Y. Wang, et al.
BioorganicChemistry95(2020)103530
J = 7.1 Hz, 4H), 1.20 (t, J = 7.1 Hz, 6H).
145.37 (s), 143.28 (s), 138.98 (s), 135.36 (s), 130.59 (s), 129.36 (s),
128.24 (s), 44.29 (s), 12.33 (s). HRMS (ESI) m/z 362.1749 [M + H]+
(calcd for 362.1751 C23H24NO3).
Synthesis of 7-(diethylamino)-2-oxo-2H-chromene-3-carbalde-
hyde (3). 4 mL of dry DMF was added dropwise to 0.4 mL of POCl3 at
20–50 °C. The mixture was stirred for 45 min at 50 °C under N2 at-
mosphere. A suspension of 0.65 g of 7-dimethylamino coumarine in
3 mL of dry DMF is then added, the mixture was warmed to 60 °C for
2 h and poured out onto ice water, and the whole was stirred for 2 h.
The crystalline precipitate was filtered off, thoroughly washed with
water and dried in vacuo at 50 °C, which afforded an orange solid
compound 4 yield 72%.1H NMR (500 MHz, CDCl3) δ 10.09 (s, 1H), 8.22
(s, 1H), 7.39 (d, J = 9.0 Hz, 1H), 6.63 (dd, J = 9.0, 2.3 Hz, 1H), 6.47
(d, J = 2.0 Hz, 1H), 3.46 (q, J = 7.1 Hz, 4H), 1.24 (t, J = 7.1 Hz, 6H).
Synthesis of (E)-7-(diethylamino)-3-(3-oxo-3-phenylprop-1-en-
1-yl)-2H-chromen-2-ones. A solution of compound 3 (0.43 mmol) in
N-butyl alcohol(5 mL) was added to piperidine(0.1 mL), glacial acetic
acid (0.1 mL) and different substituted acetophenones (0.43 mmol) and
refluxed for 10 h. After the reaction completed determined by TLC, the
mixture was concentrated in vacuo. The residue was dissolved in di-
chloromethane and purified by column chromatography eluting with
petroleum ether -dichloromethane to afford the products Xn-1-Xn-14.
(E)-7-(diethylamino)-3-(3-(3,4-dimethoxyphenyl)-3-oxoprop-1-
en-1-yl)-2H-chromen-2-one (Xn-1), red solid; m.p. 181–191 °C; IR
(KBr) v 3456.6, 1713.4, 1629.4, 1575.3, 1520.1, 1420.5, 1276.1,
1200.1, 1163.6, cm-1; 1H NMR (500 MHz, DMSO) δ 8.47 (s, 1H), 8.03
(d, J = 15.4 Hz, 1H), 7.75 (d, J = 8.3 Hz, 1H), 7.64 (d, J = 15.4 Hz,
1H), 7.54 (s, 1H), 7.49 (d, J = 8.9 Hz, 1H), 7.12 (d, J = 8.4 Hz, 1H),
6.79 (d, J = 8.8 Hz, 1H), 6.60 (s, 1H), 3.86 (d, J = 10.7 Hz, 5H), 3.53 –
3.44 (m, 3H), 1.15 (t, J = 6.8 Hz, 6H). 13C NMR (126 MHz, DMSO) δ
160.59 (s), 156.90 (s), 153.60 (s), 149.39 (s), 145.51 (s), 138.84 (s),
131.32 (s), 131.07 (s), 123.36 (s), 121.36 (s), 113.94 (s), 111.46 (s),
111.04 (s), 110.40 (s), 108.84 (s), 96.79 (s), 56.29 (s), 56.06 (s), 44.81
(s), 12.87 (s). HRMS (ESI) m/z 408.1803 [M + H]+ (calcd for 408.1805
(E)-7-(diethylamino)-3-(3-oxo-3-(o-tolyl)prop-1-en-1-yl)-2H-
