Journal of Asian Natural Products Research
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extracted with EtOAc (4 £ 20 ml).
The organic layer was washed with brine,
and dried over Na2SO4. On concentration
and flash column chromatography
(hexane:EtOAc ¼ 5:1) it gave product 1
(68.0 mg, 0.21mmol, 93%): yellow oil; IR
(neat) nmax: 3356, 2925, 2854, 1599, 1466,
1339, 1154, 995, 837, 694 cm21; 1H NMR
0.94 M of MeMgI (7.5 ml, 7.04 mmol) in
Et2O was added at 08C. After the mixture
was heated to 1008C in vacuo, the residue
was then heated at 1708C for 1 h under N2.
The cooled reaction mixture was quenched
with saturated aqueous NH4Cl (10 ml), and
extracted with EtOAc (4 £ 20 ml). The
organic layer was washed with brine and
dried over Na2SO4. Flash column chroma-
tography (hexane:EtOAc ¼ 4:1) gave pro-
duct 2 (107 mg, 0.34 mmol, 95%): white
powder; mp 85–878C; IR (KBr): nmax
3323, 2916, 2847, 1607, 1512, 1469, 1331,
(300 MHz, CDCl3)
d 6.24 (2H, d,
J ¼ 1.8 Hz, Ar), 6.17 (1H, t, J ¼ 1.8 Hz,
Ar), 5.38–5.32 (2H, m, CHvCH), 4.63
(2H, s, OH), 2.48 (2H, t, J ¼ 7.8 Hz,
ArCH2), 2.02–2.00 (4H, m, CH2-
CHvCHCH2), 1.57 (2H, m, ArCH2CH2),
1.30–1.24 (16H, m, CH2), 0.88 (3H, t,
J ¼ 6.5 Hz, CH3); 13C NMR (75 MHz,
CDCl3) d 156.3, 145.9, 129.7, 129.6,
107.8, 99.8, 35.5, 31.5, 30.8, 29.5, 29.1,
29.0, 28.9, 28.7, 27.0, 26.9, 22.4, 13.9; HR-
ESI-MS: m/z 363.1915 [M þ Na]þ (calcd
for C21H34O2, 363.1931), 318.2538 [M]þ
(calcd for C21H34O2, 318.2559).
1200, 1146, 991, 830, 721, 697, 569 cm21
;
1H NMR (300 MHz, CD3OD) d 6.12 (2H,
d, J ¼ 2.4 Hz, Ar), 6.07 (1H, t, J ¼ 2.4 Hz,
Ar), 2.46–2.40 (2H, m, ArCH2), 1.55 (2H,
m, ArCH2CH2), 1.28 (24H, m, CH2),
0.91–0.87 (3H, m, CH3); 13C NMR
(75 MHz, CD3OD) d 159.2, 159.1, 146.3,
108.0, 107.9, 101.0, 100.9, 37.1, 37.0,
33.2, 33.1, 32.5, 30.9, 30.9, 30.8, 30.6,
30.6, 30.5, 30.5, 30.4, 23.2, 23.7, 14.7,
14.5; HR-EI-MS: m/z 320.2713 [M]þ
(calcd for C21H36O2, 320.2715).
3.2.7 1,3-Dihydroxy-5-pentadecyl-
benzene
A mixture of 1,3-dimethoxy-5-[80(Z)-pen-
3.2.8 1,3-Dihydroxy-5-(70-hydroxyheptyl)-
benzene (12)
tadecen-1-yl]benzene
10
(0.21 g,
0.61 mmol) and 10% Pd/C (50 mg) in 5 ml
of dry THF was stirred under H2 for 18 h.
The reaction mixture was passed through a
short column of silica gel and eluted with
EtOAc (150 ml). On concentration it
gave 1,3-dimethoxy-5-pentadecylbenzene
(215 mg, 0.67 mmol) in quant.: white
Yield 89%: white powder; mp: 123–1258C;
IR (KBr): nmax 3420, 3256, 2939, 2855,
2536, 2422, 2277, 1595, 1464, 1336, 1161,
1065, 1036, 925, 856, 836, 698, 582,
523 cm21; 1H NMR (300MHz, CD3OD) d
6.11 (2H, d, J ¼ 2.4 Hz, Ar), 6.07 (1H, t,
J ¼ 2.4 Hz, Ar), 3.52 (2H, t, J ¼ 6.6 Hz,
CH2OH), 2.43 (2H, t, J ¼ 7.5 Hz, ArCH2),
1.60–1.51(4H,m,CH2),1.34(6H,m,CH2);
13C NMR (75 MHz, CD3OD) d 159.3,
146.3, 107.9, 101.0, 63.0, 37.0, 33.6, 32.4,
30.4, 30.3, 26.9; HR-EI-MS: m/z 224.1411
[M]þ (calcd for C13H20O3, 224.1412).
powder; mp 49–518C; IR (KBr) nmax
2917, 2849, 1599, 1346, 1293, 1206, 1151,
1056, 842, 821, 696 cm21 1H NMR
:
;
(300 MHz, CDCl3) d 6.34 (2H, s, Ar),
6.30 (1H, s, Ar), 3.78 (6H, s, OMe), 2.54
(2H, t, J ¼ 7.8 Hz, ArCH2), 1.60–1.55
(2H, m, ArCH2CH2), 1.25 (24H, m, CH2),
0.88 (3H, t, J ¼ 6.0 Hz, CH3); 13C NMR
(75 MHz, CDCl3), d 160.9, 145.7, 106.8,
106.7, 97.8, 55.4, 36.6, 32.2, 31.6, 30.0,
29.9, 29.8, 29.7, 29.6, 22.9, 14.4.
3.2.9 1,3-Dihydroxy-5-(80-pentadecynyl)-
benzene (11)
To a solution of 1,3-dimethoxy-5-
pentadecylbenzene (0.123 g, 0.35 mmol)
in dry Et2O (1.5 ml) and dry THF (0.1 ml),
Yield 80%: colorless oil; IR (neat) nmax
3388, 2929, 2856, 1706, 1602, 1466, 1336,
1155, 998, 838, 695 cm21 1H NMR
:
;