BAUMAN et al.
536
16-H), 3.19 d (1H, 8-H, J = 8.2 Hz), 3.28 d (1H, 10-H,
J = 20.0 Hz), 3.74 s (3H, 6-OCH3), 3.84 s (3H,
3-OCH3), 4.05 d (1H, 9-H, J = 8.2 Hz), 4,27 q (2H,
OCH2, J = 7.0 Hz), 4.46 d (1H, 7-H, J = 8.2 Hz),
4.72 d (1H, 5-H, J = 1.4 Hz), 5.55 d (1H, 18-H, J =
8.8 Hz), 5.78 d.d (1H, 19-H, J = 8.8, 1.5 Hz), 6.43 d
(1H, 4''b-H, J = 15.9 Hz), 6.60 d (1H, 1-H, J = 8.2 Hz),
6.68 d (1H, 2-H, J = 8.2 Hz), 7.25 d (2H, 2''-H, 6''-H,
J = 8.9 Hz), 7.55 d (2H, 3''-H, 5''-H, J = 8.9 Hz), 7.66 d
(1H, 4''a-H, J = 15.9 Hz).
5-H, J = 1.4 Hz), 5.37 d (1H, 18-H, J = 9.2 Hz),
5.81 d.d (1H, 19-H, J = 9.2, 1.4 Hz), 6.81 s (1H, 2-H),
7.01 m (2H, 2''-H, 6''-H), 7.47–7.53 m (4H, 3''-H, 5''-H,
OH). 13C NMR spectrum, δC, ppm: 24.04 (C10), 32.24
(C15), 41.15 (C8), 42.92 (17-CH3), 44.55 (C13), 44.94
(C7), 45.39 (C16), 47.92 (C14), 56.69 (C9), 75.74 (C6),
95.17 (C5), 113.38 (C1), 120.01 (C2), 122.49 (C4''),
125.85 (C11), 127.51 (2C, C2'', C6''), 129.82 (C3), 130.56
(C19), 131.84 (2C, C3'', C5''), 132.47 (C12), 133.72 (C18),
138.90 (C4), 145.67 (C1''), 175.31 (C5'), 175.90 (C2').
Mass spectrum, m/z (Irel, %): 612 [M]+ (16), 440 (11),
363 (29), 362 (60), 361 (42), 360 (100), 307 (18), 305
(16), 162 (16), 160 (21), 84 (15), 83 (23), 58 (19), 44
(59), 42 (42). Found: [M]+ 611.98961. C34H34Br2N2O7.
Calculated: M 611.989664.
Ethyl (E)-3-[4-(4,5α-epoxy-6α,14-etheno-3,6-di-
methoxy-17-methyl-2',5',7β,8β-tetrahydro-1'H-14α-
pyrrolo[3',4':7,8]morphinan-1'-yl)phenyl]prop-2-
1
enoate (XXIV). Yield 20%. H NMR spectrum, δ,
ppm: 1.30 t (3H, CH2CH3, J = 7.0 Hz), 1.86 m (1H,
15-H), 2.10–2.30 m (1H, 15-H), 2.33–2.65 m (3H,
10-H, 16-H), 2.41 s (3H, 17-CH3), 2.72–2.95 m (2H,
2'-H, 5'-H), 3.08–3.31 m (3H, 8-H, 9-H, 10-H), 3.40–
3.51 m (2H, 2'-H, 5'-H), 3.56 s (3H, 6-OCH3), 3.80 s
(3H, 3-OCH3), 3.90 d (1H, 7-H, J = 8.0 Hz), 4.21 q
(2H, OCH2, J = 7.0 Hz), 4.64 d (1H, 5-H, J = 1.5 Hz),
5.32 d (1H, 18-H, J = 8.6 Hz), 5.78 d.d (1H, 19-H, J =
8.6, 1.5 Hz), 6.18 d (1H, 4''b-H, J = 16.0 Hz), 6.41 d
(1H, 1-H, J = 9.0 Hz), 6.46–6.72 m (3H, 2''-H, 6''-H),
7.15–7.28 m (2H, 3''-H, 5''-H), 7.58 d (1H, 4''a-H,
J = 16.0 Hz).