chromen-2-one (Xn-5), red solid; m.p. 112–113 °C; IR (KBr) v 3855.5,
3483.6, 1716.1, 1619.5, 1577.9, 1510.2, 1419.9, 1355.9, 1320.8,
1273.8, 1193.6, 1134.1, 1011.2 cm-1; 1H NMR (500 MHz, DMSO) δ
8.39 (s, 1H), 7.51 (t, J = 3.5 Hz, 1H), 7.47 (d, J = 8.3 Hz, 2H), 7.43
(dd, J = 10.7, 4.2 Hz, 1H), 7.37 – 7.30 (m, 3H), 6.78 (dd, J = 9.0,
2.3 Hz, 1H), 6.58 (d, J = 2.2 Hz, 1H), 3.47 (q, J = 7.0 Hz, 4H), 2.35 (s,
3H), 1.14 (t, J = 7.0 Hz, 6H). 13C NMR (126 MHz, DMSO) δ 195.19 (s),
159.75 (s), 156.44 (s), 151.97 (s), 145.68 (s), 140.44 (s), 139.19 (s),
135.95 (s), 131.06 (s), 130.70 (s), 130.31 (s), 127.75 (s), 125.66 (s),
125.43 (s), 112.76 (s), 109.90 (s), 108.30 (s), 96.18 (s), 44.28 (s), 19.76
(s), 12.31 (s). HRMS (ESI) m/z 362.1750 [M + H]+ (calcd for 362.1751
C23H24NO3).
(E)-7-(diethylamino)-3-(3-oxo-3-(m-tolyl)prop-1-en-1-yl)-2H-
chromen-2-one (Xn-6), red solid; m.p. 155–156 °C; IR (KBr) v 3455.8,
1723.7, 1629.5, 1564.8, 1511.0, 1446.3, 1418.9, 1329.6, 1281.7,
1179.5, 1136.9, 1004.1 cm-1; 1H NMR (500 MHz, DMSO) δ 8.48 (s,
1H), 8.00 (d, J = 15.5 Hz, 1H), 7.85 – 7.81 (m, 2H), 7.66 (d,
J = 15.4 Hz, 1H), 7.53 – 7.44 (m, 3H), 6.80 (dd, J = 9.0, 2.4 Hz, 1H),
6.60 (d, J = 2.2 Hz, 1H), 3.48 (q, J = 7.0 Hz, 4H), 2.42 (s, 3H), 1.15 (t,
J = 7.0 Hz, 6H). 13C NMR (126 MHz, DMSO) δ 189.07 (s), 159.98 (s),
156.44 (s), 151.92 (s), 145.43 (s), 139.23 (s), 138.17 (s), 137.98 (s),
133.49 (s), 130.63 (s), 128.67 (s), 128.45 (s), 125.37 (s), 121.00 (s),
113.21 (s), 109.92 (s), 108.33 (s), 96.26 (s), 44.30 (s), 20.91 (s), 12.33
(s). HRMS (ESI) m/z 362.1752 [M + H]+ (calcd for 362.1751
C23H24NO3).
(E)-7-(diethylamino)-3-(3-(4-fluorophenyl)-3-oxoprop-1-en-1-
yl)-2H-chromen-2-one (Xn-7), red solid; m.p. 94–95 °C; IR (KBr) v
3457.4, 1723.4, 1627.0, 1513.6, 1416.8, 1355.4, 1287.9, 1198.0,
1134.6, 1010.1 cm-1; 1H NMR (500 MHz, DMSO) δ 8.39 (d, J = 8.8 Hz,
1H), 7.77 – 7.61 (m, 3H), 7.50 (dd, J = 15.8, 12.4 Hz, 2H), 7.41 – 7.32
(m, 2H), 6.78 (dd, J = 9.0, 2.2 Hz, 1H), 6.58 (d, J = 2.0 Hz, 1H), 3.53 –
3.43 (m, 4H), 1.13 (dd, J = 9.1, 5.1 Hz, 6H). 13C NMR (126 MHz,
DMSO) δ 188.71 (s), 187.05 (s), 159.60 (s), 159.02 (s), 156.48 (s),
152.09 (s), 146.53 (s), 140.45 (s), 133.90 (d, J = 8.8 Hz), 130.78 (s),
130.26 (d, J = 2.8 Hz), 127.16 (d, J = 13.6 Hz), 124.72 (dd, J = 20.2,
4.1 Hz), 116.61 (s), 116.43 (s), 112.69 (s), 109.93 (s), 108.35 (s), 96.17
(s), 44.31 (s), 12.32 (s). HRMS (ESI) m/z 366.1498 [M + H]+ (calcd for
366.1500 C22H21FNO3).
C
24H26NO5).
