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Can. J. Chem. Vol. 90, 2012
(CH2), 29.11 (CH2), 29.19 (CH2), 29.32 (CH2), 29.42 (CH2),
29.47 (CH2), 30.39 (CH2), 31.76 (CH2), 36.17 (CH2), 56.41
(CH3), 58.78 (CH3), 61.58 (CH3), 93.38 (CH), 101.28 (CH),
116.20 (C), 117.22 (CH), 119.46 (CH), 127.67 (C), 131.79
(CH), 138.88 (C), 148.55 (C), 153.39 (C), 163.10 (C),
197.16 (C), 198.18 (C). m/z (EI): 530 (M+, 15%), 499 (10),
261 (20), 225 (100), 195 (15). HRMScalcd for C30H42O8:
(M+) 530.2879; found: 530.2878.
low oil following general procedure 4 on a 0.23 mmol scale,
followed by column chromatography (SiO2, EtOAc–hexane
(1:2)). Rf (SiO2, EtOAc–hexane (1:2)) 0.21. IR ymax (thin
film, cm–1): 2927 (CH2), 1623 (C=O). dH (400 MHz,
CDCl3): 0.87 (3H, t, J = 6.8 Hz, CH2CH3), 1.22–1.31 (14H,
m, 7 × CH2), 1.62–1.69 (2H, m, ArCH2CH2), 2.71 (2H, t,
J = 7.5 Hz, ArCH2CH2), 3.75 (3H, s, OCH3), 3.81 (3H, s,
OCH3), 3.83 (3H, s, OCH3), 3.86 (3H, s, OCH3), 6.69 (1H,
d, J = 9.1 Hz, H-4’), 7.02 (1H, d, J = 9.1 Hz, H-3’), 7.21–
7.24 (2H, m, H-6 and H-8), 8.21 (1H, d, J = 8.1 Hz, H-5).
dC (100 MHz, CDCl3): 14.06 (CH3), 22.63 (CH2), 29.17
(CH2), 29.26 (CH2), 29.39 (CH2), 29.48 (CH2), 29.53 (CH2),
30.84 (CH2), 31.83 (CH2), 35.98 (CH2), 56.08 (CH3), 56.47
(CH3), 60.21 (CH3), 61.29 (CH3), 105.91 (CH), 115.09
(CH), 115.57 (C), 117.208 (CH), 122.61 (C), 125.41 (CH),
125.58 (CH), 142.65 (C), 146.65 (C), 148.41 (C), 149.40
(C), 151.70 (C), 153.09 (C), 156.19 (C), 174.68 (C). m/z
(EI): 482 (M+, 15%), 451 (100). HRMS calcd for C29H38O6:
(M+) 482.2669; found: 482.2668.
General procedure 4 — Cyclization
TMSOTf (1.1 equiv) was added to a stirred solution of the
diketone 25a–25g (0.3 mol/L) in dry DCM at RT under ar-
gon. After stirring at RT for 1 h, the reaction mixture was
diluted with DCM and quenched with saturated aqueous
NaHCO3. The layers were separated and the aqueous layer
extracted with DCM. The combined organics were washed
with brine, dried over magnesium sulfate, and concentrated
under vacuum. The flavone derivatives 27 were purified fur-
ther where necessary as described in the following.
7-Decyl-3,2’,4’,6’-tetramethoxyflavone (27d)
7-Decyl-3,2’,3’,4’-tetramethoxyflavone (27a)
Flavone 27d (77 mg, 37%) was obtained as a viscous oil
following general procedure 4 on a 0.43 mmol scale, fol-
lowed by column chromatography (SiO2, EtOAc–hexane
(1:2)). Rf (SiO2, EtOAc–hexane (1:2)) 0.15. dH (400 MHz,
CDCl3): 0.87 (3H, t, J = 6.7 Hz, CH2CH3), 1.26–1.31 (14H,
m, 7 × CH2), 1.61–1.69 (2H, m, ArCH2CH2), 2.70 (2H, t,
J = 7.5 Hz, ArCH2CH2), 3.76 (6H, s, 2 × OCH3), 3.79 (3H,
s, OCH3), 3.87 (3H, s, OCH3), 6.21 (2H, s, H-3’and H-5’),
7.19 (1H, dd, J = 1.4 and 8.2 Hz, H-6), 7.24 (1H, s, H-8),
8.18 (1H, d, J = 8.2 Hz, H-5). dC (100 MHz, CDCl3): 14.02
(CH3), 22.58 (CH2), 29.13 (CH2), 29.22 (CH2), 29.35 (CH2),
29.44 (CH2), 29.49 (CH2), 30.80 (CH2), 31.79 (CH2), 35.91
(CH2), 55.37 (CH3), 55.77 (CH3), 60.01 (CH3), 90.58 (CH),
102.19 (C), 117.22 (CH), 122.65 (C), 125.08 (CH), 125.45
(CH), 142.98 (C), 148.98 (C), 153.42 (C), 156.29 (C),
159.31 (C), 163.20 (C), 174.68 (C). m/z (EI): 482 (M+,
10%), 451 (100). HRMS calcd for C29H38O6: (M+)
482.2669; found: 482.2666.
Flavone 27a (251 mg, 87%) was obtained as a viscous yel-
low oil following general procedure 4 on a 0.59 mmol scale.
