Paper
NJC
0
.49 mmol). The reaction was followed by TLC (ethyl acetate/ 935, 858, 793, 753, 713. d
light petroleum, 4 : 6), and stirred at room temperature for 4 h. Hz, CH ), 1.43 (3H, t, J 7.2 Hz, NCH
Ethyl acetate was added (15 mL) and the solution was washed CH ), 2.47 (2H, t, J 7.6 Hz, CH ), 3.33 (2H, q, J 7.2 Hz, NCH CH )
H
(400 MHz; CDCl
3
) 1.01 (3H, t, J 7.4
3
2
3
CH ), 1.71–1.80 (2H, m,
2
2
2
3
with a saturated aqueous solution of sodium hydrogencarbo- 5.36 (2H, d, J 1.2 Hz, OCH ), 6.53 (1H, t, J 1.2 Hz, H-3), 6.77 (1H,
2
nate (10 mL) and water (10 mL). The organic layer was dried d, J 7.6 Hz, H-8), 7.36 (1H, d, J 9.2 Hz H-5), 7.50 (1H, t, J 7.8 Hz,
with magnesium sulfate and concentrated by evaporation, and H-9), 7.64 (1H, dd, J 8.8 and 0.4 Hz, H-6), 7.90 (1H, d, J 8.4 Hz,
the residue obtained was purified by column chromatography H-10). d
with mixtures of ethyl acetate and n-hexane of increasing 18.37 (CH
C
(100.6 MHz; CDCl
3
) 13.67 (CH
3
), 14.63 (NCH
CH ), 61.22 (OCH
2
CH
3
),
),
2
), 35.95 (CH ), 38.74 (NCH
2
2
3
2
polarity as an eluent. Compound 3a was obtained as a yellow 107.46 (C-8), 111.17 (C-10), 112.07 (C-3), 112.26 (C-4a), 116.72
ꢀ
1
solid (0.070 g, 57%). mp = 172.6–173.3. nmax/cm 3415, 2962, (C-6), 117.17 (C-5), 124.05 (C-6a), 124.14 (C-10a), 128.33 (C-9),
2
932, 1743, 1712, 1636, 1605, 1568, 1467, 1383, 1290, 1175, 143.48 (C-7), 149.49 (C-4), 151.18 (C-10b), 160.70 (C-2, CQO),
+
1132, 1090, 1074, 1024, 966, 861, 792, 750, 717. dH (400 MHz; 172.76 (CQO, ester) (ESI†). HRMS for C H NO [M + H]:
20
22
4
CDCl ) 1.01 (3H, t, J 7.2 Hz, CH ), 1.72–1.77 (2H, m, CH ), 2.46 calculated 340.15496, found 340.15467.
3
3
2
(
2H, t, J 7.2 Hz, CH
2
), 3.04 (1H, s, NCH
3
), 5.35 (2H, d, J 1.3 Hz,
(7-(Diethylamino)-2-oxo-2H-naphtho[1,2-b]pyran-4-yl)methyl
OCH
2
), 6.52 (1H, t, J 1.3 Hz H-3), 6.85 (1H, d, J 7.6 Hz, H-8), 7.37 butyrate, 4b. In the last reaction, in addition to 4a, compound
(
9
1H, d, J 9.0 Hz, H-5), 7.52 (1H, dd, J 8.4 Hz, H-9), 7.67 (1H, d, J 4b was also isolated as a yellow solid (0.010 g, 15%). mp = 94.0–
ꢀ1
.0 Hz, H-6), 7.94 (1H, d, J 8.4 Hz, H-10). d
C
(100.6 MHz; CDCl
3
)
95.0 1C. nmax/cm 2969, 2928, 1745, 1731, 1638, 1611, 1567,
1
3.66 (CH ), 18.35 (CH ), 31.38 (NCH ), 35.92 (CH
3
2
3
2
), 61.27 1502, 1469, 1429, 1384, 1305, 1255, 1173, 1105, 1030, 970, 857,
(
OCH ), 107.97 (C-8), 112.07 (C-4a), 112.10 (C-3), 112.32 811, 761. dH (400 MHz; CDCl ) 1.02 (3H, t, J 7.2 Hz, CH ), 1.07
2
3
3
(
C-10), 116.74 (C-6), 117.51 (C-5), 123.96 (C-6a), 124.39 (C-10a), (6H, t, J 7.2 Hz, N(CH CH ) ), 1.74–1.79 (2H, m, CH ), 2.48
2 3 2 2
1
28.24 (C-9), 143.67 (C-7), 149.94 (C-4), 151.09 (C-10b), 160.61 (2H, t, J 7.6 Hz, CH ), 2.93 (4H, q, J 7.2 Hz, N(CH CH ) ), 5.42
2
2
3 2
(
C-2, CQO), 172.74 (CQO, ester) (ESI†). HRMS for C19
H
20NO
4
2
(2H, d, J 1.6 Hz, OCH ), 6.58 (1H, t, J 1.4 Hz, H-3), 7.34 (1H, d,
+
[
M + H]: calculated 326.13930, found 326.13964.
