Molecules 2013, 18
7077
of 3 (0.16 g, 0.50 mmol), 7 (0.25 g, 0.50 mmol), anhydrous K2CO3 (0.09 g, 0.63 mmol), and
18-crown-6 (0.02 g, 0.05 mmol), was refluxed for 1 day under Ar. The reaction mixture was
evaporated to dryness. The solid residue was dissolved in CH2Cl2, and the solution was washed with
water and brine. The organic layer was extracted and dried over anhydrous Na2SO4, and then
evaporated to dryness. The residue was recrystallized with CH2Cl2/methanol to give 8 as white solid in
75% yield (0.24 g, 0.38 mmol). FAB-MS m/z calcd for M+ (C45H37NO9) 736, found 736 (M+);
1H-NMR (CDCl3, 20 C): (ppm) 8.61 (d, 2H, J = 7.2 Hz, ArH), 8.22 (d, 2H, J = 7.2 Hz, ArH), 8.05
(d, 4H, J = 8.5 Hz, ArH), 7.77 (t, 2H, J = 7.2 Hz, ArH), 7.49 (d, 4H, J = 8.5 Hz, ArH), 7.29 (d, 2H,
J = 8.5 Hz, ArH), 6.90 (d, 2H, J = 8.5 Hz, ArH), 6.69 (d, 2H, J = 2.4 Hz, ArH), 6.54 (t, 1H, J = 2.4 Hz,
ArH), 5.10 (s, 4H, benzyl), 4.98 (s, 2H, benzyl), 4.38–4.35 (m, 2H, benzyl), 3.93 (s, 6H, methoxy),
2.99–2.96 (m, 2H, alkyl); 13C-NMR (CDCl3, 20 C): (ppm) 166.98, 164.24, 159.99, 157.41, 142.09,
140.05, 138.70, 134.13, 131.76, 131.37, 130.18, 130.04, 129.86, 128.33, 127.16, 127.12, 122.82,
115.01, 106.57, 101.72, 69.94, 69.56, 52.31, 42.13, 33.56; IR (KBr): 3423, 2950, 1510, 1436, 1415,
1384, 1343, 1235, 1108, 1067, 1019, 844, 781, 756 cm−1.
4,4'-[[5-[[4-[2-(1,3-Dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethyl]phenoxy]methyl]-1,3-phenylene]
bis(oxymethylene)]bis-benzoic acid 9. To a THF (20 mL) solution of 8 (100 mg, 0.14 mmol) was
added an aqueous solution of NaOH (0.6 M, 20 mL), and the mixture was stirred for 12 h at 50 °C.
Then, the reaction mixture was neutralized with HClaq. The solvent was evaporated to dryness. The
residue was washed with water, and dried in vacuo to give 9 as white solid in 78% yield (74 mg,
0.11 mmol). 1H-NMR (DMSO-d6, 20 C): (ppm) 13.03 (s, 2H, COOH), 8.54 (d, 2H, J = 7.7 Hz, ArH),
8.50 (d, 2H, J = 7.7 Hz, ArH), 7.99 (d, 4H, J = 8.5 Hz, ArH), 7.91 (t, 2H, J = 7.7 Hz, ArH), 7.59 (d, 4H,
J = 8.5 Hz, ArH), 7.22 (d, 4H, J = 8.5 Hz, ArH), 6.95 (d, 2H, J = 8.5 Hz, ArH), 6.75 (d, 2H, J = 2.4 Hz,
ArH), 6.69 (t, 1H, J = 2.4 Hz, ArH), 5.22 (s, 4H, benzyl), 5.03 (s, 4H, benzyl), 4.25 (m, 2H, benzyl),
13
2.90 (m, 2H, alkyl); C-NMR (DMSO-d6, 20 C): (ppm) 168.06, 164.27, 160.32, 157.73, 142.97,
140.75, 135.34, 132.29, 131.73, 131.10, 130.60, 130.44, 128.37, 128.23, 123.02, 115.79, 107.52, 69.84,
69.66, 42.17, 33.62.
BOCNID. Compound 9 (87 mg, 0.12 mmol) was dissolved in thionyl chloride (10 mL), and the solution
was refluxed under Ar for 4 h. The reaction mixture was evaporated to dryness. The residue was mixed
with tert-butyl (3-(3-aminopropoxy)propyl)carbamate (10, 114 mg, 0.49 mmol) and N,N′-dimethyl-4-
aminopyridine (60 g, 0.49 mmol) in dry CH2Cl2 (10 mL), and the solution was refluxed under Ar for
24 h. The reaction mixture was evaporated to dryness. The residue was dissolved into CHCl3, and
washed with aqueous solutions of 1 N HCl and saturated NaHCO3. The organic layer was extracted,
dried over anhydrous Na2SO4, and evaporated to dryness. The residue was chromatographed on silica
gel with ethylacetate as eluent, where the second fraction was collected and evaporated to leave
BOCNID as white solid in 40% yield (56 mg, 0.05 mmol). FAB-MS m/z calcd for M+ (C65H76ClN5O13)
1
1169, found 1170 (M++1); H-NMR (CDCl3, 20 C): (ppm) 8.61 (d, 2H, J = 7.2 Hz, ArH), 8.23 (d,
2H, J = 8.5 Hz, ArH), 7.82–7.75 (m, 6H, ArH), 7.46 (d, 2H, J = 8.5 Hz, ArH), 7.37 (d, 2H,
J = 8.5 Hz, ArH), 7.30 (d, 2H, J = 8.5 Hz, ArH), 7.17 (br, 2H, NH), 6.93 (d, 2H, J = 8.5 Hz, ArH),
6.84 (d, 1H, J = 2.4 Hz, ArH), 6.54 (d, 1H, J = 2.4 Hz, ArH), 5.16 (s, 2H, benzyl), 5.13 (s, 2H, benzyl),
5.04 (s, 2H, benzyl), 4.91 (br, 2H, NH), 4.38 (m, 2H, benzyl), 3.60 (br, 4H, alkyl), 3.56 (t, 4H, J = 5.3 Hz,