June 2002
793
1
360.0834. H-NMR (270 MHz, DMSO-d6) d: 3.77, 3.86, 3.87 (3H each, all
s, 4Ј, 3Ј, 7-OCH3), 6.35 (1H, br s, 6-H), 6.72 (1H, br s, 8-H), 7.33 (1H, br s,
2Ј-H), 7.45 (1H, br s, 6Ј-H), 9.46, 12.35 (1H each, both br s, –OH). 13C-
NMR (68 MHz, DMSO-d6) dc: 55.9, 55.9, 59.9 (–OCH3), 91.8 (C-8), 97.3
(C-6), 103.3 (C-10), 103.9 (C-2Ј), 109.5 (C-6Ј), 125.6 (C-1Ј), 136.7 (C-3),
138.1 (C-4Ј), 146.0 (C-2), 150.1 (C-5Ј), 152.6 (C-3Ј), 155.9 (C-9), 160.1 (C-
5), 164.8 (C-7), 175.9 (C-4). EI-MS: m/z 360 (Mϩ, 100).
74.0 (C-2Љ), 75.8 (C-5Љ), 76.4 (C-3Љ), 92.2 (C-8), 97.8 (C-6), 100.7 (C-1ٞ),
101.1 (C-1Љ), 105.0 (C-10), 111.4 (C-2Ј), 115.8 (C-5Ј), 121.4 (C-1Ј), 122.4
(C-6Ј), 133.8 (C-3), 145.8 (C-3Ј), 150.1 (C-4Ј), 156.3 (C-2), 156.6 (C-9),
160.8 (C-5), 165.1 (C-4), 177.5 (C-7). Positive-ion FAB-MS: m/z 639
(MϩH)ϩ.
41: High-resolution positive-ion FAB-MS: Calcd for C30H37O16 (MϩH)ϩ:
653.2081. Found: 653.2078. 1H-NMR (270 MHz, DMSO-d6) d: 0.97 (3H, d,
Jϭ6.1 Hz, 6—H), 3.84, 3.86, 3.87 (3H each, all s, 3Ј, 4Ј, 7-OCH3), 4.41
(1H, br s, 1—H), 5.44 (1H, d, Jϭ7.4 Hz, 1Љ-H), 6.37 (1H, d, Jϭ1.8 Hz, 6-H),
6.72 (1H, d, Jϭ1.8 Hz, 8-H), 7.10 (1H, d, Jϭ8.6 Hz, 5Ј-H), 7.71 (1H, dd,
Jϭ1.8, 8.6 Hz, 6Ј-H), 7.82 (1H, d, Jϭ1.8 Hz, 2Ј-H), 12.51 (1H, br s, –OH).
13C-NMR (68 MHz, DMSO-d6) dc: 17.6 (C-1ٞ), 55.6, 55.6, 56.0 (–OCH3),
66.7 (C-6Љ), 68.2 (C-5ٞ), 70.0 (C-4Љ), 70.2 (C-2ٞ), 70.6 (C-3ٞ), 71.7 (C-4ٞ),
74.2 (C-2Љ), 75.9 (C-5Љ), 76.4 (C-3Љ), 92.4 (C-8), 97.9 (C-6), 100.8 (C-1ٞ),
101.2 (C-1Љ), 105.0 (C-10), 111.2 (C-2Ј), 112.6 (C-5Ј), 121.4 (C-1Ј), 122.3
(C-6Ј), 133.6 (C-3), 148.0 (C-3Ј), 151.1 (C-4Ј), 156.4 (C-2), 156.5 (C-9),
160.8 (C-5), 165.2 (C-7), 177.5 (C-4). Positive-ion FAB-MS: m/z 653
(MϩH)ϩ.
