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Synlett 2004(1): 165-168  
DOI: 10.1055/s-2003-43372
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© Georg Thieme Verlag Stuttgart · New York

Synthesis and Optical Properties of Donor-Acceptor Tetrakis(phenyl­ethynyl)benzenes

Jeremie J. Miller, Jeremiah A. Marsden, Michael M. Haley*
Department of Chemistry and the Materials Science Institute, University of Oregon, Eugene, Oregon 97403-1253, USA
Fax: +1(541)3460487; e-Mail: haley@oregon.uoregon.edu;
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Publication History

Received 3 September 2003
Publication Date:
04 December 2003 (online)

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Abstract

A simple and efficient synthesis of a series of donor-acceptor substituted 1,2,4,5-tetrakis(phenylethynyl)benzenes is described. The molecules constructed exhibit interesting optical properties. Preliminary studies show that the tetraynes hold promise as nonlinear optical (NLO) materials.

Key words

alkynes - arenes - chromophores - cross-coupling - palladium

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Marsden, J. A.; Miller, J. J.; Haley, M. M., manuscript in preparation.

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General Alkyne Coupling Procedure. A solution of haloarene (1 equiv) in i-Pr2NH-THF (3:1, 0.05 M) was degassed by bubbling Ar for 20 min or by three freeze-pump-thaw cycles. Pd(PPh3)2Cl2 (for iodoarene) or Pd(PPh3)4 (for bromoarene) (0.05 equiv) and CuI (0.12 equiv) were added and the flask was sealed under Ar. The terminal acetylene (1.1 equiv per halide) was then added via syringe, and the reaction mixture stirred at r.t. (for iodoarenes) or 40 °C (for bromoarenes) for 12 h. Upon completion, the reaction mixture was concentrated in vacuo, diluted with CH2Cl2, and filtered through a bed of silica gel. The filtrate was concentrated, and the crude material was purified by column chromatography on silica gel (hexanes-CH2Cl2).
4: 1H NMR (CDCl3): δ = 0.98 (t, J = 7.4 Hz, 24 H), 1.37 (sext, J = 7.5 Hz, 16 H), 1.59 (quin, J = 7.7 Hz, 16 H), 3.30 (t, J = 7.7 Hz, 16 H), 6.59 (d, J = 9.2 Hz, 8 H), 7.43 (d, J = 9.2 Hz, 8 H), 7.63 (s, 2 H). 13C NMR (CDCl3): δ = 13.96, 20.29, 29.36, 50.66, 86.31, 96.23, 108.97, 111.14, 124.60, 133.05, 133.88, 147.98.
5: 1H NMR (CDCl3): δ = 0.97 (t, J = 7.4 Hz, 8 H), 1.37 (sext, J = 7.4 Hz, 8 H), 1.59 (quin, J = 8.4 Hz, 8 H), 3.31 (t, J = 7.7 Hz, 12 H), 6.59 (d, J = 9.3 Hz, 4 H), 7.42 (d, J = 9.0 Hz, 4 H), 7.67 (d, J = 8.9 Hz, 4 H) 7.73 (s, 2 H), 8.24 (d, J = 8.9 Hz, 4 H). 13C NMR (CDCl3): δ = 13.98, 20.30, 29.32, 50.65, 86.12, 92.65, 92.80, 98.49, 108.06, 111.07, 122.66, 123.70, 126.91, 129.90, 132.20, 133.18, 134.65, 146.99, 148.37.
