The Journal of Organic Chemistry
Article
(125 MHz, CDCl3) δ 21.4, 123.7, 126.5, 127.2, 127.5, 128.4, 128.55,
128.6, 128.8, 137.2, 137.4, 138.2; LRMS (EI) m/z (% relative
intensity) 194 (M+, 100), 179 (77), 115 (11), 96 (11), 89 (10).
trans-2-Methylstilbene (3e).6 The general procedure was
followed with phenylacetylene (102.2 mg, 1.000 mmol) and 2-
iodotoluene (109.2 mg, 0.5000 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 3e as a colorless
126.3, 126.8, 127.5, 128.2, 128.8, 128.9, 130.0, 131.2, 136.7, 141.8,
166.9; LRMS (EI) m/z (% relative intensity) 238 (M+, 100), 207
(52), 179 (61), 89 (19).
trans-1-Styrylnaphthalene (3k).6 The general procedure was
followed with phenylacetylene (102.2 mg, 1.000 mmol) and 1-
iodonaphthalene (127 mg, 0.500 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 3k as a colorless
solid (96.7 mg, 84%): mp 64−66 °C; 1H NMR (500 MHz, CDCl3) δ
7.12 (d, J = 16.5 Hz, 1 H, CH), 7.28 (t, J = 7.5 Hz, 1 H, ArH), 7.38 (t,
J = 7.5 Hz, 2 H, ArH), 7.44−7.52 (m, 3 H), 7.58 (d, J = 7.5 Hz, 2 H,
ArH), 7.71 (d, J = 7.5 Hz, 1 H, ArH), 7.78 (d, J = 7.5 Hz, 1 H, ArH),
7.83−7.88 (m, 2 H), 8.20 (d, J = 7.5 Hz, 1 H, ArH); 13C NMR (125
MHz, CDCl3) δ 123.6, 123.7, 125.66, 125.75, 125.8, 126.1, 126.7,
127.7, 128.0, 128.6, 128.7, 131.4, 131.7, 133.7, 135.0, 137.6; LRMS
(EI) m/z (% relative intensity) 230 (M+, 100), 215 (16), 202 (15),
152 (54), 135 (44), 101 (17), 77 (12).
1
oil (67.0 mg, 69%): H NMR (500 MHz, CDCl3) δ 2.43 (s, 3 H,
CH3), 6.99 (d, J = 16.0 Hz, 1 H, ArH), 7.17 (d, J = 3.5 Hz, 2 H, ArH),
7.19−7.22 (m, 1 H), 7.26 (t, J = 7.5 Hz, 1 H, ArH), 7.31−7.37 (m, 3
H), 7.51 (d, J = 7.5 Hz, 2 H, ArH), 7.58 (d, J = 7.5 Hz, 1 H, ArH);
13C NMR (125 MHz, CDCl3) δ 19.9, 125.3, 126.2, 126.49, 126.53,
127.52, 127.56, 128.7, 130.0, 130.4, 135.8, 136.4, 137.6; LRMS (EI)
m/z (% relative intensity) 194 (M+, 100), 179 (98), 165 (13), 115
(26), 96 (11), 89 (10).
trans-4-tert-Butylstilbene (3f).6 The general procedure was
followed with phenylacetylene (102.2 mg, 1.000 mmol) and 4-tert-
butyliodobenzene (130.1 mg, 0.5000 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 3f as a colorless
solid (93.4 mg, 79%): mp 95−97 °C; 1H NMR (500 MHz, CDCl3) δ
1.33 (s, 9 H, CH3), 7.06 (d, J = 16.5 Hz, 1 H, CH), 7.10 (d, J = 16.5
Hz, 1 H, CH), 7.24 (t, J = 7.5 Hz, 1 H, ArH), 7.34 (t, J = 7.5 Hz, 2 H,
ArH), 7.38 (d, J = 8.5 Hz, 2 H, ArH), 7.45 (d, J = 8.5 Hz, 2 H, ArH),
7.50 (d, J = 7.5 Hz, 2 H, ArH); 13C NMR (125 MHz, CDCl3) δ 31.3,
34.6, 125.6, 126.2, 126.4, 127.4, 127.9, 128.5, 128.6, 134.5, 137.5,
150.8; LRMS (EI) m/z (% relative intensity) 236 (M+, 44), 221
(100), 178 (16), 103 (17), 91 (64), 77 (20).
