Li et al.
JOCArticle
(s, 3H), 1.12 (s, 3H), 2.17 (d, J=16.0 Hz, 1H), 2.26 (d, J=16.0 Hz,
1H), 2.48 (d, J = 17.5 Hz, 1H), 2.55 (d, J = 17.5 Hz, 1H), 3.73 (s,
3H), 4.39 (s, 1H), 6.36-7.43 (m, 12H), 13.07 (s, 1H); 13C NMR
(CDCl3, 125 MHz) δ 27.2, 29.3, 32.3, 35.10, 40.4, 50.8, 55.2, 91.5,
113.4, 117.9, 125.2, 126.8, 129.2, 129.6, 130.1, 130.8, 134.9, 136.7,
137.5, 138.2, 158.1, 158.2, 159.9, 191.5, 195.9; IR (KBr, cm-1) 1684,
1668, 1626, 1591, 1559, 1368, 1256, 827, 775, 757, 690; HRMS (ESI-
TOF, [M þ H]þ) calcdforC31H28Cl2NO4 548.1395, found 548.1385.
4-(4-Chlorophenyl)-3-(2,5-dichlorobenzoyl)-7,7-dimethyl-2-(phe-
nylamino)-7,8-dihydro-4H-chromen-5(6H)-one (5g). Pale yellow
powder; mp 169-171 °C; 1H NMR (DMSO-d6, 500 MHz) δ 0.81
(s, 3H), 1.03(s, 3H), 2.05(d, J =16.5Hz, 1H), 2.27(d, J= 16.5 Hz,
1H), 2.51 (d, J = 18.0 Hz, 1H), 2.68 (d, J = 18.0 Hz, 1H), 4.31 (s,
1H), 6.68-7.50 (m, 12H), 12.76 (s, 1H); 13C NMR (DMSO-d6, 125
MHz) δ 26.7, 29.1, 32.4, 35.0, 41.2, 50.4, 90.8, 116.1, 123.1, 125.8,
128.3, 129.9, 130.1, 130.7, 131.4, 131.7, 132.3, 136.5, 141.1, 144.2,
158.2, 161.6, 189.9, 196.1; IR (KBr, cm-1) 1685, 1668, 1622, 1594,
1564, 1364, 1205, 822, 757, 691; HRMS (ESI-TOF, [M þ H]þ) calcd
for C30H25Cl3NO3 552.0900, found 552.0885.
2.18 (d, J = 16.1 Hz, 1H), 2.26 (d, J = 16.1 Hz, 1H), 2.47 (d, J =
18.0 Hz, 1H), 2.54 (d, J= 18.0 Hz, 1H), 4.81 (s, 1H), 6.71-7.39(m,
14H), 13.17 (s, 1H); 13C NMR (DMSO-d6, 125 MHz) δ 26.8, 29.2,
32.5, 34.9, 41.7, 50.5, 91.2, 100.0, 116.5, 122.4, 125.1, 127.0, 128.5,
128.7, 129.6, 129.8, 130.2, 131.2, 137.4, 138.0, 140.9, 144.8, 157.6,
162.4, 194.6, 196.3; IR (KBr, cm-1) 1687, 1667, 1624, 1593, 1561,
1362, 1318, 841, 753, 706; HRMS (ESI-TOF, [M þ H]þ) calcd for
C30H27ClNO3 484.1679, found 484.1682.
4-(Benzo[d][1,3]dioxol-5-yl)-3-benzoyl-7,7-dimethyl-2-(phenyl-
amino)-7,8-dihydro-4H-chromen-5(6H)-one (5m). Pale yellow
powder; mp 210-212 °C; 1H NMR (CDCl3, 500 MHz) δ 0.94 (s,
3H), 1.11 (s, 3H), 2.18 (d, J = 16.0 Hz, 1H), 2.25 (d, J = 16.0 Hz,
1H), 2.47 (d, J = 17.5 Hz, 1H), 2.51 (d, J = 17.5 Hz, 1H), 4.75 (s,
1H), 5.84 (d, J = 1 Hz, 1H), 5.85 (d, J = 1 Hz, 1H), 6.22-7.40 (m,
13H), 13.13 (s, 1H); 13C NMR (DMSO-d6, 125 MHz) δ 26.9, 29.2,
32.5, 34.8, 41.5, 50.6, 91.7, 101.3, 108.0, 108.3, 117.0, 120.7, 122.3,
125.0, 127.0, 128.6, 129.8, 130.2, 137.4, 139.8, 141.0, 145.9, 147.4,
157.5, 162.2, 194.6, 196.4; IR (KBr, cm-1) 1685, 1669, 1625, 1596,
1560, 1361, 1248, 753, 700; HRMS (ESI-TOF, [M þ H]þ) calcd for
C31H28NO5 494.1967, found 494.1965.
