4-(4-(4-(4-(2-Nitro-4-dodecyloxy-5-methoxybenzyloxy)-3-methoxy-
benzyloxy)-3-methoxybenzyloxy)-3-methoxybenzyloxy)-nitrobenzene
(2c). A mixture of p-nitrophenol (49 mg, 0.35 mmol), K2CO3 (0.16 g,
1.2 mmol), 11c (0.26 g, 0.31 mmol), and DMF (5 mL) was
maintained at 35 1C for 24 h. Water (50 mL) was added and the
solution was extracted with CH2Cl2 (4 ꢁ 10 mL), dried (MgSO4),
filtered, concentrated, and purified by flash chromatography (SiO2,
7 : 3 hexanes-EtOAc gradient to 100% CH2Cl2) to afford 2c (0.17 g,
61%) as a pale yellow solid: 1H NMR (250 MHz, CDCl3) d 8.21 and
7.04 (AA0BB0 pattern J = 7.1 Hz, 4 H); 7.75 (s, 1 H); 7.46 (s, 1 H);
7.01–6.88 (m, 9 H); 5.55 (s, 2 H); 5.08 (s, 4 H); 5.07 (s, 2 H) 4.08
(t, J = 6.8 Hz, 2 H); 3.94 (s, 3 H); 3.91 (s, 3 H); 3.90 (s, 3 H); 3.88
(s, 3 H); 1.87 (quintet, J = 7.9 Hz, 2 H); 1.50–1.26 (m, 18 H); 0.88
(t, J = 6.2 Hz, 3 H); 13C NMR (CDCl3) d 163.7, 154.4, 150.0,
149.9, 149.8, 148.4, 147.9, 147.4, 147.3, 138.8, 131.0, 130.1, 129.5,
128.4, 125.9, 120.3, 120.1, 119.9, 114.8, 114.7, 114.3, 114.2, 114.1,
111.4, 111.3, 111.2, 109.6, 109.9, 71.2, 71.1, 70.8, 69.5, 68.5, 56.3,
56.0, 56.0, 56.0, 31.9, 29.65, 29.63, 29.57, 29.52, 29.3, 29.2, 28.9,
25.9, 22.7, 14.1; MS (FAB+) m/z 896.50 (M+, C50H60N2O13
calcd 896.41). Anal. Calcd for C50H60N2O13: C, 66.95; H, 6.74; N,
3.12; Found: C, 67.06; H, 7.13; N, 3.18.
17c (1.08 g, 2.04 mmol), 18-crown-6 (31 mg, 0.12 mmol), and
acetone (10 mL) was maintained at reflux for 8 h after which the
mixture was filtered and concentrated. Water (30 mL) was added
and the solution was extracted with CH2Cl2 (4 ꢁ 5 mL), dried
(MgSO4), filtered, concentrated, and purified by flash chromato-
graphy (SiO2, 7 : 3 hexanes-EtOAc) to afford 3c (1.01 g, 84%) as a
1
colorless oil: H NMR (250 MHz, CDCl3) d 8.06 (AA0BB0
pattern J = 7.1 Hz, 2 Hz); 7.10–6.81 (m, 11 H); 6.05–5.93
(m, 1 H); 5.26 (dd, J = 1.5, 17.2 Hz, 1 H); 5.12–5.07 (m, 5 H);
5.02 (s, 2 H); 4.44 (dt, J = 1.4, 5.4 Hz, 2 H); 3.85 (s, 3 H); 3.84
(s, 3 H); 3.83 (s, 3 H); 13C NMR (CDCl3) d163.7, 152.7, 152.7,
152.4, 146.2, 145.5, 134.3, 131.9, 131.7, 130.1, 125.7, 124.2, 124.0,
123.9, 121.9, 121.2, 120.1, 117.1, 114.7, 114.7, 112.5, 112.2, 111.9,
74.0, 70.0, 69.9, 65.8, 55.8, 55.7, 55.7; MS (FAB+) m/z 587.36
(M+, C33H33NO9 calcd 587.21). Anal. Calcd for C33H33NO9: C,
67.45; H, 5.66; N, 2.38; Found: C, 67.46; H, 6.00; N, 2.36.
