SHUL’TS et al.
110
136.75 (C8a), 140.76 (C1), 150.96 (C8′), 154.69 (C3),
162.07 (C7), 182.64 (C10), 184.91 (COOH), 185.08
(C9). Mass spectrum: m/z 474.23992 [M]+. C30H34O5.
Calculated: M 474.24061.
(OMe), 111.10 (C8′), 112.95 (C8), 120.80 (C6), 123.98
(C4), 125.56 (C10a), 129.48 (C2), 129.65 (C5), 130.19
(C9a), 134.93 (C4a), 136.87 (C8a), 140.78 (C1), 150.91
(C7′), 153.70 (C3), 162.0 (C2), 177.05 (C=O), 182.64
(C10), 185.08 (C9). Mass spectrum: m/z 488.25821
[M]+. C31H36O5. Calculated: M 488.25626.
(1R,3R)-2-[2-(6-Hydroxy-3-isopropyl-9,10-dioxo-
9,10-dihydroanthracen-1-yl)ethyl]-1,3-dimethyl-
3-vinylcyclohexane-1-carboxylic acid (X). [α]D20
=
Methyl (1R,3R)-2-[2-(6-hydroxy-3-isopropyl-
9,10-dioxo-9,10-dihydroanthracen-1-yl)ethyl]-1,3-
dimethyl-3-vinylcyclohexane-1-carboxylate (Xa).
mp 162–165°C (from ethyl acetate), [α]D20 = –34.1° (c =
7.3, CHCl3). UV spectrum, λmax, nm (logε): 214 (3.22),
–42.2° (c = 5.5, CHCl3). IR spectrum, ν, cm–1: 3300,
3271, 1692, 671, 1670, 1583, 1302, 1076, 898, 858,
758, 724. UV spectrum, λmax, nm (logε): 215 (4.39),
1
271 (4.53), 347 (3.75). H NMR spectrum, δ, ppm:
1
271 (3.33), 342 (2.60), 464 (1.72). H NMR spectrum,
1.12 s (3H, 6′-CH3), 1.25 d and 1.28 d (3H each,
C16H3, C17H3, J = 7.0 Hz), 1.30 s (3H, 2′-CH3), 1.39–
1.70 m (6H, 1a′-H, 4′-H, 5′-H), 1.91 m (1H, 3′-H),
2.18 m (2H, 1′-H, 3′-H), 2.72 m (2H, 1b′-H), 2.85 m
(1H, 15-H), 4.86 m and 4.92 m (1H each, 8′-H), 5.65–
5.75 m (1H, 7′-H), 6.82 d (1H, 7-H, J = 7.0, 1.5 Hz),
7.28 d (1H, 4-H, J = 1.8 Hz), 7.68 d (1H, 2-H, J =
1.8 Hz), 7.80 d (1H, 5-H, J = 1.5 Hz), 7.84 d (1H, 8-H,
J = 7.0 Hz), 8.9 br.s (1H, OH), 10.30 br.s (1H, OH).
13C NMR spectrum, δC, ppm: 18.23 (C4′), 18.28 and
18.91 (C10′, C11′), 23.23 and 23.36 (C16, C17), 29.82
(C1a′), 33.16 (C15), 34.12 (C1b′), 35.89 (C3′), 38.52 (C5′),
39.91 (C6′), 45.94 (C2′), 47.85 (C1′), 111.65 (C8′),
113.39 (C5), 121.09 (C7), 124.78 (C4), 125.62 (C8a),
129.12 (C2), 129.83 (C8), 130.95 (C9a), 133.51 (C4a),
136.25 (C10a), 139.12 (C1), 151.06 (C8′), 154.91 (C3),
161.92 (C6), 183.75 (C10), 185.00 (COOH), 185.98
(C9). Mass spectrum: m/z 474.24033 [M]+. C30H34O5.
Calculated: M 474.24061.
δ, ppm: 1.21 d and 1.26 d (3H each, C16H3, C17H3, J =
7 Hz), 1.12 s and 1.33 s (3H each, 2′-CH3, 6′-CH3),
1.37–1.62 m (5H, 1a′-H, 4′-H, 5′-H), 1.80 m (2H, 3′-H,
5′-H), 1.88–2.12 m (2H, 1′-H, 3′-H), 2.93 m (2H,
1b′-H), 2.96 m (1H, 15-H), 3.67 s (3H, OCH3), 4.81–
4.90 m (2H, 8′-H), 5.79 m (1H, 7′-H), 7.08 d.d (1H,
7-H, J = 6.8, 1.3 Hz), 7.35 d (1H, 4-H, J = 1.8 Hz),
7.47 d (1H, 5-H, J = 1.3 Hz), 7.96 d (1H, 2-H, J =
1.8 Hz), 8.08 d (1H, 8-H, J = 6.8 Hz), 8.80 br.s (1H,
OH). 13C NMR spectrum, δC, ppm: 18.12 (C4′), 18.21
and 18.96 (C10′, C11′), 23.18 and 13.29 (C16, C17), 29.99
(C1a′), 33.26 (C15), 35.08 (C1b′), 37.51 (C3′), 40.01 (C5′),
41.16 (C6′), 46.02 (C2′), 47.05 (C1′), 51.95 (OCH3),
111.10 (C8′), 112.09 (C5), 120.12 (C7), 124.08 (C4),
125.26 (C8a), 129.41 (C2), 129.76 (C5), 130.39 (C9a),
135.09 (C4a), 136.42 (C10a), 141.09 (C1), 150.68 (C7′),
152.72 (C3), 161.68 (C6), 176.88 (C=O), 183.34 (C10),
184.98 (C9). Mass spectrum: m/z 488.25821 [M]+.
