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Helvetica Chimica Acta – Vol. 89 (2006)
8-[(1E)-2-Phenylethenyl]thebaine (=(5a)-6,7,8,14-Tetradehydro-4,5-epoxy-3,6-dimethoxy-17-meth-
yl-8-[(1E)-2-phenylethyl]morphinan; 11). A soln. of 4 (0.1 g, 0.223 mmol) in toluene (30 ml) was heated
on an oil bath, with concomitant very slow (5 h) distillation of toluene. The volume of toluene in the reac-
tion flask must not be less then 10 ml (additional toluene should be added, if necessary). Then the mixture
was evaporated and the residue dried in vacuo: 11 (0.09 g, 98%). Solid foam. M.p. 83–868. 1H-NMR: 7.39
(br. d, 2 Ho of Ph); 7.31 (m, 2 Hm of Ph); 7.21 (tt, Hp of Ph); 7.02 (d, J(18,19)=16.0, HꢀC(18)); 6.65 (d,
HꢀC(19)); 6.65 (d, J(1,2)=8.2, HꢀC(2)); 6.59 (d, HꢀC(1)); 5.51, 5.25 (2s, HꢀC(5), HꢀC(7)); 4.29 (d,
J(9,10a)=6.7, HꢀC(9)); 3.84 (s, MeO); 3.73 (s, MeO); 3.35 (d, J(10a,10b)=17.9, HbꢀC(10)); 2.87
(ddd, J(16ax,16eq)=12.6, J(15ax,16ax)=12.6, J(15eq,16ax)=3.6, HaxꢀC(16)); 2.69 (dd, HaꢀC(10));
2.64 (m, HeqꢀC(16)); 2.52 (s, MeN); 2.26 (ddd, J(15ax,15eq)=12.6, J(15ax,16eq)=12.6, J(15ax,
16eq)=5.2, HaxꢀC(15)); 1.78( m, HeqꢀC(15)). MS: 413 (M+). Anal. calc. for C27H27NO3 (413.2): C
78.42, H 6.58, N 3.39; found: C 77.78, H 6.60, N 3.21.
8-[(1E)-2-Phenylethenyl]codeinone (=(5a)-7,8-Didehydro-4,5-epoxy-3-methoxy-17-methyl-8-[(1E)-
2-phenylethenyl]morphinan-6-one; 10). Ketal 4 (0.2 g, 0.45 mmol) was stirred at r.t. in 20% aq. HCl
soln. (20 ml) for 30 min. The mixture was quenched with CHCl3 (10 ml), cooled to 0–58, and made alka-
line (pH 9) with conc. NH4OH soln. The aq. layer was washed with CHCl3 (210 ml), the combined
organic extract dried (Na2SO4) and evaporated, and the oily residue purified by prep. TLC (silica gel,
1
CHCl3/MeOH/NH4OH 320 :10 :1): 10 (0.16 g, 89%). M.p. 1208 (from heptane/AcOEt 5 :1). H-NMR:
7.32–7.44 (m, Ph); 6.98( d, J(18,19)=16.0, HꢀC(18)); 6.78 (d, HꢀC(19)); 6.67 (d, J(1,2)=8.2, Hꢀ
C(2)); 6.57 (d, HꢀC(1)); 6.31 (d, J(7,14)=2.2, HꢀC(7)); 4.70 (s, HꢀC(5)); 3.86 (s, MeO); 3.72 (m,
HꢀC(9)); 3.42 (m, HꢀC(14)); 3.00 (d, J(10a,10b)=18.1, HbꢀC(10)); 2.64 (m, J(16ax,16eq)=11.8,
HeqꢀC(16)); 2.48( s, MeN); 2.30 (ddd, J(16ax,16eq)=12.3, J(15ax,16ax)=12.3, J(15eq,16ax)=4.0,
HaxꢀC(16)); 2.28( dd, J(9,10a)=5.7, HaꢀC(10)); 2.10 (ddd, J(15ax,15eq)=12.2, J(15ax,16ax)=12.2,
J(15ax,16eq)=4.7, HaxꢀC(15)); 1.90 (m, HeqꢀC(15)). MS: 399 (M+). Anal. calc. for C26H25NO3
(399.18): C 78.17, H 6.31, N 3.51; found: C 77.60, H 6.24, N 3.42.