4-(2-(2-(2-(2-Allyloxy-3-methoxybenzyloxy)-3-methoxybenzyloxy)-
3-methoxybenzyloxy)-3-methoxybenzyloxy)-nitrobenzene (3d).
A
mixture of p-nitrophenol (0.82 g, 5.1 mmol), K2CO3 (2.52 g,
18.2 mmol), 17d (3.91 g, 5.88 mmol), 18-crown-6 (78 mg,
0.29 mmol), and acetone (20 mL) was maintained at reflux for
8 h after which the mixture was filtered and concentrated. Water
(100 mL) was added and the solution was extracted with CH2Cl2
(4 ꢁ 25 mL), dried (MgSO4), filtered, concentrated, and purified by
flash chromatography (SiO2, 7 : 3 hexanes-EtOAc) to afford 3d
4-(2-Allyloxy-3-methoxybenzyloxy)-nitrobenzene (3a). A mixture
of p-nitrophenol (281 mg, 2.02 mmol), K2CO3 (0.857 g, 6.20 mmol),
17a (0.513 g, 1.99 mmol), 18-crown-6 (36 mg, 0.13 mmol), and
acetone (5 mL) was maintained at reflux for 24 h after which the
mixture was filtered and concentrated. Water (20 mL) was added
and the solution was extracted with CH2Cl2 (3 ꢁ 10 mL), dried
(MgSO4), filtered, concentrated, and purified by flash chromato-
graphy (SiO2, 100% CH2Cl2) to afford 3a (0.62 g, 99%) as an
orange oil: 1H NMR (250 MHz, CDCl3) d 8.20 (AA0BB0 pattern
J = 7.1 Hz, 2 H); 7.12–6.92 (m, 5 H); 6.10–5.97 (m, 1 H); 5.33
(dd, J = 1.5, 17.2 Hz, 1 H); 5.22–5.17 (m, 3 H); 4.58 (dt, J = 1.4,
5.4 Hz, 2 H); 3.89 (s, 3 H); 13C NMR (CDCl3) d163.7, 152.6,
145.7, 141.5, 133.9, 129.5, 125.9, 124.3, 120.7, 118.0, 114.8, 112.6,
74.2, 66.0, 55.8; MS (FAB+) m/z 315.15 (M+, C17H17NO5 calcd
315.11). Anal. Calcd for C17H17NO5: C, 64.75; H, 5.43; N, 4.44;
Found: C, 64.37; H, 5.71; N, 4.54.
1
(4.06 g, 95%) as a colorless oil: H NMR (250 MHz, CDCl3)
d 8.03 (AA0BB0 pattern J = 7.1 Hz); 7.11–6.78 (m, 14 H); 6.05–5.93
(m, 1 H); 5.24 (dd, J = 1.5, 17.2 Hz, 1 H); 5.10–5.03 (m, 7 H); 4.98
(s, 2 H); 4.42 (dt, J = 1.4, 5.4 Hz, 2 H); 3.84 (s, 3 H); 3.82 (s, 3 H);
3.76 (s, 3 H); 3.75 (s, 3 H); 13C NMR (CDCl3) d 163.7, 152.6, 152.5,
152.3, 146.3, 145.5, 145.5, 145.4, 141.2, 134.3, 132.2, 132.0, 131.5,
130.1, 125.7, 124.1, 124.0, 123.9, 123.8, 121.9, 121.2, 120.9, 120.0,
117.1, 114.7, 112.4, 112.2, 111.9, 111.8, 74.0, 70.0, 69.9, 69.6, 65.7,
55.7, 55.7, 55.6; MS (FAB+) m/z 723.43 (M+, C41H41NO11 calcd
723.27). Anal. Calcd for C41H41NO11: C, 68.04; H, 5.71; N, 1.94;
Found: C, 67.65; H, 6.04; N, 2.29.
