Chinese Journal of Organic Chemistry >
A New Method for Synthesizing Tetrathiafulvalene Vinylogues
Received date: 2018-03-31
Revised date: 2018-05-06
Online published: 2018-05-14
Supported by
Project supported by the National Natural Science Foundation of China (No. 21172105).
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.
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
[1] Segura, J. L.; Martín, N. Angew. Chem., Int. Ed. 2001, 40, 1372.
[2] Canevet, D.; Sallé, M.; Zhang, G. X.; Zhu, D. B. Chem. Commun. 2009, 2245.
[3] Nielsen, M. B.; Lomholt, C.; Becher, J. Chem. Soc. Rev. 2000, 29, 153.
[4] Chen, T.; Liu, W. J.; Cong, Z. Q.; Yin, B. Z. Chin. J. Org. Chem. 2005, 25, 570(in Chinese). (陈铁, 刘武军, 丛志奇, 尹炳柱, 有机化学, 2005, 25, 570.)
[5] Yamada, J.; Sugimoto, T. TTF Chemistry Fundamentals and Applications of Tetrathiafulvalene, Kodansha and Springer, Tokyo, 2004.
[6] Feng, M.; Gao, L.; Deng, Z. T.; Ji, W.; Guo, X. F.; Du, S. X.; Shi, D. X.; Zhang, D. Q.; Zhu, D. B.; Gao, H. J. J. Am. Chem. Soc. 2007, 129, 2204.
[7] Zhu, Y. L.; Yang, Y. J.; Yin, Q. F.; Zhu, D. B. Chin. J. Org. Chem. 2005, 25, 1167(in Chinese). (朱玉兰, 杨艳杰, 尹起范, 朱道本, 有机化学, 2005, 25, 1167.)
[8] Yoshida, Z. I.; Kawase, T.; Awaji, H.; Sugimoto, I.; Sugimoto, S.; Yoneda, S. Tetrahedron Lett. 1983, 24, 3469.
[9] Zhao, Y. M.; Chen, G.; Mulla, K.; Mahmud, I.; Liang, S.; Dongare, P.; Thompson, D. W.; Dawe, L. N.; Bouzan, S. Pure Appl. Chem. 2012, 84, 1005.
[10] Liang, S.; Chen, G.; Peddle, J.; Zhao, Y. M. Chem. Commun. 2012, 48, 3100.
[11] Massue, J.; Bellec, N.; Guerro, M.; Bergamini, J. F.; Hapiot, P.; Lorcy, D. J. Org. Chem. 2007, 72, 4655.
[12] Liang, S.; Zhao, Y. M.; Adronov, A. J. Am. Chem. Soc. 2014, 136, 970.
[13] Khadem, M.; Zhao, Y. M. J. Org. Chem. 2015, 80, 7419.
[14] Wu, W. T.; Li, J.; Zhao, Z.; Yang, X. D.; Gao, X. K. Org. Chem. Front. 2017, 4, 823.
[15] Gontier, E.; Bellec, N.; Brignou, P.; Gohier, A.; Guerro, M.; Roisnel, T.; Lorcy, D. Org. Lett. 2010, 12, 2386.
[16] Hu, Y. B.; Wang, Z. L.; Zhang, X.; Yang, X. D.; Ge, C. W.; Fu, L.; Gao, X. K. Org. Lett. 2017, 19, 468.
[17] Sen, S.; Hosono, N.; Zheng, J. J.; Kusaka, S.; Matsuda, R.; Sakaki, S.; Kitagawa, S. J. Am. Chem. Soc. 2017, 139, 18313.
[18] Lorcy, D.; Carlier, R.; Robert, A.; Tallec, A.; Maguer&s, P. L.; Ouahabo, L. J. Org. Chem. 1995, 60, 2443.
[19] Rathore, R.; Kochi, J. K. Acta Chem. Scand. 1998, 52, 114.
[20] Zhai, L. Y.; Shukla, R.; Wadumethrige, S. H.; Rathore, R. J. Org. Chem. 2010, 75, 4748.
[21] Maddala, S.; Mallick, S.; Venkatakrishnan, P. J. Org. Chem. 2017, 82, 8958.
[22] Grzybowski, M.; Skonieczny, K.; Butenschön, H.; Gryko, D. T. Angew. Chem., Int. Ed. 2013, 52, 2.
[23] Bouzan, S.; Chen, G.; Mulla, K.; Dawe, L. N.; Zhao, Y. M. Org. Biomol. Chem. 2012, 10, 7673.
[24] Bouzan, S.; Dawe, L. N.; Zhao, Y. M. Tetrahedron Lett. 2013, 54, 4666.
[25] Simonsen, K. B.; Svenstrup, N.; Lau, J.; Simonsen, O.; Mørk, P.; Kristensen, G. J.; Becher, J. Synthesis 1996, 407.
[26] Chen, G.; Mahmud, I.; Dawe, L. N.; Daniels, L.; Zhao, Y. M. J. Org. Chem. 2011, 76, 2701.
[27] Chen, G.; Mahmud, I.; Dawe, L. N.; Daniels, L.; Zhao, Y. M. Org. Lett. 2010, 12, 704.
[28] Hapiot, P.; Lorcy, D.; Tallec, A.; Carlier, R.; Robert, A. J. Phys. Chem. 1996, 100, 14823.
[29] Carlier, R.; Hapiot, P.; Lorcy, D.; Robert, A.; Tallec, A. Electro-chim. Acta 2001, 46, 3269.
/
| 〈 |
|
〉 |
