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CHERNOV et al.
q, C-15,16), 21.42 (t, C-5), 21.66 (q, CH3 at C-4'), 15 mL of methanol was heated under reflux for 2 h. The
reaction mixture was washed with 3% HCl solution,
3% NaOH solution (2 × 20 mL), and water and concen-
trated. The residue was crystallized from methanol to
give 0.59 g (43%) of ureide 6. Acidification of the aque-
ous solution, extraction with methylene chloride, and
crystallization from aqueous methanol afforded 0.26 g
(34%) of N-hydroxy maleopimarimide (3). Com-
pound 6, mp 256–258°C, [α]580 +14° (c 2.12). 1H NMR
(CDCl3, δ, ppm, J, Hz): 0.52 (s, 3H, (C-20)H3), 0.88
(dt, 1H, H-4, J 13.0 and 2.6), 0.93 and 0.96 (both d, 6H,
(C-14)H3 and (C-15)H3 , J 7.0), 1.01–1.07 (m, 3H,
H-3,5,10), 1.08 (s, 3H, (C-19)H3), 1.27–1.50 (m, 7H,
H-2,3,4,5,9,10,10a), 1.61–1.71 (m, 2H, H-2,4b), 1.93
(m, 1H, H-9), 2.43 (m, 1H, H-13), 2.59 (s, 1H, H-6),
3.00 (d, 1H, H-7, J 7.4), 3.46 (s, 3H, OCH3), 3.52 (s,
3H, OCH3), 3.65 (m, 1H, NH), 4.12 (dd, 1H, H-8, J 7.4
and 2.0), 5.19 (m, 1H, NH), 5.24 (s, 1H, H-12), 6.95 (m,
1H, Ph), 7.22 (m, 3H, Ph), 7.45 (m, 1H, Ph). 13C NMR
(δ, ppm): 15.45 (q, C-20), 16.69 (q, C-19), 16.85 (t, C-
3), 19.47 and 20.83 (both q, C-14,15), 21.45 (t, C-10),
28.52 (t, C-5), 32.61 (d, C-13), 33.64 (t, C-9), 36.21 (t,
C-2), 36.37 (d, C-8), 37.08 (s, C-4a), 37.93 (t, C-4),
41.37 (s, C-8a), 46.92 (s, C-1), 48.83 (d, C-4b), 50.87
(d, C-7), 51.03 (q, CH3), 51.53 (d, C-10a), 51.69 (q,
CH3), 57.54 (d, C-6), 120.20 (d, C-2',6'), 121.98 (d, C-
27.13 (t, C-10), 32.38 (d, C-14), 34.73 (t, C-4), 35.04
(d, C-11), 36.43 (t, C-7), 37.50 (t, C-9), 37.75 (s, C-9a),
40.59 (s, C-3b), 42.41 (d, C-11a), 46.86 (s, C-6),
49.17 (d, C-9b), 49.46 (d, C-3a), 51.75 (q, C-18), 53.83
(d, C-5a), 124.15 (d, C-13), 129.14 and 129.70 (both d,
C-2',3',5',6'), 131.07 (s, C-4'), 142.62 (s, C-1'), 147.07
(s, C-12), 168.77 and 169.81 (both s, C-1,3), 178.90 (s,
C-17).
For C32H41NO7S anal. calcd. (%): C, 65.84; H, 7.08;
N, 2.40; S, 5.49.
Found (%): C, 65.48; H, 7.18; N, 2.28; S, 5.63.
Dimethyl (1R,4aR,7R,8R)-1,4a-dimethyl-6,8a-
(11-isopropyletheno)-8-(3-methylureido)tet-
radecahydrophenanthrene-1,7-dicarboxylate (5) . A
mixture of 2.0 g (3.43 mmol) of tosylate 4, 20 mL of
methanol, and 2 mL of 10% methylamine solution in
methanol was stirred until complete dissolution (2 h).
The solution was concentrated to half volume, 50 mL of
ether was added, and the mixture was washed with 3%
NaOH solution (2 × 15 mL) and water and concen-
trated. The residue was crystallized from a methylene
chloride–methanol mixture to give 0.70 g (43%) of ure-
ide 5. The aqueous solution was acidified with hydro-
chloric acid, and the resulting precipitate was extracted
with methylene chloride. The extract was washed with 12), 122.91 (d, C-4'), 128.84 (d, C-3',5'), 138.84 (s,
water and concentrated, and the residue was crystal- C1'), 150.56 (s, C-11), 155.38 (s, C-17), 173.38 (s, C-
lized from aqueous methanol to give 0.65 g (44%) of N- 16), 178.24 (s, C-18).