1-Bromo-4,5α-epoxy-6α,14-etheno-3,6-dihy-
droxy-17-methyl-1'-phenyl-2',5',7β,8β-tetrahydro-
1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-dione
(XXVI) was isolated by column chromatography using
chloroform–ethanol (100:1) as eluent. Yield 67%,
1
mp 203–210°C (from diethyl ether). H NMR spec-
trum, δ, ppm: 1.78 m (1H, 15-H), 2.10 m (1H, 15-H),
2.29–2.48 m (2H, 10-H, 16-H), 2.45 s (3H, 17-CH3),
2.68 m (1H, 16-H), 2.98 d (1H, 8-H, J = 8.4 Hz),
3.10 d (1H, 10-H, J = 18.8 Hz), 3.99 d (1H, 9-H, J =
6.2 Hz), 4.38 d (1H, 7-H, J = 8.4 Hz), 4.51 d (1H, 5-H,
J = 1.4 Hz), 5.40 d (1H, 18-H, J = 8.6 Hz), 5.85 d.d
(1H, 19-H, J = 8.6, 1.4 Hz), 6.85 s (1H, 2-H), 7.11 m
(2H, 2''-H, 6''-H), 7.32–7.46 m (5H, 3''-H, 4''-H, 5''-H,
OH). 13C NMR spectrum, δC, ppm: 24.26 (C10), 32.33
(C15), 41.16 (C8), 43.11 (17-CH3), 44.81 (C13), 45.02
(C7), 45.54 (C16), 48.07 (C14), 56.83 (C9), 75.92 (C6),
95.40 (C5), 113.50 (C1), 120.12 (C2), 125.92 (C11),
126.18 (2C, C2'', C6''), 128.85 (C4''), 129.06 (2C, C3'',
C5''), 130.93 (C19), 131.02 (C3), 133.45 (C12), 133.73
(C18), 139.11 (C4), 145.88 (C1''), 176.00 (C5'), 176.53
(C2'). Mass spectrum, m/z (Irel, %): 534 [M]+ (30), 363
(27), 362 (56), 360 (51), 307 (28), 281 (30), 280 (100),
224 (21), 160 (25), 44 (57), 42 (51). Found: [M]+
534.07737. C27H23BrN2O5. Calculated: M 534.07907.
Demethylation of compounds VI and VII (gen-
eral procedure). Compound VI or VII, 2 mmol, was
dissolved in 20 ml of chloroform, and 20 ml of a 1 M
solution of BBr3 in chloroform was added under stir-
ring. The mixture was stirred for 3 h at room tempera-
ture, poured into dilute (1 : 1) aqueous ammonia,
cooled to 3–5°C, and stirred for 30 min at 0°C. The
organic phase was separated, and the aqueous phase
was extracted with chloroform (2×15 ml). The extracts
were combined with the organic phase, washed with
a saturated solution of sodium chloride, dried over
magnesium sulfate, and evaporated. The residue was
ground with diethyl ether, and the precipitate (com-
pound XXV from VI or compounds XXVI and XXVII
from VII) was filtered off. An analytical sample of
XXV was obtained by recrystallization from ethanol.
1-Bromo-4,5α-epoxy-6α,14-etheno-3-hydroxy-6-
methoxy-17-methyl-1'-phenyl-2',5',7β,8β-tetrahy-
dro-1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-di-
1-Bromo-1'-(4-bromophenyl)-4,5α-epoxy-6α,14-
etheno-3,6-dihydroxy-17-methyl-2',5',7β,8β-tetra-
hydro-1'H-14α-pyrrolo[3',4':7,8]morphinan-2',5'-
dione (XXV). Yield 94%, mp 200–205°C (from
1
one (XXVII). H NMR spectrum, δ, ppm (from the
spectrum of mixture XXVI/XXVII): 1.87–1.99 m (1H,
15-H), 1.99–2.15 m (1H, 15-H), 2.34–2.55 m (2H,
10-H, 16-H), 2.50 s (3H, 17-CH3), 2.61–2.73 m (1H,
16-H), 3.06 d (1H, 10-H, J = 18.8 Hz), 3.16 d (1H,
8-H, J = 8.2 Hz), 3.78 s (3H, OCH3), 4.04 d (1H, 9-H,
J = 6.4 Hz), 4.43 d (1H, 7-H, J = 8.2 Hz), 4.53 d (1H,
5-H, J = 1.4 Hz), 5.47 d (1H, 18-H, J = 8.6 Hz),
1
ethanol). H NMR spectrum, δ, ppm: 1.80 m (1H,
15-H), 1.98 m (1H, 15-H), 2.27–2.43 m (2H, 10-H,
16-H), 2.42 s (3H, 17-CH3), 2.55 m (1H, 16-H),
2.99 m (1H, 10-H), 3.11 m (2H, 8-H), 3.94 d (1H, 9-H,
J = 6.9 Hz); 4.35 d (1H, 7-H, J = 9.2 Hz), 4.46 d (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 4 2007