Synlett 2010(15): 2304-2310  
DOI: 10.1055/s-0030-1258050
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Elaborating Boron Dipyrromethene Dyes with Conjugated Polyaromatic Frameworks

Raymond Ziessel*, Thomas Bura, Jean-Hubert Olivier
Laboratoire de Chimie Organique et Spectroscopies Avancées (LCOSA, www-lmspc.u-strasbg.fr/lcosa), CNRS, UdS, ECPM, 25 Rue Becquerel, 67087 Strasbourg Cedex 2, France
e-Mail: ziessel@unistra.fr;
Further Information

Publication History

Received 11 May 2010
Publication Date:
30 August 2010 (online)

Abstract

New difluoro-bora-diaza-s-indacenes were synthesized from tetramethyl derivatives following a sequence of reactions including Knoevenagel condensation, selective cross-coupling reactions in order to extend the delocalization pathway. The introduction of flexible chains bearing a terminal ester or based on polyethylene glycol insure a good solubility and import polarity which facilitates the purification procedures. Many polyaromatic subunits (pyrene, perylene, anthracene, naphtalene, ferrocene) were fused to the main central core of the Bodipy.

    References and Notes

  • 1 Lakowicz JR. Principles of Fluorescence Spectroscopy   3rd ed.:  Springer; Heidelberg: 2006. 
  • 2 Earp AA. Smith GB. Swift PD. Franklin J. Sol. Energy  2004,  76:  655 
  • 3a Goze C. Ulrich G. Mallon LJ. Allen BD. Harriman A. Ziessel R. J. Am. Chem. Soc.  2006,  128:  10231 
  • 3b Harriman A. Izzet G. Ziessel R. J. Am. Chem. Soc.  2006,  128:  10868 
  • 4a Harriman A. Mallon LJ. Ziessel R. Chem. Eur. J.  2008,  14:  11461 
  • 4b Harriman A. Mallon LJ. Goeb S. Ulrich G. Ziessel R. Chem. Eur. J.  2009,  15:  4553 
  • 5 Ulrich G. Ziessel R. Harriman A. Angew. Chem. Int. Ed.  2008,  47:  1184 
  • 6 Saki N. Dinc T. Akkaya EU. Tetrahedron  2006,  62:  2721 
  • 7 Buyukcakir O. Bozdemir OA. Kolemen S. Erbas S. Akkaya EU. Org. Lett.  2009,  11:  4644 
  • 8 Bonardi L. Ulrich G. Ziessel R. Org. Lett.  2008,  10:  2183 
  • 9 Rihn S. Retailleau P. Bugsaliewicz N. De Nicola A. Ziessel R. Tetrahedron Lett.  2009,  50:  7008 
  • 10a Gorma A. Killoran J. O’Shea C. Kenna T. Gallagher WM. O’Shea DF. J. Am. Chem. Soc.  2004,  126:  10619 
  • 10b Zhao W. Carreira EM. Chem. Eur. J.  2006,  12:  7254 
  • 11a Chen J. Burghart A. Derecskei-Kowacs A. Burgess K. J. Org. Chem.  2000,  65:  2900 
  • 11b Umezawa K. Nakamura Y. Makino H. Citterio D. Suzuki K. J. Am. Chem. Soc.  2008,  130:  1550 
  • 12 Ulrich G. Goeb S. De Nicola A. Retailleau P. Ziessel R. Synlett  2007,  1517 
  • 13a Ziessel R. Bonardi L. Retailleau P. Ulrich G. J. Org. Chem.  2006,  71:  3093 
  • 13b Sathyamoorthi G. Boyer J.-H. Allik TH. Chandra S. Heteroat. Chem.  1994,  5:  403 
  • 14 Sathyamoorthi G. Boyer J.-H. Allik TH. Chandra S. Heteroat. Chem.  1994,  5:  403 
  • 15a Haughland RP, and Kang HC. inventors; US  4,774,339. 
  • 15b Rurack K. Kollmansberger M. Daub J. New J. Chem.  2001,  25:  289 
  • 15c Dost Z. Atilgan S. Akkaya EU. Tetrahedron  2006,  62:  8484 
  • 15d Atilgan S. Ekmekci Z. Dogan AL. Guc D. Akkaya EU. Chem. Commun.  2006,  4398 
  • 16 Knoevenagel E. Ber. Dtsch. Chem. Ges.  1898,  31:  2596 
  • 19 Hissler M. Harriman A. Khatyr A. Ziessel R. Chem. Eur. J.  1999,  11:  3366 
  • 20 Inouye M. Hyodo Y. Nakazumi H. J. Org. Chem.  1999,  64:  2704 
  • 21 Ziessel R. Retailleau P. Elliott KJ. Harriman A. Chem. Eur. J.  2009,  15:  10369 
17

