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Synlett 2013; 24(2): 231-235
DOI: 10.1055/s-0032-1317921
letter
© Georg Thieme Verlag Stuttgart · New York

On the Phosphite-Mediated Synthesis of Dithiafulvenes and π-Extended Tetrathiafulvalenes

Simon Stubbe Schou
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark   Fax: +45 35320212   Email: mbn@kiku.dk
,
Christian Richard Parker
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark   Fax: +45 35320212   Email: mbn@kiku.dk
,
Kasper Lincke
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark   Fax: +45 35320212   Email: mbn@kiku.dk
,
Karsten Jennum
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark   Fax: +45 35320212   Email: mbn@kiku.dk
,
Johan Vibenholt
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark   Fax: +45 35320212   Email: mbn@kiku.dk
,
Anders Kadziola
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark   Fax: +45 35320212   Email: mbn@kiku.dk
,
Mogens Brøndsted Nielsen*
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark   Fax: +45 35320212   Email: mbn@kiku.dk
› Author Affiliations
Further Information

Publication History

Received: 30 October 2012

Accepted after revision: 23 November 2012

Publication Date:
12 December 2012 (online)

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Abstract

By phosphite-mediated couplings between functionalized benzaldehydes and 1,3-dithiole-2-thiones we have obtained a variety of π-extended tetrathiafulvalenes (TTF). In particular, this method has provided a new stilbene-extended TTF with lateral ­alkyne functionalities, an H-type cruciform structure. This outcome is the result of a phosphite-mediated coupling between two aldehydes.

