NOVEL GLYCYRRHIZIC ACID CONJUGATES
459
1306.49). IR (ν, cm–1): 3600–3200 (ОН, NH), 1744
(COOMe), 1651 (C11=O), 1520 (CONH), 1498.
1Н NMR (300 MHz, DMSO-d6): 0.61, 0.71, 0.84,
0.90, 0.93, 1.22, 1.30 (21H, all s, 7 СН3), 1.50–3.20
(m, СН, СН2), 3.38, 3.58, 3.61 (9Н, all s, 3 ОСН3),
3.90–5.50 (m, Н1'-Н6', Н1''-Н6''), 5.70 (1Н, s, Н12),
7.20–8.30 (m, Н ar.). 13С NMR (75.5 MHz, DMSO-
d6): 198.9 (С11), 175.3 (С30), 169.2 (С13), 168.4
(С6''); 168.1 (С6'), 127.4 (С12), 103.4 (С1''), 103.3
(С1'), 88.3 (С3), 80.2 (С2'), 76.0 (С5''), 75.9 (С5'),
74.9 (С3''), 74.4 (С3', С2''), 71.4 (С4''), 71.2 (С4'), 61.0
(С9), 54.3 (С5), 47.4 (С18), 47.0 (С8), 44.6 (С14,
С20), 42.7 (С19), 37.0 (С4), 36.4 (С1), 36.2 (С22),
35.7 (С10), 33.2 (С7), 32.0 (С17), 31.1 (С21), 28.2
(С29), 28.1 С28), 27.1 (С23), 25.8 (С16), 25.5 (С15),
25.2 (С2), 22.8 (С27), 18.2 (С26), 16.8 (С6), 15.9
(С24, C25); D-PheOMe: 172.1, 171.3, 171.1, 137.8,
136.7, 136.6, 129.0, 128.9, 128.8, 128.3, 128.1, 128.0,
126.4, 126.1, 53.3, 53.1, 53.0, 51.7, 51.6.
tone-d6): 0.84, 0.93, 1.08, 1.13, 1.26, 1.37, 1.47 (21 Н,
all s, 7 СН3), 1.50–3.50 (m, СН, СН2), 3.60, 3.63,
3.72 (9Н, all s, 3 ОСН3), 3.90–5.10 (m, Н1'-Н6',
Н1''-Н6''), 5.63 (1Н, s, Н12), 7.00–7.65 (m, Н ar.),
10.1, 10.5 (3H, br. s, 3NH). 13С NMR (75.5 MHz, ace-
tone-d6): 199.0 (C11), 174.0 (С30), 170.6 (C6''), 170.5
(C6'), 169.5 (C13), 128.1 (C12), 103.7 (C1''), 102.4
(C1'), 89.5 (C3), 77.9 (C2'), 76.4 (C5''), 76.3 (С5'),
74.4 (С3',3''), 73.8 (С2''), 72.6 (С4''), 72.4 (С4'), 61.4
(C9), 54.8 (C5), 47.8 (C18), 45.1 (C8), 43.4 (C20),
43.0 (C14), 41.0 (C19), 39.3 (C4), 38.5 (С1), 37.2
(C22), 36.6 (C10), 32.4 (C7), 31.6 (C17), 30.8 (C21),
27.7 (C29), 27.3 (C28), 27.0 (C23), 26.3 (С16), 26.1
(C15), 25.4 (С2), 22.8 (C27), 18.2 (C26),17.1 (C6),
16.3 (С25), 15.8 (С24); D-TrpОМе: 172.0, 171.8,
171.4, 136.6, 136.6, 136.4, 128.1, 128.0, 124.0, 123.8,
121.3, 118.8, 118.6, 118.1, 117.9, 111.6, 111.4, 53.0, 52.5,
51.6, 51.5, 50.9.
3-О-{2-O-[N-(β-D-glucopyranosyluronoyl)-D-
tryptophan ethyl ester]-N-(β-D-glucopyranosyluro-
noyl)-D-tryptophan ethyl ester}-(3β,20β)-11-oxo-30-
(N-carbonyl-D-tryptophan ethyl ester)-30-norolean-
12-ene (V). Yield 0.86 g (58%) (method А); 0.70 g
(48%) (method B) (yellowish amorphous powder). Rf
3-О-{2-O-[N-(β-D-glucopyranosyluronoyl)-D-
thyrosine methyl ester]-N-(β-D-glucopyranosyluro-
noyl)-D-thyrosine methyl ester}-(3β,20β)-11-oxo-30-
(N-carbonyl-D-thyrosine methyl ester)-30-norolean-
12-ene (VII). Yield 0.61 g (45%) (method B). Rf 0.60
(chloroform–methanol–water, 45 : 10 : 1).
