Y. Jiang et al. / Tetrahedron 69 (2013) 3669e3676
3675
139.9, 131.7, 130.9 (d, J¼3.5 Hz), 130.6 (d, J¼8.8 Hz), 128.1, 127.5,
124.8, 119.7, 116.7, 115.7 (d, J¼21.6 Hz); IR (neat): 2972, 2904, 1721,
1605, 1510, 1227, 1072, 836, 757 cmꢁ1; HRMS (TOFMS EIþ) calcd for
C15H9FO2, m/z 240.0587, found 240.0585. Anal. Calcd for C15H9FO2:
C, 75.00; H, 3.78. Found: C, 75.13; H, 3.82.
(d, J¼9.2 Hz, 1H), 7.94 (d, J¼8.0 Hz, 1H), 8.12 (d, J¼6.8 Hz, 2H), 7.71
(t, J¼7.8 Hz, 1H), 7.59 (t, J¼7.6 Hz, 1H), 7.53e7.43 (m, 4H); 13C NMR
(100 MHz, CDCl3) d: 160.8, 153.2, 135.9, 135.2, 132.9, 130.4, 129.2,
129.0, 128.7, 128.3, 127.3, 126.2, 121.5, 116.8, 113.9; IR (neat): 2970,
1731, 1605, 1403, 1258, 1055, 758, 696 cmꢁ1; HRMS (TOFMS EIþ)
calcd for C19H12O2, m/z 272.0837, found 272.0839.
4.4.9. 3-(Naphthalen-2-yl)coumarin (5j).8 Yield: 122.4 mg, 90%.
Yellow solid. Mp: 178 ꢀC. Rf (petroleum ether/EA¼6:1) 0.3. 1H NMR
4.4.16. 6-Chloro-3-phenylcoumarin (6g).28 Yield: 44.9 mg, 35%.
White solid. Mp: 200 ꢀC. Rf (petroleum ether/EA¼6:1) 0.4. 1H NMR
(400 MHz, CDCl3) d: 8.25 (s, 1H), 7.95 (s, 1H), 7.93e7.86 (m, 3H), 7.81
(d, J¼8.8 Hz, 1H), 7.60e7.51 (m, 4H), 7.41 (d, J¼8.0 Hz, 1H), 7.33
(400 MHz, CDCl3)
d
: 7.74 (s, 1H), 7.69 (d, J¼7.2 Hz, 2H), 7.53 (s, 1H),
(t, J¼7.4 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d
: 160.8, 153.6, 140.3,
7.49e7.41 (m, 4H), 7.32 (d, J¼8.8 Hz,1H); 13C NMR (100 MHz, CDCl3)
133.4, 133.2, 132.2, 131.6, 128.6, 128.2, 128.1, 127.7, 126.9, 126.5,
126.0, 124.7, 119.8, 116.6; IR (neat): 2972, 1715, 1608, 1505, 1411,
1257, 1071, 760 cmꢁ1; HRMS (TOFMS EIþ) calcd for C19H12O2, m/z
272.0837, found 272.0838.
d: 160.2, 152.0, 138.6, 134.4, 131.5, 129.9, 129.7, 129.4, 128.7, 127.2,
120.9, 118.1; IR (neat): 2972, 2903, 1709, 1603, 1225, 1070, 780,
696 cmꢁ1; HRMS (TOFMS EIþ) calcd for C15H9ClO2, m/z 256.0291,
found 256.0293.
4.4.10. 3-(Naphthalen-1-yl)coumarin (5k).8 Yield: 112.8 mg, 83%.
Yellow solid. Mp: 154e156 ꢀC. Rf (petroleum ether/EA¼6:1) 0.3. 1H
4.4.17. 8-Chloro-3-phenylcoumarin (6h).29 Yield: 44.8 mg, 35%.
White solid. Mp: 167e169 ꢀC. Rf (petroleum ether/EA¼6:1) 0.4. 1H
NMR (400 MHz, CDCl3)
d
: 7.92 (t, J¼7.6 Hz, 2H), 7.84 (s, 1H), 7.79
NMR (400 MHz, CDCl3)
d
: 7.79 (s, 1H), 7.70 (d, J¼7.2 Hz, 2H), 7.57
(d, J¼8.4 Hz, 1H), 7.62e7.45 (m, 7H), 7.35 (t, J¼7.6 Hz, 1H); 13C NMR
(d, J¼8.0 Hz, 1H), 7.47e7.40 (m, 4H), 7.23 (t, J¼7.6 Hz, 1H); 13C NMR
(100 MHz, CDCl3)
d
: 161.0, 154.1, 143.0, 133.8, 132.8, 131.8, 131.7,
(100 MHz, CDCl3) d: 159.6, 149.4, 139.5, 134.3, 131.8, 129.3, 129.2,
129.5, 128.7, 128.4, 128.1, 127.8, 126.6, 126.2, 125.4, 125.3, 124.7,
119.4,116.8; IR (neat): 2972,1718,1685,1511,1085, 755 cmꢁ1; HRMS
(TOFMS EIþ) calcd for C19H12O2, m/z 272.0837, found 272.0838.
