References
1a
Pak JJ.
Brand SC.
Haley MM.
Top. Curr. Chem.
1999,
201:
81
1b
Bunz UHF.
Chem. Rev.
2000,
100:
1605
1c
Young JK.
Moore JS. In
Modern Acetylene Chemistry
Stang PJ.
Diederich F.
VCH;
Weinheim:
1995.
p.415-442
Inter alia:
2a
Conjugated Polymers and Related Materials: The Interconnection of Chemical and Electronic Structure
Saleneck WR.
Lundström I.
Ranby B.
Oxford University Press;
Oxford, UK:
1993.
2b
Photonic and Optoelectronic Polymers
Jenekhe SA.
Wynne KJ.
American Chemical Society;
Washington, DC:
1995.
2c
Electronic Materials: The Oligomer Approach
Müllen K.
Wegner G.
Wiley-VCH;
Weinheim, Germany:
1998.
2d
Tour JM.
Chem. Rev.
1998,
96:
537
2e
Schwab PFH.
Levin MD.
Michl J.
Chem. Rev.
1999,
99:
1863
3
Marsden JA.
Palmer JG.
Haley MM.
Eur. J. Org. Chem.
2003,
2355
4a
Pak JJ.
Weakley TJR.
Haley MM.
J. Am. Chem. Soc.
1999,
121:
8182
4b
Sarkar A.
Pak JJ.
Rayfield GW.
Haley MM.
J. Mater. Chem.
2001,
11:
2943
5 Marsden, J. A.; Miller, J. J.; Haley, M. M., manuscript in preparation.
6
Kondo K.
Yasuda S.
Sakaguchi T.
Miya M.
Chem. Commun.
1995,
55-56
7
Du C.-JF.
Hart H.
J. Org. Chem.
1987,
4311
8a
Venkataraman D.
Gardner GB.
Lee S.
Moore JS.
J. Am. Chem. Soc.
1995,
117:
11600
8b
Gardner GB.
Kiang Y.-H.
Lee S.
Asgaonkar A.
Venkataraman D.
J. Am. Chem. Soc.
1996,
118:
6946
8c
Kiang Y.-H.
Gardner GB.
Lee S.
Xu Z.
Lobkovsky EB.
J. Am. Chem. Soc.
1999,
121:
8204
9a
Swager TM.
Acc. Chem. Res.
1998,
31:
201
9b
Bunz UHF.
Angew. Chem., Int. Ed. Engl.
1994,
33:
1073
9c
Yamamoto T.
Bull. Chem. Soc. Jpn.
1999,
72:
621
10
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.
11a
Sonogashira K. In
Metal-Catalyzed Cross-Coupling Reactions
Stang PJ.
Diederich F.
VCH;
Weinheim:
1997.
p.203-229
11b
Negishi E.
Anastasia L.
Chem. Rev.
2003,
103:
1979
12
Miljanic OS.
Vollhardt KPC.
Whitener GD.
Synlett
2003,
29
13
Thorand S.
Krause W.
J. Org. Chem.
1998,
63:
8551
14 Slepkov, A. D.; Hegmann, F. A.; Marsden, J. A.; Miller, J. J.; Haley, M. M.; Tykwinski, R. R., work in progress.
15a
Reinhardt BA.
Brott LL.
Clarson SJ.
Dillard AG.
Bhatt JC.
Kannan R.
Yuan LX.
He GS.
Prasad PN.
Chem. Mater.
1998,
10:
1863
15b
Kim OK.
Lee KS.
Woo HY.
Kim KS.
He GS.
Swiatkiewicz J.
Prasad PN.
Chem. Mater.
2000,
12:
284
15c For measurement techniques: Slepkov AD.
Hegmann FA.
Zhao YM.
Tykwinski RR.
Kamada K.
J. Chem. Phys.
2002,
116:
3834