4-(4-Chlorophenyl)-3-(2-fluorobenzoyl)-7,7-dimethyl-2-(phenyl-
amino)-7,8-dihydro-4H-chromen-5(6H)-one (5h). Yellow powder;
3-Benzoyl-4-(4-bromophenyl)-7,7-dimethyl-2-(phenylamino)-
7,8-dihydro-4H-chromen-5(6H)-one (5n). Pale yellow powder;
1
mp 232-234 °C; H NMR (CDCl3, 500 MHz) δ 0.93 (s, 3H),
1
mp 248-250 °C; H NMR (CDCl3, 500 MHz) δ 0.96 (s, 3H),
1.13 (s, 3H), 2.16 (d, J=16.0 Hz, 1H), 2.26 (d, J=16.0 Hz, 1H),
2.47 (d, J = 17.5 Hz, 1H), 2.55 (d, J = 17.5 Hz, 1H), 4.60 (s, 1H),
6.69-7.44 (m, 13H), 13.13 (s, 1H); 13C NMR (CDCl3, 125 MHz)
δ 27.1, 29.3, 32.3, 34.7, 40.4, 50.7, 91.2, 115.8, 116.0, 117.2, 122.6,
124.2, 125.2, 128.0, 128.6, 128.7, 129.2, 129.3, 130.8, 130.9, 131.9,
1.14 (s, 3H), 2.18 (d, J = 16.0 Hz, 1H), 2.28 (d, J = 16.0 Hz, 1H),
2.49 (d, J = 17.5 Hz, 1H), 2.56 (d, J = 17.5 Hz, 1H), 4.82 (s, 1H),
6.67-7.43 (m, 14H), 13.17 (s, 1H); 13C NMR (CDCl3, 125 MHz)
δ 27.2, 29.3, 32.4, 34.9, 40.5, 50.8, 90.0, 117.4, 120.1, 122.5, 125.0,
126.3, 128.3, 129.3, 129.5, 129.6, 131.1, 137.0, 140.7, 144.3, 158.0,
160.9, 195.5, 195.9; IR (KBr, cm-1) 1688, 1669, 1626, 1592, 1560,
1362, 1318, 1050, 839, 753, 706; HRMS (ESI-TOF, [M þ H]þ)
calcd for C30H27BrNO3 528.1174, found 528.1179.
136.6, 143.6, 157.0, 157.8, 158.9, 160.4, 190.7, 195.8; IR (KBr, cm-1
)
1688, 1668, 1626, 1593, 1563, 1362, 769, 754; HRMS (ESI-TOF,
[M þ H]þ) calcd for C30H26ClFNO3 502.1585, found 502.1581.
4-(Benzo[d][1,3]dioxol-5-yl)-3-(2-fluorobenzoyl)-7,7-dimethyl-
2-(phenylamino)-7,8-dihydro-4H-chromen-5(6H)-one (5i). Yel-
low powder; mp 189-191 °C; 1H NMR (DMSO-d6, 500 MHz) δ
0.84 (s, 3H), 1.03 (s, 3H), 2.06 (d, J = 16.5 Hz, 1H), 2.26 (d, J =
16.0 Hz, 1H), 2.48 (d, J = 15.0 Hz, 1H), 2.67 (d, J = 15.0 Hz, 1H),
4.38 (s, 1H), 5.88 (bs, 1H), 5.91 (d, J = 1 Hz, 1H), 6.06-7.46 (m,
12H), 12.68 (s, 1H); 13C NMR (DMSO-d6, 125 MHz) δ 26.8, 29.2,
32.4, 34.7, 50.4, 92.1, 101.2, 108.1, 108.2, 116.7, 120.9, 122.9, 124.9,
125.5, 128.8, 129.0, 129.8, 131.7, 131.8, 136.7, 139.5, 145.9, 147.2,
157.6, 159.1, 161.7, 189.9, 196.2; IR (KBr, cm-1) 1684, 1671, 1615,
1598, 1558, 1490, 1366, 1307, 758; HRMS (ESI-TOF, [M þ H]þ)
calcd for C31H27FNO5 512.1873, found 512.1888.
