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D. Xu et al. / Tetrahedron 68 (2012) 1466e1474
1
4
added iodobenzene (316 mg, 1.55 mmol) and ethyl acrylate (50 mg,
0.5 mmol). The resulting mixture was stirred at 110 ꢀC for 6 h. After
being cooled to room temperature, the reaction mixture was di-
luted with 15 mL ethyl acetate, the resulting solids were removed
by filtration, the filtrate was concentrated under vacuum. The crude
product was further purified by flash column chromatography us-
ing petroleum ether (PE) and ethyl acetate (EA) as the eluent (PE/
EA¼20/1). Light yellow oil; 1H NMR (400 MHz, CDCl3, ppm):
(d, JCF¼246.4 Hz), 154.4, 136.8 (d, JCF¼3.1 Hz), 134.5 (d,
4JCF¼2.6 Hz), 131.0 (d, JCF¼7.9 Hz), 130.2 (d, JCF¼8.3 Hz), 117.5,
115.5 (d, 2JCF¼20.9 Hz), 115.0 (d, 2JCF¼21.1 Hz), 60.2, 14.0; IR (neat):
2984, 1714, 1597, 1505, 1262, 1225, 1149, 1031, 876, 835 cmꢁ1; MS
(EI, m/z) 288 (Mþ, 80%), 243 (100%), 215 (61%), 195 (30%), 123 (45%).
3
3
4.2.7. Ethyl 3,3-bis(3-fluorophenyl)acrylate (3ib). Yellow oil; 1H
NMR (400 MHz, CDCl3, ppm):
d 7.41e7.36 (m, 1H), 7.35e7.29 (m,
d
7.43e7.42 (m, 3H), 7.39e7.34 (m, 5H), 7.28e7.25 (m, 2H), 6.42 (s,
1H), 7.14e7.06 (m, 3H), 7.02e6.98 (m, 2H), 6.94 (dt, J¼9.6, 1.8 Hz,
1H), 4.10 (q, J¼7.2 Hz, 2H), 1.15 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz,
1H), 6.40 (s, 1H), 4.09 (q, J¼7.1 Hz, 2H), 1.15 (t, J¼7.2 Hz, 3H); 13C
CDCl3, ppm):
d
166.1, 156.5, 140.8, 139.0, 129.4, 129.1, 128.4, 128.3,
NMR (100 MHz, CDCl3, ppm):
d
165.4, 162.6 (d, 1JCF¼245.1 Hz),162.4
1
3
128.1, 127.9, 117.5, 60.0, 13.0. IR (neat): 2980, 1719, 1616, 1491, 1445,
1368, 1262, 1154, 1033, 865, 770, 695, 615 cmꢁ1; MS (EI, m/z) 252
(Mþ, 75%), 207 (100%), 178 (99%), 152 (32%), 105 (25%).
(d, JCF¼245.8 Hz), 153.3, 142.2 (d, JCF¼7.4 Hz), 140.4 (d,
3JCF¼7.7 Hz), 130.0 (d, 3JCF¼8.5 Hz), 129.6 (d, 3JCF¼7.6 Hz), 124.8 (d,
4JCF¼2.1 Hz), 123.7 (d, JCF¼2.0 Hz), 119.0, 116.4 (d, JCF¼21.7 Hz),
4
2
2
2
116.1 (d, JCF¼22.0 Hz), 115.2 (d, JCF¼16.1 Hz), 115.0 (d,
2JCF¼18.2 Hz), 60.3, 13.8. IR: 2983, 1720, 1613, 1582, 1483, 1442,
1369, 1266, 1227, 1188, 1155, 1116, 1034, 960, 908, 870, 820, 785,
663 cmꢁ1; MS (EI, m/z) 288 (Mþ, 76%), 243 (100%), 215 (74%), 195
(28%).
4.2.1. Ethyl (E)-cinnamate (4ab)19. Light yellow oil; 1H NMR
(400 MHz, CDCl3, ppm):
d
7.70 (d, J¼16.0 Hz, 1H), 7.54e7.52 (m, 2H),
7.40e7.38 (m, 3H), 6.45 (d, J¼16.0 Hz, 1H), 4.28 (q, J¼7.2 Hz, 2H),
1.35 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3, ppm):
d 14.2, 60.4,
118.2, 128.0, 128.8, 130.1, 134.4, 144.5, 166.9.
