358
Vol. 57, No. 4
s, 6-OH). 13C-NMR (DMSO-d6) d: 31.19 (4-C), 37.14 (3-C), 55.02 (4ꢀ- 3.06 (1H, tt, Jꢁ10.3, 4.6 Hz, 3-H), 3.97 (1H, t, Jꢁ10.3 Hz, 2-H), 4.26 (1H,
OMe), 55.58 (7-OMe), 69.99 (2-C), 100.71 (8-C), 112.87 (4a-C), 113.89
dq, Jꢁ10.3, 1.7 Hz, 2-H), 6.45 (1H, d, Jꢁ8.0 Hz, 5-H), 6.55 (1H, d,
Jꢁ8.0 Hz, 6-H), 6.72 (2H, d, Jꢁ8.6 Hz, 3ꢀ,5ꢀ-H), 7.12 (2H, d, Jꢁ8.6 Hz,
(3ꢀ,5ꢀ-C), 115.57 (5-C), 128.41 (2ꢀ,6ꢀ-C), 133.63 (1ꢀ-C), 140.01 (6-C),
146.47 (8a-C), 146.70 (7-C), 158.06 (4ꢀ-C). FAB-HR-MS m/z: Calcd for 2ꢀ,6ꢀ-H), 8.33 (1H, s, 8-OH), 9.28 (1H, s, 4ꢀ-OH). 13C-NMR (DMSO-d6) d:
C17H18O4 (Mꢅ) 286.1205, Found 286.1232.
15.69 (7-Me), 31.63 (4-C), 36.97 (3-C), 70.43 (2-C), 115.24 (3ꢀ,5ꢀ-C),
6-Hydroxy-3ꢀ,4ꢀ,7-trimethoxyisoflavane 9Ef 82% yield. Pale brown 118.83 (5-C), 119.98 (4a-C), 121.46 (6-C), 121.69 (7-C), 128.35 (2ꢀ,6ꢀ-C),
1
crystals. mp 103—104 °C (EtOH). H-NMR (DMSO-d6) d: 2.76 (1H, ddd, 131.58 (1ꢀ-C), 141.82 (8a-C), 143.13 (8-C), 156.16 (4ꢀ-C). FAB-HR-MS
Jꢁ16.0, 5.2, 1.7 Hz, 4-H), 2.88 (1H, dd, Jꢁ16.0, 10.3 Hz, 4-H), 3.06 (1H, tt,
Jꢁ10.3, 5.2 Hz, 3-H), 3.70 (3H, s, 7-OMe), 3.72 (3H, s, 4ꢀ-OMe), 3.74 (3H,
m/z: Calcd for C16H16O3 (Mꢅ) 256.1099, Found 256.1095.
8-Hydroxy-4ꢀ-methoxy-7-methylisoflavane 9Ie 55% yield. Colorless
s, 3ꢀ-OMe), 3.91 (1H, t, Jꢁ10.3 Hz, 2-H), 4.14 (1H, dq, Jꢁ10.3, 1.7 Hz, 2- crystals. mp 78—79 °C (EtOH). 1H-NMR (DMSO-d6) d: 2.08 (3H, s, 7-
H), 6.38 (1H, s, 8-H), 6.50 (1H, s, 5-H), 6.81 (1H, d, Jꢁ8.6 Hz, 6ꢀ-H), 6.89
(1H, d, Jꢁ8.6 Hz, 5ꢀ-H), 6.94 (1H, s, 2ꢀ-H), 8.35 (1H, s, 6-OH). 13C-NMR
(DMSO-d6) d: 31.20 (4-C), 37.64 (3-C), 55.49 (4ꢀ-OMe), 55.53 (3ꢀ-OMe),
55.58 (7-OMe), 70.01 (2-C), 100.71 (8-C), 111.57 (2ꢀ-C), 111.92 (5ꢀ-C),
112.93 (4a-C), 115.56 (5-C), 119.13 (6ꢀ-C), 134.19 (1ꢀ-C), 140.00 (6-C),
Me), 2.87 (1H, ddd, Jꢁ16.0, 4.6, 1.7 Hz, 4-H), 2.95 (1H, dd, Jꢁ16.0,
10.3 Hz, 4-H), 3.13 (1H, tt, Jꢁ10.3, 4.6 Hz, 3-H), 3.73 (3H, s, 4ꢀ-OMe),
4.02 (1H, t, Jꢁ10.3 Hz, 2-H), 4.27 (1H, dq, Jꢁ10.3, 1.7 Hz, 2-H), 6.46 (1H,
d, Jꢁ8.0 Hz, 5-H), 6.56 (1H, d, Jꢁ8.0 Hz, 6-H), 6.90 (2H, d, Jꢁ8.6 Hz,
3ꢀ,5ꢀ-H), 7.26 (2H, d, Jꢁ8.6 Hz, 2ꢀ,6ꢀ-H), 8.36 (1H, s, 8-OH). 13C-NMR
146.48 (8a-C), 146.69 (7-C), 147.64 (4ꢀ-C), 148.78 (3ꢀ-C). FAB-HR-MS (DMSO-d6) d: 15.74 (7-Me), 31.55 (4-C), 36.94 (3-C), 55.06 (4ꢀ-OMe),
m/z: Calcd for C18H20O5 (Mꢅ) 316.1311, Found 316.1324.
