Synthesis and Antioxidant Properties of Novel 4-Hydroxy coumarins
7
H, 5.15; N, 4.78; found: C, 73.72; H, 5.12; N, 4.79. IR 4-Hydroxy-3-(1-(4-nitrophenylimino)ethyl)-2H-
(KBr, Cm-1): 3421 (OH), 3073 (=CH)ar, 2985, 2922 and chromen-2-one 6b
2852 (CH3), 1709 (lactone C=O), 1611 (imino C=N), Anal. calcd. for C17H12N2O5 (Mol. Wt. 324.29): C,
1
1597, 1569, 1513 and 1483 (C=C)ar. H-NMR (CDCl3, 62.96; H, 3.73; N, 8.64: found: C, 62.97; H, 3.77; N,
200 MHz):
C=N), 7.09-7.65 (ABq, 4H,
7.3 (m, 1H, C6-H), 7.4 (dd, 1H,
C8-H), 7.6 (dd, 1H, = 7.8 Hz,
(m, 1H, C-7-H), 16.07 (bs, 1H, C4-OH). 13C-NMR 2.76 (s, 3H, CH3-C=N), 7.3 (m, 1H, C6-H), 7.4 (dd, 1H,
(CDCl3, 50 MHz): 20.6 (CH3-C4''), 20.8 (CH3-C=N), = 8.3 Hz, = 1.1 Hz, C8-H), 7.43 (d, 2H, = 8.9 Hz,
97.3 (C3), 116.6 (C10), 116.8 (C8), 119.3 (C5), 119.9 (C2'', C3'',5''-H), 7.6 (dd, 1H, = 7.8 Hz, = 1.7 Hz, C5-H), 7.7
C6''), 125.9 (C6), 129.3 (C7), 129.9 (C4''), 131.7 (C3'',C5''), (m, 1H, C7-H), 8.39 (d, 2H, = 8.9 Hz, C2'',6''-H), 15.95
20.8
(CH3-C=N), 97.9 (C3), 116.4 (C8), 116.9 (C10), 119.6 (C5),
δ
2.41 (s, 3H, CH3-C4''), 2.69 (s, 3H, CH3- 8.69. IR (KBr, Cm-1): 3414 (OH), 3081 and 3046
J
= 8.43 Hz, C2'',3'' 5'' 6''
= 8.3 Hz, = 1.1 Hz, C=O), 1608 (imino C=N), 1580, 1519 and 1483 (C=C)ar,
= 1.7 Hz, C5-H), 7.7 1557 and 1340 (NO2). H-NMR (CDCl3, 200 MHz):
, , -H), (=CH)ar, 2992, 2947 and 2849 (CH3), 1707 (lactone
J
J
J
1
J
δ
δ
J
J
J
J
J
J
138.4 (C1''), 163.5 (C2), 152.4 (C9), 180.4 (C4), 180.5 (bs, 1H, C4-OH). 13C-NMR (CDCl3, 50 MHz):
δ
(C1'). M.P.147-149oC.
123.2 (C2'', C6''), 125.3 (C6), 129.1 (C7), 133.2 (C3'', C5''),
136.1 (C1''), 145.3 (C4''), 152.4 (C9), 163.1 (C2), 177.5
(C1'), 180.7 (C4). M.P. 212-215oC.
4-Hydroxy-3-(1-(m-tolylimino)ethyl)-2H-chromen-
2-one 4b
Anal. calcd. for C18H15NO3 (Mol. Wt. 293.32): C, 73.71;
H, 5.15; N, 4.78: found: C, 73.72; H, 5.14; N, 4.79. IR 4-Hydroxy-3-(1-(3-nitrophenylimino)ethyl)-2H-
(KBr, Cm-1): 3417 (OH), 3067 (=CH)ar, 2982, 2929 and chromen-2-one 7b
2853 (CH3), 1697 (lactone C=O), 1606 (imino C=N), Anal. calcd. for C17H12N2O5 (Mol. Wt. 324.29): C, 62.96;
1
1600, 1566 and 1484 (C=C)ar. H-NMR (CDCl3, 200 H, 3.73; N, 8.64; found: C, 62.96; H, 3.73; N, 8.64. IR
MHz):
7.01 (dd, 1H,
(dd, 1H, = 8.12 Hz,
C2''-H), 7.25 (m, 1H, C5''-H), 7.3 (m, 1H, C6-H), 7.4 (dd, (NO2). 1H-NMR (CDCl3, 200 MHz):
δ
2.42 (s, 3H, CH3-C3''), 2.70 (s, 3H, CH3-C=N), (KBr, Cm-1): 3416 (OH), 3089 and 3062 (=CH)ar, 2980,
J
= 7.58 Hz,
= 1.14 Hz, C6''-H), 7.12 (s, 1H, C=N), 1590, 1538 and 1491 (C=C)ar, 1562 and 1353
2.61 (s, 3H, CH3-
= 1.12 Hz, C6''-H),
= 1.7 Hz, C5-H), 7.7 (m, 1H, C7-H), 15.9 (bs, 1H, 7.3 (m, 1H, C6-H), 7.34 (s, 1H, C2''-H), 7.4 (dd, 1H,
