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removed in vacuo and the residue was puri®ed by CC with CH2Cl2:ethyl acetate 9:1 as eluent to
afford 2.6 g ꢀ56.6%) of 10 as a resin.
20
D
20
546
ꢀ 52:1ꢀ, ꢀ 57:5ꢀ ꢀc 0.188, CH2Cl2); IR ꢀKBr): ꢂꢀ 2947 ꢁm, 2872 ꢀw), 1757
ꢀs), 1455 ꢀm), 1432 ꢀw), 1369 ꢀs), 1227 ꢀs), 1148 ꢀm), 1051 ꢀs), 981 ꢀw) cmÀ1; U V=Vis ꢀCH2Cl2):
ꢄ
max ꢀlogꢅ) 250 ꢀ3.299), 235 ꢀ3.293) nm; 1H NMR ꢀ400 MHz, ꢃ, CDCl3): 0.66 ꢀs, 3H, 28-H), 0.71±
0.74 ꢀm, 4H, 5-H, 24-H), 0.80±0.86 ꢀm, 1H, 16-H), 0.88±0.96 ꢀm, 10H, 1-H, 23-H, 25-H, 26-H),
0.97±1.00 ꢀm, 1H, 15-H), 1.12 ꢀs, 3H, 27-H), 1.14 ꢀs, 3H, 29-H), 1.27±1.85 ꢀm, 16H, 1-H, 2-H, 6-H,
7-H, 9-H, 11-H, 15-H, 18-H, 19-H, 21-H, 22-H), 1.89±2.10 ꢀm, 3H, 16-H, 19-H, 21-H), 1.97 ꢀs, 3H,
CH3COO), 2.03 ꢀs, 3H, CH3COO), 2.04 ꢀs, 3H, CH3COO), 2.05 ꢀs, 3H, CH3COO), 2.06 ꢀs, 3H,
CH3COO), 2.11 ꢀs, 3H, CH3COO), 2.15 ꢀs, 3H, CH3COO), 3.08 ꢀdd, J 11.5, 4.6 Hz, 1H, 3-H),
3.58±3.62 ꢀm, 1H, 50-H), 3.75 ꢀt, J 9.4 Hz, 1H, 40-H), 3.88 ꢀt, J 6.9 Hz, 1H, 500-H), 4.06±4.16 ꢀm,
3H, 60-H, 600-H), 4.44±4.52 ꢀm, 3H, 10-H, 100-H, 60-H), 4.91±4.98 ꢀm, 2H, 20-H, 300-H), 5.09±5.14 ꢀm,
2H, 200-H, 12-H), 5.20 ꢀt, J 9.3 Hz, 1H, 30-H), 5.35 ꢀd, J 3.0 Hz, 1H, 400-H), 6.90 ꢀs, 1H, CHPh2),
7.27±7.38 ꢀm, 10H, aromatic H) ppm; 13C NMR ꢀ100 MHz, ꢃ, CDCl3): 15.37 ꢀC-25), 16.32 ꢀC-24),
16.69 ꢀC-26), 18.15 ꢀC-6), 20.45, 20.57, 20.68, 20.77, 20.82 ꢀCH3COO), 23.47 ꢀC-11), 25.66 ꢀC-2),
25.85 ꢀC-27), 26.05 ꢀC-15), 26.85 ꢀC-16), 27.65 ꢀC-23), 27.92 ꢀC-28), 28.39 ꢀC-29), 31.27 ꢀC-21),
31.81 ꢀC-17), 32.58 ꢀC-7), 36.57 ꢀC-10), 38.03 ꢀC-22), 38.50 ꢀC-1), 38.81 ꢀC-4), 39.73 ꢀC-8), 41.43
ꢀC-14), 42.77 ꢀC-19), 44.19 ꢀC-20), 47.51 ꢀC-9), 47.87 ꢀC-18), 55.38 ꢀC-5), 60.79 ꢀC-600), 62.07 ꢀC-
60), 66.58 ꢀC-400), 69.09 ꢀC-200), 70.63 ꢀC-500), 70.92 ꢀC-300), 71.99 ꢀC-20), 72.31 ꢀC-50), 72.82 ꢀC-30),
76.36 ꢀCHPh2), 76.60 ꢀC-40), 90.51 ꢀC-3), 100.99 ꢀC-100), 102.70 ꢀC-10), 122.45 ꢀC-12), 126.94,
127.28, 127.66, 127.77, 128.34 ꢀaromatic C), 140.33, 140.39 ꢀaromatic Cq), 144.24 ꢀC-13), 169.01,
169.38, 169.77, 169.98, 170.07, 170.26, 170.28 ꢀCH3COO), 175.84 ꢀC-30) ppm; MS ꢀES ): m=z
ꢀ%) 1242 ꢀ20.1) [M H ], 1076 ꢀ4.4), 938 ꢀ12.5), 937 ꢀ32.0), 637 ꢀ5.6), 620 ꢀ22.6), 619 ꢀ100.0),
437 ꢀ3.8), 331 ꢀ14.7).