4.2.8. Ethyl 3,3-bis(4-chlorophenyl)acrylate (3kb). White solid; Mp
61e62 ꢀC (lit.: 62e62.5 ꢀC);20 1H NMR (400 MHz, CDCl3, ppm):
4.2.2. Ethyl 3,3-di-p-tolylacrylate (3bb). Light yellow oil; 1H NMR
(400 MHz, acetone-d6, ppm): 7.17e7.11 (m, 6H), 7.01e6.99 (d,
d
d
7.37 (d, J¼8.4 Hz, 2H), 7.30 (d, J¼8.4 Hz, 2H), 7.21 (d, J¼8.8 Hz, 2H),
J¼8.0 Hz, 2H), 6.24 (s,1H), 3.94 (q, J¼7.1 Hz, 2H), 2.32 (s, 3H), 2.28 (s,
7.14 (d, J¼8.0 Hz, 2H), 6.34 (s, 1H), 4.08 (q, J¼7.2 Hz, 2H), 1.16 (t,
3H), 1.03 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3, ppm):
d
166.2,
J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3, ppm):
d 165.6, 154.0,
1569, 139.6, 138.3, 137.9, 136.1, 129.2, 129.0, 128.5, 128.3, 116.2, 59.9,
21.4, 21.2, 14.1. IR (neat): 2980, 1719, 1605, 1510, 1447, 1368, 1263,
1150, 1036, 875, 818, 723 cmꢁ1; MS (EI, m/z) 280 (Mþ, 100%), 235
(90%), 208 (87%), 193 (50%), 119 (56%).
138.8, 136.8, 135.7, 134.4, 130.5, 129.4, 128.7, 128.2, 118.1, 60.2, 14.0;
IR (neat): 2984, 1718, 1693, 1588, 1489, 1401, 1367, 1284, 1167, 1089,
1033, 1013, 908, 827, 732 cmꢁ1; MS (EI, m/z) 320 (Mþ, 71%), 275
(100%), 248 (69%), 212 (83%), 176 (66%), 139 (49%), 128 (53%).
4.2.3. Ethyl 3,3-di-m-tolylacrylate (3cb). Light yellow oil; 1H NMR
4.2.9. Ethyl 3,3-bis(3-chlorophenyl)acrylate (3lb). Yellow oil; 1H
(400 MHz, CDCl3, ppm):
d
7.32 (t, J¼7.6 Hz, 1H), 7.28e7.19 (m, 4H),
NMR (400 MHz, CDCl3, ppm): d 7.35e7.30 (m, 3H), 7.25e7.21 (m,
7.13 (d, J¼7.2 Hz, 1H), 7.07 (d, J¼7.6 Hz, 1H), 7.06 (s, 1H), 6.38 (s, 1H),
2H), 7.16 (s, 1H), 7.11 (d, J¼7.6 Hz, 1H), 7.06 (d, J¼7.6 Hz, 1H), 6.33 (s,
4.11 (q, J¼7.2 Hz, 2H), 2.40 (s, 3H), 2.37 (s, 3H), 1.17 (t, J¼7.2 Hz, 3H);
1H), 4.04 (q, J¼7.2 Hz, 2H), 1.10 (t, J¼7.0 Hz, 3H); 13C NMR (100 MHz,
13C NMR (100 MHz, CDCl3, ppm):
d
166.2, 156.8, 140.9, 139.0, 137.9,
CDCl3, ppm): d 165.3, 153.1, 141.9, 140.0, 134.6, 134.0, 129.7, 129.6,
137.3, 130.1, 129.6, 128.8, 128.2, 127.6, 126.3, 125.6, 117.2, 59.9, 21.4,
21.3, 14.0. IR (neat): 2979, 1721, 1603, 1447, 1367, 1274, 1189, 1153,
1094,1037, 873, 786, 701, 658 cmꢁ1; MS (EI, m/z) 280 (Mþ, 98%), 235
(100%), 208 (73%), 192 (58%), 119 (51%).
129.3, 129.0, 128.4, 128.0, 127.3, 126.3, 119.3, 60.3, 13.9; IR (neat):
2981, 1720, 1619, 1592, 1564, 1472, 1419, 1367, 1346, 1255, 1158,
1082, 1033, 875, 788, 698 cmꢁ1; HRMS (TOF MS EIþ): m/z calcd for
C17H14Cl2O2: 320.0371. Found: 320.0373.
4.2.4. Ethyl 3,3-bis(4-methoxyphenyl)acrylate (3eb). Light yellow
4.2.10. Ethyl 3,3-bis(4-bromophenyl)acrylate (3nb)21. Light yellow
oil; 1H NMR (400 MHz, acetone-d6, ppm):
d
7.27 (dd, J¼7.0 Hz,
solid; Mp 64e65 ꢀC; 1H NMR (400 MHz, CDCl3, ppm):
d 7.48 (d,
2.2 Hz, 2H), 7.12 (dd, J¼6.8, 2.0 Hz, 2H), 6.96e6.92 (m, 4H), 6.22 (s,
J¼8.0 Hz, 2H), 7.42 (d, J¼8.8 Hz, 2H), 7.10 (d, J¼8.4 Hz, 2H), 7.04 (d,
1H), 4.00 (q, J¼7.1 Hz, 2H), 3.85 (s, 3H), 3.83 (s, 3H), 1.11 (t, J¼7.0 Hz,
J¼8.8 Hz, 2H), 6.31 (s, 1H), 4.04 (q, J¼7.2 Hz, 2H), 1.12 (t, J¼7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3, ppm):
d
166.4, 160.8, 159.7, 156.4,
3H); 13C NMR (100 MHz, CDCl3, ppm):
d 165.5, 154.0, 139.2, 137.2,
133.8, 131.2, 130.9, 130.0, 114.8, 113.7, 113.2, 59.8, 55.3, 55.1, 14.1; IR
(neat): 2958, 2837, 1714, 1598, 1509, 1461, 1369, 1290, 1245, 1144,
1030, 831, 745 cmꢁ1; MS (EI, m/z) 312 (Mþ, 50%), 267 (28%), 240
(54%), 135 (83%), 124 (100%), 109 (84%).
