有机化学 ›› 2018, Vol. 38 ›› Issue (8): 2116-2121.DOI: 10.6023/cjoc201803055 上一篇    下一篇

研究简报

一种合成插烯式四硫富瓦烯衍生物的新方法

赵邦屯a, 付慧敏b, 陈小纪b, 朱卫民b   

  1. a 洛阳师范学院化学化工学院 洛阳 471934;
    b 郑州大学化学与分子工程学院 郑州 450010
  • 收稿日期:2018-03-31 修回日期:2018-05-06 出版日期:2018-08-25 发布日期:2018-05-14
  • 通讯作者: 赵邦屯, 朱卫民 E-mail:zbt@lynu.edu.cn;zhuwm@zzu.edu.cn
  • 基金资助:

    国家自然科学基金(No.21172105)资助项目.

A New Method for Synthesizing Tetrathiafulvalene Vinylogues

Zhao Bangtuna, Fu Huiminb, Chen Xiaojib, Zhu Weiminb   

  1. a College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934;
    b College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450010
  • Received:2018-03-31 Revised:2018-05-06 Online:2018-08-25 Published:2018-05-14
  • Contact: 10.6023/cjoc201803055 E-mail:zbt@lynu.edu.cn;zhuwm@zzu.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21172105).

插烯式四硫富瓦烯(tetrathiafulvalene vinylogues,TTFV)化合物由于其优良的供电子性质在有机电子学研究中引人关注.TTFV类化合物的合成通常是利用烯键键链的二硫富瓦烯(diathiafulvalene,DTF)化合物通过I2以及AgBF4等氧化偶联反应来制备,其存在产率较低、毒性较大等局限.鉴于萘基团的荧光性质以及硫代丙腈基的衍生化反应特点,以亚磷酸三甲酯为偶联剂,含丙腈基硫酮化合物1与1-萘醛发生偶联反应生成二硫富瓦烯化合物2.在四氯苯醌(chloranil,CA)/甲磺酸(methanesulfonic acid,MSA)催化条件下,化合物2氧化偶联得到插烯式四硫富瓦烯化合物3.初步优化了四氯苯醌-甲磺酸(CA-MSA)催化反应条件.优化的反应条件为:1.5 equiv.的CA催化剂,甲磺酸与二氯甲烷的体积比为1:10,氮气保护下室温反应2 h,化合物3的产率可达86.7%.通过1H NMR,13C NMR,FT-IR,MS方法对插烯式四硫富瓦烯衍生物3分别进行了表征分析,同时用X射线衍射法确认了化合物3的晶体结构.与传统的I2氧化偶联反应进行了实验比较,结果表明在甲磺酸存在下,以四氯苯醌为有机氧化剂合成插烯式四硫富瓦烯衍生物的新方法简便有效.

关键词: 插烯式四硫富瓦烯, 四氯苯醌, 甲磺酸, 晶体结构, 合成

Tetrathiafulvalene vinylogues (TTFV) have attracted for organic-based electronics as their excellent electron donating properties. The most commonly used synthetic access to TTFV is by the oxidative dimerization of corresponding dithiafulvene (DTF) precursors, the oxidants like as I2 and AgBF4 have been reported to promote the dimerization reaction in most cases. However, this method is very limited to lower yield and higher toxicity. Due to the naphthyl fluorescence property and cyanoethylthiolate reactive feature, and through trimethylphosphite-mediated cross-coupling reaction, 4,5-bis(2-cyanoethylsulfanyl)-1,3-dithiole-2-thione (1) reacted with 1-naphthaldehyde to give the dithiafulvalene compound (DTF 2) with the yield of 48%. The dithiafulvalene compound 2 has subjected to an p-chloranil (CA)/methanesulfonic acid (MSA) oxidative dimerization reaction and then a brief reductive aqueous workup with Na2S2O3 to gain tetrathiafulvalene vinylogues (TTFV 3). The optimal reaction conditions achieved for the oxidative TTFV formation are 1.5 equiv. of CA catalyst, the 1:10 volume ratio of MSA and DCM, under nitrogen atomsphere and room temperature, 2.0 h reaction time, and the yield of TTFV 3 with up to 86.7%. All novel compounds were characterized by 1H NMR, 13C NMR, FT-IR and MS methods. Meanwhile, the structure of 3 was identified by X-ray diffraction analysis. Compared with the traditional I2 oxidative dimerization method, the results show that this method is simple, economic and efficient.

Key words: tetrathiafulvalene vinylogue, p-chloranil, methanesulfonic acid, crystal structure, synthesis