hydroxy maleopimarimide (3). Compound 5, mp
235–237°ë. 1H NMR (CDCl3, δ, ppm, J, Hz): 0.44 (s,
3H, (C-20)H3), 0.79 (dt, 1H, H-4, J 12.8 and 2.8), 0.87
and 0.94 (both d, 6H, (C-14)H3 and (C-15)H3, J 7.0),
0.82–0.99 (m, 3H, H-3,5,10), 0.98 (s, 3H, (C-19)H3),
1.24–1.45 (m, 7H, H-2,3,4,5,9,10,10a), 1.52–1.65 (m,
2H, H-2,4b), 1.82 (m, 1H, H-9, Jgem 13.0), 2.37 (m, 1H,
H-13), 2.49 (s, 1H, H-6), 2.50 (d, 3H, NCH3 , J 7.0),
2.86 (d, 1H, H-7, J 7.6), 3.39 (s, 3H, OCH3), 3.47 (s,
3H, OCH3), 3.91 (t, 1H, NH, J 7.0), 4.55 (d, 1H, H-8, J
Dimethyl
(3R,3aR,9R,12aR)-9,12a-dimethyl-
2,6-(13-isopropylidenemethano)-5-(methylamino)-
1,2,3,3a,6,7,8,8a,9,10,11,12,12a,12b-tetradecahy-
dronaphtho[2,1-d]indole-3,9-dicarboxylate (7). A
mixture of 0.65 g (1.38 mmol) of compound 5 and
0.5 mL of POCl3 in 8 mL of benzene was heated under
reflux for 30 min until HCl evolution ceased. The reac-
tion mixture was diluted with ether and washed with
5% aqueous ammonia solution and water. The solvent
was evaporated, and the residue was crystallized from
an ethyl acetate–petroleum ether mixture to give 0.41 g
(64%) of amidine 7. Mp 195–197°C. 1H NMR (CDCl3,
δ, ppm, J, Hz): 0.62 (s, 3H, (C-20)H3), 0.80 (dt, 1H, H-
12, J 13.2 and 2.8), 0.91 (m, 1H, H-8), 1.00 (s, 3H, (C-
19)H3), 1.18–1.27 (m, 1H, H-1), 1.30–1.42 (m, 2H, H-
7,8), 1.45–1.56 (m, 4H, H-10,11,11,12), 1.59 and 1.62
(both s, 6H, (C-17)H3 and (C-18)H3), 1.58–1.71 (m,
4H, H-1,8a,7,10), 2.56 (d, 1H, H-3, J 6.4), 2.57 (s, 3H,
NCH3), 2.83 (br s, 1H, H-12b), 2.90 (m, 1H, H-2), 2.93
(s, 1H, H-6), 3.46 (d, 1H, H-3a, J 6.4), 3.48 (s, 3H,
OCH3), 3.50 (s, 3H, OCH3), 4.65 (m, 1H, NH). 13C
NMR (δ, ppm): 13.18 (q, C-20), 16.18 (q, C-19), 16.94
(t, C-11), 19.30 and 20.30 (both q, C-17,18), 21.48 (t,
C-8), 29.30 (q, CH3), 30.02 (t, C-1), 31.96 (d, C-2),
13
7.6), 4.95 (m, 1H, NH), 5.22 (s, 1H, H-12). C NMR
(δ, ppm): 15.28 (q, C-20), 16.49 (q, C-19), 16.70 (t, C-
3), 19.37 and 20.66 (both q, C-14,15), 21.31 (t, C-10),
21.45 (q, CH3), 28.43 (t, C-5), 32.41 (d, C-13), 33.44 (t,
C-9), 36.10 (t, C-2), 36.12 (d, C-8), 36.91 (s, C-4a),
37.82 (t, C-4), 41.30 (s, C-8a), 46.80 (s, C-1), 48.77 (d,
C-4b), 49.82 (d, C-10a), 50.74 (d, C-7), 50.75 (q, CH3),
51.52 (q, CH3), 57.46 (d, C-6), 122.07 (d, C-12), 150.15
(s, C-11), 158.40 (s, C-17), 173.41 (s, C-16), 178.77 (s,
C-18).
Dimethyl (1R,4aR,7R,8R)-1,4a-dimethyl-
6,8a-(11-isopropyletheno)-8-(3-phenylureido)tet-
radecahydrophenanthrene-1,7-dicarboxylate (6). A
mixture of 1.2 g (2.06 mmol) of tosylate 4, 0.7 g
(7.5 mmol) of aniline, 1 mL of triethylamine, and 34.45 (t, C-7), 36.47 (t, C-10), 37.19 (s, C-12a), 37.44
DOKLADY CHEMISTRY Vol. 423 Part 1 2008