(E)-7-(diethylamino)-3-(3-(3-hydroxy-4-methoxyphenyl)-3-ox-
oprop-1-en-1-yl)-2H-chromen-2-one (Xn-2), red solid; m.p.
98–100 °C; IR (KBr) v 3516.5, 2976.7, 1722.9, 1625.7, 1569.5, 1512.6,
1426.9, 1417.4, 1354.8, 1315.1, 1282.6, 1192.3, 1131.4, 1031.6,
1002.8 cm-1; 1H NMR (500 MHz, DMSO) δ 10.04 (s, 1H), 8.46 (s, 1H),
8.02 (d, J = 15.4 Hz, 1H), 7.68 – 7.58 (m, 2H), 7.55 (d, J = 1.8 Hz,
1H), 7.49 (d, J = 9.0 Hz, 1H), 6.93 (d, J = 8.2 Hz, 1H), 6.79 (dd,
J = 9.0, 2.3 Hz, 1H), 6.59 (d, J = 2.2 Hz, 1H), 3.86 (s, 3H), 3.48 (q,
J = 7.0 Hz, 4H), 1.14 (t, J = 7.0 Hz, 6H). 13C NMR (126 MHz, DMSO) δ
151.76 (d, J = 6.4 Hz), 130.48 (s), 109.84 (s), 96.25 (s), 55.64 (s),
44.27 (s), 40.02 (s), 39.52 (s), 39.35 (s), 39.19 (s), 39.02 (s), 12.34 (s).
HRMS (ESI) m/z 394.1647 [M + H]+ (calcd for 394.1649 C23H24NO5).
(E)-7-(diethylamino)-3-(3-(3-methoxyphenyl)-3-oxoprop-1-en-
1-yl)-2H-chromen-2-one (Xn-3), red solid; m.p. 121–122 °C; IR (KBr)
v 3454.7, 1722.7, 1629.7, 1568.3, 1512.1, 1417.9, 1283.1, 1193.2,
1003.4 cm-1; 1H NMR (500 MHz, DMSO) δ 8.49 (s, 1H), 7.98 (d,
J = 15.5 Hz, 1H), 7.65 (dd, J = 15.0, 11.7 Hz, 2H), 7.50 (t, J = 8.6 Hz,
3H), 7.23 (dd, J = 8.0, 2.5 Hz, 1H), 6.79 (dd, J = 9.0, 2.3 Hz, 1H), 6.60
(d, J = 2.2 Hz, 1H), 3.84 (s, 3H), 3.52 – 3.42 (m, 4H), 1.14 (t,
J = 7.0 Hz, 6H). 13C NMR (126 MHz, DMSO) δ 145.43 (s), 139.39 (d,
J = 3.7 Hz), 130.65 (s), 129.96 (s), 120.89 (s), 120.60 (s), 118.79 (s),
109.93 (s), 96.25 (s), 55.32 (s), 44.30 (s), 40.22 – 39.61 (m), 39.52 (s),
39.35 (s), 39.19 (s), 39.02 (s), 12.33 (s). HRMS (ESI) m/z 378.1701
[M + H]+ (calcd for 378.1700 C23H24NO4).