70.30 (2-C), 113.94 (3ꢀ,5ꢀ-C), 118.85 (5-C), 119.90 (4a-C), 121.52 (6-C),
6-Hydroxy-4ꢀ-methoxy-7-methylisoflavane 9Fe 98% yield. Pale brown 121.75 (7-C), 128.50 (2ꢀ,6ꢀ-C), 133.45 (1ꢀ-C), 141.84 (8a-C), 143.17 (8-C),
1
crystals. mp 144—145 °C (EtOH). H-NMR (DMSO-d6) d: 2.04 (3H, s, 7- 158.14 (4ꢀ-C). FAB-HR-MS m/z: Calcd for C17H18O3 (Mꢅ) 270.1256, Found
Me), 2.79 (1H, ddd, Jꢁ16.0, 5.2, 1.7 Hz, 4-H), 2.87 (1H, dd, Jꢁ16.0, 270.1261.
10.3 Hz, 4-H), 3.07 (1H, tt, Jꢁ10.3, 5.2 Hz, 3-H), 3.73 (3H, s, 4ꢀ-OMe),
3.87 (1H, t, Jꢁ10.3 Hz, 2-H), 4.11 (1H, dq, Jꢁ10.3, 1.7 Hz, 2-H), 6.48 (1H,
7-Hydroxy-6-methoxyisoflavane 9Ja 52% yield. Pale brown crystals.
mp 104—105 °C (EtOH). H-NMR (DMSO-d6) d: 2.83 (1H, ddd, Jꢁ16.0,
1
s, 5-H), 6.50 (1H, s, 8-H), 6.89 (2H, d, Jꢁ8.6 Hz, 3ꢀ,5ꢀ-H), 7.23 (2H, d, 5.7, 1.7 Hz, 4-H), 2.91 (1H, dd, Jꢁ16.0, 10.3 Hz, 4-H), 3.10—3.16 (1H, m,
Jꢁ8.6 Hz, 2ꢀ,6ꢀ-H), 8.65 (1H, s, 6-OH). 13C-NMR (DMSO-d6) d: 15.80 (7-
3-H), 3.68 (3H, s, 6-OMe), 3.95 (1H, t, Jꢁ10.3 Hz, 2-H), 4.16 (1H, dq,
Me), 31.57 (4-C), 37.11 (3-C), 55.02 (4ꢀ-OMe), 69.98 (2-C), 113.88 (3ꢀ,5ꢀ- Jꢁ10.3, 1.7 Hz, 2-H), 6.25 (1H, s, 8-H), 6.65 (1H, s, 5-H), 7.23—7.27 (1H,
C), 114.77 (5-C), 117.53 (8-C), 119.33 (4a-C), 122.90 (7-C), 128.39 (2ꢀ,6ꢀ- m, 4ꢀ-H), 7.31—7.35 (4H, m, 2ꢀ,3ꢀ,5ꢀ,6ꢀ-H), 8.86 (1H, s, 7-OH). 13C-NMR
C), 133.61 (1ꢀ-C), 146.31 (8a-C), 148.70 (6-C), 158.05 (4ꢀ-C). FAB-HR-MS (DMSO-d6) d: 31.29 (4-C), 38.03 (3-C), 56.32 (6-OMe), 69.75 (2-C),
m/z: Calcd for C17H18O3 (Mꢅ) 270.1256, Found 270.1241.
103.57 (8-C), 111.30 (4a-C), 113.57 (5-C), 126.75 (4ꢀ-C), 127.48 (3ꢀ,5ꢀ-C),
128.52 (2ꢀ,6ꢀ-C), 141.85 (6-C), 141.91 (1ꢀ-C), 145.76 (7-C), 147.80 (8a-C).
6-Hydroxy-7,8-dimethylisoflavane 9Ga 51% yield. Colorless crystals.