3-(2-Bromobenzoyl)-4-(4-chlorophenyl)-7,7-dimethyl-2-(phenyl-
amino)-7,8-dihydro-4H-chromen-5(6H)-one (5j). Yellow powder;
mp 197-200 °C; 1H NMR (DMSO-d6, 500 MHz) δ 0.79 (s, 3H),
1.02 (s, 3H), 2.03 (d, J = 16.0 Hz, 1H), 2.27 (d, J = 16.5 Hz, 1H),
2.50 (d, J = 18.0 Hz, 1H), 2.70 (d, J = 18.0 Hz, 1H), 4.35 (s, 1H),
6.59-7.59 (m, 13H), 12.81 (s, 1H); 13C NMR (DMSO-d6, 125
MHz) δ 26.8, 29.4, 32.7, 35.3, 50.6, 90.8, 114.9, 116.6, 123.1, 125.9,
128.3, 128.5, 129.0, 130.2, 131.4, 131.5, 133.2, 136.8, 141.6, 144.4,
158.3, 162.1, 188.1, 192.86, 196.53; IR (KBr, cm-1) 1669, 1627,
1596, 1565, 1364, 1306, 752, 690; HRMS (ESI-TOF, [MþH]þ)
calcd for C30H26BrClNO3 562.0785, found 562.0796.
3-Benzoyl-7,7-dimethyl-2-(phenylamino)-4-p-tolyl-7,8-dihydro-
4H-chromen-5(6H)-one (5o). Yellow powder; mp 197-199 °C;
1H NMR (DMSO-d6, 500 MHz) δ 0.81 (s, 3H), 1.03 (s, 3H), 2.03
(d, J = 17.5 Hz, 1H), 2.13 (s, 3H), 2.25 (d, J = 17.5 Hz, 1H), 2.47
(d, J = 17.5 Hz, 1H), 2.67 (d, J = 17.5 Hz, 1H), 4.66 (s, 1H),
6.56-7.42 (m, 14H), 12.41 (s, 1H); 13C NMR (DMSO-d6, 125
MHz) δ 21.0, 26.7, 29.2, 32.4, 34.6, 41.2, 50.5, 91.7, 117.1, 122.2,
124.9, 127.0, 127.4, 128.5, 129.1, 129.8, 130.1, 135.6, 137.3, 140.9,
142.8, 157.6, 162.2, 194.5, 196.2; IR (KBr, cm-1) 1688, 1671,
1625, 1596, 1560, 1361, 1305, 1211, 897, 755, 703; HRMS (ESI-
TOF, [M þ H]þ) calcd for C31H30NO3 464.2226, found 464.2236.
3-Benzoyl-7,7-dimethyl-4-phenyl-2-(phenylamino)-7,8-dihydro-
4H-chromen-5(6H)-one (5p). Pale yellow powder; mp 166-168 °C;
1H NMR (CDCl3, 500 MHz) δ 0.95 (s, 3H), 1.14 (s, 3H), 2.19 (d,
J = 16.5 Hz, 1H), 2.28 (d, J = 16.5 Hz, 1H), 2.50 (d, J = 17.5 Hz,
1H), 2.56 (d, J = 17.5 Hz, 1H), 4.86 (s, 1H), 6.82-7.44 (m, 15H),
13.21 (s, 1H); 13C NMR (DMSO-d6, 125 MHz) δ 26.8, 29.3, 32.5,
35.2, 50.6, 91.7, 117.0, 122.3, 125.0, 126.7, 127.1, 127.6, 128.6, 128.6,
129.8, 130.2, 137.4, 141.0, 145.8, 157.7, 162.36, 194.6, 196.2; IR
(KBr, cm-1) 1686, 1668, 1625, 1594, 1561, 1362, 755, 695; HRMS
(ESI-TOF, [M þ H]þ) calcd for C30H28NO3 450.2069, found
450.2074.
