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J. Yan et al. / Journal of Organometallic Chemistry 692 (2007) 3636–3639
Table 2
3.3. Diphenylbutadiyne (2a) [6]
a
The results of the homocoupling of alkynes
PdCl2 , CuI, Et3N, THF
1H NMR (CDCl3): d = 7.32–7.36 (m, 6H), 7.50–7.55 (m,
4H); IR (film): m = 3049, 2978, 2145, 1261, 730 cmÀ1; MS
(70 eV, EI) m/z (%): 202 (M+, 100).
R
R
R
PhI(OCOCH3)2
2
1
b
Entry
1
Alkyne
Diyne
Time (h)
0.5
Yield (%)
90
2a
Ph
1a
3.4. Bis(4-methylphenyl)butadiyne (2b) [12]
1H NMR (CDCl3): d = 2.39 (s, 3H), 7.25 (d,
J = 11.0 Hz, 4H), 7.42 (d, J = 11.0 Hz, 4H); IR (film):
m = 3060, 2988, 2133, 1267, 751 cmÀ1; MS (70 eV, EI)
m/z (%): 230 (M+, 100).
2
3
4
5
6
7
2b
2c
2d
2e
2f
0.5
0.5
1.0
1.0
1.0
3.0
87
88
70
77
74
62
p-CH3-C6H4-
1b
p-C2H5-C6H4-
1c
3.5. Bis(4-ethylphenyl)butadiyne (2c) [4]
1H NMR (CDCl3): d = 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 (film): m = 3051, 2991, 2152, 1268,
743 cmÀ1; MS (75 eV, EI) m/z (%): 258 (M+, 100).
n-C4H9-
1d
n-C5H11-
1e
3.6. 5,7-Dodecadiyne (2d) [12]
1H NMR (CDCl3): d = 0.90 (t, J = 7.2 Hz, 6H), 1.36–
1.44 (m, 4H), 1.45–1.54 (m, 4H), 2.24 (t, J = 6.8 Hz, 4H);
IR (film): m = 2966, 2140, 1259, 736 cmÀ1; HRMS (EI)
calcd. for C12H18 M+ 162.1409, found: 162.1401.
n-C6H13-
1f
2g
Me
3.7. 6,8-Tetradecadiyne (2e) [12]
Me
OH
1H NMR (CDCl3): d = 0.89 (t, J = 7.2 Hz, 6H), 1.24–
1.40 (m, 8H), 1.48–1.55 (m, 4H), 2.24 (t, J = 7.2 Hz, 4H);
IR (film): m = 2971, 2152, 1256, 744 cmÀ1; HRMS (EI)
calcd. for C14H22 M+ 190.1722, found: 190.1712.
1g
a
Reaction conditions: 1.0 mmol of alkyne, 0.6 mmol of DIB, 1.1 mmol
of Et3N, PdCl2 (2.0 mol%), CuI (2.0 mol%), THF (3 mL) at RT.
b
Isolated yields.
3.8. 7,9-Hexadecadiyne (2f) [13]
1H NMR (CDCl3): d = 0.89 (t, J = 7.2 Hz, 6H), 1.18–
1.40 (m, 12H), 1.45–1.56 (m, 4H), 2.22 (t, J = 6.8 Hz,
4H); IR (film): m = 2982, 2133, 1263, 741 cmÀ1; HRMS
(EI) calcd. for C16H26 M+ 218.2035, found: 218.2022.
R
R
Pd (0)
PhI(OCOCH3)2
3.9. 2,7-Dimethylocta-3,5-diyne-2,7-diol (2g) [14]
PhI
R
R
Pd
1H NMR (CDCl3): d = 1.37 (s, 12H), 2.52 (s, 2H); IR
(film): m = 3279, 3211, 2924, 2120, 1216, 1170 cmÀ1; MS
(75 eV, EI) m/z (%): 166 (M+, 1.2), 43 (100).
Pd(OAc)2
Et3N HCl
R
CuI, Et3N
PdCl2
CuI, Et3N
Acknowledgement
R
Et3N HOAc
Scheme 1.
Financial support from the Natural Science Foundation
of China (Project 20672100) is greatly appreciated.
References
0.5 h and then separated by a silica gel plate using petro-
leum ether as developer, the product of diphenylbutadiyne
(2a) was afforded in 90% yield.
[1] V.D. Hunstman, in: S. Patai (Ed.), The Chemistry of Carbon–Carbon
Triple Bond, Wiley-Interscience, London, 1978, p. 553.