S. Avula et al. / Tetrahedron 70 (2014) 5768e5775
5773
8.02 (d, J¼4.1 Hz, 1H, AreH), 7.75 (t, J¼4.1 Hz, 2H, AreH), 7.70 (d,
J¼8.3 Hz, 2H, AreH), 7.48 (t, J¼7.9 Hz, 2H, AreH), 7.35 (d, J¼8.3 Hz,
2H, AreH), 7.24 (t, J¼7.9 Hz, 1H, AreH), 7.13 (d, J¼7.9 Hz, 2H, AreH),
7.09 (d, J¼8.3 Hz, 2H, AreH), 6.91 (d, J¼8.3 Hz, 2H, AreH), 5.11 (s,
115.3, 90.0, 50.7, 40.4, 36.7, 32.0, 29.0, 27.4, 27.3; IR (KBr, cmꢁ1): nmax
3062, 2957, 2867, 1675, 1627, 1593, 1564, 1304, 1202, 751; MS (ESI):
m/z 552 [MþH]þ, 554 [Mþ2þH]þ; HRMS: calcd for C30H24O3N-
Cl3þHþ: 552.0895, observed: 552.0876.
1H, pyran-C4H); 13C NMR (75 MHz, CDCl3):
d 193.5, 182.5, 177.0,
157.9, 141.9, 138.7, 136.6, 135.7, 134.7, 134.2, 133.1, 131.4, 130.4, 129.5,
128.7, 128.6, 127.7, 126.7, 126.5, 125.1, 121.8, 88.2, 35.8; IR (KBr,
cmꢁ1): nmax 3356, 3068, 1666, 1627, 1591, 1202; MS (ESI): m/z 552
[MþH]þ, 554 [Mþ2þH]þ; HRMS: calcd for C32H19O4NCl2þHþ:
552.0895, observed: 552.0903.
4.2.19. 4-(5-Bromo-2-methoxyphenyl)-3-(2-chlorobenzoyl)-7,7-
dimethyl-2-(phenylamino)-7,8-dihydro-4H-chromen-5(6H)-one
(8d). Pale yellow solid; mp: 213e214 ꢀC; [Found: C, 62.77; H, 4.62;
N, 2.29. C31H27O4NBrCl requires C, 62.80; H, 4.59; N, 2.36%]; 1H
NMR (300 MHz, CDCl3):
d 13.38 (s, 1H, D2O exchangeable, NH),
7.27e7.41 (m, 6H, AreH), 7.14e7.23 (m, 3H, AreH), 6.57 (d,
J¼8.30 Hz, 1H, AreH), 6.13e6.26 (m, 2H, AreH), 4.43 (s, 1H, pyran-
C4H), 3.66 (s, 3H, eOCH3), 2.55 (d, J¼17.4 Hz, 1H), 2.42 (d, J¼17.4 Hz,
1H), 2.25 (d, J¼16.6 Hz, 1H), 2.13 (d, J¼16.6 Hz, 1H), 1.11 (s, 3H,
4.2.15. 3-(4-Chlorobenzoyl)-4-(4-nitrophenyl)-2-(phenylamino)-4H-
benzo[g]chromene-5,10-dione (6e). Brick red solid; mp: 175e176 ꢀC;
1H NMR (300 MHz, CDCl3):
d 13.33 (s, 1H, D2O exchangeable, NH),
8.12e8.19 (m, 1H, AreH), 7.98e8.04 (m, 3H, AreH ortho to NO2),
7.74e7.79 (m, 2H, AreH), 7.71 (d, J¼8.3 Hz, 2H, AreH ortho to CO),
7.50 (t, J¼7.9 Hz, 2H, NePh), 7.37 (d, J¼8.3 Hz, 2H, AreH ortho to Cl),
7.28 (overlapping in CDCl3 peak, m,1H, NePh), 7.12 (d, J¼8.3 Hz, 2H,
AreH meta to NO2), 7.08 (d, J¼8.3 Hz, 2H, NePh), 5.30 (s, 1H, pyran-
eCH3), 0.92 (s, 3H, eCH3); 13C NMR (75 MHz, CDCl3):
d 195.9, 191.4,
160.9, 157.5, 139.5, 139.0, 136.7, 134.1, 133.6, 130.4, 130.3, 130.0,
129.7, 129.2, 126.6, 126.3, 124.9, 122.4, 113.9, 112.5, 112.2, 89.4, 55.7,
55.4, 50.5, 40.4, 34.0, 33.6, 32.2, 29.4, 26.6; IR (KBr, cmꢁ1): nmax
3448, 3052, 2958, 1685, 1658, 1625, 1592, 1561, 1366, 1307, 1206,
747; MS (ESI): m/z 592 [MþH]þ, 594 [Mþ2þH]þ; HRMS: calcd for
C4H); 13C NMR (75 MHz, CDCl3):
d 193.3, 182.4, 176.8, 169.4, 157.8,
150.4, 148.1, 146.9, 138.5, 136.4, 136.0, 134.8, 134.3, 131.3, 130.4,
129.6, 129.1, 128.8, 127.6, 126.8, 126.7, 125.7, 125.4, 124.0, 123.3,
122.0, 87.5, 36.6; IR (KBr, cmꢁ1): nmax 3365, 3056, 2956, 1669, 1627,
1590, 1199; MS (ESI): m/z 563 [MþH]þ, 565 [Mþ2þH]þ; HRMS:
calcd for C32H19O6N2ClþHþ: 563.1190, observed: 563.1187.
