PDF herunterladen
Synlett 2007(2): 0231-0234  
DOI: 10.1055/s-2007-968015
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Spectroscopic Studies of Various Arylene Ethynylene Fluorophores

Guang Shao, Akihiro Orita*, Hisataka Taniguchi, Kanako Ishimaru, Junzo Otera*
Department of Applied Chemistry, Okayama University of Science, Ridai-cho, Okayama 700-005, Japan
Fax: +81(86)2564292; e-Mail: orita@high.ous.ac.jp; e-Mail: otera@high.ous.ac.jp;
Weitere Informationen

Publikationsverlauf

Received 26 October 2006
Publikationsdatum:
24. Januar 2007 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

A series of arylene cores substituted by phenylene ethynylenes were synthesized by Sonogashira coupling of diethynyl ­aromatic compounds with an iododiphenylethyne which had been prepared conveniently by making use of a one-shot double-elimination reaction. Photoluminescence properties of the arylene ethynylenes thus prepared were recorded both in solution and in the solid state.

Key words

alkynes - sulfones - sldehydes - eliminations - spectro­scopy

    References and Notes

  • 1a Acetylene Chemistry: Chemistry, Biology, and Material Science   Diederich F. Stang PJ. Tykwinski RR. VCH; Weinheim: 2005. 
    Google Scholar
  • 1b Modern Acetylene Chemistry   Stang PJ. Diederich F. VCH; Weinheim: 1995. 
    Google Scholar
  • For reviews of phenylene ethynylenes, see:
  • 1c James DK. Tour JM. In Topics in Current Chemistry   Vol. 257:  Springer; Berlin: 2005.  p.33-62  
    Google Scholar
  • 1d Stone MT. Heemstra JM. Moore JS. Acc. Chem. Res.  2006,  39:  11 
    Google Scholar
  • 1e Ray CR. Moore JS. Adv. Polym. Sci.  2005,  177:  91 
    Google Scholar
  • 2 Shirai Y. Osgood AJ. Zhao Y. Kelly KF. Tour JM. Nano Lett.  2005,  5:  2330 
    CrossrefGoogle Scholar
  • 3a Wackerly JW. Moore JS. Macromolecules  2006,  39:  7269 
    CrossrefGoogle Scholar
  • 3b Elliott EL. Ray CR. Kraft S. Atkins JR. Moore JS. J. Org. Chem.  2006,  71:  5282 
    CrossrefGoogle Scholar
  • 3c Balakrishnan K. Datar A. Zhang W. Yang X. Naddo T. Huang J. Zuo J. Yen M. Moore JS. Zang L. J. Am. Chem. Soc.  2006,  128:  6576 ; and references therein
    CrossrefGoogle Scholar
  • 4 Orita A. Jiang L. Tsuruta M. Otera J. Chem. Lett.  2002,  136 
    CrossrefGoogle Scholar
  • 5 Orita A. An D.-L. Nakano T. Yaruva J. Ma N. Otera J. Chem. Eur. J.  2002,  8:  2005 
    CrossrefGoogle Scholar
  • 6 Orita A. Nakano T. An D.-L. Tanikawa K. Wakamatsu K. Otera J. J. Am. Chem. Soc.  2004,  126:  10389 
    CrossrefGoogle Scholar
  • 7 Oyamada T. Shao G. Uchiuzou H. Nakanotani H. Orita A. Otera J. Yahiro M. Adachi C. Jpn. J. Appl. Phys.  2006,  45:  1331 
    CrossrefGoogle Scholar
  • 8 A part of optical property of 4-(4-methoxyphenyl-ethynyl)phenylethyne has been reported. See: Shao G. Orita A. Nishijima K. Ishimaru K. Takezaki M. Wakamatsu K. Otera J. Chem. Lett.  2006,  35:  1284 
    CrossrefGoogle Scholar
  • 9 Orita A. Taniguchi H. Otera J. Chem. Asian J.  2006,  1:  430 
    CrossrefGoogle Scholar
10