trans-3-Styrylpyridine (3l).6 The general procedure was
followed with Cp2ZrF2 (13.0 mg, 0.0500 mmol), phenylacetylene
(102.2 mg, 1.000 mmol), and 3-iodopyridine (102.5 mg, 0.5000
mmol) for 24 h. Column chromatography (eluent as hexane) afforded
3l as a colorless solid (22.7 mg, 25%): mp 69−72 °C; 1H NMR (500
MHz, CDCl3) δ 7.08 (d, J = 16.5 Hz, 1 H, CH), 7.17 (d, J = 16.5 Hz,
1 H, CH), 7.26−7.32 (m, 2 H, ArH), 7.39 (t, J = 8.0 Hz, 2 H, ArH),
7.53 (d, J = 8.0 Hz, 2 H, ArH), 7.84 (d, J = 8.0 Hz, 1 H, ArH), 8.49
(d, J = 4.5 Hz,1 H, ArH), 8.73 (d, J = 2.0 Hz, 1 H, ArH); 13C NMR
(125 MHz, CDCl3) δ 123.5, 124.8, 126.6, 128.2, 128.8, 130.8, 132.6,
132.9, 136.6, 148.5; LRMS (EI) m/z (% relative intensity) 181 (M+,
100), 166 (24), 152 (100), 127 (50), 102 (41), 89 (35).
trans-4-Fluorostilbene (3g).6 The general procedure was
followed with phenylacetylene (102.2 mg, 1.000 mmol) and 1-
fluoro-4-iodobenzene (111 mg, 0.500 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 3g as a colorless
solid (87.2 mg, 88%): mp 117−120 °C; 1H NMR (500 MHz, CDCl3)
δ 6.99−7.08 (m, 4 H), 7.26 (t, J = 7.5 Hz, 1 H, ArH), 7.35 (t, J = 7.5
Hz, 2 H, ArH), 7.45−7.50 (m, 4 H); 13C NMR (125 MHz, CDCl3) δ
115.6 (d, J = 21.3 Hz), 126.4, 127.4, 127.7, 127.9 (d, J = 8.8 Hz),
128.5 (d, J = 2.5 Hz), 128.7, 133.5 (d, J = 3.8 Hz), 137.1, 162.3 (d, J =
246 Hz); LRMS (EI) m/z (% relative intensity) 198 (M+, 100), 183
(30), 177 (16), 98 (15), 77 (10).
trans-2-Styrylthiophene (3m).6 The general procedure was
followed with phenylacetylene (102.2 mg, 1.000 mmol) and 2-
iodothiophene (105.0 mg, 0.5000 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 3m as a colorless
solid (51.2 mg, 55%): mp 102−103 °C; 1H NMR (500 MHz, CDCl3)
δ 6.93 (d, J = 16.0 Hz, 1 H, CH), 7.00 (t, J = 4.0 Hz, 1 H, ArH), 7.06
(s, 1 H, ArH), 7.18−7.26 (m, 3 H), 7.34 (t, J = 7.5 Hz, 2 H, ArH),
7.46 (d, J = 7.5 Hz, 2 H, ArH); 13C NMR (125 MHz, CDCl3) δ
121.8, 124.3, 126.1, 126.3, 127.6, 128.3, 128.7, 136.9, 142.9; LRMS
(EI) m/z (% relative intensity) 186 (M+, 100), 171 (13), 153 (19),
141 (19), 115 (13), 92 (10), 77 (10).
trans-4-Chlorostilbene (3h).6 The general procedure was
followed with phenylacetylene (102.2 mg, 1.000 mmol) and 1-
chloro-4-iodobenzene (119.3 mg, 0.5000 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 3h as a colorless
solid (91.2 mg, 85%): mp 118−120 °C; 1H NMR (500 MHz, CDCl3)
δ 7.03 (d, J = 16.5 Hz, 1 H, CH), 7.08 (d, J = 16.5 Hz, 1 H, CH), 7.27
(d, J = 7.5 Hz, 1 H, ArH), 7.31 (d, J = 8.0 Hz, 2 H, ArH), 7.36 (t, J =
7.5 Hz, 2 H, ArH), 7.42 (d, J = 8.0 Hz, 2 H, ArH), 7.50 (d, J = 7.5 Hz,
2 H, ArH); 13C NMR (125 MHz, CDCl3) δ 126.5, 127.3, 127.6,
127.9, 128.7, 128.8, 129.3, 133.1, 135.8, 136.9; LRMS (EI) m/z (%
relative intensity) 216 ([M + 2]+, 34), 214 (M+, 100), 178 (94), 89
(25), 76 (18).
trans-4,4′-Dimethoxystilbene (4a).6 The general procedure
was followed with 4-methoxyphenylacetylene (133.2 mg, 1.000
mmol) and 4-iodoanisole (117 mg, 0.5000 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 4a as a colorless
solid (49.3 mg, 41%): mp 207−208 °C; 1H NMR (500 MHz, CDCl3)
δ 3.82 (s, 6 H, CH3), 6.89 (d, J = 9.0 Hz, 4 H, ArH), 6.93 (s, 2 H,
ArH), 7.42 (d, J = 9.0 Hz, 4 H, ArH); 13C NMR (125 MHz, CDCl3) δ
55.3, 114.1, 126.2, 127.4, 130.5, 159.0; LRMS (EI) m/z (% relative
intensity) 240 (M+, 100), 225 (50), 180 (50), 121 (80).