C
C
31H27O4N79BrClþHþ: 592.0885, observed: 592.0869; calcd for
31H27O4N81BrClþHþ: 594.0864, observed: 594.0847.
4.2.20. 4-(4-Chlorophenyl)-3-(4-ethylbenzoyl)-7,7-dimethyl-2-(phe-
nylamino)-7,8-dihydro-4H-chromen-5(6H)-one (8e). Pale yellow
solid; mp: 202e203 ꢀC; [Found: C, 74.97; H, 5.98; N, 2.68.
4.2.16. 3-(2-Chlorobenzoyl)-4-(4-chlorophenyl)-7,7-dimethyl-2-
C
32H30O3NCl requires C, 75.06; H, 5.91; N, 2.74%]; 1H NMR
(phenylamino)-7,8-dihydro-4H-chromen-5(6H)-one (8a). Pale yel-
(300 MHz, CDCl3): d 13.14 (s, 1H, D2O exchangeable, NH), 7.34e7.42
low solid; mp: 223e225 ꢀC; 1H NMR (300 MHz, CDCl3):
d
13.10 (s,
(m, 4H, AreH), 7.15 (d, J¼8.3 Hz, 2H, AreH), 7.17e7.22 (m, 1H),
7.02e7.06 (overlapping m, 4H, AreH), 6.73 (d, J¼8.3 Hz, 2H, AreH),
4.86 (s, 1H, pyran-C4H), 2.68 (q, J¼7.5 Hz, 2H, eCH2e), 2.55 (d,
J¼17.9 Hz, 1H), 2.46 (d, J¼17.9 Hz, 1H), 2.27 (d, J¼16.2 Hz, 1H), 2.17
(d, J¼16.2 Hz, 1H), 1.26 (t, J¼7.5 Hz, 3H, eCH3), 1.12 (s, 3H, eCH3),
1H, D2O exchangeable, NH), 7.37e7.48 (overlapping m, 5H, AreH),
7.19e7.23 (m, 1H, AreH), 7.00e7.10 (m, 4H, AreH), 6.69e6.82 (m,
2H, AreH), 6.43 (m, 1H, AreH), 4.48 (s, 1H, pyran-C4H), 2.54 (d,
J¼17.6 Hz, 1H), 2.48 (d, J¼17.6 Hz, 1H), 2.25 (d, J¼16.5 Hz, 1H), 2.15
(d, J¼16.5 Hz, 1H), 1.11 (s, 3H, eCH3), 0.91 (s, 3H, eCH3); 13C NMR
0.93 (s, 3H, eCH3); 13C NMR (75 MHz, CDCl3):
d 196.1, 195.6, 161.0,
(75 MHz, CDCl3þDMSO-d6):
d
194.3, 190.6, 159.3, 156.6, 135.1, 130.3,
157.7, 146.0, 143.9, 138.1, 137.1, 131.8, 129.3, 129.1, 128.2, 127.7, 126.5,
124.8,122.5,117.4, 90.1, 50.7, 40.4, 34.8, 32.4, 29.3, 28.8, 27.2,15.7; IR
(KBr, cmꢁ1): nmax 3447, 3051, 2958, 2869, 1687, 1669, 1626, 1593,
1561, 1362, 1313, 1207, 832; MS (ESI): m/z 512 [MþH]þ, 514
[Mþ2þH]þ; HRMS: calcd for C32H30O3N35ClþHþ: 512.1987, ob-
served: 512.1963; calcd for C32H30O3N37ClþHþ: 514.1958, observed:
514.1953.
128.8, 128.2, 128.1, 126.6, 125.6, 123.9, 121.1, 115.5, 89.3, 49.2, 30.9,
27.8, 25.6; IR (KBr, cmꢁ1): nmax 3051, 2956, 1666, 1623, 1590, 1563,
1362, 1310, 1204, 1147, 751; MS (ESI): m/z 518 [MþH]þ, 520
[Mþ2þH]þ, 522 [Mþ4þH]þ; HRMS: calcd for C30H25O3NCl2þHþ:
518.1650, observed: 518.1654.
4.2.17. 3-(2-Chlorobenzoyl)-7,7-dimethyl-4-phenyl-2-(phenyl-
amino)-7,8-dihydro-4H-chromen-5(6H)-one (8b). Yellow solid; mp:
145e147 ꢀC; [Found: C, 74.51; H, 5.33; N, 2.74. C30H26O3NCl requires
4.2.21. 3-(4-Ethylbenzoyl)-4-(4-methoxyphenyl)-7,7-dimethyl-2-
(phenylamino)-7,8-dihydro-4H-chromen-5(6H)-one (8f). Pale yel-
low solid; mp: 180e181 ꢀC; [Found: C, 78.17; H, 6.53; N, 2.67.
