JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Structure and Conformation on Fluorescence Properties
(M+H)+. Anal. calcd. for C23H23FN2O5: C, 64.78; H, 5.44;
N, 6.57. Found: C, 64.57; H, 5.46; N, 6.53.
cm-1): 3446, 2923, 1743, 1574, 1457, 1224, 563. 1H NMR
(400 MHz, DMSO-d6): 8.39 (s, 1H, ArH), 7.37 (s, 1H,
ArH), 7.35-7.24 (m, 5H, ArH), 4.25 (s, 2H, NCH2Ar), 4.20
(q, 2H, OCH2), 3.28 (t, 4H, CH2NCH2), 3.19-3.15 (m, 1H,
CH), 1.97-1.94 (m, 4H, 2 × CH2), 1.25 (t, 3H, CH3). MS
(MALDI-TOF): m/z = 486.38 (M+H)+. Anal. calcd. for
C24H24BrNO5: C, 59.27; H, 4.97; N, 2.88. Found: C, 59.08;
H, 4.78; N, 2.93.
Ethyl 6-fluoro-7-hydroxy-8-(1-(4-methoxyphenyl)-4-
methylpiperazine)-coumarin-3-carboxylate (3b3)
Yellow power, yield 67%, m.p. 206~207 °C. 1H NMR
(400 MHz, DMSO-d6): 8.43 (s, 1H, ArH), 7.44 (d, 1H,
ArH), 6.93-6.82 (m, 4H, PhH), 4.26 (s, 2H, NCH2Ar), 4.20
(q, 2H, OCH2), 3.64 (s, 3H, OCH3), 3.21-3.17 (m, 8H, 2 ×
NCH2CH2N), 1.26 (t, 3H, CH3). IR (KBr, cm-1): 3449,
2968, 1757, 1583, 1510, 1229, 1099. MS (MALDI-TOF):
m/z = 457.57 (M+H)+. Anal. calcd. for C24H25FN2O6: C,
63.15; H, 5.52; N, 6.14. Found: C, 63.27; H, 5.48; N, 6.20.
Ethyl 6-chloro-7-hydroxy-8-(1-methyl-4-phenylpiperi-
dine)-coumarin-3-carboxylate (3c1)
Ethyl 6-bromo-7-hydroxy-8-(1-methyl-4-phenylpiper-
azine)-coumarin-3-carboxylate (3d2)
Yellow power, yield 73%, m.p. 208~209 °C. IR (KBr,
cm-1): 3449, 2935, 1764, 1579, 1496, 1228, 557. 1H NMR
(400 MHz, DMSO-d6): 8.43 (s, 1H, ArH), 7.94 (s, 1H,
ArH), 7.24 (t, 2H, PhH), 6.97 (d, 2H, PhH), 6.84 (t, 1H,
PhH), 4.27 (s, 2H, NCH2Ar), 4.23 (q, 2H, OCH2), 3.39-
3.36 (m, 4H, CH2NCH2), 3.24-3.21 (m, 4H, CH2NCH2),
1.26 (t, 3H, CH3). MS (MALDI-TOF): m/z = 487.32
(M+H)+. Anal. calcd. for C23H23BrN2O5: C, 56.68; H, 4.76;
N, 5.75. Found: C, 56.42; H, 4.73; N, 5.81.
Yellow power, yield 70%, m.p. 222.5~222.9 °C. IR
(KBr, cm-1): 3448, 2919, 1741, 1606, 1574, 1490, 1226,
751. 1H NMR (400 MHz, DMSO-d6): 8.39 (s, 1H, ArH),
7.72 (s, 1H, ArH), 7.32 (t, 2H, PhH), 7.25-7.20 (m, 3H,
PhH), 4.24 (s, 2H, NCH2Ar), 4.19 (q, 2H, OCH2), 3.17-
3.10 (m, 4H, CH2NCH2), 2.84-2.80 (m, 1H, CH), 1.97-1.92
(m, 4H, 2 × CH2), 1.25 (t, 3H, CH3). MS (MALDI-TOF):
m/z = 442.53 (M+H)+. Anal. calcd. for C24H24ClNO5: C,
65.23; H, 5.47; N, 3.17. Found: C, 65.11; H, 5.42; N, 3.14.