1
mp 142—143 °C (EtOH). H-NMR (DMSO-d6) d: 2.01 (3H, s, 7-Me), 2.02 FAB-HR-MS m/z: Calcd for C16H16O3 (Mꢅ) 256.1099, Found 256.1089.
(3H, s, 8-Me), 2.83 (1H, ddd, Jꢁ16.0, 5.7, 1.7 Hz, 4-H), 2.93 (1H, dd,
Jꢁ16.0, 10.3 Hz, 4-H), 3.10—3.16 (1H, m, 3-H), 3.94 (1H, t, Jꢁ10.3 Hz, 2-
4ꢀ,7-Dihydroxy-6-methoxyisoflavane 9Jb 45% yield. Pale orange crys-
tals. mp 151—152 °C (EtOH) (lit.14) mp not given). 1H-NMR (DMSO-d6) d:
H), 4.24 (1H, dq, Jꢁ10.3, 1.7 Hz, 2-H), 6.39 (1H, s, 5-H), 7.24—7.27 (1H, 2.76 (1H, ddd, Jꢁ16.0, 5.7, 1.7 Hz, 4-H), 2.84 (1H, dd, Jꢁ16.0, 10.3 Hz, 4-
m, 4ꢀ-H), 7.31—7.35 (4H, m, 2ꢀ,3ꢀ,5ꢀ,6ꢀ-H), 8.56 (1H, s, 6-OH). 13C-NMR
(DMSO-d6) d: 11.82 (7-Me), 11.88 (8-Me), 31.83 (4-C), 38.03 (3-C), 70.05
H), 2.97—3.03 (1H, m, 3-H), 3.68 (3H, s, 6-OMe), 3.84 (1H, t, Jꢁ10.3 Hz,
2-H), 4.09 (1H, dq, Jꢁ10.3, 1.7 Hz, 2-H), 6.24 (1H, s, 8-H), 6.63 (1H, s, 5-
(2-C), 112.10 (5-C), 118.34 (4a-C), 121.38 (7-C), 123.78 (8-C), 126.65 (4ꢀ- H), 6.71 (2H, d, Jꢁ8.6 Hz, 3ꢀ,5ꢀ-H), 7.10 (2H, d, Jꢁ8.6 Hz, 2ꢀ,6ꢀ-H), 8.86
C), 127.41 (3ꢀ,5ꢀ-C), 128.45 (2ꢀ,6ꢀ-C), 141.87 (1ꢀ-C), 144.57 (8a-C), 148.14
(1H, s, 7-OH), 9.31 (1H, s, 4ꢀ-OH). 13C-NMR (DMSO-d6) d: 31.54 (4-C),
(6-C). FAB-HR-MS m/z: Calcd for C17H18O2 (Mꢅ) 254.1307, Found 37.23 (3-C), 56.33 (6-OMe), 70.11 (2-C), 103.53 (8-C), 111.47 (4a-C),
254.1306. 113.60 (5-C), 115.23 (3ꢀ,5ꢀ-C), 128.31 (2ꢀ,6ꢀ-C), 131.79 (1ꢀ-C), 141.83 (6-
8-Hydroxy-7-methoxyisoflavane 9Ha 47% yield. Pale brown crystals. C), 145.71 (7-C), 147.80 (8a-C), 156.13 (4ꢀ-C). FAB-HR-MS m/z: Calcd for
1
mp 100—101 °C (EtOH). H-NMR (DMSO-d6) d: 2.89 (1H, ddd, Jꢁ16.0,
5.2, 1.7 Hz, 4-H), 2.97 (1H, dd, Jꢁ16.0, 10.3 Hz, 4-H), 3.13—3.19 (1H, m,
C16H16O4 (Mꢅ) 272.1049, Found 272.1059.
7-Hydroxy-4ꢀ,6-dimethoxyisoflavane 9Je 51% yield. Colorless crys-
3-H), 3.72 (3H, s, 7-OMe), 4.04 (1H, t, Jꢁ10.3 Hz, 2-H), 4.29 (1H, dq, tals. mp 117—118 °C (EtOH). 1H-NMR (DMSO-d6) d: 2.79 (1H, ddd,
Jꢁ10.3, 1.7 Hz, 2-H), 6.49—6.52 (2H, m, 5,6-H), 7.24—7.28 (1H, m, 4ꢀ- Jꢁ16.0, 5.2, 1.7 Hz, 4-H), 2.87 (1H, dd, Jꢁ16.0, 10.3 Hz, 4-H), 3.04—3.10
H), 7.32—7.36 (4H, m, 2ꢀ,3ꢀ,5ꢀ,6ꢀ-H), 8.22 (1H, s, 8-OH). 13C-NMR
(DMSO-d6) d: 31.23 (4-C), 37.74 (3-C), 56.05 (7-OMe), 69.91 (2-C),
105.00 (6-C), 115.51 (4a-C), 118.20 (5-C), 126.74 (4ꢀ-C), 127.46 (3ꢀ,5ꢀ-C),
128.47 (2ꢀ,6ꢀ-C), 134.59 (8-C), 141.63 (1ꢀ-C), 142.73 (7-C), 146.41 (8a-C).
