Arkivoc 2019, vi, 0-0
Nazarov, M. A. et al.
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1451 (C=C). H NMR (400 MHz, CDCl3): δH 7.97-8.04 (4H, m, Ph), 7.51-7.56 (2H, m, Ph), 7.40-7.44 (4H, m, Ph),
7.02 (H, d, J 16.3 Hz, 30-CH), 6.14 (H, dd, J 2.3, 7.4 Hz, 21-CH), 6.04 (H, d, J 16.3 Hz, 31-CH), 4.74 (Н, dd, J 5.0,
10.8 Hz, 3-СН), 4.56 (H, d, J 8.2 Hz, 28-CH2), 3.88 (H, d, J 8.2 Hz, 28-CH2), 2.26 (3H, s, 33-CH3), 1.09 (3H, d, J 7.3
Hz, 29-CH3), 0.93, 0.94, 1.01, 1.04, 1.10 (15H, 5s, 5CH3). 13C NMR (100 MHz, CDCl3): δC 198.73, 166.45, 166.28,
145.31, 142.59, 135.43, 132.90, 132.67, 131.04, 130.39, 129.51 (2C), 129.47 (2C), 128.38 (2C), 128.29 (2C),
125.41, 81.54, 61.89, 55.53, 50.37, 49.00, 42.27, 41.18, 38.64, 38.51, 38.23, 37.94, 37.12, 36.94, 34.06, 31.05,
30.66, 28.12, 27.23, 27.08, 26.81, 24.54, 23.75, 21.44, 18.18, 16.78, 16.32, 16.09, 15.03; Anal. Calcd. for
C47H60O5: C, 80.07; H, 8.58. Found: C, 79.84; H, 8.87.
Method B. NaH (1.5 mmol) was added to a solution of 4 (1.5 mmol) in acetone (4 mL). The mixture was stirred
for 15 min at rt. After addition of 10% HCl, the reaction mixture was extracted with ethylacetate (30 mL x 2).
The organic layer was separated, washed with H2O, and dried over anhydrous MgSO4. The solvent was
evaporated, and the residue was subjected to silica gel CC (eluent: light petroleum−ethylacetate 5:1). Yield:
57%.
21β,28-Epoxy-3β-hydroxy-30-(2-oxopropylidene)-18αH,19βH,20αH-ursane (7). Acetone (5 mL) was added to
a solution of mixture of aldehyde 4 (0.2 mmol) and sodium methoxide (1.0 mmol) in anhydrous benzene (10
mL). The reaction mixture was stirred for 3 h under boiling, and then washed with 10% solution of HCl. The
product was extracted with ethylacetate (30 mL x 2). The organic layer was separated, washed with H2O, and
dried over anhydrous MgSO4. The solvent was evaporated, and the residue was subjected to silica gel CC
(eluent: light petroleum−ethylacetate 5:1). Yield: 5%; mp 198.53 °С; [] 2D1 +4.74 (с 0.95, CHCl3). IR (solution in
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CH3ОН, сm-1): 3427 (ОН), 1668 (С=O). H NMR (400 MHz, CDCl3): δH 6.72 (H, dd, J 9.0, 16.2 Hz, 30-CH), 5.98
(H, d, J 16.2 Hz, 31-CH), 4.17 (H, d, J 8.2 Hz, 28-CH2), 4.00 (H, dd, J 1.2, 5.6 Hz, 21-CH), 3.35 (H, d, J 8.2 Hz, 28-
CH2), 3.18 (Н, dd, J 5.0, 11.0 Hz, 3-СН), 2.24 (3H, s, 33-CH3), 1.00 (3H, d, J 5.5 Hz, 29-CH3), 0.96 (6H, s, 2CH3),
0.75, 0.84, 0.97 (9H, 3s, 3CH3). 13C NMR (100 MHz, CDCl3): δC 199.04, 150.46, 131.68, 78.96, 77.32, 73.86,
56.93, 55.34, 50.14, 49.46, 45.16, 44.55, 42.33, 41.95, 40.99, 38.86, 38.81, 37.11, 34.31, 33.64, 32.54, 29.52,
27.99, 27.81, 27.41, 26.40, 24.28, 21.46, 18.29, 16.29, 15.97, 15.37, 14.27; Anal. Calcd. for C33H52O3: C, 79.79;
H, 10.55. Found: C, 79.99; H, 10.31.
20-(1´-Acetyl-3´-methyl-4´,5´-dihydro-1H-pyrazol-5´(S)-yl)-3β,28-dibenzoyloxy-30-nor-18αH,19βH-urs-
20(21)-ene (8). Compound 6 (0.1 mmol) was dissolved in 5 mL of acetic acid, and then hydrazine acetate (0.5
mmol) was added. The mixture was refluxed and monitored by TLC until starting material completely
disappeared (4 h). The product was extracted with ethylacetate (20 mL x 2). The organic layer was separated,
washed with H2O, and dried over anhydrous MgSO4. The solvent was evaporated, and the residue was
subjected to silica gel CC (eluent: light petroleum−ethylacetate 5:1). Yield: 61%; mp 273.3 °С; [] 2D1 +22.6 (с
0.5, CHCl3). IR (solution in CH3ОН, сm-1): 1714 (ОCOPh), 1658 (С=N), 1452 (C=C). 1H NMR (400 MHz, CDCl3): δH
0.91, 0.93, 1.10 (9H, 3s, 3CH3), 0.99 (6H, s, 2CH3), 1.01 (3H, d, J 6.8 Hz, 29-CH3), 2.01 (3H, s, 3’-CH3), 2.17 (1’-
COCH3), 2.63 (1H, dd, J 5.3, 18.9 Hz, H-4’), 3.15 (1H, dd, J 11.7, 18.9 Hz, H-4’), 4.23 (1H, d, J 11.1 Hz, H-28), 4.48
(1H, dd, J 5.5, 11.7 Hz, H-5’), 4.64 (1H, d, J 11.1 Hz, H-28), 4.72 (1H, dd, J 5.4, 10.8 Hz, H-3), 5.44 (H, dd, J 1.6,
7.2 Hz, H-21); 7.37-7.43 (4H, m, Ph); 7.48-7.55 (2H, m, Ph), 7.95-8.04 (4H, m, Ph). 13C NMR (100 MHz, CDCl3):
δC 167.84, 166.30, 166.04, 155.00, 145.82, 132.64, 132.43, 131.07, 129.71, 129.51 (2C), 129.46 (2C), 128.28
(2C), 128.20 (2C), 118.04, 81.65, 61.83, 58.79, 55.55, 50.37, 49.05, 46.38, 42.21, 41.21, 38.56, 38.52, 38.45,
38.22, 37.10, 35.58, 35.14, 34.08, 30.83, 28.12, 27.58, 26.87, 23.77, 23.20, 21.52, 21.41, 18.20, 16.77, 16.31,
16.10, 15.97, 14.92; Anal. Calcd. for C49H64N2O5: C, 77.33; H, 8.48; N, 3.68. Found: C, 77.61; H, 8.82; N, 3.44.
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