products are known and were characterized by comparison of
their spectral data with those of authentic samples.
1,4-Bis(2-thienyl) buta-1,3-diyne (2k). 1H NMR (500 MHz,
CDCl3): d 7.36–7.32 (m, 4H, ArH), 7.01–6.99 (dd, J = 3.5 Hz,
J = 8.5 Hz, 2H, ArH); 13C NMR (125 MHz, CDCl3): d 134.5,
129.0, 127.3, 112.0, 77.9, 76.7; EI-MS m/z 214 [M+].
Characterization data for 1,3-diyne compounds
1,4-Bis(3-thienyl) buta-1,3-diyne (2l). 1H NMR (500 MHz,
CDCl3): d 7.59–7.58 (dd, J = 1.0 Hz, J = 4.0 Hz, 2H, ArH),
7.29–7.27 (dd, J = 3.0 Hz, J = 8.0 Hz, 2H, ArH), 7.18–7.16 (dd,
J = 1.0 Hz, J = 6.0 Hz, 2H, ArH); 13C NMR (125 MHz, CDCl3):
d 131.3, 130.3, 125.7, 121.0, 76.7, 73.0.
1,4-Bis(3-pyridyl) buta-1,3-diyne (2m). 1H NMR (500 MHz,
CDCl3): d 8.76 (d, J = 1.0 Hz, 2H, ArH), 8.59–8.58 (dd, J = 1.5
Hz, J = 6.0 Hz, 2H, ArH), 7.82–7.79 (m, 2H, ArH), 7.30–7.27
(dd, J = 5.0 Hz, J = 13.0 Hz, 2H, ArH); 13C NMR (125 MHz,
CDCl3): d 153.2, 149.6, 139.5, 123.2, 118.9, 79.2, 76.7; EI-MS
m/z 204 [M+].
1,4-Diphenyl buta-1,3-diyne (2a). 1H NMR (500 MHz,
CDCl3): d 7.58–7.56 (dd, J = 1.5 Hz, J = 9.5 Hz, 4H, ArH),
7.41–7.34 (m, 6H, ArH); 13C NMR (125 MHz, CDCl3): d 132.6,
129.3, 128.5, 121.8, 81.6, 74.0; EI-MS m/z 202 [M+].
1,4-Bis(3-methylphenyl) buta-1,3-diyne (2b). 1H NMR (500
MHz, CDCl3): d 7.38–7.20 (m, 8H, ArH), 2.37 (s, 6H, CH3); 13
C
NMR (125 MHz, CDCl3): d 138.3, 133.1, 130.2, 129.7, 128.4,
121.7, 81.7, 73.7, 21.3; EI-MS m/z 230 [M+].
1,4-Bis(4-methylphenyl) buta-1,3-diyne (2c). 1H NMR (500
MHz, CDCl3): d 7.42 (d, J = 8.5 Hz, 4H, ArH), 7.14 (d, J = 8.0
Hz, 4H, ArH), 2.37 (s, 6H, CH3); 13C NMR(125 MHz, CDCl3):
d 139.6, 132.5, 129.3, 118.9, 81.6, 73.5, 21.7; EI-MS m/z 230
[M+].
Tetradeca-6,8-diyne (2n). 1H NMR (500 MHz, CDCl3): d
2.22 (t, J = 7.0 Hz, 4H, CH2), 1.54–1.47 (m, 4H, CH2), 1.37–
1.26 (m, 8H, CH2), 0.87 (t, J = 7.0 Hz, 6H, CH3); 13C NMR (125
MHz, CDCl3): d 77.5, 65.3, 31.1, 28.1, 22.2, 19.2, 14.0; EI-MS
m/z 190 [M+].
1,4-Bis(4-ethylphenyl) buta-1,3-diyne (2d). 1H NMR (500
MHz, CDCl3): d 7.46 (d, J = 8.5 Hz, 4H, ArH), 7.18 (d, J =
8.0 Hz, 4H, ArH), 2.67 (q, J = 7.5 Hz, 4H, CH2), 1.25 (t, J =
7.5 Hz, 6H, CH3); 13C NMR (125 MHz, CDCl3): d 145.8, 132.6,
128.1, 119.1, 81.7, 73.5, 29.0, 15.3.
Eicosa-9,11-diyne (2o). 1H NMR (500 MHz, CDCl3): d 2.22
(t, J = 6.0 Hz, 4H, CH2), 1.62–1.25 (m, 24H, CH2), 0.86 (t, J =
5.5 Hz, 6H, CH3); 13C NMR (125 MHz, CDCl3): d 77.5, 65.3,
31.9, 29.2, 29.1, 28.9, 28.4, 22.7, 19.3, 14.1; EI-MS m/z 274 [M+].
1,4-Bis(4-n-propylphenyl) buta-1,3-diyne (2e). 1H NMR (500
MHz, CDCl3): d 7.44 (d, J = 8.5 Hz, 4H, ArH), 7.15 (d, J = 8.5
Hz, 4H, ArH), 2.59 (t, J = 8.0 Hz, 4H, CH2), 1.67–1.60 (m,
4H, CH2), 0.94 (t, J = 7.5 Hz, 6H, CH3); 13C NMR (125 MHz,
CDCl3): d 144.3, 132.5, 128.7, 119.1, 81.7, 73.6, 38.1, 24.4, 13.9;
EI-MS m/z 286 [M+].