FAB-HR-MS m/z: Calcd for C16H16O3 (Mꢅ) 256.1099, Found 256.1077.
8-Hydroxy-4ꢀ,7-dimethoxyisoflavane 9He 53% yield. Colorless crys-
tals. mp 97—98 °C (EtOH). 1H-NMR (DMSO-d6) d: 2.85 (1H, ddd, Jꢁ16.0,
(1H, m, 3-H), 3.68 (3H, s, 4ꢀ-OMe), 3.73 (3H, s, 6-OMe), 3.89 (1H, t,
Jꢁ10.3 Hz, 2-H), 4.11 (1H, dq, Jꢁ10.3, 1.7 Hz, 2-H), 6.24 (1H, s, 8-H),
6.64 (1H, s, 5-H), 6.89 (2H, d, Jꢁ8.6 Hz, 3ꢀ,5ꢀ-H), 7.23 (2H, d, Jꢁ8.6 Hz,
2ꢀ,6ꢀ-H), 8.84 (1H, s, 7-OH). 13C-NMR (DMSO-d6) d: 31.45 (4-C), 37.17
(3-C), 55.04 (4ꢀ-OMe), 56.32 (6-OMe), 69.97 (2-C), 103.54 (8-C), 111.37
(4a-C), 113.57 (5-C), 113.92 (3ꢀ,5ꢀ-C), 128.43 (2ꢀ,6ꢀ-C), 133.64 (1ꢀ-C),
141.87 (6-C), 145.72 (7-C), 147.79 (8a-C), 158.08 (4ꢀ-C). FAB-HR-MS m/z:
5.2, 1.7 Hz, 4-H), 2.93 (1H, dd, Jꢁ16.0, 10.3 Hz, 4-H), 3.07—3.13 (1H, m, Calcd for C17H18O4 (Mꢅ) 286.1205, Found 286.1206.
3-H), 3.72 (3H, s, 7-OMe), 3.73 (3H, s, 4ꢀ-OMe), 3.97 (1H, t, Jꢁ10.3 Hz, 2-
6,7-Dimethoxyisoflavane 9Ka 76% yield. Pale brown crystals. mp
H), 4.25 (1H, dq, Jꢁ10.3, 1.7 Hz, 2-H), 6.48—6.51 (2H, m, 5,6-H), 6.90 77—78 °C (EtOH). 1H-NMR (DMSO-d6) d: 2.87 (1H, ddd, Jꢁ16.0, 5.7,
(2H, d, Jꢁ8.6 Hz, 3ꢀ,5ꢀ-H), 7.25 (2H, d, Jꢁ8.6 Hz, 2ꢀ,6ꢀ-H), 8.21 (1H, s, 8-
OH). 13C-NMR (DMSO-d6) d: 31.40 (4-C), 36.91 (3-C), 55.03 (4ꢀ-OMe),
56.04 (7-OMe), 70.14 (2-C), 104.94 (6-C), 113.91 (3ꢀ,5ꢀ-C), 115.59 (4a-C),
118.19 (5-C), 128.44 (2ꢀ,6ꢀ-C), 133.43 (1ꢀ-C), 134.56 (8-C), 142.72 (7-C),
1.7 Hz, 4-H), 2.94 (1H, dd, Jꢁ16.0, 10.3 Hz, 4-H), 3.13—3.19 (1H, m, 3-H),
3.68 (3H, s, 6-OMe), 3.70 (3H, s, 7-OMe), 3.99 (1H, t, Jꢁ10.3 Hz, 2-H),
4.20 (1H, dq, Jꢁ10.3, 1.7 Hz, 2-H), 6.43 (1H, s, 8-H), 6.70 (1H, s, 5-H),
7.24—7.27 (1H, m, 4ꢀ-H), 7.32—7.35 (4H, m, 2ꢀ,3ꢀ,5ꢀ,6ꢀ-H). 13C-NMR
146.39 (8a-C), 158.10 (4ꢀ-C). FAB-HR-MS m/z: Calcd for C17H18O4 (Mꢅ) (DMSO-d6) d: 31.16 (4-C), 37.86 (3-C), 55.50 (7-OMe), 56.09 (6-OMe),
286.1205, Found 286.1214.