Double Elimination Method for 1 and 7: 1-(3,7-Di-methyloctyloxy)-4-(4-ethynylphenylethynyl)benzene ( 1). To a THF solution (15 mL) of 4-(3,7-dimethyloctyl-oxy)phenylmethyl phenyl sulfone (3, 466 mg, 1.2 mmol), 4-(trimethylsilylethynyl)benzaldehyde (4, 202 mg, 1.0 mmol) and diethylchlorophosphate (0.17 mL, 1.2 mmol) was added a THF solution of LiHMDS (1.0 M, 5.0 mL, 5.0 mmol) at 0 °C, and the mixture was stirred at r.t. for 16 h under argon. After usual work-up, the organic layer was evaporated and the residue was subjected to a column chromatography on silica gel (10% EtOAc-hexane) to give 1-(3,7-dimethyl-octyloxy)-4-[4-(trimethylsilylethynyl)phenyl-ethynyl]benzene in a pure form (358 mg, 83%). To a solution of 1-(3,7-dimethyloctyloxy)-4-[4-(trimethylsilyl-ethynyl)phenylethynyl]benzene (2.15 g, 5.0 mmol) in THF (25 mL) and MeOH (25 mL) was added 6.91 g of K2CO3. The reaction mixture was stirred for 1.5 at r.t. After H2O had been added, the aqueous layer was extracted with EtOAc. The combined organic layer was washed with brine, dried over MgSO4 and filtered. The solvents were evaporated, and the residue was subjected to column chromatography on silica gel (20% CH2Cl2-hexane) to afford 1 in a pure form (1.63 g, 91%).
Compound 1: 1H NMR (300 MHz, CDCl3): δ = 0.87 (d, J = 6.5 Hz, 6 H), 0.94 (d, J = 6.3 Hz, 3 H), 1.14-1.32 (m, 6 H), 1.48-1.64 (m, 3 H), 1.78-1.84 (m, 1 H), 3.16 (s, 1 H), 3.98-4.03 (m, 2 H), 6.87 (d, J = 8.9 Hz, 2 H), 7.43-7.46 (m, 6 H). 13C NMR (125 MHz, CDCl3): δ = 19.6, 22.5, 22.6, 24.6, 27.9, 29.8, 36.0, 37.2, 39.2, 66.3, 78.6, 83.3, 87.5, 91.6, 114.5, 114.6, 121.3, 124.1, 131.2, 132.0, 133.0, 159.4.
According to the same procedure, compound 7 was prepared from 3 and 4-iodobenzaldehyde.
Compound 7: 68%. 1H NMR (500 MHz, CDC13): δ = 0.88 (d, J = 6.7 Hz, 6 H), 0.95 (d, J = 6.7 Hz, 3 H), 1.15-1.34 (m, 6 H), 1.52-1.68 (m, 3 H), 1.80-1.85 (m, 1 H), 3.99-4.03 (m, 2 H), 6.88 (d, J = 7.9 Hz, 2 H), 7.24 (d, J = 8.2 Hz, 2 H), 7.45 (d, J = 8.6 Hz, 2 H), 7.68 (d, J = 8.6 Hz, 2 H). 13C NMR (125 HMz CDC13): δ = 19.6, 22.6, 22.7, 24.6, 28.0, 29.8, 36.1, 37.3, 39.2, 66.4, 87.1, 91.0, 93.6, 114.6, 114.6, 123.2, 132.9, 133.0, 137.4, 159.4.