Ethyl 6-chloro-7-hydroxy-8-(1-methyl-4-phenylpiper-
azine)-coumarin-3-carboxylate (3c2)
Ethyl 6-bromo-7-hydroxy-8-(1-(4-methoxyphenyl)-4-
methylpiperazine)-coumarin-3-carboxylate (3d3)
Yellow power, yield 67%, m.p. 214~215 °C. IR (KBr,
cm-1): 3513, 2946, 1766, 1606, 1579, 1193, 557. 1H NMR
(400 MHz, DMSO-d6): 8.43 (s, 1H, ArH), 7.95 (s, 1H,
ArH), 6.93 (d, 2H, PhH), 6.84 (d, 2H, PhH), 4.25 (q, 2H,
OCH2), 4.19 (s, 2H, NCH2Ar), 3.68 (s, 3H, OCH3), 3.34-
3.25 (m, 8H, 2 × NCH2CH2N), 1.26 (t, 3H, CH3). MS: m/z =
517.13 (M+H)+. Anal. calcd. for C24H25BrN2O6: C, 55.72;
H, 4.87; N, 5.41. Found: C, 55.54; H, 4.81; N, 5.47.
Procedure
Yellow power, yield 71%, m.p. 196~198 °C. IR (KBr,
cm-1): 3442, 2937, 1763, 1581, 1498, 1228, 761. 1H NMR
(400 MHz, DMSO-d6): 8.43 (s, 1H, ArH), 7.76 (s, 1H,
ArH), 7.24 (t, 2H, PhH), 6.97 (d, 2H, PhH), 6.83 (t, 1H,
PhH), 4.27 (s, 2H, NCH2Ar), 4.21 (q, 2H, OCH2), 3.39-
3.37 (m, 4H, CH2NCH2), 3.27-3.24 (m, 4H, CH2NCH2),
1.25 (t, 3H, CH3). MS (MALDI-TOF): m/z = 443.51
(M+H)+. Anal. calcd. for C23H23ClN2O5: C, 62.37; H, 5.23;
N, 6.33. Found: C, 62.11; H, 5.27; N, 6.28.
Quantum Yield Measurements
The fluorescence quantum yields of all compounds
were estimated by comparison with quinine sulfate (jf =
0.55) in 0.05 M sulfuric acid as the standard reference [20].
All the coumarin-based dyes in DMSO and methanol (1.0 ×
10-3mol·L-1) were diluted to 1.5 × 10-5mol·L-1 with metha-
nol and twice-distilled water. The measurements were per-
formed in 10 mL volumetric tube. To a test tube containing
1.0 mL of sample solution (1.5 × 10-5mol·L-1), 1.0 mL of
buffer solution (pH 7.4) was added and the solution was di-
luted to 10 mL with twice-distilled water. The result solu-
tion was allowed to stand at room temperature for 10 min,
and then the absorption spectra and emission spectra were
recorded. For fluorescence intensity measurement, the ex-
citation wavelength was set at 366 nm.
Ethyl 6-chloro-7-hydroxy-8-(1-(4-methoxyphenyl)-4-
methylpiperazine)-coumarin-3-carboxylate (3c3)
Yellow power, yield 68%, m.p. 224~225 °C. IR (KBr,
cm-1): 3504, 2958, 1758, 1577, 1506, 1224, 784. 1H NMR
(400 MHz, DMSO-d6): 8.44 (s, 1H, ArH), 7.95 (s, 1H,
ArH), 6.94-6.83 (m, 4H, PhH), 4.29 (s, 2H, NCH2Ar), 4.20
(q, 2H, OCH2), 3.68 (s, 3H, OCH3), 3.32-3.25 (m, 8H, 2 ×
NCH2CH2N), 1.26 (t, 3H, CH3). MS (MALDI-TOF): m/z =
473.43 (M+H)+. Anal. calcd. for C24H25ClN2O6: C, 60.95;
H, 5.23; N, 5.92. Found: C, 60.81; H, 5.18; N, 5.77.
Ethyl 6-bromo-7-hydroxy-8-(1-methyl-4-phenylpiperi-
dine)-coumarin-3-carboxylate (3d1)
Cyclodextrin Titration
Yellow power, yield 73%, m.p. 226~228 °C. IR (KBr,
Solutions of 3a3 (final concentration: 5 mM) in pH 7.4
J. Chin. Chem. Soc. 2012, 59, 000-000
© 2012 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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