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CH), 129.9 (2 CH), 130.1 (CH), 130.5 (C), 131.1 (C), 133.5
(CH), 138.2 (C), 147.1 (C), 166.1 (C) ppm; HRMS:
m/z calcd. for [M ? H]? ([C24H24NO4]?) 390.1700, found
390.1698; EI-MS: m/z (%) = 389 (M?, 52), 268 (33).
H-7 and H-15), 2.05 (s, Ac, 3H), 2.22 (td, J = 12.2,
3.6 Hz, H-16), 2.35 (m, H-14), 2.40 (s, NCH3), 2.45 (dd,
J = 18.6, 5.5 Hz, H-10), 2.58 (dd, J = 12.2, 4.3 Hz,
H-16), 3.07 (d, J = 18.6 Hz, H-10), 3.16 (m, H-9), 4.70
(d, J = 6.0 Hz, H-5), 5.53 (m, H-6), 6.57 (d, J = 8.1 Hz,
H-2), 6.63 (d, J = 8.1 Hz, H-1), 7.28 (t, J = 7.8 Hz,
benzoyl H-meta), 7.43 (t, J = 7.9 Hz, benzoyl H-para),
7.48 (d, J = 7.5 Hz, benzoyl H-ortho) ppm; 13C NMR
(151 MHz, CDCl3): d = 18.6 (CH2), 20.5 (CH2), 21.6
(CH2), 26.4 (CH2), 34.3 (CH2), 39.5 (CH2), 41.1 (NCH3),
41.5 (CH), 47.7 (C), 61.0 (CH), 67.9 (CH), 87.4 (CH),
119.0 (CH), 123.0 (CH), 127.3 (C), 128.0 (2 CH), 129.7 (2
CH), 130.4 (C), 131.2 (C), 133.1 (CH), 136.7 (C), 149.6
(C), 165.1 (C), 171.1 (C) ppm; HRMS: m/z calcd. for
[M ? H]? ([C26H28NO5]?) 434.1962, found 434.1957;
EI-MS: m/z (%) = 433 (M?, 5), 391 (8).
4,5-Epoxy-3-methoxy-17-methyl-(5a,6a)-morphinane-6-ol
benzoate (5a, C25H27NO4)
Yields: 72 % (NEt3), 76 % (DMAP); m.p.: 163 °C (ether);
1H NMR (600 MHz, CDCl3): d = 1.35 (m, H-8), 1.57 (m,
H-8), 1.70 (t, J = 13.5 Hz, H-7), 1.88 (d, J = 12.5 Hz,
H-15), 1.98 (d, J = 14.9 Hz, H-7), 2.47 (t, J = 12.4 Hz,
H-15), 2.74 (t, J = 12.3 Hz, H-16), 2.88 (s, NCH3), 3.06
(m, H-14), 3.09 (dd, J = 18.9, 5.1 Hz, H-10), 3.20 (d,
J = 18.9 Hz, H-10), 3.29 (d, J = 12.3 Hz, H-16), 3.31 (s,
OCH3), 3.89 (br s, H-9), 4.79 (d, J = 6.2 Hz, H-5), 5.68
(m, H-6), 6.60 (d, J = 8.2 Hz, H-1), 6.76 (d, J = 8.2 Hz,
H-2), 7.26 (t, J = 7.7 Hz, benzoyl H-meta), 7.34 (t,
J = 7.8 Hz, benzoyl H-para), 7.46 (d, J = 7.4 Hz, ben-
zoyl H-ortho) ppm; 13C NMR (151 MHz, CDCl3):
d = 20.5 (CH2), 21.8 (CH2), 28.2 (CH2), 37.6 (CH2),
43.1 (NCH3), 44.0 (CH), 44.3 (C), 48.3 (CH), 56.4 (OCH3),
60.6 (CH), 69.7 (CH), 89.4 (CH), 116.3 (CH), 120.3 (CH),
127.9 (C), 128.1 (2 CH), 129.3 (2 CH), 131.3 (C), 133.4
(C), 134.1 (CH), 140.4 (C), 147.3 (C), 166.8 (C) ppm;
HRMS: m/z calcd. for [M ? H]? ([C25H28NO4]?)
406.2013, found 406.2020; EI-MS: m/z (%) = 405 (M?,
35), 300 (15).