1,4-Dicyclopropyl buta-1,3-diyne (2p). 1H NMR (500 MHz,
CDCl3): d 1.28–1.22 (m, 2H), 0.78–0.72 (m, 8H); 13C NMR (125
MHz, CDCl3): d 80.0, 60.9, 8.8, 1.1.
1,4-Bis(cyclohex-1-enyl) buta-1,3-diyne (2q). 1H NMR (500
MHz, CDCl3): d 6.24–6.22 (m, 2H), 2.12–2.08 (m, 8H), 1.63–
1.55 (m, 8H); 13C NMR (125 MHz, CDCl3): d 138.2, 120.0, 82.8,
71.6, 28.8, 25.9, 22.2, 21.4; EI-MS m/z 210 [M+].
1,4-Bis(4-n-pentylphenyl) buta-1,3-diyne (2f). 1H NMR (500
MHz, CDCl3): d 7.44 (d, J = 8.0 Hz, 4H, ArH), 7.15 (d, J =
8.0 Hz, 4H, ArH), 2.61 (t, J = 8.0 Hz, 4H, CH2), 1.64–1.26 (m,
12H, CH2), 0.89 (t, J = 7.0 Hz, 6H, CH3); 13C NMR (125 MHz,
CDCl3): d 144.6, 132.5, 128.7, 119.1, 81.7, 73.6, 36.1, 31.5, 31.0,
22.6, 14.1.
Acknowledgements
The authors thank the National Natural Science Foundation
of China (No: 20872087, 20902057 and 21002061), the Key
Laboratory of Synthetic Chemistry of Natural Substances,
Chinese Academy of Sciences, Leading Academic Discipline
Project of Shanghai Municipal Education Commission (No:
J50101) and the Innovation Fund of Shanghai University for
financial support.
1,4-Bis(4-methoxylphenyl) buta-1,3-diyne (2g). 1H NMR
(500 MHz, CDCl3): d 7.47–7.44 (m, 4H, ArH), 6.86–6.84 (m,
4H, ArH), 3.82 (s, 6H, CH3); 13C NMR (125 MHz, CDCl3): d
160.3, 134.1, 114.2, 114.0, 81.3, 73.0, 55.4; EI-MS m/z 262 [M+].
(4,4¢-(buta-1,3-diyne-1,4-diyl)bis(4,1-phenylene)) dimetha nol
(2h). 1H NMR (500 MHz, DMSO): d 7.56 (d, J = 7.5 Hz,
4H, ArH), 7.37 (d, J = 7.5 Hz, 4H, ArH), 5.33 (t, J = 5.0 Hz,
2H, OH), 4.54–4.53 (d, J = 5.0 Hz, 4H, CH2); 13C NMR (125
MHz, DMSO): d 144.8, 132.2, 126.6, 118.5, 81.9, 73.2, 62.4.
References
1 (a) M. L. Lerch, M. K. Harper and D. J. Faulkner, J. Nat. Prod.,
2003, 66, 667; (b) D. Lechner, M. Stavri, M. Oluwatuyi, R. Perda-
Miranda and S. Gibbons, Phytochemistry, 2004, 65, 331; (c) C. P.
Constable and G. H. N. Towers, Ibid., 1989, 55, 35; (d) Y. Z. Zhou,
H. Y. Ma, H. Chen, L. Qiao, Y. Yao, J. Q. Cao and Y. H. Pei, Chem.
Pharm. Bull., 2006, 54, 1455; (e) M. Ladika, T. E. Fisk, W. W. Wu
and S. D. Jons, J. Am. Chem. Soc., 1994, 116, 12093; (f) S. F. Mayer,
A. Steinreiber, R. V. A. Orru and K. Faber, J. Org. Chem., 2002, 67,
9115; (g) G. Zeni, R. B. Panatieri, E. Lissner, P. H. Menezes, A. L.
Braga and H. A. Stefani, Org. Lett., 2001, 3, 819; (h) A. Stu¨ts, Angew.
Chem., Int. Ed. Engl., 1987, 26, 320.
2 M. Gholami and R. R. Tykwinski, Chem. Rev., 2006, 106, 4997.
3 (a) P. N. W. Baxter and R. Dali-Youcef, J. Org. Chem., 2005, 70, 4935;
(b) J. A. Marsden and M. M. Haley, J. Org. Chem., 2005, 70, 10213.
4 F. Cataldo, ed., Polyynes: Synthesis Properties, and Applications,
CRC Press/Taylor & Francis, Boca Raton, Florida, 2005.
1,4-Bis(3-chlorophenyl) buta-1,3-diyne (2i). 1H NMR (500
1
MHz, DMSO): d H NMR (500 MHz, CDCl3): d 7.69 (s, 2H,
ArH), 7.59–7.55 (m, 4H, ArH), 7.47–7.44 (m, 2H, ArH); 13C
NMR (125 MHz, DMSO): d 133.4, 131.7, 131.2, 130.7, 130.3,
122.1, 80.7, 74.2.
1,4-Bis(4-fluorophenyl) buta-1,3-diyne (2j). 1H NMR (500
MHz, CDCl3): d 7.53–7.49 (m, 4H, ArH), 7.04 (t, J = 8.5 Hz,
4H,ArH); 13C NMR (125 MHz, CDCl3): d 164.2, 162.2, 134.7,
134.6, 117.96, 117.93, 116.1, 116.9, 80.5, 73.6; EI-MS m/z 238
[M+].
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