7-(Dimethylamino)-2-oxo-2H-naphtho[1,2-b]pyran-4-yl)methyl
butyrate, 3b. In the last reaction, in addition to 3a, compound 3b (100.6 MHz; CDCl
was also isolated as a yellow solid (0.010 g, 8%). mp = 105.3– (CH ), 35.96 (CH ), 47.97 (N(CH
J 7.2 Hz, H-8), 7.47 (1H, d, J 9.2 Hz, H-5), 7.59 (1H, t, J 7.8 Hz,
H-9), 8.23 (1H, d, J 8.4 Hz, H-6), 8.30 (1H, d, J 8.0 Hz, H-10). d
) 12.21 (N(CH CH ), 13.68 (CH ), 18.38
CH ), 61.30 (OCH ), 112.09
(
C
3
2
3
)
2
3
2
2
2
3
)
2
2
ꢀ1
1
1
1
06.2 1C. nmax/cm 2965, 2934, 2833, 2803, 2786, 1746, 1729, (C-3), 112.33 (C-4a), 117.64 (C-10), 117.85 (C-5), 121.08 (C-6),
634, 1605, 1565, 1502, 1469, 1418, 1402, 1380, 1344, 1317, 1299, 121.29 (C-8), 124.61 (C-10a) 127.16 (C-9), 132.86 (C-6a), 148.11
269, 1258, 1225, 1181, 1128, 1106, 1073, 1045, 1020, 985, 709. dH (C-7), 150.20 (C-4), 151.20 (C-10b), 160.79 (C-2, CQO), 172.78
+
(
400 MHz; CDCl
CH ), 2.48 (2H, t, J 7.2 Hz, CH
d, J 1.6 Hz, OCH ), 6.59 (1H, t, J 1.2 Hz, H-3), 7.31 (1H, d, J 8.5 Hz,
H-8), 7.51 (1H, d, J 9.0 Hz, H-5), 7.59 (1H, t, J 8.5 Hz, H-9), 8.16
1H, d, J 9.0 Hz, H-6), 8.29 (1H, d, J 8.5 Hz, H-10). d
(100.6 MHz; A 1 ꢁ 10 M methanol/HEPES (80 : 20) solution of compounds
CDCl ) 13.68 (CH ), 18.38 (CH ), 35.96 (CH ), 45.37 (N(CH ) ), 2–4 (5 mL) were placed in a quartz tube and irradiated in a
3 3
) 1.01 (3H, t, J 7.2 Hz, CH ), 1.73–1.78 (2H, m, (CQO, ester) (ESI†). HRMS for C22
H26NO
4
[M + H]: calculated
2
2 3 2
), 2.93 (6H, s, N(CH ) ), 5.42 (2H, 368.18628, found 368.18654.
2
Photolysis
ꢀ4
(
C
3
3
2
2
3 2
6
1.28 (OCH ), 112.38 (C-3), 112.45 (C-4a), 117.41 (C-10), 117.43 Rayonet RPR-100 reactor at the desired wavelength. The lamps
2
(
1
C-8), 118.21 (C-5), 120.81 (C-6), 124.61 (C-10a), 127.40 (C-9), used for irradiation were of 254, 300, 350 and 419 ꢂ 10 nm.
28.99 (C-6a), 130.86 (C-7), 150.12 (C-4), 151.21 (C-10b), 160.63 HEPES buffer solution was prepared in distilled water with
(
C-2, CQO), 172.77 (CQO, ester) (ESI†). HRMS for C20
H
22NO
4
HEPES (4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid)
(10 mM), sodium chloride (120 mM), potassium chloride (3 mM),
calcium chloride (1 mM) and magnesium chloride (1 mM) and pH
+
[M + H]: calculated 340.15496, found 340.15469.
(
7-(Ethylamino)-2-oxo-2H-naphtho[1,2-b]pyran-4-yl)methyl
butyrate, 4a. To a solution of (7-amino-2-oxo-2H-naphtho[1,2- adjusted to 7.2 with aqueous 1 M sodium hydroxide solution.
b]pyran-4-yl)methyl butyrate 2 (1 equiv., 0.057 g, 0.18 mmol) in Aliquots of 100 mL were taken at regular intervals and analysed
dry DMF (5 mL) ethyl iodide was added (1.7 equiv., 0.026 mL, by RP-HPLC using a Licrospher 100 RP18 (5 mm) column in a
0.31 mmol). The reaction was followed by TLC (ethyl acetate/ JASCO HPLC system composed of a PU-2080 pump and a UV-2070
light petroleum, 4 : 6), and stirred at room temperature for 4 h. detector with ChromNav software. The eluent was acetonitrile/
ꢀ1
ꢀ1
Ethyl acetate was added (15 mL) and the solution was washed water, 75: 25 at a flow rate of 0.8 mL min or 1.0 mL min (4b),
with a saturated aqueous solution of sodium hydrogencarbo- previously filtered through a Millipore, type HN 0.45 mm filter
nate (10 mL) and water (10 mL). The organic layer was dried and degassed by ultra-sound for 30 min. The chromatograms
with magnesium sulfate and concentrated by evaporation; the were traced by detecting UV absorption at the wavelength of
obtained residue was purified by column chromatography with maximum absorption for each compound (retention time: 2, 4.4;
ethyl acetate and n-hexane with mixtures of increasing polarity 3a, 6.3; 3b, 13.7; 4a, 7.9; 4b, 13.4 min).
as an eluent. Compound 4a was obtained as a yellow solid
ꢀ
1
Fluorescence measurements
(0.025 g, 50%). mp = 94.0–95.0 1C. nmax/cm 3418, 2968, 2932,
2
1
870, 1727, 1609, 1572, 1526, 1471, 1435, 1387, 1359, 1301, Time-resolved fluorescence measurements made use of the
284, 1256, 1204, 1177, 1162, 1128, 1089, 1041, 1026, 982, 959, time-correlated single-photon counting (TCSPC) technique
New J. Chem.
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