4-(2-(2-Nitro-4-dodecyloxy-5-methoxybenzyloxy)-3-methoxy-
benzyloxy)-nitrobenzene (4a). A mixture of p-nitrophenol (66 mg,
0.47 mmol), K2CO3 (0.18 g, 1.3 mmol), 18a (0.24 g, 0.45 mmol),
and DMF (4 mL) was maintained at ambient temperature for
24 h. Water (100 mL) was added and the solution was extracted
with CH2Cl2 (4 ꢁ 25 mL), washed with H2O (100 mL), brine
(100 mL), dried (MgSO4), filtered, and concentrated. Flash
chromatography (SiO2, 7 : 3 hexanes-CH2Cl2) afforded 4a
4-(2-(2-Allyloxy-3-methoxybenzyloxy)-3-methoxybenzyloxy)-nitro-
benzene (3b). A mixture of p-nitrophenol (0.40 g, 2.8 mmol), K2CO3
(1.07 g, 7.74 mmol), 17b (1.11 g, 2.83 mmol), 18-crown-6 (34 mg,
0.13 mmol), and acetone (10 mL) was maintained at reflux for 5 h
after which the mixture was filtered and concentrated. Water
(50 mL) was added and the solution was extracted with CH2Cl2
(4 ꢁ 5 mL), dried (MgSO4), filtered, concentrated, and purified
by flash chromatography (SiO2, 8 : 2 hexanes-EtOAc) to afford 3b
1
(0.21 g, 75%) as a yellow solid: H NMR (250 MHz, CDCl3)
1
(1.03 g, 81%) as a colorless solid: H NMR (250 MHz, CDCl3) d
d 8.14 and 6.93 (AA0BB0 pattern J = 7.1 Hz, 4 H); 7.66 (s, 1 H);
7.45 (s, 1 H); 7.16–6.99 (m, 3 H); 5.45 (s, 2 H); 5.16 (s, 2 H); 4.03
(t, J = 6.8 Hz, 2 H); 3.88 (s, 3 H); 3.87 (s, 3 H); 1.88 (quintet, J =
8.12 (AA0BB0 pattern J = 7.1 Hz, 2 Hz); 7.11–6.84 (m, 8 H);
6.10–5.96 (m, 1 H); 5.29 (dd, J = 1.5, 17.2 Hz, 1 H); 5.22–5.12
(m, 3 H); 5.06 (s, 2 H); 4.46 (dt, J = 1.4, 5.4 Hz, 2 H); 3.92 (s, 3 H);
3.84 (s, 3 H); 13C NMR (CDCl3) d163.7, 152.7, 152.5, 146.0, 145.6,
141.3, 134.2, 131.4, 130.0, 125.7, 124.3, 124.0, 121.9, 120.2, 117.3,
114.8, 112.4, 112.4, 74.1, 70.1, 65.8, 55.8, 55.7; MS (FAB+) m/z
451.16 (M+, C25H25NO7 calcd 451.16). Anal. Calcd for C25H25NO7:
C, 65.51 H, 5.58; N, 3.10; Found: C, 65.48; H, 5.70; N, 3.27.
7.9 Hz, 2 H); 1.50–1.26 (m, 18 H); 0.88 (t, J = 6.2 Hz, 3 H); 13
C
NMR (CDCl3) d 163.6 154.0, 152.8, 147.3, 146.0, 141.5, 138.9,
129.5, 129.4, 125.8, 124.9, 121.4, 114.5, 113.0, 109.7, 108.7, 71.8,
69.5, 66.3, 56.3, 55.8, 31.9, 29.65, 29.63, 29.57, 29.52, 29.3, 28.9,
25.9, 22.7, 14.1; MS (FAB+) m/z 624.37 (M+, C34H44N2O9 calcd
624.30). Anal. Calcd for C34H44N2O9: C, 65.37; H, 7.10; N, 4.48;
Found: C, 65.51; H, 7.36; N, 4.61.
4-(2-(2-(2-Allyloxy-3-methoxybenzyloxy)-3-methoxybenzyloxy)-
3-methoxybenzyloxy)-nitrobenzene (3c). A mixture of p-nitro-
phenol (0.29 g, 2.1 mmol), K2CO3 (0.98 g, 7.1 mmol),
4-(2-(2-(2-Nitro-4-dodecyloxy-5-methoxybenzyloxy)-3-methoxy-
benzyloxy)-3-methoxybenzyloxy)-nitrobenzene (4b). A mixture of
c
498 New J. Chem., 2012, 36, 492–505
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012