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15. Kim, H. C.; Park, B. K.; Hong, S. Y.; Jhoo, W. K. Meth.
Find. Exp. Clin. Pharmacol. 1997, 19, 627.
16. Orrel, M.; Camphell, P. G. Br. Med. J. 1986, 293, 1242.
17. Su, T. P. Eur. J. Biochem. 1991, 200, 633.
18. Rammer, L.; Hormgren, P.; Sander, H. Forensic Sci. Int.
1988, 37, 766.
3.24–3.11 (m, 2H), 2.92 (m, 2H), 2.62–2.52 (m, 2H), 2.34 (d,
J=12.57 Hz, 1H), 2.03 (td, 1H), 1.83 (q, J=9.70 Hz, 1H), 1.74
(td, 1H), 1.63 (q, J=2.52 Hz, 1H), 1.50 (t, J=8.83 Hz, 1H),
1.49–1.27 (m, 5H), 1.12 (m, 1H); 13C NMR (100 MHz, CDCl3)
d 158.16, 141.78, 135.95, 129.74, 128.42, 117.36, 111.06,
110.62, 58.28, 55.81, 55.15, 45.45, 45.05, 41.81, 37.77, 36.59,
26.79, 26.54, 23.84, 22.21; IR (film) 2900, 1810, 1500, 1460,
1370, 1280, 1240, 1180, 1110, 1030, 920, 860 cmÀ1. 3-Allyloxy-
morphinan (8): 1H NMR (400 MHz, CDCl3) d 7.01 (d, J=3.83
Hz, 1H), 6.82 (d, J=3.14 Hz, 1H), 6.70 (m, 1H), 6.05 (m, 1H),
5.41 (d, J=17.35, 1H), 5.27 (d, J=10.35 Hz, 1H), 4.50 (q, 2H),
4.11 (q, J=7.12 Hz, 1H), 3.14–2.95 (m, 2H), 2.79–2.57 (m,
3H), 2.39 (s, 1H), 2.28 (t, J=9.54 Hz, 1H), 2.04 (s, 2H), 1.74
(q, J=3.26 Hz, 1H), 1.65–1.49 (m, 3H), 1.41–1.30 (m, 5H),
1.25 (t, J=7.07 Hz, 2H), 1.11–1.03 (m, 1H); 13C NMR
(100 MHz, CDCl3) d 157.22, 141.71, 133.63, 130.25, 128.50,
117.62, 112.06, 111.56, 68.87, 51.17, 45.99, 42.73, 39.23, 38.31,
37.03, 33.62, 26.89, 26.76, 22.14; IR (film) 3900, 3800, 3700,
3100, 2950, 2850, 2700, 2400, 2300, 1700, 1300, 1250 cmÀ1. 3-
Allyloxy-17-cyclopropylmethylmorphinan (9): 1H NMR
(400 MHz, CDCl3) d 6.98 (d, J=8.36 Hz, 1H), 6.83 (d, J=2.56
Hz, 1H), 6.68 (q, J=8.40 Hz, 1H), 6.05 (m, 1H), 5.40 (q,
J=1.51 Hz, 1H), 5.28 (q, J=1.29 Hz, 1H), 3.08 (s, 1H), 2.88
(d, J=18.12 Hz, 1H), 2.70 (q, 1H), 2.57 (q, 1H), 2.48 (q, 1H),
2.31 (t, 2H), 2.00 (m, 1H), 1.86 (d, J=12.69 Hz, 1H), 1.76 (m,
1H), 1.56 (m, 2H), 1.43–1.21 (m, 7H), 1.14 (m, 1H), 0.06 (m,
2H), 0.49 (m, 2H), 0.10 (m, 2H); 13C NMR (100 MHz, CDCl3)
d 157.19, 141.96, 133.63, 130.16, 128.39, 117.62, 111.93,
111.50, 68.86, 60.00, 55.86, 45.80, 45.13, 41.93, 37.92, 36.69,
26.91, 26.64, 23.91, 22.29, 9.45, 4.09, 3.64; IR (film) 3944,
3757, 3691, 3054, 2987, 2932, 2685, 2521, 2410, 2305, 2254,
1422, 1254, 1155 cmÀ1. 3-Cyclopropylmethoxy-17-allylmorphi-
19. Kim, H. C.; Jhoo, W. K.; Kwon, M. S.; Hong, J. S. Arch.
Pharm. Res. 1995, 18, 267.
20. Sperk, G. Prog. Neurobiol. 1994, 42, 1.
21. 3-Methoxymorphinan HCl (3): 1H NMR (400 MHz,
.
DMSO-d6) d 9.45 (d, J=19.36 Hz, 2H), 7.22 (d, J=8.34 Hz,
1H), 6.93 (d, 1H), 6.90 (dd, 1H), 3.83 (s, 3H), 3.70 (s, 1H), 3.19
(m, 1H), 3.11 (s, 1H), 3.07 (s, 1H), 2.52 (d, 2H), 2.03 (q, 1H),
1.88 (m, 1H), 1.70 (d, J=12.13 Hz, 1H), 1.57 (t, 3H), 1.41 (td,
2H), 1.23 (t, 1H), 1.00 (qd, 1H); 13C NMR (100 MHz, DMSO-
d6) d 158.44, 138.98, 129.04, 126.33, 112.07, 110.84, 55.01,
49.87, 40.32, 37.84, 36.86, 36.18, 35.15, 27.15, 25.45, 25.06,
21.45. 4-Hydroxymorphinan HBr (4): 1H NMR (400 MHz,
.
