2744
13. Kharasch, M. S.; Reinmuth, O. Grignard Reactions of Nonmetallic Substances: Prentice Hall: New York, 1954; pp. 1046.
14. Erdik E. Tetrahedron 1984, 40, 641.
15. Typical procedure for coupling of 1 was as follows: A solution of (E)-1 (0.53 g, 2 mmol) and Pd(PPh3)4 (0.115 g, 0.1mmol)
in the THF (10 ml) was added via syringe to a solution of phenylethynylzinc chloride (4 mmol), prepared by the reaction of
phenylacetylene (0.4 ml, 4 mmol) and n-BuLi (4 mmol) in THF (10 ml) at 0–5°C and subsequent transmetallation with THF
solution of ZnCl2 (0.7 g, 5 mmol) at room temperature. The reaction mixture was then refluxed until (E)-1 was consumed.
Usual work-up with aqueous NH4Cl gave crude product that was chromatographed on silica gel (petroleum ether:ether, 3:2).
Recrystallization from petroleum ether gave 0.23 g (58 %) of (E)-2g: m.p. 109.5–110.2°C; 1H NMR: 7.50 (m, 2 H, arom);
7.39 (m, 3H, arom), 6.82 (t, J=3.2 Hz, 1H), 4.45 (t, J=7.3 Hz, 2H), 3.16 (dt, J=3.2 Hz, 7.3 Hz, 2H); 13C NMR: 170.2, 135.7,
131.8, 129.5, 128.5, 122.1, 116.9, 102.0, 85.7, 65.4, 27.3, IR: 2067, 1741, 1645, cm−1. Anal. calcd for C13H10O2: C, 78.8%;
H, 5.1%; found: C, 78.6%; H, 5.5%.
16. Selected physical and spectroscopic data of newly synthesized compounds: (E)-2d: m.p. 130.3–131.2°C; 1H NMR (CDCl3,
500 MHz) 7.76 (s, 1H), 7.56 (d, J=4.9 Hz, 1H), 7.33 (d, J=3.3 Hz, 1H), 7.16 (m, 1H), 4.49 (t, J=7.3 Hz, 2H), 3.15 (dt, J=2.7
Hz, 7.3 Hz, 2H); 13C NMR: 172.1, 139.1, 132.3, 130.2, 129.1, 128.1, 121.1, 65.3, 27.4; IR: 1736, 1641 cm−1. Anal. calcd
for C9H8O2S: C, 60 %; H, 4.5 %; found: C, 60.3%; H, 4.3%. (E)-2h: m.p. 44.2–45.1°C; 1H NMR (CDCl3, 500 MHz): 6.57
(t, J=3.1 Hz, 1H), 4.41 (t, J=7.2 Hz, 2H), 3.07 (dt, J=3.1 Hz, 7.2 Hz, 2H), 0.23 (s, 9H); 13C NMR: 170.1, 137.1, 116.7,
108.9, 100.6, 65.4, 27.3, −0.2; IR: 2197, 1751, 1646 cm−1. Anal. calcd for C10H14O2Si: C, 61.8%; H, 7.3%; found: C,
61.5%; H, 7.3%. (Z)-2c: m.p. 88–89°C; 1H NMR (CDCl3, 500 MHz) 7.78 (d, J=3.6 Hz, 1H), 7.45 (d, J=1.3 Hz, 1H), 6.85 (t,
J=2.3 Hz, 1H), 6.50 (m, 1H), 4.39 (t, J=7.4 Hz, 2H), 3.15 (dt, J=2.3 Hz, 7.4 Hz, 2H); 13C NMR: 169.9, 157.0, 143.9, 121.9,
120.9, 117.5, 106.7, 65.3, 28.4; IR: 1729, 1642 cm−1. Anal. calcd for C9H8O3: C, 65.8%; H, 4.9%; found: C, 65.5%; H,
5.0%. (Z)-2d: m.p. 96.5–97.3°C; 1H NMR (CDCl3, 500 MHz) 7.57 (d, J=3.5 Hz, 1H), 7.33 (d, J=5.1 Hz, 1H), 7.12 (s, 1H),
7.07 (m, 1H), 4.41 (t, J=7.4 Hz, 2H), 3.12 (dt, J=2.0 Hz, 7.4 Hz, 2H); 13C NMR: 169.5, 139.1, 136.9, 134.6, 131.1, 126.8,
119.1, 65.3, 30.5; IR: 1726, 1633 cm−1. Anal. calcd for C9H8O2S: C, 60%; H, 4.5%; found C, 60.3%; H, 4.3%. (Z)-2g: m.p.
75.4–76.5°C; 1H NMR (CDCl3, 500 MHz): 7.57 (m, 2H), 7.35 (m, 3H), 6.35 (t, J=2.6 Hz, 1H), 4.37 (t, J=7.3 Hz, 2H), 3.10
(dt, J=2.3 Hz, 7.3 Hz, 2H); 13C NMR: 167.3, 134.7, 130.8, 128.9, 128.4, 121.2, 115.9, 101.9, 84.7, 64.8, 26.6; IR: 2198,
1745, 1635 cm−1. Anal. calcd for C13H10O2: C, 78.8 %; H, 5.1%; found: C, 78.8%; H, 5.5%. (Z)-2h: m.p. 64.2–65.0°C;
1H NMR (CDCl3, 500 MHz): 6.14 (t, J=2.7 Hz, 1H), 4.32 (t, J=7.2 Hz, 2H), 3.03 (dt, J=2.7 Hz, 7.3 Hz, 2H), 0.20 (s, 9H);
13C NMR: 167.6, 135.5, 116.5, 108.9, 99.6, 64.7, 28.9, −0.2; IR: 2113, 1742, 1638 cm−1. Anal. calcd for C10H14O2Si: C,
61.8%; H, 7.3%; found: C, 61.5%; H, 7.3%.
17. Ji, J.; Zhang, C.; Lu, X. J. Org. Chem. 1995, 60, 1160.