HETEROCYCLES, Vol. 90, No. 1, 2015
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Hz, 6-H), 3.30 (1H, dd, J = 17.2, 3.4 Hz, 14-Hα), 3.50 (3H, s, 13-OCH3), 3.55 (3H, s, 4-OCH3), 3.61 (3H,
s, 2-OCH3), 3.64 (3H, s, 11-OCH3), 3.69 (3H, s, 10-OCH3), 3.75 (3H, s, 1-OCH3), 3.99 (1H, d, J = 2.4 Hz,
15-H), 4.19-4.22 (1H, overlapped, 14a-H), 4.21 (1H, d, J = 2.4 Hz, 7-H), 4.39 (1H, t, J = 4.7 Hz, 9-H),
4.48 (1H, dd, J = 11.6, 4.7 Hz, 17-H), 4.53 (1H, dd, J = 11.6, 4.7 Hz, 17-H), 7.42 (2H, t, J = 7.5 Hz, 3'-H),
7.53 (1H, t, J = 7.5 Hz, 4'-H), 8.04 (2H, d, J = 7.5 Hz, 2'-H). C (100 MHz) 9.1 (3-CH3), 9.2 (12-CH3),
21.6 (C-5), 22.8 (C-14), 42.0 (NCH3), 53.4 (C-14a), 55.5 (C-6), 56.6 (C-9), 57.5 (C-15), 59.5 (13-OCH3),
59.5 (4-OCH3), 59.7 (2-OCH3), 59.8 (11-OCH3), 60.2 (10-OCH3), 60.3 (1-OCH3), 60.7 (C-7), 66.3
(C-17), 119.8 (CN), 122.2 (C-13a), 122.5 (C-4a), 123.1 (C-12), 123.4 (C-15a), 126.0 (C-9a), 128.3 (C-3’),
129.7 (C-2’), 130.2 (C-1’), 132.8 (C-4’), 144.1 (C-10), 147.7 (C-1), 148.5 (C-2), 148.9 (C-11), 151.2
(C-4), 151.5 (C-13), 166.3 (PhCO). EIMS m/z (%): 657 (M+, 7), 523 (8), 522 (22), 495 (22), 289 (10),
288 (59), 249 (37), 248 (100), 234 (10), 218 (14), 105 (11). HREIMS m/z calcd for C37H43N3O8,
657.3050. Found: 657.3043.
(4bS*,6aS*,7S*,13R*,13aS*)-1,3,4,9,11,12-Hexamethoxy-2,10,15-trimethyl-4b,5,6a,7,8,13,13a,14-octa-
hydro-6-oxa-14a1,15-diaza-7,13-methanobenzo[g]benzo[5,6]cycloocta[1,2,3-cd]indene (18)
Hydrazine monohydrate (2.0 mL, 40 mmol) was added to a solution of 17b (262.8 mg, 0.40 mmol) in
EtOH (10 mL) at 25 oC, and the reaction mixture was stirred at 60 oC for 3 h. As the starting material still
remained at this stage, additional hydrazine monohydrate (0.5 mL, 10 mmol) was introduced to the
o
reaction mixture and the whole was heated at 60 C for 3 h. The reaction mixture was diluted with 1 M
HCl (50 mL) and extracted with CHCl3 (3 x 50 mL). The combined extracts were washed with brine (50
mL), dried, and concentrated in vacuo to give a residue (246.9 mg), which was subjected to column
chromatography on SiO2 (10 g) with CHCl3-MeOH (98:2) to furnish 18 (198.1 mg, 94.2%) as a colorless
amorphous powder. An analytical sample was obtained by recrystallization from hexane-EtOAc as
colorless prisms, mp 105-107 oC.
max (CHCl3) 3019, 2995, 2938, 2833, 1464, 1410, 1207, 1113, 1072, 1009 cm-1. H (400 MHz) 2.15 (3H,
s, 2-CH3), 2.18 (1H, dd, J = 16.3, 12.1 Hz, 14-Hβ), 2.19 (3H, s, 10-CH3), 2.46 (3H, s, NCH3), 2.58 (1H, d,
J = 18.2 Hz, 8-Hβ), 3.08 (1H, dd, J = 16.3, 2.6 Hz, 14-Hα), 3.11 (1H, dd, J = 18.2, 8.4 Hz, 8-Hα), 3.22
(1H, ddd, J = 12.1, 2.6, 2.6 Hz, 13a-H), 3.59 (1H, dd, J = 8.4, 1.5 Hz, 7-H), 3.62 (3H, s, 1-OCH3), 3.71
(1H, dd, J = 8.7, 7.2 Hz, 5-H), 3.713 (3H, s, 9-OCH3), 3.75 (3H, s, 3-OCH3), 3.77 (3H, s, 4-OCH3), 3.78
(3H, s, 11-OCH3), 3.86 (3H, s, 12-OCH3), 4.03 (1H, d, J = 2.6 Hz, 13-H), 4.23 (1H, dd, J = 8.7, 7.2 Hz,
5-H), 4.37 (1H, t, J = 8.7 Hz, 4a-H), 4.56 (1H, d, J = 1.5 Hz, 6a-H). C (100 MHz) 9.2 (3-CH3), 9.4
(10-CH3), 21.0 (C-8), 27.2 (C-14), 41.1 (NCH3), 52.7 (C-13a), 53.3 (C-7), 55.9 (C-13), 59.5 (9-OCH3),
59.6 (1-OCH3), 59.8, 59.9, and 60.0 (3-OCH3, 4-OCH3 and 11-OCH3), 59.9 (C-4a), 60.2 (12-OCH3), 67.8