trans-4-Butyl-4′-methoxystilbene (4b).16 The general proce-
dure was followed with 4-butylphenylacetylene (158.2 mg, 1.000
mmol) and 4-iodoanisole (118.0 mg, 0.5000 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 4b as a pale yellow
solid (82.6 mg, 62%): mp 110−112 °C; 1H NMR (500 MHz, CDCl3)
δ 0.93 (t, J = 7.5 Hz, 3 H, CH3), 1.36 (sext, J = 7.7 Hz, 2 H, CH2),
1.59 (sext, J = 7.7 Hz, 2 H, CH2), 2.61 (t, J = 7.5 Hz, 2 H, CH2), 3.83
(s, 3 H, OCH3), 6.89 (d, J = 8.0 Hz, 2 H, ArH), 6.95 (d, J = 16.0 Hz,
1 H, CH), 7.02 (d, J = 16.0 Hz, 1 H, CH), 7.16 (d, J = 8.0 Hz, 2 H,
ArH), 7.40 (d, J = 8.0 Hz, 2 H, ArH), 7.44 (d, J = 8.0 Hz, 2 H, ArH);
13C NMR (125 MHz, CDCl3) δ 14.0, 22.4, 33.6, 35.4, 55.3, 114.1,
126.1, 126.6, 127.2, 127.6, 128.7, 130.4, 135.0, 142.2, 159.1; LRMS
(EI) m/z (% relative intensity) 266 (M+, 100), 223 (100), 208 (10),
165 (15), 135 (11), 73 (13); HRMS (FAB-Magnetic Sector) calcd for
[M]+ (C19H22O) m/z 266.1671, found 266.1674.
trans-4-Bromostilbene (3i).6 The general procedure was
followed with phenylacetylene (102.2 mg, 1.000 mmol) and 1-
bromo-4-iodobenzene (141.5 mg, 0.5000 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 3i as a colorless
solid (110.1 mg, 85%): mp 135−137 °C; 1H NMR (500 MHz,
CDCl3) δ 7.02 (d, J = 16.5 Hz, 1 H, CH), 7.09 (d, J = 16.5 Hz, 1 H,
CH), 7.27 (t, J = 7.5 Hz, 1 H, ArH), 7.36 (t, J = 8.0 Hz, 4 H, ArH),
7.47 (d, J = 8.0 Hz, 2 H, ArH), 7.50 (d, J = 7.5 Hz, 2 H, ArH); 13C
NMR (125 MHz, CDCl3) δ 121.3, 126.5, 127.4, 127.9, 128.0, 128.7,
129.4, 131.8, 136.2, 136.9; LRMS (EI) m/z (% relative intensity) 260
([M + 2]+, 65), 258 (M+, 70), 178 (100), 152 (11), 89 (25), 76 (18).
trans-4-Methoxycarbonylstilbene (3j).15 The general proce-
dure was followed with phenylacetylene (102.2 mg, 1.000 mmol) and
methyl 4-iodobenzoate (133 mg, 0.500 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 3j as a colorless
solid (81.0 mg, 68%): mp 158−160 °C; 1H NMR (500 MHz, CDCl3)
δ 3.92 (s, 3 H, CH3), 7.12 (d, J = 16.5 Hz, 1 H, CH), 7.22 (d, J = 16.5
Hz, 1 H, CH), 7.30 (t, J = 7.5 Hz, 1 H, ArH), 7.38 (t, J = 7.5 Hz, 2 H,
ArH), 7.53 (d, J = 7.5 Hz, 2 H, ArH), 7.56 (d, J = 8.5 Hz, 2 H, ArH),
8.02 (d, J = 8.5 Hz, 2 H, ArH); 13C NMR (125 MHz, CDCl3) δ 52.1,
trans-4-Chloro-4′-methoxystilbene (4c).6 The general proce-
dure was followed with 4-chlorophenylacetylene (136.6 mg, 1.000
mmol) and 4-iodoanisole (117 mg, 0.500 mmol) for 24 h. Column
chromatography (99/1 = hexane/EtOAc) afforded 4c as a colorless
solid (88.1 mg, 72%): mp 170−172 °C; 1H NMR (500 MHz, CDCl3)
δ 3.83 (s, 3 H, CH3), 6.89−6.93 (m, 3 H), 7.03 (d, J = 16.0 Hz, 1 H,
CH), 7.30 (d, J = 8.5 Hz, 2 H, ArH), 7.40 (d, J = 8.5 Hz, 2 H, ArH),
F
J. Org. Chem. XXXX, XXX, XXX−XXX