Compound 5b: ¹H (400.13 MHz, CDCl3): δ = 8.61 (d, ³ J = 8.2 Hz, 2 H), 8.53 (d, ³ J = 9.3 Hz, 2 H), 8.46 (d, ³ J = 16.6 Hz, 2 H), 8.27-8.16 (m, 6 H), 8.12 (d, ³ J = 9.3 Hz, 2 H), 8.09-7.96 (M, 6 H), 7.93 (d, ³ J = 8.2 Hz, 2 H), 7.89 (d, ³ J = 8.2 Hz, 2 H), 7.37 (d, ³ J = 8.2 Hz, 2 H), 7.00 (s, 2 H), 1.26 (s, 6 H). ¹³C{H} (100.61 MHz, CDCl3): δ = 158.2, 156.6, 156.2, 154.3, 155.5, 148.2, 136.8, 139.5, 132.8, 135.7, 133.6, 135.5, 134.9, 133.6, 130.7, 129.7, 124.9, 128.9, 127.5, 128.9, 127.0, 128.6, 127.0, 125.8, 124.7, 120.4, 96.9, 15.4. MS (EI): m/z (%) = 874.1 (100) [M]. Anal. Calcd for C53H34N2BF2I (Mr = 874.56): C, 72.79; H, 3.92; N, 3.20. Found: C, 72.44; H, 3.67; N, 3.02.

18

Compound 9b: ¹H (400 MHz, CDCl3): δ = 7.70 (d, ³ J = 16.3 Hz, 2 H), 7.56-7.48 (m, 10 H), 7.27 (d, ³ J = 8.2 Hz, ca. 2 H + solvent overlap), 7.18 (d, ³ J = 16.3 Hz, 2 H), 6.64 (s, 2 H), 4.16 (q, ³ J = 7.1 Hz, 2 H), 2.50 (t, ³ J = 7.0 Hz, 2 H), 2.39 (t, ³ J = 7.3 Hz, 2 H), 1.87-1.82 (m, 2 H), 1.72-1.68 (m, 2 H), 1.49 (s, 6 H), 1.28 (t, ³ J = 7.1 Hz, 3 H). ¹³C{¹H} (100 MHz, CDCl3): δ = 173.9, 152.9, 142.8, 139.2, 135.9, 135.4, 134.6, 133.8, 132.7, 132.4, 1296.3, 128.8, 125.3, 123.4, 120.2, 118.4, 91.8 (C≡C), 80.7 (C≡C), 60.8, 34.3, 28.5, 24.7, 19.6, 15.3 (CH3), 14.7 (CH3). MS (EI): m/z (%) = 811.0 (50) [M], 810.0 (100) [M], 808.0 (45) [M]. Anal. Calcd for C42H37N2BF2Br2O2 (Mr = 810.37): C, 62.25; H, 4.60; N, 3.46. Found: C, 61.89; H, 4.39; N, 3.27.

22

Compound 14: ¹H (400 MHz, CDCl3): δ = 8.72 (d, ³ J = 7.8 Hz, 1 H), 8.35 (d, ³ J = 7.6 Hz, 1 H), 8.38-8.03 (m, 14 H), 7.83-7.52 (m 12 H), 7.58-7.62 (m, 4 H), 7.35-7.26 (m, 4 H), 6.74 (s, 1 H), 6.72 (s, 1 H), 4.16 (q, ³ J = 7.2 Hz, 2 H), 2.52 (t, ³ J = 7.0 Hz, 2 H), 2.39 (t, ³ J = 7.2 Hz, 2 H), 1.92-1.80 (m, 2 H), 1.73-1.67 (m, 2 H), 1.48 (s, 6 H), 1.29 (t, ³ J = 7.1 Hz, 3 H). ¹³C{¹H} (100 MHz, CDCl3): δ = 173.8, 153.3, 152.5, 142.9, 142.4, 139.0, 136.9, 132.7, 132.5, 132.4, 131.6, 130.1, 128.9, 128.0, 127.8, 127.7, 126.7, 126.1, 125.0, 121.4, 121.2, 121.0, 118.6, 96.5 (C≡C), 91.9 (C≡C), 91.4 (C≡C) 90.6 (C≡C), 90.2 (C≡C), 80.8 (C≡C), 60.8, 34.3, 28.5, 27.3, 24.7, 19.6, 15.30 (CH3), 14.7 (CH3). MS (EI): m/z (%) = 1151.2 (90) [M], 1150.2 (100) [M]. Anal. Calcd for C82H57N2BF2O2 (Mr = 1151.15): C, 85.56; H, 4.99; N, 2.43. Found: C, 85.33; H, 4.62; N, 2.15.