Synthesis 2016; 48(06): 845-854
DOI: 10.1055/s-0035-1560400
© Georg Thieme Verlag Stuttgart · New York

Vilsmeier–Haack Type Formylation on 6-Aryl-1,4-dithiafulvenes and Syntheses of Novel Extended Tetrathiafulvalene Donors

Atsushi Fujiokaa, Takashi Kuboa, Miho Watanabea, Masafumi Uedaa, Hisakazu Miyamotoa, Yohji Misaki*a, b
  • aDepartment of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577, Japan   Email:
  • bElements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520, Japan
Further Information

Publication History

Received: 30 October 2015

Accepted after revision: 14 December 2015

Publication Date:
11 January 2016 (eFirst)


The Vilsmeier–Haack type formylations on various 6-aryl-1,4-dithiafulvenes were examined. The furyl derivatives on treatment with an excess of POCl3 in DMF at room temperature mainly afforded dialdehydes substituted at the 6-position and the furan ring, while the thienyl derivatives and the phenyl derivatives mainly gave monoformylated derivatives substituted at the 6-position. The obtained mono- and dialdehydes were converted into monoaryl-substituted 2,2′-ethanediylidene-bis(1,3-dithiole) derivatives and heteroaromatic ring-inserted [3]dendralene derivatives with triple 1,3-dithiol-2-ylidenes and their TTF-fused analogues. Electrochemical properties of the new π-electron donors were also investigated by cyclic voltammetry.

Supporting Information

  • References

  • 1 Present address: Department of General Education of Science, National Institute of Technology, Kurume College, Komorino, Kurume 830-8555, Japan.
    • 3a Kato M, Ogi D, Yao M, Misaki Y. Chem. Lett. 2013; 42: 1556
    • 3b Kato M, Senoo M, Yao M, Misaki Y. J. Mater. Chem. A 2014; 2: 6747
    • 3c Iwamoto S, Inatomi Y, Ogi D, Shibayama S, Murakami Y, Kato M, Takahashi K, Tanaka K, Hojo N, Misaki Y. Beilstein J. Org. Chem. 2015; 11: 1136
  • 4 Imakubo T, Iijima T, Kobayashi K, Kato R. Synth. Met. 2001; 120: 899
  • 5 Misaki Y, Matsumura Y, Sugimoto T, Yoshida Z. Tetrahedron Lett. 1989; 30: 5289
  • 6 Nishiwaki M, Nakamura K, Shirahata T, Misaki Y. Chem. Lett. 2011; 40: 452
  • 7 Benahmed-Gasmi AS, Frère P, Garrigues B, Gorgues A, Jubault M, Carlier R, Texier F. Tetrahedron Lett. 1992; 33: 6457
  • 8 Misaki Y, Sasaki T, Ohta T, Fujiwara H, Yamabe T. Adv. Mater. 1996; 8: 804
    • 9a Hansen TK, Lakshmikantham MV, Cava MP, Niziurski-Mann RE, Jensen F, Becher J. J. Am. Chem. Soc. 1992; 114: 5035
    • 9b Takahashi K, Nihira T, Yoshifuji M, Tomitani K. Bull. Chem. Soc. Jpn. 1993; 66: 2330
  • 10 For a preliminary report on our synthesis of the thiophene derivatives 11T, see: Hasegawa T, Fujioka A, Kubo T, Honda T, Miyamoto H, Misaki Y. Chem. Lett. 2008; 37: 474
  • 11 Lorcy D, Carlier R, Robert A, Tallec A, Le Magueres P, Ouahab L. J. Org. Chem. 1995; 60: 2443
  • 12 Misaki Y, Kubo A, Matsuda W, Fueno H, Tanaka K. Curr. Appl. Phys. 2006; 6: 939
  • 13 Sato M, Gonnella NC, Cava MP. J. Org. Chem. 1979; 44: 928
  • 14 Moore AJ, Bryce MR. Tetrahedron Lett. 1992; 33: 1373
  • 15 Akiba K, Ishikawa K, Inamoto N. Bull. Chem. Soc. Jpn. 1978; 51: 2674
  • 16 Takahashi K, Tanioka H, Fueno H, Misaki Y, Tanaka K. Chem. Lett. 2002; 10: 1002
  • 17 Large-scale synthesis by using 10 mmol of 5 has only little influence on the yield, and there was no particular problem in the experimental operation.