Arch. Pharm. Chem. Life Sci. 2007, 340, 244–250
Natural Dihydrostilbenes and Their Analogues
249
(1H, s), 6.53 (1H, d, J = 7.8 Hz), 6.58 (1H, d, J = 7.8 Hz), 7.00 (1H, t, J
= 7.8 Hz); MS (EI) m/z 271 [M]+ (35), 165 (100), 106 (24), 77 (16);
Anal. Calcd. for C16H17NO3: C, 70.83; H, 6.32; N, 5.16. Found: C,
70.96; H, 6.53; N, 5.01.
4-(Benzyloxy)-6-(4-fluorostyryl)benzo[d][1,3]dioxole 13f
Yield 48.9%; mp 97–998C; 1H-NMR (300 MHz, CDCl3) d: 5.21 (2H,
s), 5.99 (2H, s), 6.68 (1H, d, J = 1.2 Hz), 6.74 (1H, d, J = 1. 2Hz), 6.86
(2H, s), 7.03 (2H, t), 7.35 (2H, m), 7.39–7.46 (5H, m); MS (EI) m/z
348 [M+] (32), 91 (100).
6-(3-Aminophenethyl)benzo[d][1,3]dioxol-4-ol 1d
1
Yield 97.3%; mp 135–1388C; H-NMR (300 MHz, DMSO) d: 2.64
4-(Benzyloxy)-6-(4-methoxystyryl)benzo[d][1,3]dioxole
(4H, s), 4.90 (2H, brs), 5.88 (2H, s), 6.26 (1H, s), 6.30 (1H, s), 6.36
(1H, d, J = 7.8 Hz), 6.38 (1H, d, J = 7.8 Hz), 6.41 (1H, s), 6.90 (1H, t, J
= 7.8 Hz), 9.49 (1H, s); MS (EI) m/z 257 [M]+ (40), 151 (100), 106 (11),
77 (8); Anal. Calcd. for C15H15NO3: C, 70.02; H, 5.88; N, 5.44.
Found: C, 70.36; H, 5.91; N, 5.23.
13g
Yield 55.8%; mp 98–1008C; 1H-NMR (600 MHz, CDCl3) d: 3.82 (3H,
s), 5.21 (2H, s), 5.98 (2H, s), 6.68 (1H, d, J = 1.2 Hz), 6.74 (1H, d, J =
1.2 Hz), 6.82 (1H, d, J = 16.2 Hz), 6.86 (1H, d, J = 16.2 Hz), 6.88 (2H,
d, J = 8.4 Hz), 7.31–7.40 (5H, m), 7.46 (2H, d, J = 8.4 Hz); MS (EI) m/z
360 [M]+ (9), 91 (100).
4-(2-(7-Methoxybenzo[d][1,3]dioxol-5-yl)ethyl)phenol 1e
Yield 96.4%, oil; H-NMR (300 MHz, CDCl3) d: 2.79 (4H, brs), 3.85
(3H, s), 5.92 (2H, s), 6.27 (1H, d, J = 1.2 Hz), 6.36 (1H, d, J = 1.2 Hz),
6.74 (2H, d, J = 7.8 Hz), 7.02 (2H, d, J = 7.8 Hz); MS (EI) m/z 272 [M]+
(16), 165 (100), 107 (42), 77 (22); Anal. Calcd. for C16H16O4: C,
70.57; H, 5.92. Found: C, 70.85; H, 6.09.
1
4-(2-(7-(Benzyloxy)benzo[d][1,3]dioxol-5-yl)vinyl)-N,N-
dimethylbenzenamine 13h
Yield 52.9%; mp 154–1568C;1H-NMR (300 MHz, CDCl3) d: 2.99 (6H,
s), 5.21 (2H, s), 5.97 (2H, s), 6.70 (1H, d, J = 16.2 Hz), 6.80 (1H, d, J =
1.2Hz), 6.85 (1H, d, J = 16.2 Hz), 6.85 (1H, s), 6.86 (1H, d, J = 1.2 Hz),
6.89(1H, s), 7.32-7.47 (7H, m); MS(EI) m/z 373 [M]+(13), 91 (100).
6-(4-Hydroxyphenethyl)benzo[d][1,3]dioxol-4-ol 1f
1
Yield 97.4%; mp 129–1308C; H-NMR (300 MHz, CDCl3) d: 2.77
6-(4-(Benzyloxy)-3-methoxystyryl)-4-
(4H, brs), 5.92 (2H, s), 6.29 (1H, s), 6.31 (1H, s), 6.74 (2H, d, J = 7.8
Hz), 7.02 (2H, d, J = 7.8 Hz); MS (EI) m/z 258 [M]+ (12), 151 (86), 107
(100), 77 (37); Anal. Calcd. for C15H14O4: C, 69.76; H, 5.46. Found:
C, 69.62; H, 5.32.
methoxybenzo[d][1,3]dioxole 13i
1
Yield 50.3%; mp 108–1108C; H-NMR (600 MHz, CDCl3) d: 3.94
(3H, s), 3.95 (3H, s), 5.18 (2H, s), 5.98 (2H, s), 6.63 (1H, s), 6.73 (1H,
s), 6.85 (1H, d, J = 16.2 Hz), 6.86 (1H, d, J = 16.2 Hz), 6.87 (1H, d, J =
7.8 Hz), 6.95 (1H, d, J = 7.8 Hz), 7.05 (1H, s), 7.29–7.45 (5H, m); MS
(EI) m/z 390 [M]+ (20), 91 (100).
