中文摘要：

羟甲基或碘甲基取代的3,4．亚乙基二氧噻吩（EDOT）衍生物与含氰乙基或羧酸基的四硫代富瓦烯（TTF）衍生物通过酯化或醚化反应可生成EDOT．TTF类型的化合物．在此过程中发现，由3,4-二羟基噻吩-2，5-二羧酸甲酯（1）与环氧溴丙烷经醚化反应生成的关环产物是一个由3,4-二氧-羟甲基乙基噻吩-2，5-二羧酸甲酯（2）与3,4-2氧-2’-羟基亚丙基噻吩-2．5-二羧酸甲酯（2’）组成的混合物，两者很难用常规手段分离．由（2＋2’）衍生的2，5-二羧酸甲酯-3，4-二氧-碘代甲基亚乙基噻吩（3）和3,4-二氧-碘代亚丙基噻吩-2，5-2羧酸甲酯（3’）以及3,4-2氧-羟甲基亚乙基噻吩（4）与3,4-二氧-2’-羟基亚丙基噻吩（4t）与2．氰乙基硫。3-甲基硫-6，7-二（正己基硫）-四硫代富瓦烯（TTF—1）或2·羧甲基硫-3-甲基硫-6，7-二（正己基硫1-四硫代富瓦烯（TTF-3）进行醚化或酯化反应表现出了高度的选择性，只有3能与TTF-1反应生成结构单一的EDOT-TTF1．同样只有4能与TTF-3反应生成结构单一的EDOT-TTF2．

英文摘要：

3,4-Ethylenedioxythiophene （EDOT） and its derivatives contained hydroxyl groups are good blocks for the synthesis of the functional molecules based on EDOT. However, the products of the reaction between dimethyl 3,4-dihydroxy-thiophene-2,5-dicarboxylate （1） and epibromohydrin via Williamson etherification were a mixture of dimethyl 2＇-hydroxymethyl-3,4-ethylendioxy-thiophene-2,5-dicarboxylate （2） and dimethyl 2＇-hydroxypropyl-3,4-dioxythiophene- 2,5-dicarboxylate （2＇）, which is difficult to separate. Dimethyl 2＇-iodomethyl-3,4-ethylendioxy-thiophene-2,5-dicarboxylate （3） and dimethyl 2＇-iodopropyl-3,4-dioxythiophene-2,S-dicarboxylate （3＇） as well as 3,4-ethylendioxy-2＇-hydroxymethyl-thio- phene （4） and 3,4-dioxy-2＇-hydroxypropyl-thiophene （4＇） were synthesized by using the mixture. They are still mixtures and difficult to separate. It is very surprising that when an etherification reaction between the mixture （3＋3＇） and cyano- ethyl-carried tetrathiafulvalene （TTF-1） was conducted, the reaction showed highly selectivity, i.e., only 3 could react with TTF-1. The same situation happened when an esterification between the mixture （4＋4＇） and carboxylic acid carried tetrathia- fulvalene （TTF-3） was made, only 4 could react with TTF-3. Both the reactions afforded a single product, i.e., EDOT-TTF 1 and EDOT-TTF 2, respectively, whose chemical structures were characterized by 1H NMR, 13C NMR, MS, and HRMS.