M. Mao, Q.-H. Song / Dyes and Pigments 92 (2012) 975e981
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2.2.4. 7-[(4-Methanesulfonyl-phenyl)-octyl-amino]-4-
methylcoumarin (6b)
CDCl3): d 0.86e0.90 (m, 3H, CH3), 1.28e1.32 (m, 10 H, CH2), 1.69 (m,
2 H, CH2), 2.31 (s, 3 H, CH3), 3.46 (t, J ¼ 7.5 Hz, 2 H, CH2), 3.91 (s, 3 H,
CH3), 4.65 (s, 2 H, CH2), 5.96 (s,1 H, ArH), 6.51e6.55 (m, 2 H, ArH), 7.24
(d, J ¼ 8.1 Hz, 2 H, ArH), 7.34 (d, J ¼ 8.7 Hz,1 H, ArH), 7.98 (d, J ¼ 8.1 Hz,
Based on an analogous method with 6a, 6b was obtained as
a colorless solid (0.42 g) in a yield 85%. Rf ¼ 0.63 (CH2Cl2). Mp
68e69 ꢀC. 1H NMR (300 MHz, CDCl3):
d
0.85 (t, J ¼ 6.3 Hz, 3 H, CH3),
2 H, ArH).13C NMR (75 MHz, CDCl3):
d 14.11,18.4, 22.6, 27.1, 27.2, 29.3,
1.21e1.28 (m,10 H, CH2),1.43e1.36 (m, 2 H, CH2), 2.43e2.44 (m, 6 H,
CH3), 3.54 (t, J ¼ 6.9 Hz, 2 H, CH2), 6.29 (s, 1 H, ArH), 6.86 (d,
J ¼ 2.1 Hz, 1 H, ArH), 7.23e7.24 (m, 1 H, ArH), 7.27 (d, J ¼ 8.1 Hz, 2 H,
ArH), 7.46 (d, J ¼ 8.1 Hz, 2 H, ArH), 7.58 (d, J ¼ 8.4 Hz, 1 H, ArH). 13C
29.4, 31.8, 52.0, 52.1, 54.4, 98.6, 108.9, 109.5, 110.0,125.5, 126.2, 129.3,
130.2, 143.1, 151.1, 152.8, 155.8, 162.0, 166.8. IR (KBr, cmꢁ1): 2926 (s),
1721 (s),1630 (s),1606 (s),1525 (m),1407 (s),1369 (m),1279 (s),1170
(m). TOFMS (EI) calcd for (Mþ) C27H33NO4: 435.2410, found 435.2408.
NMR (75 MHZ, CDCl3):
d 13.7, 18.3, 21.2, 22.2, 26.0, 27.7, 28.6, 28.8,
31.3, 49.9, 114.8, 115.3, 118.8, 124.6, 127.2, 129.3, 134.5, 142.2, 143.6,
151.6, 153.2, 160.0. IR (KBr, cmꢁ1): 2930 (s), 1730 (s), 1610 (s), 1388
(m), 1344 (s), 1162 (s), 1091 (m), 670 (m). TOFMS (EI) calcd for (Mþ)
C25H31NO4S: 441.1974, found 441.1980.
2.2.9. 4-{[Ethyl-(4-methylcoumarin-7-yl)-amino]-methyl}-benzoic
acid (9a)
8a (0.33 g, 0.95 mmol) and tetrabutylammonium hydroxide
(TBAþOHꢁ, 40% w/w, 1.56 mL, 2.40 mmol) were added to a mixture
of THF (10 mL) and water (10 mL) and stirred overnight. The
reaction mixture was acidified with aq. HCl to pH ¼ 4, and extracted
with dichloromethane three times. The organic solution was
evaporated in vacuo and the residue was purified by column
chromatography to give product as a white powder 9a (0.28 g, 89%).
Mp 147e149 ꢀC. Rf ¼ 0.16 (CH2Cl2/EtOAc 4:1). Mp 180e181 ꢀC. 1H
2.2.5. 7-Ethylamino-4-methylcoumarin (7a)
Compound 6a (0.63 g, 1.75 mmol) was added to conc. sulfuric
acid (5 mL) and the solution was stirred for 12 h at 90 ꢀC. The
reaction mixture was cooled and carefully poured into water. The
mixture was neutralized with saturated sodium bicarbonate aq.
and extracted with CH2Cl2 three times. The organic solution was
dried and evaporated to give a yellow powder 7a (0.33 g, 94%).
