H. Sajiki et al.
253 (100) [M+], 233 (15), 207 (15), 163 (20); the 1H NMR spectrum was
7.11 (m, 1H), 4.15 (brs, 1H), 3.76 (dd, J=6.3, 2.6 Hz, 2H), 2.63 ppm (dd,
J=6.3, 2.9 Hz, 2H); MS (EI): m/z: 147 (80) [M+], 117 (100); the
1H NMR spectrum was identical to that reported in the literature.[17]
3-(2-Phenylethynyl)pyridine (Table 5, entry 18): 1H NMR: d=8.53 (s,
1H), 8.37 (dd, J=4.8, 1.7 Hz, 1H), 7.60 (dd, J=6.2, 1.7 Hz, 1H), 7.15–
7.11 (m, 1H), 4.15 (brs, 1H), 3.76 (dd, J=6.3, 2.6 Hz, 2H), 2.63 ppm (dd,
J=6.3, 2.9 Hz, 2H); MS (EI): m/z; 147 (80) [M+], 117 (100); the
1H NMR spectrum was identical to that reported in the literature.[11]
identical to that reported in the literature.[12]
1-[4-(4-Hydroxybut-1-ynyl)phenyl]ethanone (Table 5, entry 5): 1H NMR:
d=7.89 (d, J=8.5 Hz, 2H), 7.49 (d, J=8.5 Hz, 2H), 3.84 (td, J=6.3,
6.3 Hz, 2H), 2.73 (t, J=6.3 Hz, 2H), 2.60 (s, 3H), 1.78 ppm (t, J=6.3 Hz,
1H); MS (EI): m/z: 188 (90) [M+], 173 (100), 143 (48), 115 (30); the
1H NMR spectrum was identical to that reported in the literature.[13]
1-[4-(2-Phenylethynyl)phenyl]ethanone (Table 5, entry 6): 1H NMR: d=
7.94 (d, J=8.3 Hz, 2H), 7.61 (d, J=8.3 Hz, 2H), 7.57–7.54 (m, 2H), 7.38–
7.36 (m, 3H), 2.62 ppm (s, 3H); MS (EI): m/z: 220 [M+] (70), 205 (100),
176 (35), 151 (15); the 1H NMR spectrum was identical to that reported
in the literature.[11]
3-{2-[2-(Trifluoromethyl)phenyl]ethynyl}pyridine (Table 5, entry 19):
Yellow oil; 1H NMR: d=8.78 (d, J=1.6 Hz, 1H), 8.58 (dd, J=5.0,
1.6 Hz, 1H), 7.84–7.81 (m, 1H), 7.70 (d, J=7.6 Hz, 1H), 7.68 (d, J=
7.6 Hz, 1H), 7.53 (t, J=7.6 Hz, 1H), 7.45 (t, J=7.6 Hz, 1H), 7.32–
7.28 ppm (m, 1H); 13CNMR: d=152.2, 149.0, 138.5, 133.7, 131.8, 131.5,
128.5, 125.9 (q, 3JCF =4.9 Hz), 123.5 (q, 1JCF =273.6 Hz), 123.0, 120.7,
119.9, 91.3, 88.5 ppm; MS (EI): m/z: 247 (100) [M+], 226 (215); HRMS
(EI): calcd for C14H8NF3: 247.06088 [M+]; found: 247.06069; elemental
analysis calcd (%) for C15H8F3NO2·1/8H2O: C61.39, H 2.83, N 4.77;
found: C61.74, H 3.16, N 4.87.