Diazomethane Methylation of 8, 12, 24, 38, 43, 50, and 60 A solution
of apigenin (8, 20 mg, 0.074 mmol) in MeOH (2.0 ml) was treated with ethe-
real diazomethane (CH2N2–Et2O) until the yellow color persisted. The reac-
tion solution was stirred at room temperature for 30 min. Removal of the sol-
vent under reduced pressure furnished a residue, which was purified by sil-
ica gel column chromatography [500 mg, n-hexane–AcOEt (2 : 1)] to give 9
(21 mg, 94%). A solution of luteolin (12, 100 mg, 0.35 mmol) in MeOH
(5.0 ml) was treated with CH2N2–Et2O and the whole mixture was stirred at
room temperature for 1 h. The reaction mixture was purified by HPLC
[YMC-Pack ODS-A, 20ϫ250 mm, i.d., MeOH–1% aqueous AcOH (80 : 20,
v/v)] to give pilloin (14, 36 mg, 33%) and 15 (63 mg, 55%). Through a simi-
lar procedure, rhamnetin (25, 81 mg, 22%), tamarixetin (26, 7 mg, 2%), 27
(50 mg, 13%), ombuine (28, 64 mg, 16%), ayanin (29, 127 mg, 32%), and 31
(59 mg, 14%) were obtained from quercetin [24, 350 mg, 1.16 mmol, HPLC
conditions: YMC-Pack ODS-A, 20ϫ250 mm, i.d., MeOH–1% aqueous
AcOH (75 : 25, v/v)]. From rutin (38, 400 mg, 0.66 mmol), rhamnetin 3-O-
rutinoside (39, 71 mg, 17%), ombuin 3-O-rutinoside (40, 132 mg, 32%), and
41 (143 mg, 33%) were obtained [HPLC conditions: YMC-Pack ODS-A,
20ϫ250 mm, i.d., MeOH–1% aqueous AcOH (70 : 30, v/v)]. From myricetin
(43, 125 mg, 0.39 mmol), mearnsetin (44, 41 mg, 31%), 45 (33 mg, 25%), 46
(8 mg, 6%), and 47 (12 mg, 9%) were obtained [HPLC conditions: YMC-
Pack ODS-A, 20ϫ250 mm, i.d., MeOH–1% aqueous AcOH (70 : 30, v/v)].
From myricitrin (50, 400 mg, 0.86 mmol), 52 (107 mg, 25%), 53 (61 mg,
14%), 54 (114 mg, 26%), and 55 (85 mg, 19%) were obtained [HLPC condi-
tions: YMC-Pack ODS-A, 20ϫ250 mm, i.d., MeOH–1% aqueous AcOH
(70 : 30, v/v)]. A solution of liquiritin (60, 100 mg, 0.24 mmol) was treated
with a similar procedure, then the reaction mixture was removed and puri-
fied by silica gel column chromatography [2 g, n-hexane–AcOEt (1 : 1)] to
give 61 (104 mg, quant.).
45: High-resolution EI-MS: Calcd for C16H12O8 (Mϩ): 332.0532. Found:
332.0533. 1H-NMR (270 MHz, DMSO-d6) d: 3.87 (3H, s, 7-OCH3), 6.34
(1H, br s, 6-H), 6.63 (1H, br s, 8-H), 7.30 (2H, br s, 2Ј, 6Ј-H). 13C-NMR
(68 MHz, DMSO-d6) dc: 55.8 (–OCH3), 91.5 (C-8), 97.2 (C-6), 103.8 (C-
10), 107.2 (C-2Ј, 6Ј), 120.5 (C-1Ј), 135.8, 135.9 (C-3, 4Ј), 145.5 (C-2),
147.1 (C-3Ј, 5Ј), 155.7 (C-9), 160.1 (C-5), 164.6 (C-7), 175.5 (C-4). EI-MS:
m/z 332 (Mϩ, 100).