1-{(5a,6a,7a,14a)-4,5-Epoxy-3,6-dimethoxy-17-methyl-19-[(1E)-2-phenylethenyl]-6,14-ethenomor-
phinan-7-yl)ethanone (14). A mixture of 4 (50 mg, 0.112 mmol) and methyl vinyl ketone (0.07 ml, 0.864
mmol) was refluxed in toluene (5 ml) for 6 h. After evaporation the products were separated by prep.
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TLC (silica gel, CHCl3/MeOH/NH4OH 320 :9 :1): 14 (50 mg, 87%). Colorless solid. M.p. 65–688. H-
NMR: 7.18–7.29 (m, Ph); 6.59 (d, J(1,2)=8.2, HꢀC(2)); 6.39 (d, HꢀC(1)); 6.31, 5.98(2 d, J(20,
21)=15.6, HꢀC(20), HꢀC(21)); 5.96 (s, HꢀC(18)); 4.58 (s, HꢀC(5)); 3.84 (s, MeO); 3.62 (s, MeO);
3.39 (d, J(9,10a)=6.8, HꢀC(9)); 3.15 (d, J(10a,10b)=18.6, HbꢀC(10)); 3.06 (dd, J(7,8b)=9.4, Hbꢀ
C(8)); 2.95 (m, HꢀC(7)); 2.51 (m, HeqꢀC(16)); 2.49 (dd, HaꢀC(10)); 2.39 (ddd, J(16ax,16eq)=12.0,
J(15ax,16ax)=12.0, J(15eq,16ax)=4.2, HaxꢀC(14)); 2.37 (s, MeN); 2.11 (s, Ac); 1.98( ddd, J(15ax,
15eq)=12.5, J(15ax,16ax)=12.4, J(15ax,16eq)=5.8, HaxꢀC(15)); 1.92 (m, HeqꢀC(15)); 1.41 (dd, J(8a,
8b)=12.5, J(7,8a)=6.6, HaꢀC(8)). MS: 483 (M+), 413 ([MꢀC4H6O]+), 70 (C4
N
G
C31H33NO4 (483.24): C 76.99, H 6.88, N 2.90; found: C 76.80, H 6.82, N 2.61.
Crystals of 14 for X-ray diffraction analysis were obtained by crystallization from a benzene soln.
after very slow addition of hexane until the formation of a slightly turbid soln. occurred by standing at
r.t. overnight. The product precipitated as 14·C6H6. M.p. 88–908.
8-[(1E)-2-Phenyletheny])codeine
(=(5a,6a)-7,8-Didehydro-4,5-epoxy-3-methoxy-17-methyl-8-
[(1E)-2-phenylethenyl]morphinan; 5). NaBH4 (0.10 g, 2.64 mmol) was added in small portions to a stirred
soln. of 10 (0.20 g, 0.50 mmol) in MeOH (8ml). After stirring for 1 h at r.t., the mixture was concentrated
to ca. 13 of the initial volume and diluted with 10% aq. NaOH soln. (10 ml) and CHCl3 (15 ml). The result-
ing mixture was heated momentarily to boiling and diluted with H2O (10 ml), the aq. soln. extracted with
CHCl3 (28ml), the combined org. phase dried (Na 2SO4) and evaporated, and the oily residue purified
by prep. TLC (silica gel, CHCl3/MeOH/NH4OH 250 :10 :1): 5 (170 mg, 83%). M.p. 187–1888 (from
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MeOH). H-NMR: 7.26–7.29 (m, 2 Ho, 2 Hm of Ph); 7.18–7.23 (m, Hp of Ph); 6.64 (d, J(1,2)=8.2, Hꢀ
C(2)); 6.51 (d, HꢀC(1)); 6.36, 6.43 (2d, J(18,19)=15.9, HꢀC(18), HꢀC(19)); 5.87 (br. s, HꢀC(7));
4.87 (dd, J(5,6)=6.5, J(5,7)=1.0, HꢀC(5)); 4.26 (m, HꢀC(6)); 3.85 (s, MeO); 3.64 (dd, J(9,10a)=6.4,
J(9,14)=3.0, HꢀC(9)); 2.98( d, J(10a,10b)=18.6, HbꢀC(10)); 2.93 (br. s, OH); 2.84 (m, HꢀC(14));
2.58( ddd, J(16ax,16eq)=12.3; J(15eq,16eq)=1.0, HeqꢀC(16)); 2.45 (s, MeN); 2.38( ddd, J(15eq,