Rf ¼ 0.31 (CH2Cl2). Mp 147e149 ꢀC. 1H NMR (300 MHz, CDCl3):
NMR (CDCl3, 300 MHz):
d
1.29 (t, J ¼ 7.1 Hz, 3 H, CH3), 2.33 (d,
J ¼ 0.9 Hz, 3 H, CH3), 3.58 (q, J ¼ 7.1 Hz, 2 H, CH2), 4.66 (s, 2 H, CH2),
5.98 (d, J ¼ 1.2 Hz, 1 H, ArH), 6.53e6.59 (m, 2 H, ArH), 7.31 (d,
J ¼ 8.4 Hz, 2 H, ArH), 7.37 (d, J ¼ 8.7 Hz, 1 H, ArH), 8.07 (d, J ¼ 8.4 Hz,
d
1.29 (t, J ¼ 6.9 Hz, 3 H, CH3), 2.34 (s, 3 H, CH3), 3.21e3.23
(q, J ¼ 6.9 Hz, 2 H, CH2), 4.14 (br, 1 H, NH), 5.97 (s, 1 H, ArH), 6.44
2 H, ArH). 13C NMR (75 MHz, CDCl3):
d 12.1, 18.3, 46.0, 53.8, 98.5,
(s, 1 H, ArH), 6.49 (d, J ¼ 7.8 Hz, 1 H, ArH), 7.34 (d, J ¼ 7.8 Hz, 1 H,
108.9, 109.6, 110.1, 125.6, 126.3, 128.4, 130.8, 144.1, 150.9, 152.7,
155.8, 162.0, 171.3. IR (KBr, cmꢁ1): 1714 (s), 1700 (s), 1576 (m), 1525
(m), 1410 (s), 1288 (s), 1174 (m), 1070 (m), 816 (m). TOFMS (EI) calcd
for (Mþ) C20H19NO4: 337.1314, found 337.1284.
ArH). 13C NMR (75 MHz, CDCl3):
d 14.4, 18.5, 38.0, 97.9, 109.1, 110.3,
125.5, 151.7, 153.1, 162.1. IR (KBr, cmꢁ1): 3338 (s), 1692 (s), 1632 (s),
1601 (s), 1504 (m), 1403 (m), 1347 (m), 1169 (m), 850 (m). TOFMS
(EI) calcd for (Mþ) C12H13NO2: 203.0946, found 203.0952.
2.2.10. 4-{[(4-Methylcoumarin-7-yl)-octyl-amino]-methyl}-
benzoic acid (9b)
2.2.6. 7-Octylamino-4-methylcoumarin (7b)
Similarly, 7b was obtained as a yellow powder (0.40 g) in a yield
9b was prepared by an analogous method with 9a, as a white
powder (0.33 g) in a yield 87%. Rf ¼ 0.24 (CH2Cl2/EtOAc 4:1). Mp
80%. Rf ¼ 0.41 (CH2Cl2). Mp 109e110 ꢀC. 1H NMR (300 MHz, CDCl3):
d
0.87e0.89 (m, 3 H, CH3), 1.29e1.39 (m, 10 H, CH2), 1.58e1.67 (m,
134e135 ꢀC. 1H NMR (300 MHz, CDCl3):
d 0.86e0.89 (m, 3 H, CH3),
2 H, CH2), 2.34 (d, J ¼ 0.9 Hz, 3 H, CH3), 3.16 (t, J ¼ 6.9 Hz, 2 H, CH2),
4.20 (br, 1 H, NH), 5.97 (s, 1 H, ArH), 6.43 (d, J ¼ 2.4 Hz, 1 H, ArH),
6.49 (dd, J ¼ 8.7 Hz, 2.4 Hz, 1 H, ArH), 7.34 (d, J ¼ 8.7 Hz, 1 H, ArH).
1.28e1.33 (m, 10 H, CH2), 1.68e1.70 (m, 2 H, CH2), 2.32 (s, 3 H, CH3),
3.47 (t, J ¼ 7.8 Hz, 2 H, CH2), 4.67 (s, 2 H, CH2), 5.97 (s, 1 H, ArH),
6.48e6.55 (m, 2 H, ArH), 7.28 (d, J ¼ 8.1 Hz, 2 H, ArH), 7.35
(d, J ¼ 8.7 Hz, 1 H, ArH), 8.06 (d, J ¼ 8.1 Hz, 2 H, ArH). 13C NMR
13C NMR (75 MHz, CDCl3):
d 14.0, 18.4, 22.5, 26.9, 29.0, 29.1, 29.2,
31.7, 43.4, 97.7, 108.9, 110.1, 125.3, 151.7, 152.9, 155.9, 162.0. IR (KBr,
cmꢁ1): 3332 (s), 2925 (s), 2851 (s), 1695 (s), 1637 (s), 1603 (s), 1504
(m), 1404 (m), 1347 (m), 831 (m). TOFMS (EI) calcd for (Mþ)
C18H25NO2: 287.1885, found 287.1893.
