DENISOV et al.
708
dried. Yield 0.91 g (77%), mp 204–206оС, Rf 0.76, [α]D20
+131.1 (c 0.5, ethanol). IR spectrum, cm–1: 3450 br
(ОН), 2974, 1724 (С=О), 1674 (С=О), 1563, 1550,
63.15; Н 7.06; N 4.53. C31H39BrN2O3·Н2О. Calculated,
%: С 63.68; H 6.93; N 4.79.
1-Isopropyl-3-{2-[(4bS,8R)-2-isopropyl-4b,8-
dimethyl-8-(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-
octahydrophenanthren-3-yl]-2-oxoethyl}-1Н-
benzimidazol-3-ium bromide, solvate with ethanol
(Vb). Yield 48%, mp 223–225°C, Rf 0.55, [α]D20 +89.3
(c 1, ethanol). IR spectrum, cm–1: 3400 br (ОН), 2933,
1720 (С=О), 1690 (С=О), 1608, 1561, 1461, 1433,
1
1498, 1432, 1246, 1223, 1197, 1134, 1110, 754. Н
NMR spectrum, δ, ppm: 1.18 d (6Н, Mе, J 6.6 Hz),
1.20 d (6Н, Mе, J 6.6 Hz), 1.28 s (6Н, Mе), 1.29 s (6Н,
Mе), 1.45–1.94 m (14Нaliph), 2.21 m (2Н, Н5е), 2.60 m
(2Н, Н8а), 2.95 m (4Н, Н10), 3.49 m (2Н, НСAr), 3.68
s (6Н, ОMе), 6.17 d (2Н, NCH, J 18.0 Hz), 6.40 d
(2Н, NCH, J 18.0 Hz), 7.15 s (2Н, Н1), 7.50 m
(2Нarom), 7.62 m (2Нarom), 7.86 s (2Н, Н4), 11.10 s (1Н,
N=СH). 13С NMR spectrum, δ, ppm: 16.27, 18.17,
21.03, 23.74, 23.84, 24.78, 28.45, 29.98, 36.43, 36.98,
37.74, 44.49, 47.30, 51.73, 54.93, 112.94, 125.29,
127.01, 127.61, 130.38, 131.61, 141.47, 144.21,
146.78, 147.47, 178.66 (С=О), 191.62 (С=О). Found,
%: С 65.63; Н 6.99; N 2.62. C53H67BrN2O6·3Н2О.
Calculated, %: С 66.17; H 7.65; N 2.91.
1
1247, 1213, 1135, 753. Н NMR spectrum, δ, ppm:
1.19 t (3Н, СН3СН2ОН, J 6.0 Hz), 1.29 m (6Н, 2Mе),
1.41 d (3Н, Mе, J 6.6 Hz), 1.44 s (3Н, Mе, J 6.6 Hz),
1.48–1.78 m (6Нaliph), 1.84 d [6Н, (СН3)2СН, J 6.6 Hz],
2.21 m (1Н, Н5a), 2.48 m (1Н, Н5e), 2.72 m (1Н, Н8а),
2.94 m (2Н, Н10), 3.44 m (1Н, НСAr), 3.65 q (2Н,
СН3СН2ОН, J 6.0 Hz), 3.67 с (3Н, ОMе), 5.02 m
(1Н, NCH, J 6.6 Hz), 5.50 s (1Н, ОНethanolа), 6.36 d
(1Н, NCH, J 18.0 Hz), 6.59 d (1Н, NCH, J 18.0 Hz),
7.13 s (1Н, Н1), 7.55 m (2Нarom), 7.65 m (2Нarom), 7.84
m (1Нarom), 7.96 s (1Н, Н4), 11.21 s (1Н, N=СH). 13С
NMR spectrum, δ, ppm: 16.33, 18.28, 21.10, 22.11,
23.93, 24.85, 28.58, 30.05, 36.53, 37.11, 37.75, 44.59,
47.40, 51.66, 53.11, 55.00, 63.38, 112.96, 113.33,
125.47, 126.89, 127.22, 127.54, 130.24, 130.77,
132.30, 141.32, 141.86, 146.43, 147.65, 178.80 (С=О),
193.04 (С=О). Found, %: С 64.70; Н 6.75; N 4.36.
C33H43BrN2O3·С2Н5ОН. Calculated, %: С 65.51; H
7.70; N 4.37.