128.7, 126.5, 124.8, 121.4, 121.1; IR (neat): 2972, 2904, 1711, 1600,
1450, 1225, 1109, 1072, 778, 692 cmꢁ1; HRMS (TOFMS EIþ) calcd for
C15H9ClO2, m/z 256.0291, found 256.0292.
4.4.11. 6-Methoxy-3-phenylcoumarin (6b).24 Yield: 107.3 mg, 85%.
Pale yellow solid. Mp: 155e157 ꢀC. Rf (petroleum ether/EA¼6:1) 0.5.
4.4.18. 6-Bromo-3-phenylcoumarin (6i).4d Yield: 58.7 mg, 39%.
White solid. Mp: 170e171 ꢀC. Rf (petroleum ether/EA¼6:1) 0.4. 1H
1H NMR (400 MHz, CDCl3)
d
: 7.78 (s, 1H), 7.70 (d, J¼7.2 Hz, 2H),
NMR (400 MHz, CDCl3) d: 7.73 (s, 1H), 7.70e7.68 (m, 3H), 7.62 (dd,
7.47e7.41 (m, 3H), 7.31 (d, J¼9.2 Hz, 1H), 7.14 (dd, J¼9.2, 2.4 Hz, 1H),
J¼8.8, 2.0 Hz, 1H), 7.48e7.43 (m, 3H), 7.26 (t, J¼4.0 Hz,1H); 13C NMR
6.98 (d, J¼2.4 Hz, 1H), 3.87 (s, 3H); 13C NMR (100 MHz, CDCl3)
d
:
(100 MHz, CDCl3) d: 160.1, 152.4, 138.5, 134.3, 134.2, 130.3, 129.6,
160.9, 156.3, 148.1, 139.8, 134.9, 129.0, 128.8, 128.7, 128.6, 120.2,
119.3, 117.6, 110.1, 56.0; IR (neat): 2969, 1722, 1611, 1511, 1255, 1051,
752 cmꢁ1; HRMS (TOFMS EIþ) calcd for C16H12O3, m/z 252.0786,
found 252.0789.
129.4, 128.7, 121.3, 118.3, 117.2; IR (neat): 2971, 1710, 1607, 1218,
1054, 835, 756 cmꢁ1; HRMS (TOFMS EIþ) calcd for C15H9BrO2, m/z
299.9786, found 299.9784.
4.4.19. 8-Bromo-3-phenylcoumarin (6j).29 Yield: 70.7 mg, 47%.
White solid. Mp: 185e186 ꢀC. Rf (petroleum ether/EA¼8:1) 0.3. 1H
4.4.12. 7-Methoxy-3-phenylcoumarin (6c).6c Yield: 71.8 mg, 57%.
White solid. Mp: 122e124 ꢀC. Rf (petroleum ether/EA¼6:1) 0.4. 1H
NMR (400 MHz, CDCl3)
d
: 7.78 (s, 1H), 7.75 (dd, J¼7.8, 1.4 Hz, 1H),
NMR (400 MHz, CDCl3)
d
: 7.76 (s, 1H), 7.69 (d, J¼7.6 Hz, 2H),
7.70 (dd, J¼8.0, 1.6 Hz, 2H), 7.51e7.41 (m, 4H), 7.18 (t, J¼7.8 Hz, 1H);
7.45e7.36 (m, 4H), 6.87 (d, J¼7.6 Hz, 1H), 6.86 (s, 1H), 3.89 (s, 3H);
13C NMR (100 MHz, CDCl3)
d: 159.7, 150.3, 139.5, 134.9, 134.2, 129.3,
13C NMR (100 MHz, CDCl3)
d: 162.7, 161.6, 155.4, 140.2, 135.1, 129.0,
129.1, 128.7, 128.6, 127.3, 125.3, 121.0, 110.0; IR (neat): 2976, 2906,
1713, 1598, 1400, 1221, 1068, 782, 697 cmꢁ1; HRMS (TOFMS EIþ)
calcd for C15H9BrO2, m/z 299.9786, found 299.9785.
128.6, 128.5, 124.9, 113.5, 112.9, 100.5, 55.9; IR (neat): 2973, 1717,
1238, 1607, 1506, 1238, 1055, 753 cmꢁ1; HRMS (TOFMS EIþ) calcd
for C16H12O3, m/z 252.0786, found 252.0788.
4.4.20. 6-Methyl-3-phenylcoumarin (6k).1c Yield: 101.5 mg, 86%.
White solid. Mp: 144e145 ꢀC. Rf (petroleum ether/EA¼6:1) 0.4. 1H
4.4.13. 8-Methoxy-3-phenylcoumarin (6d).25 Yield: 100.7 mg, 80%.