DMSO-d6) d 9.24 (s, 1H), 8.82 (s, 1H), 7.00 (d, J=8.26 Hz,
1H), 6.71 (s, 1H), 6.64 (q, 1H), 3.65 (s, 1H), 3.07 (m, 2H), 2.90
(d, J=18.9 Hz, 1H), 2.46 (d, J=9.05 Hz, 1H), 2.30 (d,
J=13.45 Hz, 1H), 1.88 (d, J=12.29, 1H), 1.73 (td, 1H), 1.55
(dd, 2H), 1.43 (d, J=12.48 Hz, 2H), 1.31 (m, 2H), 1.08 (m,
1H), 0.91 (m, 1H); 13C NMR (100 MHz, DMSO-d6) d 156.43,
138.63, 128.93, 124.26, 113.97, 111.55, 50.15, 40.44, 38.81,
37.92, 37.14, 35.94, 35.19, 27.20, 25.44, 25.04, 21.44. 3-Allyl-
oxy-17-methylmorphinan (5): 1H NMR (400 MHz, CDCl3) d
7.00 (d, J=8.3 Hz, 1H), 6.82 (d, J=2.5 Hz, 1H), 6.69 (q,
J=8.3 Hz, 1H), 6.05 (m, J=5.2 Hz, 1H), 5.34 (q, 2H), 4.50 (d,
J=5.3 Hz, 2H), 2.96 (d, J=18.1 Hz, 1H), 2.80 (m, 1H), 2.57
(q, J=5.7 Hz, 1H), 2.38 (m, J=5.7 Hz, 1H), 2.38 (m, 5H),
2.08 (m, 1H), 1.82 (q, 1H), 1.73 (m, 1H), 1.63 (d, 1H), 1.51 (d,
1H), 1.25 (m, 6H); 13C NMR (100 MHz, CDCl3) d 156.2,
140.7, 132.6, 129.0, 127.4, 116.5, 110.9, 110.5, 67.8, 57.0, 46.3,
44.4, 41.8, 41.1, 36.2, 35.7, 25.8, 25.6, 22.3, 21.2; IR (film)
2900, 1810, 1500, 1460, 1370, 1280, 1240, 1180, 1110, 1030,
920, 860 cmÀ1. 3-Cyclopropylmethoxy-17-methylmorphinan (6):
1H NMR (400 MHz, CDCl3) d 7.00 (d, J=8.4 Hz, 1H), 6.82
(d, J=2.4 Hz, 1H), 6.67 (q, 1H), 3.76 (d, J=6.9 Hz, 2H), 2.97
(d, J=18.1 Hz, 1H), 2.80 (m, 1H), 1.82 (t, 1H), 1.73 (m, 1H),
1.63 (d, 1H), 1.50 (d, 1H), 1.25 (m, 7H), 0.63 (m, 2H), 0.34 (q,
2H); 13C NMR (100 MHz, CDCl3) d 158.0, 142.0, 130.2, 128.8,
112.2, 111.6, 73.1, 58.4, 47.7, 45.8, 43.2, 42.5, 37.6, 37.0, 27.2,
27.0, 23.7, 22.7, 10.8, 3.6, 3.5; IR (film) 2900, 1800, 1500, 1450,
1280, 1240, 1150, 1100, 1020, 860, 800 cmÀ1. 3-Methoxy-17-
allylmorphinan (7): 1H NMR (400 MHz, CDCl3) d 7.02 (d,
J=8.36 Hz, 1H), 6.80 (d, J=2.61 Hz, 1H), 6.69 (q, J=8.36
Hz, 1H), 5.94–5.85 (m, 1H), 5.22–5.11 (m, 2H), 3.78 (s, 3H),
1
nan (10): H NMR (400 MHz, CDCl3) d 7.00 (d, J=8.33 Hz,
1H), 6.82 (d, J=2.56 Hz, 1H), 6.67 (q, 1H), 5.88 (m, 1H), 5.18
(q, 1H), 5.11 (s, J=10.18 Hz, 1H), 3.76 (d, J=6.94 Hz, 2H),
3.15 (m, 2H), 3.91 (t, 2H), 2.55 (m, 2H), 2.35 (t, 1H), 2.03 (m,
2H), 1.81 (d, J=12.61 Hz, 1H), 1.72 (td, 1H), 1.56 (m, 2H),
1.41–1.21 (m, 4H), 1.14 (m, 1H), 0.63 (m, 2H), 0.34 (q, 2H);
13C NMR (100 MHz, CDCl3) d 157.57, 141.85, 136.26,
129.87, 128.34, 117.10, 111.87, 111.79, 72.70, 58.34, 55.81,
45.45, 45.22, 41.93, 37.82, 36.63, 26.83, 26.59, 23.87, 22.28,
10.36, 3.17, 3.12; IR (film) 3944, 3757, 3691, 3052, 2987,
2685, 2521, 2410, 2305, 1551, 1422, 1252, 1156, 909, 693
cmÀ1
.
22. Kim, H. C.; Jhoo, W. K.; Ko, K. H.; Kim, W. K.; Bing,
G.; Kwon, M. S.; Shin, E. J.; Suh, J. H.; Lee, Y. G.; Lee, D. W.
Life Sci. 2000, 66, 317.
23. Racine, R. J. EEG Clin. Neurophysiol. 1972, 32, 281.