69.81 (2-C), 100.83 (8-C), 112.38 (4a-C), 113.21 (5-C), 126.75 (4ꢀ-C),
127.47 (3ꢀ,5ꢀ-C), 128.53 (2ꢀ,6ꢀ-C), 141.74 (1ꢀ-C), 142.78 (6-C), 147.75 (8a-
C), 148.11 (7-C). FAB-HR-MS m/z: Calcd for C17H18O3 (Mꢅ) 270.1256,
Found 270.1232.
4ꢀ-Hydroxy-6,7-dimethoxyisoflavane 9Kb 43% yield. Colorless crys-
tals. mp 183—184 °C (EtOH). 1H-NMR (DMSO-d6) d: 2.80 (1H, ddd,
Jꢁ16.0, 5.7, 1.7 Hz, 4-H), 2.87 (1H, dd, Jꢁ16.0, 10.3 Hz, 4-H), 3.03 (1H, tt,
Jꢁ10.3, 5.7 Hz, 3-H), 3.67 (3H, s, 6-OMe), 3.69 (3H, s, 7-OMe), 3.88 (1H,
t, Jꢁ10.3 Hz, 2-H), 4.14 (1H, dq, Jꢁ10.3, 1.7 Hz, 2-H), 6.42 (1H, s, 8-H),
8-Hydroxy-7-methylisoflavane 9Ia 75% yield. Colorless crystals. mp
1
96—97 °C (EtOH). H-NMR (DMSO-d6) d: 2.09 (3H, s, 7-Me), 2.91 (1H,
ddd, Jꢁ16.0, 5.2, 1.7 Hz, 4-H), 2.99 (1H, dd, Jꢁ16.0, 10.3 Hz, 4-H), 3.17—
3.22 (1H, m, 3-H), 4.08 (1H, t, Jꢁ10.3 Hz, 2-H), 4.32 (1H, dq, Jꢁ10.3,
1.7 Hz, 2-H), 6.47 (1H, d, Jꢁ8.0 Hz, 5-H), 6.57 (1H, d, Jꢁ8.0 Hz, 6-H),
7.24—7.28 (1H, m, 4ꢀ-H), 7.33—7.36 (4H, m, 2ꢀ,3ꢀ,5ꢀ,6ꢀ-H), 8.34 (1H, s, 8-
OH). 13C-NMR (DMSO-d6) d: 15.68 (7-Me), 31.35 (4-C), 37.74 (3-C),
70.05 (2-C), 118.82 (5-C), 119.78 (4a-C), 121.53 (6-C), 121.78 (7-C),
126.74 (4ꢀ-C), 127.48 (3ꢀ,5ꢀ-C), 128.49 (2ꢀ,6ꢀ-C), 141.61 (1ꢀ-C), 141.84 6.68 (1H, s, 5-H), 6.72 (2H, d, Jꢁ8.6 Hz, 3ꢀ,5ꢀ-H), 7.11 (2H, d, Jꢁ8.6 Hz,
(8a-C), 143.14 (8-C). FAB-HR-MS m/z: Calcd for C16H16O2 (Mꢅ) 240.1150,
Found 240.1145.
2ꢀ,6ꢀ-H), 9.30 (1H, s, 4ꢀ-OH). 13C-NMR (DMSO-d6) d: 31.43 (4-C), 37.09
(3-C), 55.48 (7-OMe), 56.10 (6-OMe), 70.18 (2-C), 100.79 (8-C), 112.56
(4a-C), 113.24 (5-C), 115.25 (3ꢀ,5ꢀ-C), 128.33 (2ꢀ,6ꢀ-C), 131.70 (1ꢀ-C),
4ꢀ,8-Dihydroxy-7-methylisoflavane 9Ib 72% yield. Pale gray crystals.
1
mp 149—150 °C (EtOH). H-NMR (DMSO-d6) d: 2.08 (3H, s, 7-Me), 2.84 142.70 (6-C), 147.75 (8a-C), 148.05 (7-C), 156.14 (4ꢀ-C). FAB-HR-MS m/z:
(1H, ddd, Jꢁ15.8, 4.6, 1.7 Hz, 4-H), 2.91 (1H, dd, Jꢁ15.8, 10.3 Hz, 4-H), Calcd for C17H18O4 (Mꢅ) 286.1205, Found 286.1206.