3-[2-(4-Methoxyphenyl)ethynyl]pyridine (Table 5, entry 20): 1H NMR:
d=8.74 (d, J=1.7 Hz, 1H), 8.52 (dd, J=5.1, 1.7 Hz, 1H), 7.77 (dt, J=
7.7, 1.9, 1.9 Hz, 1H), 7.48 (d, J=8.7 Hz, 2H), 7.28–7.25 (m, 1H), 6.89 (d,
J=8.7 Hz, 2H), 3.84 ppm (s, 3H); MS (EI): m/z: 209 [M+], 100), 194
(40), 166 (25); the 1H NMR spectrum was identical to that reported in
the literature.[11]
1-{4-[2-(2-Trifluoromethylphenyl)ethynyl]phenyl}ethanone
(Table 5,
entry 7): Pale-yellow solid; m.p. 82–84; 1H NMR: d=8.24 (dd, J=8.6,
1.6 Hz, 2H), 7.72–7.68 (m, 2H), 7.63 (dd, J=8.6, 1.6 Hz, 1H), 7.55 (t, J=
7.7 Hz, 1H), 7.46 (t, J=7.7 Hz, 1H), 2.62 ppm (s, 3H); 13CNMR: d=
197.4, 136.9, 134.1, 132.3, 132.0, 131.7, 128.7, 128.5, 127.7, 126.2 (q, JCF
3
=
5.0 Hz), 123.8 (q, 1JCF =273.4 Hz), 121.1 (q, 2JCF =2.2 Hz), 94.1, 88.6,
26.7 ppm; MS (EI): m/z: 288 (55) [M+], 273 (100), 245 (20), 225 (20);
HRMS (EI): calcd for C17H11OF3: 288.07621 [M+]; found: 288.07505; ele-
mental analysis calcd (%) for C17H11OF3: C70.83, H 3.85; found: C
70.95, H 3.89.
1-{4-[2-(4-Methoxyphenyl)ethynyl]phenyl}ethanone (Table 5, entry 8):
1H NMR: d=7.93 (d, J=8.8 Hz, 2H), 7.58 (d, J=8.8 Hz, 2H), 7.49 (d,
J=9.0 Hz, 2H), 6.89 (d, J=9.0 Hz, 2H), 3.84 (s, 3H), 2.61 ppm (s, 3H);
1
MS (EI): m/z: 250 (100) [M+], 207 (15), 163 (20); the H NMR spectrum
was identical to that reported in the literature.[11]
4-Phenyl-but-3-yn-1-ol (Table 5, entry 9): 1H NMR: d=7.42–7.40 (m,
2H), 7.30–7.28 (m, 2H), 3.81 (td, J=6.1, 6.1 Hz, 2H), 2.69 (t, J=6.1 Hz,
2H), 1.85 ppm (t, J=6.1 Hz, 1H); MS (EI): m/z: 146 (50) [M+], 128 (10),
Acknowledgements
We sincerely thank the N. E. Chemcat Corporation for the kind gift of
Pd/C.
1
115 (100); the H NMR spectrum was identical to that reported in the lit-
erature.[14]
Diphenylacetylene (Table 5, entry 10): 1H NMR: d=7.54–7.50 (m, 4H),
7.36–7.32 ppm (m, 6H); MS (EI): m/z: 178 (100) [M+], 173 (100); the
1H NMR spectrum was identical to that reported in the literature.[11]
[1] a) Chemistry and Biology of Naturally Occurring Acetylenes and Re-
lated Compounds (Eds.: J. Lam, H. Breteler, T. Arnason, L.
Hansen), Elsevier, Amsterdam, 1988; b) Z. Novꢁk, A. Kotschy, Org.
Lett. 2003, 5, 3495.
16, 4467; for reviews of the Sonogashira coupling reaction, see:
2007, 107, 874.
