JOURNAL OF CHEMICAL RESEARCH 2008 219
Ph
PhI(OAc)2
R
CuCl, Et3N
R
R
Cu
R
R
I
R
PhI
Scheme 2
Eicosa-9,11-diyne (2g): Oil;7 1H NMR (400 MHz, CDCl3), δ: 0.88
(t, J = 7.0 Hz, 6H), 1.20–1.40 (m, 20H), 1.48–1.52 (m, 4H), 2.24 (t,
J = 6.8 Hz, 4H); IR (film), ν/cm-1: 2982, 2133, 1263, 741; EIMS
(70eV), m/z (%): 274 (M+, 100).
Experimental
M.p.s were determined on a digital m.p. apparatus and were not
corrected. IR spectra were recorded on a FT-170 SX instrument,
1H NMR spectra were measured on a VARAIN-400 spectrometer,
and Mass spectra were determined on MS-EI instrument
(FINNIGAN Trace DSQ) mass spectrometer. All terminal alkynes
are commercially available.
Received 5 March 2008; accepted 17 April 2008
A typical procedure for the coupling reaction of alkynes
References
To a mixture of phenylacetylene (1.0 mmol), DIB (0.6 mmol),
Et3N (2.0 mmol) and CuCl (1.0 mol), CH3CN (5 ml) was added.
The mixture was stirred at room temperature for 10 min and then
separated by a silica gel plate using petroleum ether as developer, the
product of diphenylbutadiyne (2a) was afforded in 85% yield.
Diphenylbutadiyne (2a): M.p. 86–88°C (Lit.8 87–88°C); 1H NMR
(400 MHz, CDCl3), δ: 7.32–7.36 (m, 6H), 7.50–7.55 (m, 4H);
IR (KBr), ν/cm-1: 3049, 2978, 2145, 1261, 730; EIMS (70eV), m/z
(%): 202 (M+, 100).
1
2
3
C. Glaser, Ber. Dtsch. Chem. Ges., 1869, 2, 422.
C. Glaser, Ann. Chem. Pharm., 1870, 154, 137.
P. Siemsen, R.C. Livingston and F. Diederich, Angew. Chem., Int. Ed.
Engl., 2000, 39, 2634.
4
5
6
7
A.S. Has, J. Org. Chem., 1962, 27, 3320.
R. Rossi, A. Carpita and C. Bigelli, Tetrahedron Lett., 1985, 26, 523.
A. Lei, M. Srivastava and X. Zhang, J. Org. Chem., 2002, 67, 1969.
M. Vlasa, I. Ciocan-Tarta, F. Margineanu and I. Oprean, Tetrahedron,
1996, 52, 1337.
Bis(4-methylphenyl)butadiyne (2b): M.p. 137–139°C (Lit.18 138–
140°C); 1H NMR (400 MHz, CDCl3), δ: 2.39 (s, 3H), 7.25 (d,
J = 11.0 Hz, 4H), 7.42 (d, J = 11.0 Hz, 4H); IR (KBr), ν/cm-1: 3060,
2988, 2133, 1267, 751; EIMS (70eV), m/z (%): 230 (M+, 100).
Bis(4-ethylphenyl)butadiyne (2c): M.p. 97–99°C (Lit.19 98–99°C);
1H NMR (400 MHz, CDCl3), δ: 1.23 (t, J = 7.6 Hz, 6H), 2.65
(q, J = 7.6 Hz, 4H), 7.14 (d, J = 8.0 Hz, 4H), 7.42 (d, J = 8.0 Hz, 4H)
IR (KBr), ν/cm-1: 3051, 2991, 2142, 1268, 743; EIMS (75eV), m/z
(%): 258 (M+, 100).
8
9
Q. Liu and D.J. Burton, Tetrahedron Lett., 1997, 38, 4371.
K. Sonogashira, Y. Tohda and N. Hagihara, Tetrahedron Lett., 1975, 16,
4467.
10 I.J.S. Fairlamb, P.S. Bauerlein, L.R. Marrison and J.M. Dickinson, Chem.
Commun., 2003, 632.
11 J. Yan, J.L. Wu and H.W. Jin, J. Organomet. Chem., 2007, 692, 3636.
12 A. Varvoglis, Hypervalent iodine in organic synthesis, Academic Press:
London, 1997.
13 P.J. Stang and V.V. Zhdankin, Chem. Rev., 1996, 96, 1123.
14 V.V. Zhdankin and P.J. Stang, Chem. Rev., 2002, 102, 2523.
15 T. Okuyama, Acc. Chem. Res., 2002, 35, 12.
16 V.V. Grushin, Chem. Soc. Rev., 2000, 29, 315.
17 L. Brandsma, H.D. Verkruijsse and B. Walda, Synth. Commun., 1991, 21,
137.
18 J.H. Li, Y. Liang and X.D. Zhang, Tetrahedron, 2005, 61, 1903.
19 A. Uchida, T. Nakazawa, I. Kondo, N. Iwata and S. Matsuda, J. Org.
Chem., 1972, 37, 3749.
20 B. Grant, Mol. Cryst. Liq. Cryst., 1978, 48, 175.
21 E. Shirakawa, Y. Nakao, Y. Murota and T. Hiyama, J. Organomet. Chem.,
2003, 670, 132.
Bis(4-propylphenyl)butadiyne (2d): M.p. 115–117°C (Lit.20 117–
1
119°C); H NMR (400 MHz, CDCl3), δ: 0.90 (t, J = 7.2 Hz, 6H),
1.76–1.52 (m, 4H), 2.51 (q, J = 7.6 Hz, 4H), 7.01 (d, J = 8.0 Hz, 4H),
7.35 (d, J = 8.0 Hz, 4H); IR (KBr), ν/cm-1: 3058, 2995, 2141, 1269,
745; EIMS (75eV), m/z (%): 286 (M+, 100).
Bis(2-trifluoromethylphenyl)butadiyne (2e): M.p. 72–73°C (Lit.21
74–76°C); 1H NMR (400 MHz, CDCl3), δ: 7.47–4.50 (m, 2H),
7.2–7.56 (m, 2H), 7.68–7.72 (m, 4H); IR (KBr), ν/cm-1: 3060, 2988,
2133, 1267, 751; EIMS (75eV), m/z (%): 338 (M+, 100).
Dodeca-5,7-diyne (2f): Oil ;22 1H NMR (400 MHz, CDCl3), δ: 0.90
(t, J = 7.2 Hz, 6H), 1.38–1.41 (m, 4H), 1.42–1.45 (m, 4H), 2.25 (t,
J = 6.8 Hz, 4H); IR (film), ν/cm-1: 2966, 2140, 1259, 736; EIMS
(70eV), m/z (%): 162 (M+, 100).
22 S.V. Damle, D. Seomoon and P.H. Lee, J. Org. Chem., 2003, 68, 7085.
PAPER: 08/5135