新型exTTF衍生物的合成及其与四氯对苯醌的电子转移  

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

作　　者：赵邦屯[1] 陈秀华[2] 李佳佳[2] 朱卫民[2] 

机构地区：[1]洛阳师范学院化学化工学院,洛阳471022 [2]郑州大学化学与分子工程学院,郑州450010

出　　处：《有机化学》2014年第7期1417-1423,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21172105;20872058)资助项目~~

摘　　要：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.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-dihydroanthracen （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）eth^xy）ethyl）thio]-1,3-dithiol-2-ylidene]-10-[4,5- （ethylenedithio）-l,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 andp-chloranil may be promoted by specific metal ions such as Sc3＋, Al3＋ and Pb2＋.

关 键 词：exTTF 晶体结构 四氯对苯醌 电子转移 

分 类 号：O621.25[理学—有机化学]