【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.更多还原

【Abstract】 Using the ethyl acetoacetate / Cu2 O system,4,5-bis( pyridin-2-ylthio)-1,3-dithiole-2-thione( 2a),4,5-bis( pyridin-3-ylthio)-1,3-dithiole-2-thione( 2b) and 4,5-bis( pyridin-4-ylthio)-1,3-dithiole-2-thione( 2c) were prepared by the reaction of di( tetraehylammonium)-bis( 1,3-dithiol-2-thione-4,5-dithiocate) zincate with 2-iodopyridine( 1a),3-iodopyridine( 1b) and 4-iodopyridine( 1c) with the yields of 88%,55% and60%,respectively. Thiones 2a,2b and 2c were conversed to 4,5-bis( pyridin-2-ylthio)-1,3-dithiole-2-one( 3a),4,5-bis( pyridin-3-ylthio)-1,3-dithiole-2-one( 3b) and 4,5-bis( pyridin-4-ylthio)-1,3-dithiole-2-one( 3c) under the presence of Hg( OAc)2in almost quantitative yields. Consequently,the pyridine-tetrathiafulvalene compounds 2,3,6,7-tetrakis( pyridine-2-ylthio) tetrathiafulvalene( 4a),2,3,6,7-tetrakis( pyridine-3-ylthio) tetrathiafulvalene( 4b) and 2,3,6,7-tetrakis( pyridine-4-ylthio) tetrathiafulvalene( 4c) were obtained correspondingly through triethylphosphite-mediated self-coupling reactions of 3a,3b and 3c with the yields of80%,74% and 69%. All novel compounds were characterized by proton and carbon nuclear magnetic resonance spectroscopy(1H NMR and13 C NMR),fourier transform infrared spectroscopy( FTIR) and mass spectroscopy( MS) methods. Meanwhile,the structures of 4b and 4c was identified by X-ray diffraction analysis.The cyclic voltammograms showed that the pyridine- tetrathiafulvalene 4a,4b and 4c displayed two-electron quasi-reversible redox processes. Combined with quantum chemical calculations,the effects of the different pyridyl substituted tetrathiafulvalenes 4a,4b and 4c on electrochemical potentials were analysised.更多还原