新型四硫富瓦烯硫杂冠醚衍生物的合成

在高度稀释条件下, 经4,5-二溴甲基-1,3-二硫杂环戊烯-2-硫酮(7)和多缩乙二醇的1,ω-二巯基衍生物的缩合反应, 方便地合成了4,5-位带二硫杂冠醚残基的2-硫代-1,3-二硫杂环戊烯的衍生物8a～8d, 中间体硫杂冠醚8c～8d的合成中有明显的“模板效应”. 在亚磷酸三乙酯存在下, 8a～8d经自偶联生成新型的对称双臂四硫富瓦烯(TTF)硫杂冠醚衍生物10a～10d, 而与4,5-二甲硫基-1,3-二硫杂环戊烯-2-酮(9)经交叉偶联生成新型的非对称单臂四硫富瓦烯硫杂冠醚衍生物11a～11d. 用循环伏安法研究了上述目标化合物的电化学性质和离子传感性质.

Synthesis of Novel Dithia-crown Ether Annulated Tetrathiafulvalene Derivatives

In this paper, a series of 4,5-dithiacrown ether annulated 1,3-dithiole-2-thiones 8a～8d were prepared via condensing 4,5-bis(bromomethyl)-1,3-dithiole-2-thione (7) with 1,ω-dimercapto polyglycol derivatives in high dilution. The obvious template effect was found during the synthesis of 8c～8d. Self-coupling of crown-ether derivatives 8a～8d afforded the symmetric bis-crown-ether TTF derivatives 10a～10d and cross-coupling with 4,5-dimethylthio-1,3-dithiole-2-one (9) gave asymmetric mono crown-ether TTF derivatives 11a～11d in net triethyl phosphite. The electrochemical and ion-sensing properties of crown-ether TTF derivatives were studied by means of cyclic voltammetry.