含吡啶基四硫富瓦烯衍生物的合成、结构和电化学性质
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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.
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.
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.
引文
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[3]Segura J.L.,Martín N.,Angew.Chem.Int.Ed.,2001,40,1372—1409
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[5]Canevet D.,SalléM.,Zhang G.X.,Zhu D.B.,Chem.Commun.,2009,(17),2245—2269
[6]Bergkamp J.J.,Decurtins S.,Liu S.X.,Chem.Soc.Rev.,2015,44,863—874
[7]Zhao B.T.,Chen X.H.,Ma S.X.,Zhu W.M.,Chem.Res.Chinese Universities,2015,31(6),930—935
[8]Wen Z.,Kan Y.H.,Yan W.Y.,Ding Y.Y.,Wang.X.L.,Chem.J.Chinese Universities,2013,34(6),1483—1489(温智,阚玉和,闫文艳,丁艳艳,王新龙.高等学校化学学报,2013,34(6),1483—1489)
[9]Li Q.,Geng Y.,Duan Y.A.,Wang G.Y.,Su Z.M.,Chem.J.Chinese Universities,2014,35(7),1471—1479(李倩,耿允,段雨爱,王光宇,苏忠民.高等学校化学学报,2014,35(7),1471—1479)
[10]Fabrice P.,Boris L.G.,Olivier M.,Olivier C.,Lahcéne O.,Acc.Chem.Res.,2015,48,2834—2842
[11]Chahma M.,Wang X.S.,Van des Est A.,Pilkington M.,J.Org.Chem.,2006,71,2750—2755
[12]Goeb S.,Bivaud S.,CrouéV.,Vajpayee V.,Allain M.,SalléM.,Materials,2014,7,611—622
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[14]Balandier J.Y.,Belyasmine A.,SalléM.,Eur.J.Org.Chem.,2008,(2),269—276
[15]Ota A.,Ouahab L.,Golhen S.,Cador O.,Yoshida Y.,Saito G.,New J.Chem.,2005,29,1135—1140
[16]Wang Q.,Day P.,Griffiths J.P.,Nie H.,Wallis J.D.,New J.Chem.,2006,30,1790—1800
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[20]Sun J.B.,Lu X.F.,Shao J.F.,Li X.X.,Zhang S.X.,Wang B.L.,Zhao J.L.,Shao Y.L.,Fang R.,Wang Z.H.,Yu W.,Shao X.F.,Chem.Eur.J.,2013,19,12517—12525
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[23]Yu Z.X.,Cheong P.H.,Liu P.,Legault C.Y.,Wender P.A.,Houk K.N.,J.Am.Chem.Soc.,2008,130,2378—2379