46: High-resolution EI-MS: Calcd for C17H14O8 (Mϩ): 346.0688. Found:
346.0682. 1H-NMR (270 MHz, DMSO-d6) d: 3.80, 3.87 (3H each, both s, 3,
7-OCH3), 6.36 (1H, d, Jϭ2.2 Hz, 6-H), 6.64 (1H, d, Jϭ2.2 Hz, 8-H), 7.16
(2H, br s, 2Ј, 6Ј-H). 13C-NMR (68 MHz, DMSO-d6) dc: 55.9, 59.5 (–OCH3),
92.0 (C-8), 97.6 (C-6), 105.1 (C-10), 107.7 (C-2Ј, 6Ј), 119.5 (C-1Ј), 136.9,
137.9 (C-3, 4Ј), 145.8 (C-3Ј, 5Ј), 156.0, 156.1 (C-2, 9), 160.9 (C-5), 165.0
(C-7), 177.9 (C-4). EI-MS: m/z 346 (Mϩ, 100).
47: High-resolution EI-MS: Calcd for C17H14O8 (Mϩ): 346.0688. Found:
1
346.0681. H-NMR (270 MHz, DMSO-d6) d: 3.79, 3.87 (3H each, both s,
4Ј, 7-OCH3), 6.35 (1H, br s, 6-H), 6.64 (1H, br s, 8-H), 7.27 (2H, br s, 2Ј, 6Ј-
H). 13C-NMR (68 MHz, DMSO-d6) dc: 55.8, 59.6 (–OCH3), 91.6 (C-8), 97.2
(C-6), 103.9 (C-10), 107.2 (C-2Ј, 6Ј), 125.5 (C-1Ј), 136.6, 137.1 (C-3, 4Ј),
146.2 (C-2), 150.3 (C-3Ј, 5Ј), 155.8 (C-9), 160.1 (C-5), 164.7 (C-7), 175.9
(C-4). EI-MS: m/z 346 (Mϩ, 100).
Compounds 9, 14, 15, 25, 27, 28, 39, and 44 were identified by compari-
son of the physical data with reported values.33—38,40,42) The structures of
26,37) 29,37) 31,39) 40,41) 41,32) 45,43) 46,44) and 4745) were confirmed by the
following physical data.
52: High-resolution positive-ion FAB-MS: Calcd for C23H25O12 (MϩH)ϩ:
493.1346. Found: 493.1341. 1H-NMR (270 MHz, DMSO-d6) d: 0.84 (3H, d,
Jϭ5.2 Hz, 6Љ-H), 3.76, 3.87 (3H each, both s, 4Ј, 7-OCH3), 5.20 (1H, br s,
1Љ-H), 6.39 (1H, d, Jϭ2.0 Hz, 6-H), 6.65 (1H, d, Jϭ2.0 Hz, 8-H), 6.85 (2H,
br s, 2Ј, 6Ј-H), 9.39 (2H, br s, –OH), 12.55 (1H, br s, –OH). 13C-NMR
(68 MHz, DMSO-d6) dc: 17.4 (C-6Љ), 56.0, 59.6 (–OCH3), 69.9 (C-5Љ), 70.2
(C-2Љ), 70.4 (C-3Љ), 71.1 (C-4Љ), 92.1 (C-8), 97.7 (C-6), 102.0 (C-1Љ), 105.0
(C-10), 108.0 (C-2Ј, 6Ј), 124.4 (C-1Ј), 134.8 (C-3), 137.7 (C-4Ј), 150.3 (C-
3Ј, 5Ј), 156.2 (C-2), 157.4 (C-9), 160.7 (C-5), 165.0 (C-7), 177.7 (C-4). Pos-
itive-ion FAB-MS: m/z 493 (MϩH)ϩ. Negative-ion FAB-MS: m/z 491
(MϪH)Ϫ, 345 (MϪC6H11O4)Ϫ.
26: High-resolution EI-MS: Calcd for C16H12O7 (Mϩ): 316.0583. Found:
316.0575. 1H-NMR (270 MHz, DMSO-d6) d: 3.85 (3H, s, 4Ј-OCH3), 6.19
(1H, d, Jϭ1.8 Hz, 6-H), 6.42 (1H, d, Jϭ1.8 Hz, 8-H), 7.08 (1H, d, Jϭ8.4 Hz,
5Ј-H), 7.67 (1H, d, Jϭ2.1 Hz, 2Ј-H), 7.65 (1H, dd, Jϭ2.1, 8.4 Hz, 6Ј-H).