Key words

cruciform - heterocycles - phosphite - sulfur - tetrathia­fulvalene

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
  • Supporting Information
 

  • References and Notes

  • 1 Fabre JM. Chem. Rev. 2004; 104: 5133
    Crossref
    • 2a Leriche P, Roquet S, Pillerel N, Mabon G, Frère P. Tetrahedron Lett. 2003; 44: 1623
      Crossref
    • 2b Nielsen MB, Gisselbrecht J.-P, Thorup N, Piotto SP, Boudon C, Gross M. Tetrahedron Lett. 2003; 44: 6721
      Crossref
    • 2c Andersson AS, Qvortrup K, Torbensen ER, Mayer J.-P, Boudon C, Gross M, Kadziola A, Kilså K, Nielsen MB. Eur. J. Org. Chem. 2005; 3660
    • 2d Iwamoto S, Watanabe S, Fueno H, Tanaka K, Misaki Y. Chem. Lett. 2008; 37: 82
      Crossref
    • 2e Guerro M, Pham NH, Massue J, Bellec N, Lorcy D. Tetrahedron 2008; 64: 5285
      Crossref
    • 2f Cocherel N, Leriche P, Ripaud E, Gallego-Planas N, Frère P, Roncali J. New J. Chem. 2009; 33: 801
      Crossref
    • 2g Ripaud E, Leriche P, Cocherel N, Cauchy T, Frère P, Roncali J. Org. Biomol. Chem. 2011; 9: 1034
      Crossref
    • 2h Bouzan S, Chen G, Mulla K, Dawe LN, Zhao Y. Org. Biomol. Chem. 2012; 10: 7673
      Crossref
  • 3 Parker CR, Wei Z, Arroyo CR, Jennum K, Li T, Santella M, Bovet N, Zhao G, Hu W, van der Zant HS. J, Vanin M, Solomon GC, Laursen BW, Nørgaard K, Nielsen MB. Adv. Mater. 2012; in press; DOI: 10.1002/adma.201201583
    • 4a Christensen CA, Batsanov AS, Bryce MR. J. Org. Chem. 2007; 72: 1301
      Crossref
    • 4b Chen G, Bouzan S, Zhao Y. Tetrahedron Lett. 2010; 51: 6552
      Crossref
  • 5 Zucchero AJ, McGrier PL, Bunz UH. F. Acc. Chem. Res. 2010; 43: 397
    Crossref
  • 6 Simonsen KB, Svenstrup N, Lau J, Simonsen O, Mørk P, Kristensen GJ, Becher J. Synthesis 1996; 407
    Article in Thieme Connect
    • 7a Synthesis of 4 A suspension of 4-iodobenzaldehyde (2, 1.005 g, 4.34 mmol) and the thione 2 (3.303 g, 10.85 mmol) in dry degassed P(OEt)3 (12.5 mL) was heated to 110 °C under an atmosphere of Ar. During the heating, the solid dissolved, and the color of the solution was a brown yellow color. Monitoring the reaction by TLC revealed that the reaction was complete after 2 h. The solvent was removed under reduced pressure. The brown-yellow colored residue was washed with PE to remove any excess P(OEt)3. The residue was dissolved in minimal CH2Cl2 and purified by flash column chromatography (SiO2, PE–CH2Cl2 = 1:4); the first yellow fraction gave the desired compound as a yellow oil or as a fine pale yellow crystalline material (2.043 g, 96%), which darkens over time; mp 97–100 °C. 1H NMR (500 MHz, CDCl3): δ = 7.67 (d, J = 8.4 Hz, 2 H), 6.93 (d, J = 8.4 Hz, 2 H), 6.42 (s, 1 H), 3.12–3.04 (m, 4 H), 2.79–2.71 (m, 4 H). 13C NMR (125 MHz, CDCl3): δ = 137.77, 135.23, 131.27, 128.65, 127.85, 125.02, 117.60, 117.54, 115.54, 91.53, 31.15, 31.13, 19.07, 19.02. IR (ATR): ν = 2995 (m), 2870 (m), 2926 (m), 2246 (m, CN), 1738 (s), 1679 (m), 1571 (s), 1543 (s), 1491 (m), 1478 (s), 1407 (s), 1391 (s) cm–1. MS–FAB: m/z = 487 [M]+. Anal. Calcd (%) for C16H13IN2S4: C, 39.34; H, 2.68; N, 5.74. Found: C, 39.41; H, 2.54; N, 5.63.
  • 8 Jennum K, Vestergaard M, Pedersen AH, Fock J, Jensen J, Santella M, Led JJ, Kilså K, Bjørnholm T, Nielsen MB. Synthesis 2011; 539
    Article in Thieme Connect
  • 9 Synthesis of 1 To a mixture of the dialkyne 5 (50 mg, 0.072 mmol), thione 4 (105 mg, 0.214 mmol), PdCl2(PPh3)2 (5 mg, 0.0072 mmol), and CuI (1.4 mg, 0.0072 mmol) was added a degassed solution of THF (7 mL) and Et3N (0.1 mL). The reaction was stirred for 2 d during which time a red colored precipitate formed. The solvent was removed, and the residue was purified by flash column chromatography (SiO2) initially with CH2Cl2 as eluent to remove some impurities and unreacted 4, then a gradient of 1–20% EtOAc was added to the eluent mixture to get the major orange/red band, which afforded 1 as an orange-red colored solid (61 mg, 60%). Characterization data are in accordance to previously reported data.3
    • 10a Sallé M, Belyasmine A, Gorgues A, Jubault M, Soyer N. Tetrahedron Lett. 1991; 32: 2897
      Crossref
    • 10b Formigué M, Johannsen I, Boubekeur K, Nelson C, Batail P. J. Am. Chem. Soc. 1993; 115: 3752
      Crossref
