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Synthesis 2016; 48(15): 2438-2448
DOI: 10.1055/s-0035-1561418
paper
© Georg Thieme Verlag Stuttgart · New York

Synthesis of 1,2′-Biazulenes by Palladium-Catalyzed Unusual Homocoupling Reaction of 1-Haloazulenes in the Presence of Ferrocene

Taku Shoji*
a   Department of Chemistry, Faculty School of Science, Shinshu University, Matsumoto 390-8621, Nagano, Japan   Email: tshoji@shinshu-u.ac.jp
b   Department of Material Science, Graduate School of Science and Technology, Shinshu University, Matsumoto 390-8621, Nagano, Japan
,
Kanami Miyashita
a   Department of Chemistry, Faculty School of Science, Shinshu University, Matsumoto 390-8621, Nagano, Japan   Email: tshoji@shinshu-u.ac.jp
,
Takanori Araki
a   Department of Chemistry, Faculty School of Science, Shinshu University, Matsumoto 390-8621, Nagano, Japan   Email: tshoji@shinshu-u.ac.jp
,
Miwa Tanaka
a   Department of Chemistry, Faculty School of Science, Shinshu University, Matsumoto 390-8621, Nagano, Japan   Email: tshoji@shinshu-u.ac.jp
,
Akifumi Maruyama
b   Department of Material Science, Graduate School of Science and Technology, Shinshu University, Matsumoto 390-8621, Nagano, Japan
,
Ryuta Sekiguchi
c   Graduate School of Science and Technology, Hirosaki University, Hirosaki 036-8561, Aomori, Japan
,
Shunji Ito
c   Graduate School of Science and Technology, Hirosaki University, Hirosaki 036-8561, Aomori, Japan
,
Tetsuo Okujima
d   Department of Chemistry and Biology, Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577, Ehime, Japan
› Author Affiliations
Further Information

Publication History

Received: 26 January 2016

Accepted after revision: 22 February 2016

Publication Date:
22 March 2016 (online)

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Abstract

The synthesis of 1,2′-biazulenes was established by palladium-catalyzed homocoupling reactions of the corresponding 1-haloazulenes in the presence of ferrocene. The optical properties of the novel 1,2′-biazulenes were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behaviors of 1,2′-biazulenes were also examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV).

Key words

azulene - 1,2′-biazulene - homocoupling - UV/Vis spectrum - cyclic voltammetry

Supporting Information

    Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1561418.
  • Supporting Information
 