C31H36O5. Calculated: M 488.25626.
Methyl (1R,3R)-2-[2-(7-hydroxy-3-isopropyl-
9,10-dioxo-9,10-dihydroanthracen-1-yl)ethyl]-1,3-
dimethyl-3-vinylcyclohexane-1-carboxylate (IXb).
mp 148–151°C (from ethyl acetate), [α]D20 = –29.5° (c =
5.3, CHCl3). UV spectrum, λmax, nm (logε): 214 (3.22),
271 (3.33), 342 (2.60), 464 (1.72). IR spectrum, ν,
8-Hydroxy-24-isopropyl-5,9-dimethyl-14,21-di-
oxohexacyclo[10.6.2.01,10.04,9.013,22.015,20]tetracosa-
13(22),15,17,19-tetraene-5-carboxylic acid (XIa,
6,12b-etheno-10-hydroxy-16-isopropyl-1,4-dimeth-
yl-7,12-dioxo-1,1a,2,3,4,4a,4b,5,6,7,12,12b,13,14-
tetradecahydrobenzo[b]chrysene-1-carboxylic
1
cm–1: 3372 (OH); 1669, 1724 (C=O). H NMR spec-
trum, δ, ppm: 1.21 d and 1.24 d (3H each, C16H3,
C17H3, J = 7 Hz), 1.12 s and 1.30 s (3H each, 2′-CH3,
6′-CH3), 1.47–1.62 m (5H, 1a′-H, 4′-H, 5′-H), 1.78–
1.92 m (2H, 5′-H, 3′-H), 2.10 m (2H, 1′-H, 3′-H),
2.76 m (2H, 1b′-H), 2.92 m (1H, 15-H), 3.67 s (3H,
OCH3), 4.81–4.90 m (2H, 8′-H), 5.79 m (1H, 7′-H),
7.08 d.d (1H, 6-H, J = 6.8, 1.5 Hz), 7.37 d (1H, 4-H,
J = 1.8 Hz), 7.57 d (1H, 8-H, J = 1.5 Hz), 8.03 d (1H,
5-H, J = 6.8 Hz), 8.10 d (1H, 2-H, J = 1.8 Hz),
8.88 br.s (1H, OH). 13C NMR spectrum, δC, ppm:
18.03 (C4′), 18.12 and 19.08 (C10′, C11′), 23.30 (C16,
C17), 29.32 (C1a′), 33.42 (C15), 34.50 (C1b′), 35.79 (C3′),
39.69 (C5′), 40.09 (C6′), 45.84 (C2′), 47.56 (C1′), 51.95
acid). mp 142–144°C (from ethyl acetate), [α]D20
=
1
–28.6° (c = 3.0, CHCl3). H NMR spectrum, δ, ppm:
0.68 (3H, 4a-CH3), 0.97 d and 1.02 d (3H each, C17H3,
C18H3, J = 7 Hz), 1.17 s (3H, 1-CH3), 1.11–1.52 m
(9H, 2-H, 3-H, 4-H, 4a-H, 5-H, 14-H), 1.70–2.12 m
(4H, 3-H, 4-H, 13-H, 14a-H), 2.47 m (1H, 16a-H),
2.58 m (1H, 13-H), 3.88 m (1H, 6-H), 5.58 s (1H,
15-H), 7.03 d.d (1H, 8-H, J = 8.0, 1.6 Hz), 7.39 s (1H,
11-H, J = 1.6 Hz), 7.87 d (1H, 8-H, J = 8.0 Hz),
13
8.80 br.s (1H, OH), 11.85 s (1H, OH). C NMR spec-
trum, δC, ppm: 15.03 (4a-CH3), 16.12 (1-CH3), 17.28
(C3), 21.38 and 21.62 (C17, C18), 21.92 (C14), 27.85
(C5), 32.20 (C16a), 32.48 (C12b), 36.48 (C13), 37.62 (C6),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 1 2009