6-(4-Fluorophenethyl)-4-methoxybenzo[d][1,3]dioxole 1g
Yield 95.5%; mp 39–418C; 1H-NMR (300 MHz, CDCl3) d: 2.81 (4H,
m), 3.84 (3H, s), 5.93 (2H, s), 6.25 (1H, d, J = 1.0 Hz), 6.35 (1H, d, J =
1.0 Hz), 6.95 (2H, m), 7.08 (2H, m); MS (EI) m/z 274 [M]+ (11), 165
(100), 109 (22), 77 (22); Anal. Calcd. for C16H15FO3: C, 70.06; H,
5.51. Found: C, 70.22; H, 5.37.
Synthesis, yields and spectroscopic date of compounds
1a–1k
6-(4-Fluorophenethyl)benzo[d][1,3]dioxol-4-ol 1h
Yield 94.7%; mp 91–938C; 1H-NMR (300 MHz, CDCl3) d: 2.78 (4H,
m), 4.70 (1H, brs), 5.93 (2H, s), 6.28 (1H, s), 6.29 (1H, s), 6.95 (2H,
m), 7.09 (2H, m); MS (EI) m/z 260 [M]+ (12), 151 (100), 109 (69), 95
(5); Anal. Calcd. for C15H13FO3: C, 69.22; H, 5.03. Found: C, 69.46;
H, 5.09.
3-(2-(7-Methoxybenzo[d][1,3]dioxol-5-yl)ethyl)phenol 1a
A solution of 11a (0.120 g, 0.333 mmol) in EtOAc (10.0 mL) was
stirred in the presence of 10% Pd-C (0.006 g) under a hydrogen
atmosphere at room temperature for 48 h. The catalyst was
removed by filtration and washed with EtOAc. The filtrate was
concentrated in vacuo and purified by column chromatography
(n-hexane:EtOAc = 3:1) to give dihydrostilbene 1a (0.0857 g,
94.5%) as a white powder: mp 55–578C; 1H-NMR (300 MHz,
CDCl3) d: 2.81 (4H, brs), 3.85 (3H, brs), 4.82 (1H, brs), 5.93 (2H, s),
6.29 (1H, d, J = 1.5 Hz), 6.38 (1H, d, J = 1.5Hz), 6.65 (1H, s), 6.67 (1H,
d, J = 7.5 Hz), 6.74 (1H, d, J = 7.5Hz), 7.14 (1H, t, J = 7.5 Hz); MS (EI)
m/z 272 [M]+ (13), 165 (100), 77 (36); Anal. Calcd. for C16H16O4: C,
70.57; H, 5.92. Found: C, 70.80; H, 5.69.
3.3.9 6-(4-Methoxyphenethyl)benzo[d][1,3]dioxol-4-ol 1i
Yield 96.8%; mp 96–978C; 1H-NMR (300 MHz, CDCl3) d: 2.78 (4H,
brs), 3.78 (3H, s), 5.90 (2H, s), 6.29 (1H, s), 6.31 (1H, s), 6.80 (2H, d, J
= 7.8 Hz), 7.05 (2H, d, J = 7.8 Hz); MS (EI) m/z 272 [M]+ (7), 151 (21),
121 (100), 77 (11); Anal. Calcd. for C16H16O4: C, 70.57; H, 5.92.
Found: C, 70.64; H, 5.88.
Compounds 1b–k were prepared using the same method.
6-(4-(Dimethylamino)phenethyl)benzo[d][1,3]-dioxol-4-ol
6-(3-Hydroxyphenethyl)benzo[d][1,3]dioxol-4-ol 1b
1j
1
1
Yield 98.3%; mp 125–1288C; H-NMR (300 MHz, DMSO) d: 2.50
Yield 99.1%; mp 189–1918C; H-NMR (300 MHz, CDCl3) d: 2.64
(2H, brs), 2.68 (2H, brs), 5.88 (2H, s), 6.25 (1H, s), 6.31 (1H, s), 6.56
(1H, s), 6.57 (1H, d, J = 7.5 Hz), 6.59 (1H, d, J = 7.5 Hz), 7.04 (1H, t, J
= 7.5 Hz), 9.24 (1H, s), 9.53 (1H, s); MS (EI) m/z 258 [M]+ (19), 151
(100), 77 (13); Anal. Calcd. for C15H14O4: C, 69.76; H, 5.46. Found:
C, 69.99; H, 5.24.
(4H, brs), 2.82 (6H, s), 5.86 (2H, s), 6.24 (1H, d, J = 1.2Hz), 6.29 (1H,
d, J = 1.2Hz), 6.62 (2H, d, J = 7.8 Hz), 7.00 (2H, d, J = 7.8 Hz); MS (EI)
m/z 285 [M]+ (5), 134 (100); Anal. Calcd. for C17H19NO3: C, 71.56; H,
6.71; N, 4.91. Found: C, 71.20; H, 6.53.
2-Methoxy-4-(2-(7-methoxybenzo[d][1,3]dioxol-5-
3-(2-(7-Methoxybenzo[d][1,3]dioxol-5-yl)ethyl)benzen-
yl)ethyl)phenol 1k
Yield 97.2%; mp 59–618C; 1H-NMR (300 MHz, CDCl3) d: 2.79 (4H,
s), 3.85 (6H, s), 5.45 (1H, brs), 5.93 (2H, s), 6.28 (1H, d, J = 1.2 Hz),
6.37 (1H, d, J = 1.2 Hz), 6.64 (1H, dd, J = 7.9 Hz, J = 1.2 Hz), 6.68 (1H,
amine 1c
Yield 97.8%, oil; 1H-NMR (300 MHz, CDCl3) d 2.78 (4H, s), 3.85 (3H,
s), 5.91 (2H, s), 6.30 (1H, d, J = 1.2 Hz), 6.38 (1H, d, J = 1.2 Hz), 6.50
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