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Synthesis 2003(14): 2199-2205  
DOI: 10.1055/s-2003-41058
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of 2,3-Dihydrothieno[2,3-b]-1,4-dithiine, 2,3-Dihydrothieno-[3,2-b]-1,4-oxathiine, 2,3-Dihydrothieno[2,3-b]-1,4-oxathiine and Their Transformation­ into Corresponding End-Capped Oligomers [1]

Jonas Hellberg*, Tommi Remonen, Fredrik Allared, Johnny Slätt, Mats Svensson
Organic Chemistry, Dept of Chemistry, Royal Institute of Technology, 100 44 Stockholm, Sweden
Fax: +46(8)7912333; e-Mail: jhel@kth.se;
Further Information

Publication History

Received 19 May 2003
Publication Date:
24 September 2003 (online)

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Abstract

Three new heterocyclic parent compounds, 2,3-dihydrothieno[2,3-b][1,4]dithiine (TDT), 2,3-dihydrothieno[3,2-b][1,4]oxathiine (TOT), and 2,3-dihydrothieno[2,3-b][1,4]oxathiine, have been synthesized by acid-catalyzed transformations starting from 3-methoxythiophene. Two of the new compounds have been transformed to the corresponding end-capped dimeric, trimeric and tetrameric oligothiophenes. These oligomers show very stable cationic and dicationic states as judged by cyclic voltammetry, and their UV-Vis spectra are considerably red-shifted compared to previously synthesized end-capped oligomers.

