray diffraction analysis. The cyclic voltammetry results show that the compounds 4a4b and 4c exhibit quasi-reversible two-electron transfer process. The influence of pyridyl groups in different positions on the electrochemical potential of tetrathiafulvalene was analyzed.
【作者单位】：洛阳师范学院化学化工学院;郑州大学化学与分子工程学院;
【基金】：国家自然科学基金(批准号:201172105)资助~~
【分类号】：O641.4

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