J = 1.14 Hz, C4''-H), 7.04 2936 and 2853 (CH3), 1705 (lactone C=O), 1609 (imino
J
J
δ
1H,
Hz,
J
J
= 8.3 Hz, J = 1.1 Hz, C8-H), 7.6 (dd, 1H, J = 7.8 C=N), 7.26 (dd, 1H, J = 8.02 Hz, J
J
=
C4-OH). 13C-NMR (CDCl3, 50 MHz):
δ
20.9 (CH3-C=N), 8.3 Hz,
J
= 1.1 Hz, C8-H), 7.54 (m, 1H, C5''-H), 7.6 (dd,
21.0 (CH3-C3''), 97.2 (C3), 116.7 (C8), 116.9 (C10), 118.9 1H,
J
= 7.8 Hz,
J
= 1.7 Hz, C5-H), 7.7 (m, 1H, C7-H),
= 1.12 Hz, C4''-H), 16.02 (bs,
19.2 (CH3-
(C6''), 119.3 (C5), 121.9 (C2''), 124.0 (C4''), 125.9 (C6), 8.09 (dd, 1H,
J = 8.5 Hz, J
129.3 (C7), 130.7 (C5''), 139.1 (C1''), 139.1 (C3''), 163.6 1H, C4-OH). 13C-NMR (CDCl3, 50 MHz):
δ
(C2), 152.1 (C9), 180.3 (C1'), 180.6 (C4). M.P. 109-110oC. C=N), 97.9 (C3), 116.4 (C8), 116.5 (C10), 117.8 (C2''),
119.4 (C5), 121.4 (C4''), 125.5 (C6), 127.3 (C6''), 129.3 (C7),
4-Hydroxy-3-(1-(o-tolylimino)ethyl)-2H-chromen- 131.5 (C5''), 141.9 (C1''), 163.5 (C2), 148.2 (C3''), 152.1
2-one 5b
(C9), 177.4 (C1'), 180.1 (C4). M.P. 209-210oC.
Anal. calcd. for C18H15NO3 (Mol. Wt. 293.32): C, 73.71;
H, 5.15; N, 4.78: found: C, 73.75; H, 5.21; N, 4.73. IR 3-(1-(Benzylimino)ethyl)-4-hydroxy-2H-chromen-
(KBr, Cm-1): 3467(OH), 3072.51 (=CH)ar, 2935 and 2-one 8b
2856 (CH3), 1712 (lactone C=O), 1611 (imino C=N), Anal. calcd. for C18H15NO3 (Mol. Wt. 293.32): C, 73.71;
1
1594, 1563 and 1486 (C=C)ar. H-NMR (CDCl3, 200 H, 5.15; N, 4.78; found: C, 73.73; H, 5.13; N, 4.73. IR
MHz):
7.23 (dd, 1H,
1H, C4''-H), 7.28 (dd, 1H,
H), 7.3 (m, 1H, C6-H), 7.4 (dd, 1H,
Hz, C8-H), 7.37 (m, 1H, C5''-H), 7.6 (dd, 1H,
δ
2.30 (s, 3H, CH3-C1''), 2.81 (s, 3H, CH3-C=N), (KBr, Cm-1): 3406 (OH), 3032 and 3012 (=CH)ar, 2930
J
= 8.01 Hz,
J
= 1.12 Hz, C6''-H), 7.13 (m, (CH2), 1698 (lactone C=O), 1612 (imino C=N), 1586,
J
= 7.62 Hz,
J
= 1.11 Hz, C3''- 1572 and 1485 (C=C)ar. 1H-NMR (CDCl3, 200 MHz):
δ
J
= 8.3 Hz,
J
= 1.1 2.64 (s, 3H, CH3-C=N), 3.25 (s, 2H, CH2-N=C), 7.29
J
= 7.8 Hz, (m, 2H, C3'',5''-H), 7.26 (m, 1H, C4''-H), 7.39 (dd, 2H, J =
J
= 1.7 Hz, C5-H), 7.7 (m, 1H, C7-H), 15.8 (bs, 1H, C4- 7.7 Hz,
J
= 1.1 Hz, C2'',6''-H), 7.3 (m, 1H, C6-H), 7.4 (dd,
= 8.3 Hz, = 1.1 Hz, C8-H), 7.6 (dd, 1H, = 7.8
= 1.7 Hz, C5-H), 7.7 (m, 1H, C7-H), 16.01 (bs, 1H,
17.9 (CH3-C=N),
OH). 13C-NMR (CDCl3, 50 MHz):
20.9 (CH3-C2''), 97.8 (C3), 116.1 (C10), 116.8 (C8), 118.9 Hz,
δ
20.2 (CH3-C=N), 1H,
J
J
J
J
(C6''), 119.3 (C5), 122.7 (C2''), 124.1 (C4''), 125.8 (C6), C4-OH). 13C-NMR (CDCl3, 50 MHz):
δ
129.1 (C7), 129.8 (C5''), 138.9 (C1''), 139.1 (C3''), 163.5 57.4 (C=N-CH2), 97.7 (C3), 116.7 (C10), 116.8 (C8),
(C2), 152.5 (C9), 179.6 (C1'), 180.4 (C4). M.P. 138-139oC. 119.3 (C5), 125.9 (C6), 126.7 (C4''), 127.0 (C2'', C6''), 128.3
(C3'', C5''), 129.3 (C7), 138.7 (C1''), 163.5 (C2), 167.1 (C1'),