1-{2-[2-(Trifluoromethyl)phenyl]ethynyl}benzene (Table 5, entry 11):
1H NMR: d=7.64 (d, J=7.7 Hz, 1H), 7.62 (d, J=7.7 Hz, 1H), 7.55–7.53
(m, 2H), 7.46 (t, J=7.7 Hz, 1H), 7.37–7.32 ppm (m, 4H); MS (EI): m/z:
1
246 (100) [M+], 225 (15); the H NMR spectrum was identical to that re-
ported in the literature.[15]
1-[2-(4-Methoxyphenyl)ethynyl]benzene (Table 5, entries 12 and 14):
1H NMR: d=7.52–7.46 (m, 4H), 7.34–7.32 (m, 3H), 6.88 (d, J=9.1 Hz,
2H), 3.83 ppm (s, 3H); MS (EI): m/z: 208 (100) [M+], 165 (30); the
1H NMR spectrum was identical to that reported in the literature.[11]
4-(4-Methoxyphenyl)but-3-yn-1-ol (Table 5, entry 13): 1H NMR: d=7.34
(d, J=8.8 Hz, 2H), 6.81 (d, J=8.8 Hz, 2H), 3.79 (s, 3H), 3.79 (t, J=
6.3 Hz, 2H), 2.66 (t, J=6.3 Hz, 2H), 2.02 ppm (brs, 1H); 13CNMR: d=
159.3, 133.0, 115.4, 113.8, 84.7, 82.2, 61.2, 55.2, 23.8 ppm; MS (EI): m/z:
176 (55) [M+], 145 (100); HRMS (EI): calcd for C11H12O2: 176.08373
[M+]; found: 176.08334.
6403; b) V. P. W. Bohm, W. A. Herrmann, Eur. J. Org. Chem. 2000,
2002, 43, 6673; d) M. Pal, K. Parasuraman, S. Gupta, K. R. Yeles-
Commun. 2003, 1934.
[5] a) A. Mori, J. Kawashima, T. Shimada, M. Suguro, K. Hirabayashi,
2004, 45, 4337; e) J. Cheng, Y. Sun, F. Wang, M. Guo, J. Xu, Y. Pan,
1-[2-(4-Methoxyphenyl)ethynyl](trifluoromethyl)benzene
(Table 5,
entry 15): Yellow solid; m.p. 68–72; 1H NMR: d=7.64–7.59 (m, 2H),
7.55–7.53 (m, 2H), 7.48–7.42 (m, 1H), 7.32 (t, J=7.7 Hz, 1H), 6.85 (d,
J=8.2 Hz, 2H), 3.77 ppm (s, 3H); 13CNMR: d=159.8, 133.1, 132.9,
131.8, 131.5, 131.3, 131.0, 130.7, 130.4, 129.3, 127.8, 127.2, 126.4, 126.3,
125.5 (q, 3JCF =5.2 Hz), 123.4 (q, 1JCF =273.4 Hz), 121.6 (q, 2JCF =2.2 Hz),
114.5, 113.9, 113.7, 94.9, 84.0, 54.9 ppm; MS (EI): m/z: 276 (100) [M+],
233 (20); HRMS (EI): calcd for C16H11OF3: 276.07621 [M+]; found:
276.07696; elemental analysis calcd (%) for C16H11OF3: C69.56, H 4.01;
found: C69.30, H 4.07.
[6] S. Urgaonkar, J. G. Verkade, J. Org. Chem. 2004, 69, 5428.
1,2-Bis(4-methoxyphenyl)ethyne (Table 5, entry 16): 1H NMR: d=7.44
(d, J=8.5 Hz, 4H), 6.86 (d, J=8.5 Hz, 4H), 3.82 ppm (s, 3H); MS (EI):
m/z: 238 (100) [M+], 223 (55), 195 (10), 152 (10); the 1H NMR spectrum
was identical to that reported in the literature.[16]
4-(Pyridin-3-yl)but-3-yn-1-ol (Table 5, entry 17): 1H NMR: d=8.53 (s,
1H), 8.37 (dd, J=4.8, 1.7 Hz, 1H), 7.60 (dd, J=6.2, 1.7 Hz, 1H), 7.15–
À
[7] For a review of C Ccoupling reactions catalyzed by heterogeneous
6998
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 6994 – 6999