11

Typical Procedure for Sonogashira Coupling.
A 50 mL flask was charged with 7 (318 mg, 0.69 mmol), 1,4-diethyl-2,5-diethynylbenzene (55 mg, 0.30 mmol), Pd(PPh3)4 (34 mg, 0.03 mmol), CuI (5.0 mg, 0.03 mmol), i-Pr2NH (1.0 mL) and toluene (20 mL), and the mixture was heated at 65 °C for 12 h. After filtration, the filtrate was poured into aq NH4Cl and extracted with CH2Cl2. The combined organic layer was washed with brine, dried over MgSO4 and filtered. After evaporation, the residue was subjected to column chromatography to afford 2a as white powder in a pure form (228 mg, 90%).
Compound 2a: mp 151-153 °C. 1H NMR (500 MHz, CDCl3): δ = 0.87 (d, J = 6.7 Hz, 12 H), 0.94 (d, J = 6.4 Hz, 6 H), 1.15-1.20 (m, 6 H), 1.25-1.37 (m, 12 H), 1.50-1.67 (m, 6 H), 1.82-1.85 (m, 2 H), 2.85 (q, J = 7.5 Hz, 4 H), 3.99-4.05 (m, 4 H), 6.88 (d, J = 8.8 Hz, 4 H), 7.39 (s, 2 H), 7.45-7.49 (m, 12 H). 13C NMR (125 MHz, CDCl3): δ = 14.7, 19.6, 22.6, 22.7, 24.6, 27.1, 27.9, 29.8, 36.0, 37.2, 39.2, 66.4, 88.0, 89.8, 91.5, 94.1, 114.5, 114.7, 122.4, 122.7, 123.5, 131.3, 131.4, 131.5, 133.0, 143.4, 159.3. Anal. Calcd for C62H70O2: C, 87.90; H, 8.33. Found: C, 88.12; H, 8.60.
Compound 2b: mp 178-181 °C. 1H NMR (500 MHz, CDCl3): δ = 0.87 (d, J = 6.4 Hz, 12 H), 0.94 (d, J = 6.7 Hz, 6 H), 1.15-1.34 (m, 12 H), 1.50-1.69 (m, 6 H), 1.80-1.86 (m, 2 H), 3.97-4.04 (m, 4 H), 6.87 (d, J = 8.8 Hz, 4 H), 7.17 (s, 2 H), 7.45-7.48 (m, 12 H). 13C NMR (125 MHz, CDCl3): δ = 19.6, 22.6, 22.7, 24.6, 27.9, 29.8, 36.0, 37.2, 39.2, 66.4, 83.9, 87.7, 91.8, 94.0, 114.5, 114.7, 121.8, 123.9, 124.6, 131.3, 131.4, 132.0, 133.0, 159.4. ESI-MS: m/z calcd for C56H60O2S [M + H+]: 797.4; found: 797.3.
Compound 2c: mp 235-238 °C. 1H NMR (500 MHz, CDCl3): δ = 0.87 (d, J = 6.7 Hz, 12 H), 0.94 (d, J = 6.7 Hz, 6 H), 1.15-1.37 (m, 12 H), 1.49-1.67 (m, 6 H), 1.80-1.86 (m, 2 H), 3.97-4.05 (m, 4 H), 6.87 (d, J = 8.8 Hz, 4 H), 7.45-7.50 (m, 10 H), 7.56 (d, J = 8.2 Hz, 4 H), 7.69 (t, J = 7.7 Hz, 1 H). 13C NMR (125 MHz, CDCl3): δ = 19.6, 22.5, 22.6, 24.6, 27.9, 29.8, 36.0, 37.2, 39.2, 66.3, 87.6, 89.4, 89.7, 91.9, 114.5, 114.6, 121.3, 124.4, 126.3, 131.3, 132.0, 133.1, 136.4, 143.6, 159.4. ESI-MS: m/z calcd for C57H61NO2 [M + H+]: 792.3; found: 792.5.
Compound 2d: mp 208-212 °C. 1H NMR (500 MHz, CDCl3): δ = 0.86 (d, J = 6.7 Hz, 12 H), 0.93 (d, J = 6.7 Hz, 6 H), 1.14-1.33 (m, 12 H), 1.50-1.65 (m, 6 H), 1.80-1.84 (m, 2 H), 3.97-4.01 (m, 4 H), 6.77 (d, J = 7.6 Hz, 2 H), 6.85 (d, J = 8.8 Hz, 4 H), 6.91 (s, 2 H), 7.15 (t, J = 7.4 Hz, 2 H), 7.35-7.43 (m, 14 H), 7.55 (d, J = 7.6 Hz, 2 H), 7.82 (d, J = 7.9 Hz, 2 H), 7.87 (d, J = 7.6 Hz, 2 H). 13C NMR (125 MHz, CDCl3): δ = 19.6, 22.5, 22.6, 24.6, 27.9, 29.8, 36.0, 37.2, 39.2, 65.5, 66.3, 87.7, 89.9, 91.3, 91.5, 114.5, 114.7, 120.1, 120.2, 122.4, 122.6, 123.4, 124.1, 127.2, 128.0, 128.1, 131.2, 131.3, 131.5, 133.0, 141.2, 141.7, 147.6, 149.2, 159.3. Anal. Calcd for C77H72O2: C, 89.84; H, 7.05. Found: C, 89.79; H, 7.27.
Compound 2e: mp 263-266 °C. 1H NMR (500 MHz, CDCl3): δ = 0.87 (d, J = 6.4 Hz, 12 H), 0.95 (d, J = 6.4 Hz, 6 H), 1.15-1.37 (m, 12 H), 1.49-1.67 (m, 6 H), 1.80-1.87 (m, 2 H), 2.49 (d, J = 13.4 Hz, 2 H), 3.32 (d, J = 13.4 Hz, 2 H), 3.97-4.05 (m, 4 H), 6.88 (d, J = 8.8 Hz, 4 H), 6.99 (s, 2 H), 7.31 (t, J = 7.1 Hz, 2 H), 7.43-7.56 (m, 20 H), 7.73 (d, J = 7.9 Hz, 2 H), 8.07 (d, J = 8.2 Hz, 4 H). 13C NMR (125 MHz, CDCl3): δ = 19.6, 22.6, 22.7, 24.6, 28.0, 29.8, 36.1, 37.3, 39.2, 42.4, 61.0, 66.4, 87.8, 89.7, 91.5, 91.8, 114.6, 114.8, 120.1, 121.9, 122.7, 123.4, 125.3, 125.8, 127.4, 127.6, 128.0, 128.4, 128.9, 131.3, 131.4, 131.5, 131.9, 133.1, 133.2, 134.5, 135.6, 138.8, 151.4, 159.4. ESI-MS: m/z calcd for C87H80O2 [M + H+]: 1157.5; found: 1157.6.