7,8-Didehydro-4,5-epoxy-17-methyl-(5a,6a)-morphinan-
3,6-diol 3-acetate 6-benzoate (6a, C26H25NO5)
Yield: 74 %; m.p.: 115–117 °C (ether); 1H NMR
(600 MHz, CDCl3): d = 1.98 (s, Ac, 3H), 2.00 (d,
J = 12.6 Hz, H-15), 2.35 (td, J = 12.9, 4.7 Hz, H-15),
2.60 (td, J = 12.6, 4.1 Hz, H-16), 2.66 (s, NCH3), 3.04 (dd,
J = 12.8, 3.7 Hz, H-16), 3.13 (d, J = 19.1 Hz, H-10), 3.18
(m, H-14), 3.62 (dd, J = 19.0, 6.0 Hz, H-10), 3.83 (m,
H-9), 5.31 (d, J = 7.1 Hz, H-5), 5.42 (s, H-6), 5.51 (d,
J = 10.0 Hz, H-8), 5.82 (d, J = 10.0 Hz, H-7), 6.66 (d,
J = 8.1 Hz, H-1), 6.81 (d, J = 8.1 Hz, H-2), 7.45 (t,
J = 7.7 Hz, benzoyl H-meta), 7.57 (t, J = 7.7 Hz, benzoyl
H-para), 8.09 (d, J = 7.8 Hz, benzoyl H-ortho) ppm; 13C
NMR (151 MHz, CDCl3): d = 20.5 (CH2), 20.9 (CH3),
32.1 (CH2), 37.3 (CH2), 40.4 (NCH3), 43.2 (C), 46.4 (CH),
60.1 (CH), 61.3 (CH), 90.2 (CH), 119.7 (CH), 121.3 (CH),
126.0 (C), 128.6 (CH), 128.9 (2 CH), 129.2 (C), 129.9 (2
CH), 131.2 (C), 132.3 (CH), 133.3 (CH), 136.1 (C), 145.2
(C), 165.8 (C), 170.5 (C) ppm; HRMS: m/z calcd. for
[M ? H]? ([C26H26NO5]?) 432.1805, found 432.1798;
EI-MS: m/z (%) = 431 (M?, 3).
4,5-Epoxy-17-methyl-(5a,6a)-morphinan-3,6-diol
6-benzoate (5b, C24H25NO4)
1
Yield: 66 %; m.p.: 253–255 °C (ethyl acetate); H NMR
(600 MHz, CDCl3): d = 1.30 (m, H-8), 1.42 (m, H-8), 1.52
(m, H-7), 1.67 (d, J = 12.5 Hz, H-15), 1.88–1.90 (m, H-7
and H-15), 2.25 (td, J = 12.2, 3.6 Hz, H-16), 2.30 (m,
H-14), 2.39 (s, NCH3), 2.46 (dd, J = 18.6, 5.5 Hz, H-10),
2.56 (dd, J = 12.2, 4.3 Hz, H-16), 3.04 (d, J = 18.6 Hz,
H-10), 3.14 (m, H-9), 4.69 (d, J = 6.0 Hz, H-5), 5.52 (m,
H-6), 6.57 (d, J = 8.1 Hz, H-2), 6.63 (d, J = 8.1 Hz, H-1),
7.28 (t, J = 7.8 Hz, benzoyl H-meta), 7.43 (t, J = 7.9 Hz,
benzoyl H-para), 7.48 (d, J = 7.5 Hz, benzoyl H-ortho)
ppm; 13C NMR (151 MHz, CDCl3): d = 20.4 (CH2), 21.5
(CH2), 28.0 (CH2), 37.8 (CH2), 43.2 (NCH3), 43.6 (CH),
44.1 (C), 48.5 (CH), 60.9 (CH), 70.0 (CH), 88.8 (CH),
118.2 (CH), 120.2 (CH), 126.7 (C), 128.2 (2 CH), 130.3
(C), 131.0 (2 CH), 132.5 (C), 134.1 (CH), 139.4 (C), 146.3
(C), 166.8 (C) ppm; HRMS: m/z calcd. for [M ? H]?
([C24H26NO4]?) 392.1856, found 392.1853; EI-MS:
m/z (%) = 391 (M?, 27).
7,8-Didehydro-4,5-epoxy-17-(2-propenyl)-(5a,6a)-
morphinan-3,6-diol 3-acetate 6-benzoate
(6b, C28H27NO5)
Yield: 62 %; m.p.: 97–99 °C (p. ether); 1H NMR (600
MHz, CDCl3): d = 1.87 (s, Ac, 3H), 1.99 (d, J = 12.6 Hz,
H-15), 2.31 (td, J = 12.7, 4.7 Hz, H-15), 2.52 (td,
J = 12.6, 3.5 Hz, H-16), 2.55 (td, J = 19.0, 5.9 Hz,
H-10), 3.08 (d, J = 18.9 Hz, H-10), 3.10–3.13 (m, H-14
and H-16), 3.43 (m, 1H of allyl), 3.53 (m, 1H of allyl), 3.93
(dd, J = 5.8, 3.1 Hz, H-9), 5.30 (m, H-5 and 1H of allyl),
5.34 (d, J = 16.2 Hz, 1H of allyl), 5.42 (m, H-6), 5.51 (d,
J = 10.0 Hz, H-8), 5.80 (d, J = 10.0 Hz, H-7), 6.03 (m,
1H of allyl), 6.63 (d, J = 8.1 Hz, H-1), 6.81 (d,
J = 8.1 Hz, H-2), 7.44 (t, J = 7.7 Hz, benzoyl H-meta),
7.57 (t, J = 7.6 Hz, benzoyl H-para), 8.07 (d, J = 7.8 Hz,
4,5-Epoxy-17-methyl-(5a,6a)-morphinan-3,6-diol
3-acetate 6-benzoate (5c, C26H27NO5)
Yield: 56 %; m.p.: 120–122 °C (p.ether); 1H NMR
(600 MHz, CDCl3): d = 1.35 (m, H-8), 1.40 (m, H-8),
1.55 (m, H-7), 1.64 (d, J = 12.5 Hz, H-15), 1.90–1.80 (m,
123