4-(Benzo[d][1,3]dioxol-5-yl)-3-(2-bromobenzoyl)-7,7-dimethyl-
2-(phenylamino)-7,8-dihydro-4H-chromen-5(6H)-one (5k). Yel-
low powder; mp 176-179 °C; 1H NMR (DMSO-d6, 500 MHz)
δ 0.84 (s, 3H), 1.04 (s, 3H), 2.07 (d, J = 16.0 Hz, 1H), 2.27 (d, J =
16.0 Hz, 1H), 2.53 (d, J = 17.5 Hz, 1H), 2.68 (d, J = 17.5 Hz, 1H),
4.28 (s, 1H), 5.89 (bs, 1H), 5.91 (d, J = 1 Hz, 1H), 6.10-7.62 (m,
12H), 12.79 (s, 1H); 13C NMR (DMSO-d6, 125 MHz) δ 26.7, 29.0,
32.4, 35.0, 50.3, 91.1, 101.1, 108.0, 108.5, 116.8, 121.2, 122.7, 125.4,
127.8, 128.6, 129.8, 130.8, 132.8, 136.6, 139.3, 141.5, 145.8, 147.1,
157.8, 161.4, 192.6, 196.0; IR (KBr, cm-1) 1682, 1672, 1627, 1597,
1561, 1361, 1297, 1248, 751; HRMS (ESI-TOF, [M þ H]þ) calcd
for C31H27BrNO5 572.1073, found 572.1091.
3-Benzoyl-4-(4-methoxyphenyl)-7,7-dimethyl-2-(phenylamino)-
7,8-dihydro-4H-chromen-5(6H)-one (5q). Pale yellow powder; mp
172-174 °C; 1H NMR (DMSO-d6, 500 MHz) δ 0.81 (s, 3H), 1.03
(s, 3H), 2.06 (d, J = 16.0 Hz, 1H), 2.24 (d, J = 16.0 Hz, 1H), 2.48
(d, J = 17.5 Hz, 1H), 2.67 (d, J = 17.5 Hz, 1H), 3.60 (s, 3H), 4.64
(s, 1H), 6.59-7.42 (m, 14H), 12.41 (s, 1H); 13C NMR (DMSO-d6,
125 MHz) δ 26.7, 29.2, 32.4, 34.2, 50.5, 55.3, 91.8, 113.8, 117.2,
122.2, 124.9, 127.0, 128.5, 128.6, 129.8, 130.1, 137.3, 137.8, 140.9,
157.5, 157.9, 162.0, 194.6, 196.2; IR (KBr, cm-1) 1688, 1670,
1624, 1596, 1559, 1361, 1241, 834, 753, 702; HRMS (ESI-TOF,
[M þ H]þ) calcd for C31H30NO4 480.2175, found 480.2164.
3-Benzoyl-7,7-dimethyl-4-(4-nitrophenyl)-2-(phenylamino)-7,8-
dihydro-4H-chromen-5(6H)-one (5r). Pale yellow powder; mp
3-Benzoyl-4-(4-chlorophenyl)-7,7-dimethyl-2-(phenylamino)-7,8-
dihydro-4H-chromen-5(6H)-one (5l). Pale yellow powder; mp 254-
255 °C; 1H NMR (CDCl3, 600 MHz) δ 0.93 (s, 3H), 1.13 (s, 3H),
1
262-264 °C; H NMR (CDCl3, 600 MHz) δ 0.92 (s, 3H), 1.14
(s, 3H), 2.17 (d, J = 16.5 Hz, 1H), 2.28 (d, J=16.5 Hz, 1H), 2.50
8530 J. Org. Chem. Vol. 75, No. 24, 2010