C, 74.45; H, 5.41; N, 2.89%]; 1H NMR (300 MHz, CDCl3):
d 13.10 (s,
1H, D2O exchangeable, NH), 6.76e7.28 (overlapping multiplets,
14H, AreH), 4.48 (s, 1H, pyran-C4H), 2.54 (d, J¼17.6 Hz, 1H), 2.48 (d,
J¼17.6 Hz,1H), 2.25 (d, J¼16.5 Hz,1H), 2.14 (d, J¼16.5 Hz,1H), 1.11 (s,
C
33H33O4N requires C, 78.08; H, 6.55; N, 2.76%]; 1H NMR
(300 MHz, CDCl3):
d 13.14 (s, 1H, D2O exchangeable, NH),
7.35e7.44 (overlapping m, 4H, AreH), 7.11e7.21 (m, 1H, AreH),
7.14 (d, J¼8.1 Hz, 2H), 7.08 (d, J¼8.1 Hz, 2H, AreH), 6.74 (d,
J¼8.7 Hz, 2H, AreH), 6.62 (d, J¼8.7 Hz, 2H, AreH), 4.83 (s, 1H,
pyran-C4H), 3.71 (s, 3H, eOCH3), 2.67 (q, J¼7.5 Hz, 2H, eCH2e),
2.53 (d, J¼17.9 Hz, 1H), 2.46 (d, J¼17.9 Hz, 1H), 2.27 (d, J¼16.2 Hz,
1H), 2.17 (d, J¼16.2 Hz, 1H), 1.25 (t, J¼7.5 Hz, 3H, eCH3), 1.12 (s, 3H,
3H, eCH3), 0.91 (s, 3H, eCH3); 13C NMR (75 MHz, CDCl3):
d 195.7,
160.1, 158.0, 136.7, 129.7, 129.2, 128.1, 127.8, 126.5, 126.2, 126.3,
124.9, 122.5, 114.7, 50.6, 40.4, 35.1, 32.3, 29.2, 27.1; IR (KBr, cmꢁ1):
nmax 3058, 2957, 1670, 1625, 1594, 1561, 1306, 1200, 1143, 753; MS
(ESI): m/z 484 [MþH]þ, 486 [Mþ2þH]þ; HRMS: calcd for
C
30H26O3NClþHþ: 484.1674, observed: 484.1667.
eCH3), 0.93 (s, 3H, eCH3); 13C NMR (75 MHz, CDCl3):
d 196.1,
195.6, 160.6, 157.8, 145.7, 138.2, 137.7, 137.2, 129.2, 128.6, 127.5,
126.6, 124.5, 122.2, 118.1, 113.3, 90.8, 55.1, 50.7, 40.4, 34.3, 32.3,
29.2, 28.7, 27.2, 15.5; IR (KBr, cmꢁ1): nmax 3047, 3000, 2958, 2833,
1669, 1625, 1590, 1558, 1506, 1362, 1311, 1206, 1033, 830, 751; MS
(ESI): m/z 508 [MþH]þ; HRMS: calcd for C33H33O4NþHþ:
508.2482, observed: 508.2456.
4.2.18. 3-(2-Chlorobenzoyl)-4-(2,3-dichlorophenyl)-7,7-dimethyl-2-
(phenylamino)-7,8-dihydro-4H-chromen-5(6H)-one (8c). Yellow
solid; mp: 209e210 ꢀC; [Found: C, 65.28; H, 4.29; N, 2.45.
30H24O3NCl3 requires C, 65.17; H, 4.38; N, 2.53%]; 1H NMR
(300 MHz, CDCl3): 13.35 (s, 1H, D2O exchangeable, NH), 7.30e7.42
C
d
(m, 5H, AreH), 7.12e7.27 (m, 5H, AreH), 6.72e6.75 (m, 1H, AreH),
6.28e6.42 (m, 2H, AreH), 4.87 (s, 1H, pyran-C4H), 2.44e2.54 (m,
2H), 2.20 (d, J¼15.9 Hz, 1H), 2.14 (d, J¼15.9 Hz, 1H), 1.10 (s, 3H,
4.2.22. 4-(2,3-Dichlorophenyl)-3-(4-ethylbenzoyl)-7,7-dimethyl-2-
(phenylamino)-7,8-dihydro-4H-chromen-5(6H)-one (8g). Pale yel-
low solid; mp: 215e216 ꢀC; [Found: C, 70.29; H, 5.41; N, 2.50.
eCH3), 0.98 (s, 3H, eCH3); 13C NMR (75 MHz, CDCl3):
d 196.0, 191.7,
161.2, 158.2, 142.7, 139.9, 136.4, 133.2, 131.3, 130.2, 129.8, 129.4,
129.1, 128.6, 128.5, 128.4, 127.0, 126.6, 126.4, 126.0, 125.3, 123.0,
C
32H29O3NCl2 requires C, 70.33; H, 5.35; N, 2.56%]; 1H NMR
(300 MHz, CDCl3):
d 13.17 (s, 1H, D2O exchangeable, NH), 7.40 (t,