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

Simon Stubbe Schou; Christian Richard Parker; Kasper Lincke; Karsten Jennum; Johan Vibenholt; Anders Kadziola; Mogens Brøndsted Nielsen

doi:10.1055/s-0032-1317921

Synlett, Table of Contents

Synlett 2013; 24(2): 231-235
DOI: 10.1055/s-0032-1317921

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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

Abstract

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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

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References

References and Notes
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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

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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
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

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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
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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.

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