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有机化学 ›› 2011, Vol. 31 ›› Issue (07): 1027-1031. 上一篇    下一篇

研究论文

两亲性四硫富瓦烯衍生物的合成及其性质研究

赵邦屯*,1，吴圣江2，冶保献*,2   

  1. (1洛阳师范学院化学化工学院 洛阳 471022)
    (2郑州大学化学系 郑州 450001)
  • 收稿日期:2010-11-21 修回日期:2011-01-09 发布日期:2011-02-17
  • 通讯作者: 赵邦屯 E-mail:zbt@lynu.edu.cn

Synthesis and Properties of Amphiphilic Tetrathiafulvalene Derivatives

Zhao Bangtun*,1 Wu Shengjiang2 Ye Baox-ian*,2   

  1. (1 Department of Chemistry, Luoyang Normal University, Luoyang 471022)
    (2 Department of Chemistry, Zhengzhou University, Zhengzhou 450001)
  • Received:2010-11-21 Revised:2011-01-09 Published:2011-02-17

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1079

被引次数

3 | 2

二-(1,3-二硫环戊烯-2-硫酮-4,5-二硫)合锌酸四乙基铵盐(Zincate盐)分别与溴代十四烷和溴代十八烷在乙腈中回流, 合成相应的1,3-二硫环戊烯-2-硫酮2a和2b. 以亚磷酸三乙酯为偶联剂, 其分别和4,5-二氰基乙硫基-1,3-二硫环戊烯-2-酮(3)发生交叉偶合反应合成四硫富瓦烯(TTF)衍生物4a和4b. 在氢氧化铯的存在下, 4a和4b分别与2-碘乙氧基乙醇反应生成含羟基的四硫富瓦烯(TTF)衍生物5a和5b. 以三乙胺为缚酸剂, 其与对甲基苯磺酰氯反应, 生成含活化羟基的TTF衍生物6a和6b. 在氢氧化钠的存在下, 6a和6b分别与巯基噻二唑反应生成含有疏水长链烷烃和亲水醚键连接的噻二唑两亲性TTF衍生物7a～7d, 并对其进行了1H NMR, 13C NMR, IR, MS的表征以及初步电化学行为和Langmuir-Blodgett膜性能研究.

关键词: 两亲性, 四硫富瓦烯, 合成, 电化学, Langmuir-Blodgett膜

The 1,3-dithionle-2-thiones 2a and 2b were prepared by the reaction of di(tetraethylammonium) bis(1,3-dithiol-2-thione-4,5-dithiolate) zincate with myristyl bromide and octadecyl bromide in refluxing acetonitrile, respectively. Then, two tetrathiafulvalenes 4a and 4b were obtained by the cross-coupling of 2a and 2b with 4,5-biscyanoethylthio-1,3-dithiole-2-one mediated by triethylphosphite, respectively. And the sequent reac-tion of 4a and 4b with 2-(2-iodoethoxy)ethanol in the presence of cesium hydroxide af-forded tetrathiafulvalenes 5a and 5b, which reacted with tosyl chloride to give the corre-sponding tetrathiafulvalene tosylates 6a and 6b. A series of amphiphilic tetrathiafulvalenes 7a～7d were easily synthesized by the reaction of 6a and 6b with 2-mercapto-thiadiazoles in the presence of sodium hydroxide, respectively. All amphiphilic tetrathiafulvalenes 7a～7d were characterized by 1H NMR, 13C NMR, IR, MS tech-niques and elemental analyses, together with their preliminary electrochemical behaviours and Lang-muir-Blodgett (LB) films.

Key words: amphiphilicity, tetrathiafulvalene, synthesis, electrochemistry, LB film