  • 11 Synthesis of 8 A mixture of terephthalaldehyde 6 (100 mg, 0.74 mmol), thione 7 (673 mg, 2.98 mmol), and P(OEt)3 (4 mL) was heated to 100 °C under an argon atmosphere for 2 h. The reaction mixture was then allowed to cool to r.t., and the yellow precipitate was isolated and washed thoroughly with MeOH (100 mL) to provide the product as yellow crystals (286 mg, 79%); mp 164–165 °C. 1H NMR (500 MHz, CDCl3): δ = 7.20 (s, 4 H), 6.45 (s, 2 H), 2.44 (s, 6 H), 2.43 (s, 6 H). 13C NMR (125 MHz, CDCl3): δ = 133.88, 131.87, 127.50, 127.06, 124.54, 114.66, 19.19, 19.07. MS (MALDI): m/z = 490 [M+]. Anal. Calcd (%) for C18H18S8: C, 44.04; H, 3.70. Found: C, 44.02; H, 3.57.
  • 12 Synthesis of 10 A mixture of 9 (80.2 mg, 0.49 mmol) and thione 7 (1.01 g, 4.45 mmol) in dry degassed P(OEt)3 (5 mL) was stirred at 110 °C for 4 d. The mixture was then concentrated under reduced pressure. The residue was subjected to dry column vacuum chromatography (SiO2, heptane to heptane–EtOAc = 4:1, 5% increase per fraction) to provide the product as a brown solid (68 mg, 20%). 1H NMR (500 MHz, CDCl3): δ = 6.85 (s, 3 H), 6.46 (s, 3 H), 2.44 (s, 18 H). 13C NMR (125 MHz, CDCl3): δ = 136.85, 133.22, 127.20, 124.71, 122.70, 114.50, 19.29, 19.08. HRMS (ESI+): m/z calcd for C24H24S12 +: 695.8521; found: 695.8496 [M+].
  • 13 Sørensen JK, Vestergaard M, Kadziola A, Kilså K, Nielsen MB. Org. Lett. 2006; 8: 1173
    Crossref
  • 14 Le Narvor N, Robertson N, Wallace E, Kilburn JD, Underhill AE, Bartlett PN, Webster M. J. Chem. Soc., Dalton Trans. 1996; 823
    • 15a Synthesis of 14 Compounds 11 (0.30 g, 0.92 mmol) and 12 (0.92 g, 3.62 mmol) were dissolved in P(OEt)3 (5 mL, 29 mmol). The mixture was stirred under argon at 100 °C for 6 h. The mixture was allowed to cool to r.t. and was then poured into MeOH (100 mL). The product 14 precipitated and was collected on a filter as a red solid (130 mg, 27%); mp 150–170 °C (decomp.). 1H NMR (500 MHz, CDCl3): δ = 7.82 (s, 2 H), 7.63 (s, 2 H), 7.39 (s, 2 H), 6.91 (s, 2 H), 2.90 (q, J = 7.4 Hz, 4 H), 2.88 (q, J = 7.4 Hz, 4 H) 1.36 (t, J = 7.4 Hz, 6 H), 1.34 (t, J = 7.4 Hz, 6 H), 0.36 (s, 18 H), 0.28 (s, 18 H). 13C NMR (125 MHz, CDCl3): δ = 136.62, 136.03, 135.98, 128.79, 128.70, 128.48, 126.75, 125.09, 122.66, 121.52, 111.52, 103.11, 103.07, 101.81, 101.25, 30.72, 30.47, 15.20, 15.10, 0.23, 0.09. IR (ATR): ν = 2958 (s), 2923 (m), 2151 (s, C≡C), 1694 (w), 1558 (vs), 1494 (s), 1474 (m), 1445 (m), 1402 (m), 1374 (m) cm–1. HRMS (ESI+): m/z calcd for C50H65S8Si4 +: 1033.1924; found: 1033.1901 [MH+].
    • 15b Synthesis of 15 Compounds 11 (0.22 g, 0.69 mmol) and 13 (0.64 g, 2.06 mmol) were dissolved in dry degassed P(OEt)3 (4 mL, 18 mmol). The mixture was stirred under argon at 100 °C for 5 h and then allowed to cool to r.t. The solvent was removed under reduced pressure at 60 °C, and the crude residue was subjected to flash column chromatography (SiO2, 10% toluene in heptane) to give the product 15 as a red solid (67 mg, 17%); mp 188–190 °C (slight color change from ca. 110 °C). 1H NMR (500 MHz, CDCl3): δ = 7.82 (s, 2 H), 7.63 (s, 2 H) 7.39 (s, 2 H) 6.91 (s, 2 H) 2.85 (t, J = 7.4 Hz, 4 H), 2.85 (t, J = 7.4 Hz, 4 H), 1.68–1.61 (m, 8 H), 1.47 (q, J = 7.4 Hz, 4 H), 1.44 (q, J = 7.4 Hz, 4 H), 0.94 (t, J = 7.4 Hz, 6 H), 0.94 (t, J = 7.4 Hz, 6 H), 0.35 (s, 18 H), 0.27 (s, 18 H). 13C NMR (125 MHz, CDCl3): δ = 136.57, 136.14, 135.84, 128.65, 128.53, 128.43, 126.62, 125.04, 122.59, 121.40, 111.36, 103.03, 103.00, 101.74, 101.19, 36.16, 35.89, 31.94, 31.85, 21.84, 21.82, 13.81, 13.77, 0.20, 0.06. IR (ATR): ν = 2957 (vs), 2928 (s), 2871 (m), 2150 (s, C≡C), 1696 (w), 1672 (w), 1553 (vs), 1492 (s), 1464 (m), 1402 (m), 1340 (vw) cm–1. HRMS (ESI+): m/z calcd for C58H81S8Si4 +: 1145.3176; found: 1145.3116 [MH+]. Anal. Calcd (%) for C58H80S8Si4: C, 60.78; H, 7.04. Found: C, 60.26; H, 6.94.
  • 16 Ramirez F, Bhatia SB, Smith CP. Tetrahedron 1967; 23: 2067
    Crossref
  • 17 Arbuzov A, Zoroastrova VM. Izv. Akad. Nauk. U.S.S.R., Otd. Khim. Nauk 1960; 1030 ; Chem. Abstr. 1960, 54, 24627g
    • 18a Ramirez F, Yamanaka H, Basedow OH. J. Org. Chem. 1959; 24: 1838
      Crossref
    • 18b Ramirez F, Yamanaka H, Basedow OH. J. Am. Chem. Soc. 1961; 83: 173
      Crossref
  • 19 Tamura H, Shinohara Y, Arai T. Chem. Lett. 2010; 40: 129
  • 20 Yamaguchi S, Iimura K, Tamao K. Chem. Lett. 1998; 27: 89
  • 21 Zhou N, Wang L, Thompson DW, Zhao Y. Tetrahedron 2011; 67: 125
    Crossref