  • References

  • 1 Zeller K.-P. Azulene . In Houben-Weyl . 4th ed., Vol. V, Part 2c; Kropf H. Georg Thieme Verlag; Stuttgart: 1985: 127
    Search in Google Scholar
    • 2a Kurihara T, Suzuki T, Wakabayashi H, Ishikawa S, Shindo K, Shimada Y, Chiba H, Miyashi T, Yasunami M, Nozoe T. Bull. Chem. Soc. Jpn. 1996; 69: 2003
      CrossrefSearch in Google Scholar
    • 2b Hünig S, Ort B. Liebigs Ann. Chem. 1984; 1959
    • 2c Hünig S, Ort B. Liebigs Ann. Chem. 1984; 1936
    • 3a Razus AC. J. Chem. Soc., Perkin Trans. 1 2000; 981
    • 3b Razus AC, Nitu C. J. Chem. Soc., Perkin Trans. 1 2000; 989
    • 3c Razus AC, Nitu C, Carvaci S, Birzan L, Razus SA, Pop M, Tarko L. J. Chem. Soc., Perkin Trans. 1 2001; 1227
    • 3d Shoji T, Ito S, Toyota K, Yasunami M, Morita N. Tetrahedron Lett. 2007; 48: 4999
      CrossrefSearch in Google Scholar
    • 3e Shoji T, Higashi J, Ito S, Toyota K, Asao T, Yasunami M, Fujimori K, Morita N. Eur. J. Org. Chem. 2008; 1242
    • 3f Shoji T, Shimomura E, Inoue Y, Maruyama M, Yamamoto A, Fujimori K, Ito S, Yasunami M, Morita N. Heterocycles 2013; 87: 303
      CrossrefSearch in Google Scholar
    • 3g Shoji T, Maruyama A, Maruyama M, Ito S, Okujima T, Higashi J, Toyota K, Morita N. Bull. Chem. Soc. Jpn. 2014; 87: 141
      CrossrefSearch in Google Scholar
  • 5 Crombie AL, Kane JL. Jr, Shea KM, Danheiser RL. J. Org. Chem. 2004; 69: 8652
    CrossrefPubMedSearch in Google Scholar
  • 6 Hanke M, Jutz C. Angew. Chem., Int. Ed. Engl. 1979; 18: 214
    CrossrefSearch in Google Scholar
  • 9 Morita T, Takase K. Bull. Chem. Soc. Jpn. 1982; 55: 1144
    CrossrefSearch in Google Scholar
  • 10 Lin S.-J, Jiang S.-Y, Huang T.-C, Dai C.-S, Tsai P.-F, Takeshita H, Lin Y.-S, Nozoe T. Bull. Chem. Soc. Jpn. 1997; 70: 3071
    CrossrefSearch in Google Scholar
  • 11 Dyker G, Borowski S, Heiermann J, Körning J, Opwis K, Henkel G, Köckerling M. J. Organomet. Chem. 2000; 606: 108
    CrossrefSearch in Google Scholar
  • 12 Kurotobi K, Takakura K, Murafuji T, Sugihara Y. Synthesis 2001; 1346
    Thieme Connect
  • 15 A small amount of ferrocene was sublimated in the evaporation process of the solvent.
  • 16 Nozoe T, Ishikawa S, Shindo K. Chem. Lett. 1989; 353
    • 17a Shoji T, Higashi J, Ito S, Okujima T, Yasunami M, Morita N. Chem. Eur. J. 2011; 17: 5116
      CrossrefSearch in Google Scholar
    • 17b Shoji T, Shimomura E, Maruyama M, Maruyama A, Ito S, Okujima T, Toyota K, Morita N. Eur. J. Org. Chem. 2013; 7785
    • 17c Shoji T, Ito S, Okujima T, Morita N. Chem. Eur. J. 2013; 19: 5721
      CrossrefSearch in Google Scholar
  • 18 No reaction was also observed in the reaction of 7 with NIS.
  • 21 Anderson AG. Jr, Gale DJ, McDonald RN, Anderson RG, Rhodes RC. J. Org. Chem. 1964; 29: 1373
    CrossrefSearch in Google Scholar
  • 22 Elwahy AH. M, Hafner K. Eur. J. Org. Chem. 2010; 265
  • 23 Lash TD, Lammer AD, Idate AS, Colby DA, White K. J. Org. Chem. 2012; 77: 2368
    CrossrefSearch in Google Scholar
  • 24 Nefedov VA, Tarygina LK. Zh. Org. Khim. 1976; 12: 1763
    Search in Google Scholar
  • 25 Compound 14a was prepared by the reaction of 7 with NIS, according to the literature: Dubovik J., Bredihhin A.; Synthesis; 2015, 47: 2663.
  • 26 Anderson AG. Jr, Nelson JA, Tazuma JJ. J. Am. Chem. Soc. 1953; 75: 4980
    CrossrefSearch in Google Scholar
  • 27 Since attempts to separate 22 and 23 by both silica gel column chromatography and GPC were unsuccessful, the ratio of the products was determined by 1H NMR spectral measurement.
  • 28 Lu Y, Lemal DM, Jasinski JP. J. Am. Chem. Soc. 2000; 122: 2440
    CrossrefSearch in Google Scholar
  • 29 Hassan J, Sevignon M, Gozzi C, Schulz E, Lemaire M. Chem. Rev. 2002; 102: 1359
    CrossrefPubMedSearch in Google Scholar
  • 30 Ram RM, Singth V. Tetrahedron Lett. 2006; 47: 7625
    CrossrefSearch in Google Scholar
  • 31 Silverira PB, Lando VR, Dupont J, Monteiro AL. Tetrahedron Lett. 2002; 43: 2327
    CrossrefSearch in Google Scholar
  • 32 Seganish WM, Mowery ME, Riggleman S, DeShong P. Tetrahedron 2005; 61: 2117
    CrossrefSearch in Google Scholar
  • 33 The B3LYP/6-31G** time-dependence density functional calculations were performed with Spartan′10, Wavefunction, Irvine, CA.
  • 34 Ito S, Yamazaki S, Kudo S, Sekiguchi R, Kawakami J, Takahashi M, Matsuhashi T, Toyota K, Morita N. Tetrahedron 2014; 70: 2796
    CrossrefSearch in Google Scholar
  • 35 The voltammetry measurements were performed with a BAS 100B/W electrochemical workstation equipped with a standard three-electrode configuration and all measurements were carried out under an argon atmosphere. Et4NClO4 (0.10 M) in PhCN was used as a supporting electrolyte, with a Pt wire auxiliary and disk working electrodes. Reference electrode was formed from Ag/AgNO3 (0.01 M) in MeCN containing Bu4NClO4 (0.10 M). The half-wave potential of the ferrocene/ferrocenium ion couple (Fc/Fc+) under these conditions using this reference electrode was observed at +0.15 V on CV. Accuracy of the reference electrode was confirmed by CV measurements of the couple in each sample as an internal ferrocene standard.
  • 36 McDaniel DH, Brown HC. J. Org. Chem. 1958; 23: 420
    CrossrefSearch in Google Scholar
  • 37 Since the 3-position of azulene should be correspond to the meta-position of the azulene ring, Hammett substitution constant σm was applied in this case.
  • 38 Correlations between Hammett substitution constants and redox potential of ferrocene derivatives are previously reported: Komenda J, Tirouflet J. C. R. Seances Acad. Sci. 1962; 254: 3093
    Search in Google Scholar