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有机化学 ›› 2013, Vol. 33 ›› Issue (01): 148-153.DOI: 10.6023/cjoc201208017 上一篇    下一篇

研究论文

羟甲基和碘甲基取代的3,4-亚乙基二氧噻吩衍生物及其选择性酯化与醚化

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 E-mail:yjshen@ecust.edu.cn
  • 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).

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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3,4-二氧-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-2,5-二羧酸甲酯(3')以及3,4-二氧-羟甲基亚乙基噻吩(4)与3,4-二氧-2'-羟基亚丙基噻吩(4')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)-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-TTF 1. 同样只有4能与TTF-3反应生成结构单一的EDOT-TTF 2.

关键词: 3,4-亚乙基二氧噻吩, 四硫代富瓦烯, 酯化, 醚化, 选择性

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