有机化学 ›› 2014, Vol. 34 ›› Issue (7): 1417-1423.DOI: 10.6023/cjoc201312004 上一篇    下一篇

研究论文

新型exTTF衍生物的合成及其与四氯对苯醌的电子转移

赵邦屯a, 陈秀华b, 李佳佳b, 朱卫民b   

  1. a 洛阳师范学院化学化工学院 洛阳 471022;
    b 郑州大学化学与分子工程学院 郑州 450010
  • 收稿日期:2013-12-03 修回日期:2014-01-20 发布日期:2014-03-14
  • 通讯作者: 赵邦屯, 朱卫民 E-mail:zbt@lynu.edu.cn;zhuwm@zzu.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.21172105,20872058)资助项目.

Synthesis of A Novel exTTF Derivative and Its Electron Transfer towards p-Chloranil

Zhao Bangtuna, Chen Xiuhuab, Li Jiajiab, Zhu Weiminb   

  1. a College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022;
    b College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001
  • Received:2013-12-03 Revised:2014-01-20 Published:2014-03-14
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21172105, 20872058)

以9,10-二蒽醌和1,3-二硫代环戊烯-2-硫酮(13)为原料,利用亚磷酸三乙酯为偶联剂的Wittig交叉偶合反应合成exTTF化合物9-(4,5-二氰乙基硫基-1,3-二硫代环戊烯-2-亚甲基)-10-[(4,5-亚乙基硫基)-1,3-二硫代环戊烯-2-亚甲基]-9,10-二氢蒽(4). 在氢氧化铯存在下,化合物4与2-氯乙氧基乙醇反应得到exTTF化合物9-[4-氰乙基硫基-5-(2-(2-羟乙氧基)乙基硫基-1,3-二硫代环戊烯-2-亚甲基)]-10-[(4,5-亚乙基硫基)-1,3-二硫代环戊烯-2-亚甲基]-9,10-二氢蒽(5). 利用Mitsunobu反应,在偶氮二甲酸二乙酯和三苯基膦催化下,化合物5与对硝基苯酚反应得到exTTF化合物9-{4-氰乙基硫基-5-[2-(2-对硝基苯氧乙氧基)乙基硫基]-1,3-二硫代环戊烯-2-亚甲基}-10-[(4,5-亚乙基硫基)-1,3-二硫代环戊烯- 2-亚甲基]-9,10-二氢蒽(6). 同时,X射线衍射分析了exTTF化合物4的晶体结构. 循环伏安法研究表明化合物6呈现准可逆的两电子转移过程. 利用紫外光谱法研究了exTTF化合物6与四氯对苯醌分子间的电子转移行为. 结果表明,非氧化性金属阳离子Sc3+,Al3+和Pb2+可以有效促进电子供体6与电子接受体四氯对苯醌的分子间的电子转移行为.

关键词: exTTF, 晶体结构, 四氯对苯醌, 电子转移

Using anthraquinone and 1,3-dithiol-2-thiones (1 and 3) as starting materials, the exTTF compound 9-[4,5- bis((2-cyanoethyl)thio)-1,3-dithiol-2-ylidene]-10-[4,5-(ethylenedithio)-1,3-dithiol-2-ylidene]-9,10-dihydroanthracene (4) was prepared by tripmethyl phosphite-induced Wittig cross-coupling reaction. In the presence of cesium hydroxide, the exTTF 4 was reacted with 2-(chloroethoxy)ethanol to obtain the exTTF compound 9-[4-[(2-cyanoethyl)-5-[(2-(2-hydroxyethoxy)- ethyl)thio]-1,3-dithiol-2-ylidene]-10-[4,5-(ethylenedithio)-1,3-dithiol-2-ylidene]-9,10-dihydroathracene (5) in 76% yield. The target exTTF compound 9-[4-[(2-cyanoethyl)-5-[(2-(2-(4-nitrophenoxy)ethoxy)ethyl)thio]-1,3-dithiol-2-ylidene]-10-[4,5- (ethylenedithio)-1,3-ditiol-2-ylidene]-9,10-dihydroanthracene (6) was obtained by Mitsunobu reaction of 5 and p-nitrophenol using diethyl azodicarboxy/triphenylphosphine (DEAD/PPh3) system in 24% yield. Meanwhile, the structure of exTTF 4 was identified by X-ray diffraction analysis. The cyclic voltammogramsed showed that the compound 6 displayed two-electron quasi-reversible redox processes. Moreover, the UV-Vis absorption studies show that intermolecular electron transfer between exTTF 6 and p-chloranil may be promoted by specific metal ions such as Sc3+, Al3+ and Pb2+.

Key words: exTTF, crystal structure, p-chloranil, electron transfer