White solid. Mp: 154e156 ꢀC. Rf (petroleum ether/EA¼6:1) 0.4. 1H
NMR (400 MHz, CDCl3)
d
: 7.73 (s, 1H), 7.68 (dd, J¼8.2, 1.4 Hz, 2H),
NMR (400 MHz, CDCl3)
d
: 7.80 (s, 1H), 7.72 (d, J¼7.2 Hz, 2H),
7.45e7.38 (m, 3H), 7.31 (d, J¼7.6 Hz, 1H), 7.30 (s, 1H), 7.23
7.47e7.40 (m, 3H), 7.22 (d, J¼8.0 Hz, 1H), 7.12 (d, J¼8.0 Hz, 1H), 7.08
(d, J¼9.2 Hz, 1H), 2.40 (s, 3H); 13C NMR (100 MHz, CDCl3)
d: 160.9,
(d, J¼8.0 Hz, 1H), 3.99 (s, 3H); 13C NMR (100 MHz, CDCl3)
d: 160.1,
151.7, 140.0, 134.9, 134.3, 132.6, 128.9, 128.6, 128.5, 128.2, 127.8,
119.5, 116.2, 20.9; IR (neat): 2971, 2905, 1718, 1618, 1294, 1104, 1073,
958, 787, 694 cmꢁ1; HRMS (TOFMS EIþ) calcd for C16H12O2, m/z
236.0837, found 236.0836.
147.1, 143.2, 140.1, 134.8, 129.0, 128.6, 124.5, 120.4, 119.4, 113.3, 56.3;
IR (neat): 2977, 1713, 1608, 1508, 1277, 1100, 752 cmꢁ1; HRMS
(TOFMS EIþ) calcd for C16H12O3, m/z 252.0786, found 252.0788.
4.4.14. 3-Phenyl-benzo[h]coumarin (6e).26 Yield: 39.5 mg, 29%.
Yellow solid. Mp: 213e215 ꢀC. Rf (petroleum ether/EA¼5:1) 0.4. 1H
4.4.21. 8-Methyl-3-phenylcoumarin (6l).25 Yield: 98.0 mg, 83%.
White solid. Mp: 112e114 ꢀC. Rf (petroleum ether/EA¼5:1) 0.4. 1H
NMR (400 MHz, CDCl3)
d
: 8.61e8.59 (m, 1H), 7.95 (s, 1H), 7.90e7.88
NMR (400 MHz, CDCl3)
d
: 7.79 (s, 1H), 7.71 (dd, J¼8.2, 1.4 Hz, 2H),
(m, 1H), 7.79 (d, J¼6.8 Hz, 2H), 7.70 (d, J¼8.8 Hz, 1H), 7.67e7.64
7.19 (t, J¼7.4 Hz, 1H), 7.48e7.40 (m, 3H), 7.37 (d, J¼7.6 Hz, 2H), 2.50
(m, 2H), 7.53e7.41 (m, 4H); 13C NMR (100 MHz, CDCl3)
d
: 160.9,
(s, 3H); 13C NMR (100 MHz, CDCl3)
d: 160.8, 152.0, 140.4, 135.0,
150.8, 140.8, 135.0, 134.8, 129.0, 128.8, 128.7, 128.6, 128.0, 127.8,
127.4, 124.7, 123.9, 123.1, 122.6, 115.3; IR (neat): 2976, 1729, 1605,
1403, 1265, 1124, 1053, 752, 692 cmꢁ1; HRMS (TOFMS EIþ) calcd for
C19H12O2, m/z 272.0837, found 272.0838.
132.8, 128.9, 128.6, 128.0, 126.0, 125.8, 124.2, 119.5, 15.6; IR (neat):
2971, 2905, 1712, 1602, 1227, 1109, 1062, 777, 736, 696 cmꢁ1; HRMS
(TOFMS EIþ) calcd for C16H12O2, m/z 236.0837, found 236.0837.
4.4.22. 6,8-Di-tert-butyl-3-phenylcoumarin (6m). Yield: 93.6 mg,
56%. White solid. Mp: 140e141 ꢀC. Rf (petroleum ether/EA¼6:1) 0.5.
4.4.15. 2-Phenyl-benzo[f]coumarin (6f).27 Yield: 120.9 mg, 89%.
Yellow solid. Mp: 181e182 ꢀC. Rf (petroleum ether/EA¼6:1) 0.4. 1H
1H NMR (400 MHz, CDCl3)
d: 7.84 (s, 1H), 7.77e7.75 (m, 2H), 7.61
NMR (400 MHz, CDCl3)
d
: 8.61 (s, 1H), 8.32 (d, J¼8.4 Hz, 1H), 8.00
(d, J¼2.4 Hz, 1H), 7.47e7.38 (m, 4H), 1.58 (s, 9H), 1.40 (s, 9H); 13C