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摘要
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 12 and AgBF 4 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 pro perty and cyanoethylthiolate reactive feature, and through trimethylphosplrite-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 H-1 NMR, C-13 NMR, FT-IR and MS methods. Meanwhile, the structure of 3 was identified by X-ray diffraction analysis. Compared with the traditional I-2 oxidative dimerization method, the results show that this method is simple, economic and efficient.
