新型exTTF衍生物的合成及其与四氯对苯醌的电子转移
收稿日期: 2013-12-03
修回日期: 2014-01-20
网络出版日期: 2014-03-14
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
Received date: 2013-12-03
Revised date: 2014-01-20
Online 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（1和3）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.
赵邦屯 , 陈秀华 , 李佳佳 , 朱卫民 . 新型exTTF衍生物的合成及其与四氯对苯醌的电子转移[J]. 有机化学, 2014 , 34(7) : 1417 -1423 . DOI: 10.6023/cjoc201312004
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
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