Chin. J. Org. Chem. ›› 2013, Vol. 33 ›› Issue (01): 148-153.DOI: 10.6023/cjoc201208017 Previous Articles     Next Articles



左虎进, 张磊, 吴长智, 王成云, 沈永嘉   

  1. 结构可控先进功能材料及其制备教育部重点实验室 华东理工大学精细化工研究所 上海 200237
  • 收稿日期:2012-08-18 修回日期:2012-09-10 发布日期:2012-09-12
  • 通讯作者: 沈永嘉
  • 基金资助:

    国家自然科学基金(Nos. 21076078, 20872035, 20676036)资助项目.

Synthesis of 3,4-Ethylenedioxythiophene Substituted with Hydroxymethyl and Iodomethyl Groups and Their Selective Esterification and Etherification

Zuo Hujin, Zhang Lei, Wu Changzhi, Wang Chengyun, Shen Yongjia   

  1. Laboratory for Advanced Materials, Institute of Fine Chemicals, East China University of Science and Technology, Shanghai 200237
  • Received:2012-08-18 Revised:2012-09-10 Published:2012-09-12
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21076078, 20872035, 20676036).

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-2,5-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 cyanoethyl-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 tetrathiafulvalene (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.

Key words: 3,4-ethylendioxythiophene, tetrathiafulvalene, esterification, etherification, selectivity