131.6, 131.2, 130.8, 129.7, 124.1, 122.6, 118.1, 60.2, 14.0; IR (neat):
2983, 1693, 1582, 1485, 1396, 1367, 1282, 1171, 1104, 1071, 1031,
1008, 899, 822, 760 cmꢁ1; MS (EI, m/z) 410 (Mþ, 100%), 365 (94%),
338 (82%), 258 (69%), 256 (71%), 176 (94%).
4.2.5. Ethyl 3,3-bis(3-methoxyphenyl)acrylate (3fb). Yellow oil; 1H
4.2.11. Ethyl 3,3-bis(3-bromophenyl)acrylate (3ob). Light yellow oil;
NMR (400 MHz, CDCl3, ppm):
d
7.31 (t, J¼7.8 Hz, 1H), 7.25 (t,
1H NMR (400 MHz, CDCl3, ppm):
d 7.55e7.49 (m, 2H), 7.45 (d,
J¼7.8 Hz, 1H), 6.95e6.91 (m, 3H), 6.88 (s, 1H), 6.83 (d, J¼7.2 Hz, 1H),
J¼1.6 Hz, 1H), 7.35 (t, J¼1.6 Hz, 1H), 7.28e7.26 (m, 1H), 7.23e7.18 (m,
6.78 (s, 1H), 6.39 (s, 1H), 4.09 (q, J¼7.2 Hz, 2H), 3.80 (s, 3H), 3.78 (s,
2H), 7.16e7.13 (dt, J¼7.6, 1.4 Hz, 1H), 6.36 (s, 1H), 4.08 (q, J¼7 Hz,
3H), 1.14 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3, ppm):
d
165.9,
2H), 1.14 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3, ppm):
d 165.2,
159.5, 159.1, 155.8, 141.9, 140.2, 129.3, 128.8, 121.5, 120.7, 117.7, 114.7,
114.6, 113.9, 113.5, 60.0, 55.2, 55.1, 13.9; IR (neat): 2939, 2835, 1719,
1578, 1485, 1458, 1429, 1367, 1284, 1244, 1211, 1155, 1038, 866, 781,
696 cmꢁ1; MS (EI, m/z) 312 (Mþ, 100%), 267 (70%), 239 (69%), 135
(30%).
152.9, 142.2, 140.2, 132.5, 131.8, 131.3, 130.9, 130.0, 129.5, 127.7,
126.8, 122.8, 122.1, 119.4, 60.3, 13.9. IR (neat): 2980, 1719, 1619,1558,
1470, 1416, 1367, 1345, 1254, 1157, 1072, 1033, 994, 875, 785, 697,
670 cmꢁ1; HRMS (TOF MS EIþ): m/z calcd for C17H14Br2O2:
407.9361. Found: 407.9362.
4.2.6. Ethyl 3,3-bis(4-fluorophenyl)acrylate (3hb). Light yellow
4.2.12. Ethyl 3,3-bis(4-acetylphenyl)acrylate (3qb). White solid; Mp
solid; Mp 57e58 ꢀC; 1H NMR (400 MHz, CDCl3, ppm):
d
7.29e7.24
77e78 ꢀC; 1H NMR (400 MHz, CDCl3, ppm):
d
8.00 (d, J¼8.4 Hz, 2H),
(m, 2H), 7.21e7.16 (m, 2H), 7.08 (t, J¼8.6 Hz, 2H), 7.02 (t, J¼8.6 Hz,
7.90 (d, J¼8.4 Hz, 2H), 7.36 (d, J¼8.4 Hz, 2H), 7.31 (d, J¼8.0 Hz, 2H),
2H), 6.30 (s, 1H), 4.07 (q, J¼7.1 Hz, 2H), 1.15 (t, J¼7.2 Hz, 3H); 13C
6.48 (s, 1H), 4.07 (q, J¼8.4 Hz, 2H), 2.63 (s, 3H), 2.59 (s, 3H), 1.14 (t,
NMR (100 MHz, CDCl3, ppm):
d
165.8, 163.6 (d, 1JCF¼248.1 Hz),162.8
J¼8.4 Hz, 3H); 13C NMR (100 MHz, CDCl3, ppm):
d 197.5,197.3,165.3,