(E)-3-(3-(4-bromophenyl)-3-oxoprop-1-en-1-yl)-7-(diethyla-
mino)-2H-chromen-2-one (Xn-8), red solid; m.p. 209–211 °C; IR (KBr)
v 3455.4, 1707.8, 1620.6, 1574.4, 1510.9, 1412.2, 1314.1, 1280.0,
1196.6, 135.2, 1067.6, 1004.3 cm-1; 1H NMR (500 MHz, DMSO) δ 8.49
(s, 1H), 8.02 – 7.95 (m, 3H), 7.79 (d, J = 8.5 Hz, 2H), 7.67 (d,
J = 15.4 Hz, 1H), 7.49 (d, J = 9.0 Hz, 1H), 6.80 (dd, J = 9.0, 2.4 Hz,
1H), 6.61 (d, J = 2.2 Hz, 1H), 3.49 (d, J = 7.1 Hz, 4H), 1.15 (t,
J = 7.0 Hz, 6H). 13C NMR (126 MHz, DMSO) δ 159.93 (s), 156.51 (s),
152.05 (s), 145.84 (s), 139.97 (s), 131.88 (s), 130.72 (s), 130.12 (s),
120.40 (s), 113.04 (s), 110.01 (s), 108.35 (s), 96.27 (s), 44.33 (s), 12.34
(s). HRMS (ESI) m/z 426.0696 [M + H]+ (calcd for 426.0699
C
22H21BrNO3).
(E)-3-(3-(4-butylphenyl)-3-oxoprop-1-en-1-yl)-7-(diethyla-
mino)-2H-chromen-2-one (Xn-9), red solid; m.p. 70–71 °C; IR (KBr) v
3452.2, 2927.6, 1705.9, 1625.9, 1574.8, 1514.2, 1448.8, 1416.5,
1331.9, 1314.1, 1281.2, 1201.0, 1175.1, 1133.1, 1008.1 cm-1; 1H NMR
(500 MHz, DMSO) δ 8.47 (s, 1H), 8.02 (d, J = 15.5 Hz, 1H), 7.96 (d,
J = 8.2 Hz, 2H), 7.64 (d, J = 15.4 Hz, 1H), 7.49 (d, J = 9.0 Hz, 1H),
7.39 (d, J = 8.2 Hz, 2H), 6.79 (dd, J = 9.0, 2.4 Hz, 1H), 6.60 (d,
J = 2.3 Hz, 1H), 3.48 (q, J = 7.0 Hz, 4H), 2.69 – 2.62 (m, 2H), 1.61 –
1.55 (m, 2H), 1.32 (dd, J = 14.9, 7.5 Hz, 2H), 1.14 (t, J = 7.0 Hz, 6H),
0.90 (t, J = 7.4 Hz, 3H). 13C NMR (126 MHz, DMSO) δ 188.45 (s),
159.98 (s), 156.41 (s), 151.88 (s), 147.97 (s), 145.40 (s), 138.98 (s),
135.62 (s), 130.60 (s), 128.70 (s), 128.27 (s), 120.95 (s), 113.26 (s),
(E)-7-(diethylamino)-3-(3-oxo-3-(p-tolyl)prop-1-en-1-yl)-2H-
chromen-2-one (Xn-4), red solid; m.p. 144–146 °C; IR (KBr) v 3456.6,
2971.9, 1704.7, 1627.4, 1573.8, 1449.3, 1417.8, 1331.5, 1313.6,
1281.6, 1199.7, 1176.9, 1135.0, 1010.6 cm-1; 1H NMR (500 MHz,
DMSO) δ 8.48 (s, 1H), 8.02 (d, J = 15.5 Hz, 1H), 7.95 (d, J = 8.2 Hz,
2H), 7.65 (d, J = 15.4 Hz, 1H), 7.50 (d, J = 9.0 Hz, 1H), 7.38 (d,
J = 8.0 Hz, 2H), 6.80 (dd, J = 9.0, 2.4 Hz, 1H), 6.61 (d, J = 2.3 Hz,
1H), 3.48 (q, J = 7.0 Hz, 4H), 2.40 (s, 3H), 1.15 (t, J = 7.0 Hz, 6H). 13
C
NMR (126 MHz, DMSO) δ 188.41 (s), 159.98 (s), 156.41 (s), 151.88 (s),
5