IR ymax (thin film, cm–1): 2929 (CH2), 1621 (C=O). dH
(400 MHz, CDCl3): 0.88 (3H, t, J = 6.8 Hz, CH2CH3),
1.26–1.31 (14H, m,
7 × CH2), 1.62–1.70 (2H, m,
ArCH2CH2), 2.72 (2H, t, J = 7.5 Hz, ArCH2CH2), 3.80 (3H,
s, OCH3), 3.93 (3H, s, OCH3), 3.94 (3H, s, OCH3), 3.95
(3H, s, OCH3), 6.78 (1H, d, J = 8.7 Hz, H-5’), 7.19–7.25
(3H, m, H-6, 8 and 6’), 8.18 (1H, d, J = 8.2 Hz, H-5). dC
(100 MHz, CDCl3): 14.06 (CH3), 22.63 (CH2), 29.15 (CH2),
29.39 (CH2), 29.49 (CH2), 29.54 (CH2), 29.54 (CH2), 30.89
(CH2), 31.84 (CH2), 35.99 (CH2), 56.07 (CH3), 60.40 (CH3),
60.88 (CH3), 61.48 (CH3), 107.00 (CH), 117.03 (CH),
118.04 (C), 122.47 (C), 125.40 (CH), 125.46 (CH), 125.60
(CH), 141.69 (C), 142.37 (C), 149.55 (C), 152.36 (C),
155.61 (C), 155.75 (C), 155.78 (C), 174.76 (C). m/z (EI):
482 (M+, 60%), 467 (75), 451 (100). HRMS calcd for
C29H38O6: (M+) 482.2669; found: 482.2666.
7-Decyl-3,2’,3’,4’,5’-pentamethoxyflavone (27e)
7-Decyl-3,2’,3’,5’-tetramethoxyflavone (27b)
Flavone 27e (305 mg, 48%) was obtained as a viscous yel-
low oil following general procedure 4 on a 1.23 mmol scale,
followed by column chromatography (SiO2, EtOAc–hexane
(1:2)). Rf (SiO2, EtOAc–hexane (1:2)) 0.24. IR ymax (thin
film, cm–1): 2927 (CH2), 1646 (C=O). dH (400 MHz,
CDCl3): 0.88 (3H, t, J = 6.8 Hz, CH2CH3), 1.24–1.32 (14H,
m, 7 × CH2), 1.63–1.71 (2H, m, ArCH2CH2), 2.73 (2H, t,
J = 7.6 Hz, ArCH2CH2), 3.84 (3H, s, OCH3), 3.86 (3H, s,
OCH3), 3.89 (3H, s, OCH3), 3.99 (6H, s, 2 × OCH3), 6.77
(1H, s, H-6’), 7.23 (1H, dd, J = 1.3 and 8.2 Hz, H-6), 7.26
(1H, s, H-8), 8.19 (1H, d, J = 8.2 Hz, H-5). dC (100 MHz,
CDCl3): 14.01 (CH3), 22.58 (CH2), 29.10 (CH2), 29.20
(CH2), 29.33 (CH2), 29.44 (CH2), 29.48 (CH2), 30.82 (CH2),
31.78 (CH2), 35.94 (CH2), 56.23 (CH3), 60.42 (CH3), 61.14
(2 × CH3), 61.65 (CH3), 107.86 (CH), 116.98 (CH), 119.33
(C), 122.40 (C), 125.51 (CH), 125.57 (CH), 141.59 (C),
144.97 (C), 146.25 (C), 147.24 (C), 149.18 (C), 149.62 (C),
155.37 (C), 155.69 (C), 174.66 (C). m/z (EI): 512 (M+, 50%),
497 (80), 481 (100), 280 (70), 91 (55). HRMS calcd for
C30H40O7: (M+) 512.2774; found: 512.2772.
Flavone 27b (102 mg, 77%) was obtained as a viscous yel-
low oil following general procedure 4 on a 0.27 mmol scale.
IR ymax (thin film, cm–1): 2925 (CH2), 1619 (C=O). dH
(400 MHz, CDCl3): 0.88 (3H, t, J = 6.8 Hz, CH2CH3),
1.24–1.32 (14H, m,
7 × CH2), 1.62–1.70 (2H, m,
ArCH2CH2), 2.72 (2H, t, J = 7.5 Hz, ArCH2CH2), 3.81 (6H,
s, 2 × OCH3), 3.82 (3H, s, OCH3), 3.91 (3H, s, OCH3), 6.65
(1H, d, J = 2.9 Hz, H-4’), 6.66 (1H, d, J = 2.9 Hz, H-6’),
7.22–7.25 (2H, m, H-6 and H-8), 8.19 (1H, d, J = 8.1 Hz,
H-5). dC (100 MHz, CDCl3): 14.08 (CH3), 22.64 (CH2),
29.16 (CH2), 29.27 (CH2), 29.40 (CH2), 29.50 (CH2), 29.55
(CH2), 30.87 (CH2), 31.85 (CH2), 36.01 (CH2), 55.72 (CH3),
55.90 (CH3), 60.56 (CH3), 61.50 (CH3), 102.68 (CH), 104.60
(CH), 117.08 (CH), 125.38 (C), 125.60 (CH), 125.65 (CH),
141.60 (C), 141.72 (C), 149.74 (C), 153.69 (C), 155.79 (C),
174.75 (C). m/z (EI): 482 (M+, 55%), 467 (70), 451 (100).
HRMS calcd for C29H38O6: (M+) 482.2669; found: 482.2666.
7-Decyl-3,2’,3’,6’-tetramethoxyflavone (27c)
Flavone 27c (77 mg, 75%) was obtained as a viscous yel-
Published by NRC Research Press