13C-NMR (68 MHz, DMSO-d6) dc: 55.5 (–OCH3), 93.2 (C-8), 98.0 (C-6),
102.8 (C-10), 111.7 (C-5Ј), 114.4 (C-2Ј), 119.5 (C-6Ј), 123.2 (C-1Ј), 135.8
(C-3), 145.9 (C-3Ј), 146.0 (C-2), 149.0 (C-4Ј), 155.9 (C-5), 160.4 (C-9),
163.6 (C-7), 175.6 (C-4). EI-MS: m/z 316 (Mϩ, 100).
Ayanin (29): High-resolution EI-MS: Calcd for C18H16O7 (Mϩ): 344.0896.
Found: 344.0891. 1H-NMR (270 MHz, DMSO-d6) d: 3.81, 3.87, 3.87 (3H
each, all s, 3, 4Ј, 7-OCH3), 6.36 (1H, br s, 6-H), 6.70 (1H, br s, 8-H), 7.10
(1H, d, Jϭ8.8 Hz, 5Ј-H), 7.58 (1H, br s, 2Ј-H), 7.58 (1H, br d, Jϭca. 9 Hz,
6Ј-H), 9.33, 12.62 (1H each, both br s, –OH). 13C-NMR (68 MHz, DMSO-
d6) dc: 55.6, 55.9, 59.6 (–OCH3), 92.1 (C-8), 97.5 (C-6), 105.0 (C-10), 111.7
(C-5Ј), 114.9 (C-2Ј), 120.1 (C-6Ј), 122.0 (C-1Ј), 138.0 (C-3), 146.1 (C-3Ј),
150.0 (C-2), 155.3 (C-4Ј), 156.0 (C-5), 160.7 (C-9), 164.8 (C-7), 177.7 (C-
4). EI-MS: m/z 344 (Mϩ, 100).
53: High-resolution positive-ion FAB-MS: Calcd for C23H25O12 (MϩH)ϩ:
493.1346. Found: 493.1349. 1H-NMR (270 MHz, DMSO-d6) d: 0.79 (3H, d,
Jϭ5.9 Hz, 6Љ-H), 3.75, 3.84 (3H each, both s, 4Ј, 3Ј-OCH3), 5.21 (1H, br s,
1Љ-H), 6.22 (1H, d, Jϭ2.0 Hz, 6-H), 6.41 (1H, d, Jϭ2.0 Hz, 8-H), 6.97 (2H,
br s, 2Ј, 6Ј-H), 9.48, 10.84, 12.52 (1H each, all br s, –OH). 13C-NMR
(68 MHz, DMSO-d6) dc: 17.4 (C-6Љ), 55.9, 59.9 (–OCH3), 69.9 (C-5Љ), 70.3
(C-2Љ), 70.4 (C-3Љ), 71.0 (C-4Љ), 93.6 (C-8), 98.6 (C-6), 101.8 (C-1Љ), 104.1
(C-6Ј), 104.7 (C-10), 110.0 (C-2Ј), 124.7 (C-1Ј), 134.6 (C-3), 138.6 (C-4Ј),
150.2 (C-5Ј), 152.5 (C-3Ј), 156.3 (C-2), 156.8 (C-9), 161.0 (C-5), 164.0 (C-
7), 177.4 (C-4). Positive-ion FAB-MS: m/z 493 (MϩH)ϩ. Negative-ion
FAB-MS: m/z 491 (MϪH)Ϫ, 345 (MϪC6H11O4)Ϫ.