ꢁ-D-Galactopyranosyl-)1 ! 4)-ꢁ-D-glucopyranosyl-3-O-18ꢁ-glycyrrhetic acid ꢀ11; C42H66O14)
1.05 g ꢀ0.83 mmol) of 8 were dissolved in 11 cm3 of dry CHCl3 and cooled to À20ꢀC. 1 g of Na in
20 cm3 MeOH cooled to À20ꢀC was added, and the mixture was allowed to stand for 1.5 h at this
temperature. Then, ice water and brine were added. The mixture was extracted ®ve times with
CHCl3, and the combined organic layers were washed with a saturated aqueous solution of NH4Cl
and H2O, dried over Na2SO4, and ®ltered. The solvent was evaporated in vacuo, and the residue
ꢀ550 mg) was dissolved in 36 cm3 of dry MeOH. 500 mg of Pd=C ꢀ10%) were added, and the mixture
was allowed to shake with H2 overnight at a pressure of 3450 hPa at room temperature. The solids
were ®ltered off, and the solvent was evaporated in vacuo at room temperature. The residue was
puri®ed in portions of 200 mg by preparative TLC ꢀCH2Cl2:MeOH 8:2) yielding 180 mg ꢀ27.2%)
of 11 as an amorphous solid.
20
D
20
546
M.p.: 283±285ꢀC ꢀdecomp.); ꢀ 66:4ꢀ, ꢀ 69:1ꢀ ꢀc 0.219, CH3OH); IR ꢀKBr):
ꢂꢀ 3406 ꢁs, 2949 ꢀm), 2875 ꢀm), 1648 ꢀm), 1560 ꢀm), 1465 ꢀw), 1389 ꢀm), 1362 ꢀw), 1288 ꢀw),
1215 ꢀw), 1075 ꢀs), 1049 ꢀs) cmÀ1; 1H NMR ꢀ400 MHz, ꢃ, CD3OD): 0.79 ꢀd, J 12.1 Hz, 1H, 5-H),
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3H, 29-H), 1.14 ꢀs, 3H, 26-H), 1.15 ꢀs, 3H, 25-H), 1.22±1.35 ꢀm, 3H, 16 -H, 21-H, 22-H), 1.42 ꢀs,
0.82 ꢀs, 3H, 28-H), 0.87 ꢀs, 3H, 24-H), 0.90±1.03 ꢀm, 2H, 1-H, 15 -H), 1.08 ꢀs, 3H, 23-H), 1.09 ꢀs,
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3H, 27-H), 1.46±1.97 ꢀm, 11H, 2-H, 6-H, 7-H, 15 -H, 19-H, 21-H, 22-H), 2.15 ꢀdt, J 13.0, 3.8 Hz,
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1H, 16 -H), 2.31 ꢀd, b, J 11.5 Hz, 1H, 18-H), 2.44 ꢀs, 1H, 9-H), 2.71 ꢀdt, J 13.0, 3.0 Hz, 1H, 1-
H), 3.19 ꢀdd, J 11.9, 4.4 Hz, 1H, 3-H), 3.30 ꢀt, J 8.4 Hz, 1-H, 20-H), 3.40±3.43 ꢀm, 1H, 50-H),
3.51±3.64 ꢀm, 5H, 200-H, 30-H, 300-H, 40-H, 500-H), 3.73 ꢀdd, J 11.6, 4.1 Hz, 1H, 600-H), 3.77±3.87
ꢀm, 4H, 400-H, 60-H, 600-H), 4.38 ꢀd, J 8.4 Hz, 1H, 10-H), 4.40 ꢀd, J 9.1 Hz, 1H, 100-H), 5.70 ꢀs, 1H,
12-H) ppm; 13C NMR ꢀ100 MHz, ꢃ, CD3OD): 17.30 ꢀC-24, C-25), 18.74 ꢀC-6), 19.65 ꢀC-26), 24.16
ꢀC-27), 27.29 ꢀC-2), 27.90, 27.99 ꢀC-15, C-16), 28.82 ꢀC-23), 29.65 ꢀC-28), 29.86 ꢀC-29), 33.27 ꢀC-
17, C-21), 34.16 ꢀC-7), 38.33 ꢀC-10), 39.78 ꢀC-22), 40.62 ꢀC-1), 40.79 ꢀC-4), 44.01 ꢀC-19), 44.91 ꢀC-
8 ), 46.47 ꢀC-20), 47.01 ꢀC-14 ), 50.15 ꢀC-18), 56.83 ꢀC-5), 62.34 ꢀC-60), 62.80 ꢀC-600), 63.38 ꢀC-9),
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