Citation: Zhao Bangtun, Fu Huimin, Chen Xiaoji, Zhu Weimin. A New Method for Synthesizing Tetrathiafulvalene Vinylogues[J]. Chinese Journal of Organic Chemistry, ;2018, 38(8): 2116-2121. doi: 10.6023/cjoc201803055 shu

A New Method for Synthesizing Tetrathiafulvalene Vinylogues

Zhao Bangtun ^a,, ,
Fu Huimin ^b ,
Chen Xiaoji ^b ,
Zhu Weimin ^b,,

a.
College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934
b.
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450010

Corresponding author: Zhao Bangtun, zbt@lynu.edu.cn Zhu Weimin, zhuwm@zzu.edu.cn
Received Date: 31 March 2018
Revised Date: 6 May 2018
Available Online: 11 August 2018
Fund Project: Project supported by the National Natural Science Foundation of China (No. 21172105)the National Natural Science Foundation of China 21172105

Figures(6)

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.
- tetrathiafulvalene vinylogue,
- p-chloranil,
- methanesulfonic acid,
- crystal structure,
- synthesis
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