6: 1H NMR (CDCl3): δ = 0.98 (t, J = 7.4 Hz, 8 H), 1.38 (sext, J = 7.5 Hz, 8 H), 1.58 (quin, J = 7.9 Hz, 8 H), 3.30 (t, J = 7.7 Hz, 12 H), 6.57 (d, J = 9.0 Hz, 4 H), 7.35 (d, J = 9.0 Hz, 4 H), 7.66 (d, J = 9.0 Hz, 4 H) 7.66 (s, 1 H), 7.68 (s, 1 H), 8.18 (d, J = 9.0 Hz, 4 H). 13C NMR (CDCl3): δ = 13.98, 20.30, 29.32, 50.65, 85.76, 92.55, 93.35, 98.87, 107.77, 111.14, 122.06, 123.64, 127.85, 130.18, 132.25, 133.12, 134.00, 135.20, 146.93, 148.50.
7: 1H NMR (CDCl3): δ = 0.97 (t, J = 7.4 Hz, 8 H), 1.37 (sext, J = 7.5 Hz, 8 H), 1.57 (quin, J = 7.8 Hz, 8 H), 3.31 (t, J = 7.7 Hz, 12 H), 6.59 (d, J = 9.0 Hz, 4 H), 7.35 (d, J = 9.0 Hz, 4 H), 7.71 (d, J = 9.0 Hz, 4 H) 7.72 (s, 2 H), 8.23 (d, J = 9.0 Hz, 4 H). 13C NMR (CDCl3): δ = 13.95, 20.25, 29.30, 50.60, 85.49, 92.92, 93.27, 98.10, 107.84, 111.10, 123.58, 124.09, 125.74, 130.05, 132.32, 132.99, 134.55, 146.95, 148.37.
8: 1H NMR (CDCl3): δ = 0.98 (t, J = 7.2 Hz, 8 H), 1.38 (sext, J = 7.5 Hz, 8 H), 1.59 (quin, J = 8.2 Hz, 8 H), 3.31 (t, J = 7.7 Hz, 12 H), 6.59 (d, J = 9.0 Hz, 4 H), 7.39 (d, J = 9.0 Hz, 4 H), 7.60 (br s, 4 H), 7.66 (d, J = 1.8 Hz, 2 H). 13C NMR (CDCl3): δ = 13.98, 20.28, 29.31, 50.65, 85.95, 91.93, 92.73, 98.35, 108.11, 111.10, 111.67, 118.40, 122.74, 126.76, 127.88, 131.97, 132.10, 133.2, 134.63, 148.30.
9: 1H NMR (CDCl3): δ = 0.97 (t, J = 7.4 Hz, 12 H), 1.37 (sext, J = 7.5 Hz, 8 H), 1.59 (quin, J = 7.5 Hz, 8 H), 3.30 (t, J = 7.7 Hz, 8 H), 6.58 (d, J = 8.7 Hz, 4 H), 7.36 (d, J = 8.7 Hz, 4 H), 7.65 (s, 4 H), 7.69 (s, 1 H) 7.71 (s, 1 H). 13C NMR (CDCl3): δ = 14.00, 20.31, 29.33, 50.66, 85.63, 92.36, 92.72, 98.65, 107.78, 111.15, 111.55, 118.56, 122.24, 127.67, 128.17, 132.11, 133.12, 134.04, 135.08, 148.45.
10: 1H NMR (CDCl3): δ = 0.97 (t, J = 7.4 Hz, 12 H), 1.38 (sext, J = 7.8 Hz, 4 H), 1.58 (quin, J = 7.7 Hz, 4 H), 3.31 (t, J = 7.7 Hz, 4 H), 6.58 (d, J = 9.0 Hz, 4 H), 7.35 (d, J = 9.0 Hz, 4 H), 7.65 (s, 8 H), 7.70 (s, 2 H). 13C NMR (CDCl3): δ = 13.86, 18.84, 20.17, 29.21, 47.06, 50.54, 54.62, 85.29, 92.20, 92.99, 97.89, 107.74, 111.06, 111.55, 118.40, 124.07, 125.63, 127.96, 131.97, 132.04, 132.89, 134.44, 148.29.
15: 1H NMR (CDCl3): δ = 0.26 (s, 18 H), 7.69 (s, 2 H). 13C NMR (CDCl3): δ = -0.16, 100.84, 100.05, 124.46, 126.05, 136.54.
16: 1H NMR (CDCl3): δ = 0.27 (s, 18 H), 1.13 (s, 63 H), 7.53 (s, 2 H). 13C NMR (CDCl3): δ = -0.04, 11.29, 18.75, 97.46, 100.60, 102.11, 104.22, 125.10, 125.16, 137.02.
17: 1H NMR (CDCl3): δ = 0.96 (t, J = 7.4 Hz, 8 H), 1.14 (s, 42 H), 1.36 (sext, J = 7.4 Hz, 8 H), 1.58 (quin, J = 7.6 Hz, 8 H), 3.29 (t, J = 7.5 Hz, 12 H), 6.57 (d, J = 9.0 Hz, 4 H), 7.41 (d, J = 9.0 Hz, 4 H), 7.57 (s, 2 H). 13C NMR (CDCl3): δ = 11.32, 13.98, 18.77, 20.31, 29.36, 50.66, 85.97, 96.06, 97.11, 104.98, 108.56, 111.14, 123.76, 125.72, 133.16, 135.95, 148.17.

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Slepkov, A. D.; Hegmann, F. A.; Marsden, J. A.; Miller, J. J.; Haley, M. M.; Tykwinski, R. R., work in progress.