31: High-resolution EI-MS: Calcd for C19H18O7 (Mϩ): 358.1052. Found:
1
358.1046. H-NMR (270 MHz, CDCl3) d: 3.86, 3.87, 3.97, 3.97 (3H each,
all s, 4Ј, 7, 3, 3Ј, –OCH3), 6.35 (1H, br s, 6-H), 6.44 (1H, br s, 8-H), 6.99
(1H, d, Jϭ8.4 Hz, 5Ј-H), 7.69 (1H, br s, 2Ј-H), 7.71 (1H, dd like, 6Ј-H),
12.63 (1H, br s, –OH). 13C-NMR (68 MHz, CDCl3) dc: 55.8, 56.0, 56.0, 60.2
(–OCH3), 92.1 (C-8), 97.7 (C-6), 105.9 (C-10), 110.7 (C-5Ј), 111.1 (C-2Ј),
122.0 (C-6Ј), 122.8 (C-1Ј), 138.8 (C-3), 148.6 (C-3Ј), 151.2 (C-2), 155.6 (C-
4Ј), 156.5 (C-5), 161.8 (C-9), 165.2 (C-7), 178.5 (C-4). EI-MS: m/z 358
(Mϩ, 100).
54: High-resolution positive-ion FAB-MS: Calcd for C24H27O12 (MϩH)ϩ:
507.1502. Found: 507.1496. 1H-NMR (270 MHz, DMSO-d6) d: 0.82 (3H, d,
Jϭ5.2 Hz, 6Љ-H), 3.77, 3.87, 3.88 (3H each, all s, 4Ј, 3Ј, 7-OCH3), 5.25 (1H,
br s, 1Љ-H), 6.39 (1H, br s, 6-H), 6.68 (1H, br s, 8-H), 7.00, 7.02 (1H each,
both br s, 2Ј, 6Ј-H), 9.50, 12.52 (1H each, both br s, –OH). 13C-NMR
(68 MHz, DMSO-d6) dc: 17.4 (C-6Љ), 55.9, 56.0, 59.9 (–OCH3), 69.9 (C-5Љ),
70.3 (C-2Љ), 70.4 (C-3Љ), 71.0 (C-4Љ), 92.2 (C-8), 97.8 (C-6), 101.9 (C-1Љ),
104.7, 110.1 (C-2Ј, 6Ј), 105.0 (C-10), 124.6 (C-1Ј), 134.9 (C-3), 138.7 (C-
4Ј), 150.3 (C-5Ј), 152.5 (C-3Ј), 156.2 (C-2), 157.1 (C-9), 160.7 (C-5), 165.0
(C-7), 177.6 (C-4). Positive-ion FAB-MS: m/z 507 (MϩH)ϩ. Negative-ion
FAB-MS: m/z 505 (MϪH)Ϫ, 359 (MϪC6H11O4)Ϫ.
Ombuine 3-O-Rutinoside (40): High-resolution positive-ion FAB-MS:
Calcd for C29H35O16 (MϩH)ϩ: 639.1925. Found: 639.1918. H-NMR (270
1
MHz, DMSO-d6) d: 0.98 (3H, d, Jϭ6.1 Hz, 6—H), 3.87, 3.87 (3H each,
both s, 4Ј, 7-OCH3), 4.50 (1H, br s, 1—H), 5.39 (1H, d, Jϭ7.1 Hz, 1Љ-H),
6.37 (1H, d, Jϭ2.1 Hz, 6-H), 6.67 (1H, d, Jϭ2.1 Hz, 8-H), 7.04 (1H, d,
Jϭ8.5 Hz, 5Ј-H), 7.55 (1H, d, Jϭ2.2 Hz, 2Ј-H), 7.72 (1H, dd, Jϭ2.2, 8.5 Hz,
6Ј-H). 13C-NMR (68 MHz, DMSO-d6) dc: 17.6 (C-1ٞ), 55.6, 56.0 (–OCH3),
66.8 (C-6Љ), 68.1 (C-5ٞ), 69.8 (C-4Љ), 70.3 (C-2ٞ), 70.5 (C-3ٞ), 71.8 (C-4ٞ),
55: High-resolution positive-ion FAB-MS: Calcd for C25H29O12 (MϩH)ϩ:
521.1659. Found: 521.1652. 1H-NMR (270 MHz, DMSO-d6) d: 0.81 (3H, d,