Key words

ring-closure - tandem reactions - oligothiophenes - Suzuki coupling

    References

  • 1 Parts of this paper have been presented at ICSM 1998. Hellberg J. Remonen T. Slätt J. Synth. Met.  1999,  101:  103 
    Google Scholar
  • 4 Present address: AstraZeneca R&D, SE-151 85 Södertälje, Sweden.
  • 5a Kirschbaum T. Azumi R. Mena-Osteritz E. Bäuerle P. New J. Chem.  1999,  241 
    CrossrefGoogle Scholar
  • 5b Mitschke U. Bäuerle P. J. Mater. Chem.  2000,  10:  1471 
    CrossrefGoogle Scholar
  • 5c Mitschke U. Mena-Osteritz E. Debaerdemaeker T. Sokolowski M. Bäuerle P. Chem.-Eur. J.  1998,  4:  2211 
    CrossrefGoogle Scholar
  • 5d Horowitz G. Adv. Mater.  1998,  10:  365 
    CrossrefGoogle Scholar
  • 5e Katz HE. J. Mater. Chem.  1997,  7:  369 
    CrossrefGoogle Scholar
  • 5f Geiger F. Stoldt M. Schweizer H. Bäuerle P. Umbach E. Adv. Mater.  1993,  5:  922 
    CrossrefGoogle Scholar
  • 5g Brown AR. Pompt A. Hart CM. de Leeuw DM. Science  1995,  270:  972 
    CrossrefGoogle Scholar
  • 5h Yu G. Gao J. Hummelen JC. Wudl F. Heeger AJ. Science  1995,  270:  1789 
    CrossrefGoogle Scholar
  • 5i Hiller M. Kranz C. Huber J. Bäuerle P. Schuhmann W. Adv. Mater.  1996,  8:  219 
    CrossrefGoogle Scholar
  • 5j Williams JM. Kini AM. Wang HH. Carlson KD. Geiser U. Montgomery LK. Pyrka GJ. Watkins DM. Kommers JM. Boryschuk SJ. Strieby Crouch AV. Kwok WK. Schirber JE. Overmyer DL. Jung D. Whangbo M.-H. Inorg. Chem.  1990,  29:  3272 
    CrossrefGoogle Scholar
  • 6 Müllen K. Wegner G. Adv. Mater.  1998,  10:  433 
    Google Scholar
  • 7 Bäuerle P. Segelbacher U. Maier A. Mehring M. J. Am. Chem. Soc.  1993,  115:  10217 
    CrossrefGoogle Scholar
  • 8a Schultz AJ. Wang HW. Williams JM. J. Am. Chem. Soc.  1986,  108:  7853 
    CrossrefGoogle Scholar
  • 8b Whangbo M.-H. William JM. Schultz AJ. Emge TJ. Beno MA. J. Am. Chem. Soc.  1987,  109:  90 
    CrossrefGoogle Scholar
  • 9 Hellberg J. Moge M. von Schütz J.-U. Törnroos K.-W. Synth. Met.  1997,  86:  1877 
    Google Scholar
  • 12a Zotti G. Gallazzi MC. Zerbi G. Meille SV. Synth. Met.  1995,  73:  217 
    Google Scholar
  • 12b Faid K. Leclerc M. Chem. Commun.  1996,  2761 
    Google Scholar
  • 12c Goldoni F. Langeveld-Voss BMW. Meijer EW. Synth. Commun.  1998,  28:  2237 
    Google Scholar
  • 13 3-Methoxythiophene (10) is commercially available, but it can also be readily synthesized from 3-bromothiophene: Keegstra MA. Peters THA. Brandsma L. Synth. Commun.  1990,  20:  213 
    Google Scholar
  • 14 The NMR shifts of the thiophene protons of the main product are more consistent with the structure 13 than with 12. The aromatic part of the spectrum resembles the spectrum for 16, which is similar to 13, but the shift for the 2-proton is considerable higher than for the 2-proton in 3-methoxythiophene 10 and other 3-alkoxythiophenes. For spectral data for a derivative of 12, see: Chaffin JDE. Barker JM. Huddleston PR. J. Chem. Soc., Perkin. Trans. 1  2001,  1398 
    CrossrefGoogle Scholar
  • 15 Capon B. Kwok F.-C. Tetrahedron  1987,  43:  69 
    CrossrefGoogle Scholar
  • 16 Wolter M. Nordmann G. Job GE. Buchwald SL. Org. Lett.  2002,  4:  973 
    CrossrefGoogle Scholar
  • 17a De Jong F. Janssen MJ. J. Org. Chem.  1971,  36:  1645 
    Google Scholar
  • 17b Stoyanovich FM. Federov BP. Zh. Org. Khim.  1965,  1:  1282 ; Chem. Abstr. 1965, 63, 16288h
    Google Scholar
  • 18 Iyoda M. Sato K. Oda M. Tetrahedron Lett.  1985,  26:  3829 
    CrossrefGoogle Scholar
  • 19 Parakka JP. Jeevarajan JA. Jeevarajan AS. Kispert LD. Cava MP. Adv. Mater.  1996,  8:  54 
    CrossrefGoogle Scholar
  • 20 Gronowitz S. Bobosik V. Lawitz K. Chem. Script.  1984,  23:  120 
    Google Scholar
  • 21a Wright SW. Hageman DL. McClure LD. J. Org. Chem.  1994,  59:  6095 
    CrossrefGoogle Scholar
  • 21b Kirschbaum T. Briehn CA. Bäuerle P. J. Chem. Soc., Perkin Trans. 1  2000,  1211 
    CrossrefGoogle Scholar
  • 22 During the preparation of this manuscript, a similar synthesis of 27 was reported: Melucci M. Barbarella G. Sotgiu G. J. Org. Chem.  2002,  67:  8877 
    CrossrefGoogle Scholar
  • 23 Hill MG. Penneau J.-F. Zinger B. Mann KR. Miller LL. Chem. Mater.  1992,  4:  1106 
    CrossrefGoogle Scholar
2

Present address: Acreo AB, Bredgatan 34, SE-602 21 Norrköping, Sweden.

3

Present address: Unit for Organic Chemistry, Department of Biosciences, Karolinska Institute and Södertörn University College, Novum Research Park, SE-141 57 Huddinge, Sweden.

10

In order to have a useful shorthand nomenclature for the oligothiophenes, we named TDT for thienodithiine 5 and TOT for thienooxathiine 7. The oligothiophenes were then called TDTnT for the dithiino end-capped series, and TOTnT for the oxathiino end-capped series, where n is the number of thiophene units, as for the ECnT oligomers [7] . For instance, TOT3T 29 is a terthiophene, which is end-capped with thioxano rings.

11

A literature search with Beilstein Commander and Scifinder Scholar in May 2003 found 20 substances containing 5 as a substructure, other than those reported by us in preliminary communications. Only 3 of these contain a peripheral ethylenedithio bridge. No compound with the substructure 6 was found, and only 3 compounds based on 7.