(75 MHz, CDCl3): d 14.0, 18.3, 22.6, 27.0, 27.1, 29.2, 29.4, 31.7, 52.0,
54.4, 98.5, 108.9, 109.4, 110.0, 125.5, 126.3, 128.5, 130.7, 144.0, 151.1,
152.8, 155.7, 162.0, 171.3. IR (KBr, cmꢁ1): 2923 (s), 1721 (s), 1697 (s),
1620 (s), 1606 (s), 1525 (m), 1408 (s), 1296 (m), 1170 (m). TOFMS (EI)
calcd for (Mþ) C26H31NO4: 421.2253, found 421.2251.
2.2.7. 4-{[Ethyl-(4-methylcoumarin-7-yl)-amino]-methyl}-benzoic
acid methyl ester (8a)
2.2.10.1. Dendrimer 1. 11 (37 mg, 0.05 mmol) and 4 (0.21 g,
0.60 mmol) were dissolved in 2 mL of dry DMF, and K2CO3 (0.11 g,
0.80 mmol) and 18-crown-6 (20 mg) were added, and heated to
60 ꢀC, stirring overnight. The reaction mixture was poured into
CH2Cl2 (50 mL), and filtered and washed with 0.1 M NaHSO4 three
times, brine once, dried over MgSO4, filtered, and the solvent in the
filtrate was removed in vacuo. Purification by means of silica gel
column chromatography (CH2Cl2/THF ¼ 10:1) afforded purple
power 1 (0.12 g, 85%). Rf ¼ 0.33 (CH2Cl2/THF 20:1). 1H NMR
7a (0.35 g, 1.75 mmol), 4-(bromomethyl)benzoate (0.54 g,
2.34 mmol) and K2CO3 (1.21 g, 8.76 mmol) were mixed in freshly
distilled CH3CN (50 mL) and refluxed for 72 h. The solvent was
evaporated in vacuo and the residue was purified by column chro-
matography to give product as pale yellow syrup 8a (0.52 g, 85%).
Rf ¼ 0.26 (CH2Cl2). 1H NMR (300 MHz, CDCl3):
d
1.28 (t, J ¼ 7.0 Hz,
3 H, CH3), 2.32 (s, 3 H, CH3), 3.56e3.58 (q, J ¼ 7.0 Hz, 2 H, CH2), 3.91 (s,
3 H; CH3), 4.64 (s, 2 H, CH2), 5.96 (s, 1H, ArH), 6.53e6.58 (m, 2 H,
ArH), 7.27 (d, J ¼ 7.5 Hz, 1 H, ArH), 7.36 (d, J ¼ 8.7 Hz, 2 H, ArH), 7.99
(300 MHz, CDCl3):
d
ꢁ2.89 (s, 2 H, NH), 2.34 (s, 24 H, CH3), 5.12 (s,
(d, J ¼ 7.8 Hz, 2 H, ArH). 13C NMR (75 MHz, CDCl3):
d
11.8, 18.0, 45.7,
16H, CH2), 5.24 (s, 16 H, CH2), 6.10 (s, 8 H, ArH), 6.85e6.90 (m, 16 H,
ArH), 7.05 (s, 4 H, ArH), 7.43e7.51 (m, 48 H, ArH), 8.84 (s, 8 H,
51.7, 53.5, 98.1, 108.6, 109.0, 110.0, 125.3, 125.9, 128.9, 130.0, 142.9,
150.7, 152.5, 155.4, 161.5, 166.4. IR (KBr, cmꢁ1): 1695 (s), 1631 (s),
1604 (s), 1525 (m), 1407 (s), 1350 (m), 1278 (s), 1107 (m). TOFMS (EI)
calcd for (Mþ) C21H21NO4: 351.1471, found 351.1479.
pyrrole-H). 13C NMR (75 MHz, CDCl3):
d 18.6, 70.0, 70.2, 101.9, 112.1,
112.9, 113.8, 115.4, 119.7, 125.6, 127.9, 128.0, 135.8, 137.1, 144.0, 152.4,
155.2, 157.9, 161.2, 161.6. IR (KBr, cmꢁ1): 1724 (s), 1612 (s), 1388 (s),
1368 (m), 1279 (m), 1146 (s), 1107 (s). MALDIeTOF MS: calcd for
(Mþ) C188H142N4O32: 2968.9674, found 2968.4294.
2.2.8. 4-{[(4-Methylcoumarin-7-yl)-octyl-amino]-methyl}-benzoic
acid methyl ester (8b)
According to similar method, 8b was prepared as pale yellow
2.2.10.2. Dendrimer 2. 11 (37 mg, 0.05 mmol), 9a (0.20 g,
0.60 mmol) and DPTS were dissolved in THF solution (5 mL), and
syrup (0.53 g) in a yield 70%. Rf ¼ 0.30 (CH2Cl2). 1H NMR (300 MHz,