Compounds Vа–Ve. In 40 mL of acetonitrile was
dissolved 0.435 g (1 mmol) of 12-(bromoacetyl)-
dehydroabietic acid methyl ester (I) and 1 mmol of an
appropriate N-substituted benzimidazole IVa–IVe, the
mixture was refluxed for 5–8 h (TLC monitoring). The
solvent was distilled off in a vacuum, the residue was
heated in 10–15 mL of ethyl acetate till the formation
of a fine crystalline precipitate which was filtered off,
washed with 10 mL of ethyl acetate, and dried. The
samples for analysis were obtained by recrystallization
from a mixture ethyl acetate–acetonitrile.
1-Benzyl-3-{2-[(4bS,8R)-2-isopropyl-4b,8-di-
methyl-8-(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-
octahydrophenanthren-3-yl]-2-oxoethyl}-1Н-
benzimidazol-3-ium bromide, semihydrate (Vc).
Yield 35%, Rf 0.67, [α]D24 +50.9 (c 0.5, chloroform),
mp 231–233оС. IR spectrum (thin film), cm–1: 2940,
2778, 2437, 1709 (С=О), 1609 (C=N), 1559, 1449,
3-{2-[(4bS,8R)-2-Isopropyl-4b,8-dimethyl-8-
(methoxycarbonyl)-4b,5,6,7,8,8a,9,10-octahydro-
phenanthren-3-yl]-2-oxoethyl}-1-methyl-1Н-
benzimidazol-3-ium bromide, monohydrate (Vа).
Yield 80%, mp 214–218°C, Rf 0.55, [α]D24 +58.6 (c
0.52, chloroform). IR spectrum, cm–1: 3400 br (ОН),
2949, 2923, 1721 (С=О), 1692, 1610, 1572, 1553,
1
1374, 1245, 1130, 1023, 893, 814, 751, 704, 572. Н
1
1490, 1432, 1384, 1225, 1177, 1133, 1109, 755. Н
NMR spectrum, δ, ppm: 1.09 d (3Н, Mе, J 6.6 Hz),
1.11 d (3Н, Mе, J 6.6 Hz), 1.20 s (3Н, Mе), 1.21 s (3Н,
Mе), 1.42–1.82 m (7Нaliph), 2.13 m (1Н, Н5е), 2.60 m
(1Н, Н8а), 2.87 m (2Н, Н10), 3.36 m (1Н, НСAr), 3.59
s (3Н, ОMе), 5.67 s (2Н, NCH2), 6.22 d (1Н, NCH, J
18.0 Hz), 6.50 d (1Н, NCH, J 18.0 Hz), 7.05 s (1Н,
Н1), 7.30–7.38 m (6Нarom), 7.47 m (3Нarom), 7.86 s (1Н,
Н4), 11.35 s (1Н, N=СH). 13С NMR spectrum, δ, ppm:
16.47, 18.36, 21.23, 23.92, 24.01, 24.99, 28.72, 30.20,
36.65, 37.24, 37.93, 44.70, 47.52, 51.72, 51.90, 55.20,
112.95, 113.68, 125.65, 127.12, 127.33, 127.75, 128.04,
129.40, 129.49, 130.63, 130.79, 131.95, 132.37. Found,
%: С 66.95; Н 6.15; N 4.01. C37H43BrN2O3·1/2Н2О.
Calculated, %: С 66.66; H 6.65; N 4.20.
NMR spectrum, δ, ppm: 1.16 d (3Н, Me, J 6.6 Hz),
1.18 d (3Н, Me, J 6.6 Hz), 1.29 m (6Н, 2Mе),1.38–
1.94 m (7Нaliph), 2.21 m (1Н, Н5а), 2.68 m (1Н, Н8а),
2.94 m (2Н, Н10), 3.42 m (1Н, НСAr), 3.67 s (3Н,
ОMе), 4.52 s (3Н, NMe), 6.32 d (1Н, NCH, J 18.0 Hz),
6.54 d (1Н, NCH, J 18.0 Hz), 7.14 s (1Н, Н1), 7.50 m
(1Нarom), 7.58–7.76 m (3Нarom), 7.93 s (1Н, Н4), 11.10
с (1Н, N=СH). 13С NMR spectrum, δ, ppm: 16.39,
18.29, 21.15, 23.84, 23.92, 24.91, 28.63, 30.13, 33.88,
36.55, 37.14, 37.81, 44.61, 47.43, 51.88, 55.06,
112.81, 122.36, 125.58, 127.13, 127.33, 127.67,
130.53, 131.53, 131.88, 141.62, 143.74, 146.75,
147.68, 178.84 (С=О), 192.50 (С=О). Found, %: С
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 5 2014