+45
[α]D20
0.58 (chloroform–ethanol, 5 : 1).
+40 1° (c
[α]D20
1° (с 0.04, EtOH). Found, %: C 63.57; H 7.23; N
0.06, EtOH). Found, %: С 66.20; Н 7.32; N 5.58.
2.95. С72Н95N2O22. Calcd., %: C 63.84; H 7.07; H N
С81Н104N6O19. Calcd., %: С 66.37; Н 7.15; N 5.73 (Мr
3.10. (Mr 1354.49). IR (ν, сm–1): 3600–3200 (ОН,
1465.7). IR (ν, cm–1): 3400–3200 (ОН, NH), 1740
(COOEt), 1655 (C11=O), 1651 (Ph), 1529 (CONH). NH), 1736 (COOMe), 1652 (C11=O), 1520 (CONH),
1Н NMR (300 MHz, CD3OD): 0.84, 1.03, 1.07, 1.10, 1500 (Ph). 1Н NMR (300 MHz, CD3OD.): 0.86, 1.04,
1.27, 1.36, 1.42 (21Н, all s, 7 СН3), 1.50–3.20 (m, СН, 1.14, 1.22, 1.31, 1.42, 1.45 (21H, s, 7CH3), 1.40–3.20
СН2), 3.31, 3.63, 3.67, 3.71 (15Н, all s, 3 СН2СН3), (m, СН, СН2), 3.30, 3.68, 3.74 (9Н, all s, 3ОСН3),
3.80–4.70 (m, Н1'-Н6', Н1''- Н6''), 5.64 (1Н, s, 3.80–4.90 (m, Н1'-Н6', Н1''-Н6''), 5.72 (1Н, s, Н12),
6.40–7.35 (m, Н ar.). 13С NMR (75.5 MHz, СD3OD):
201.2 (С11), 174.0 (С30), 171.8 (С13), 171.4 (С6',
С6''), 128.2 (С12), 105.2 (С1''), 104.2 (С1'), 90.9
Н12), 7.05, 7.07, 7.12, 7.29, 7.31, 7.36, 7.39, 7.47, 7.50,
7.53, 7.55, 7.88 (15Н, m, Н ar.). 13С NMR (75.5 MHz,
CD3OD): 202.6 (C11), 175.9 (С30), 171.9 (С13), 171.8
(C6''), 171.7 (C6'), 129.2 (C12), 105.2 (C1''), 103.9 (С3), 80.1 (С2'), 77.6 (С5''), 77.1 (С5'), 75.7, 75.3
(C1'), 91.1 (C3), 83.0 (С2), 79.5 (C5''), 79.3 (C5'), (С2'', С3', С3''), 73.5 (С4'), 73.1 (С4''), 63.1 (С9), 56.4
77.8 (С3'), 77.6 (C3''), 75.7 (C2''), 74.9 (C4''), 73.5 (С5), 47.5 (C18), 46.8 (С8), 44.9 (С20), 43.7 (С14),
(C4'), 63.0 (C9), 56.3 (C5), 46.8 (C8), 44.9 (C20), 42.4 (С19), 40.8 (С4), 40.3 (С1), 38.6 (С22), 38.1
44.6 (C14), 42.5 (C19), 40.7 (C4), 39.9 (С1), 38.6 (С10), 33.76 (С7), 33.0 (С17), 32.2 (С21), 29.2 (С29),
(C22), 38.0 (C10), 33.8 (C7), 33.0 (C17), 32.2 (C21), 28.9 (С28), 28.2 (С23), 27.6 (С16), 27.4 (С15), 26.6
29.7 (C29), 28.9 (C28), 28.5 (C23), 27.6 (C16), 27.5 (С2), 23.9 (С27), 19.4 (С26), 18.5 (С6), 17.1 (С24),
(C15), 26.6 (C2), 23.9 (C27), 19.4 (C26), 18.4 (C6), 17.4 (С25); D-TyrOMe: 173.0, 172.0, 171.8, 131.5,
17.5 (C25), 17.0 (C24); D-TrpОEt: 174.4, 173.4, 172.5, 131.3, 129.2, 129.0, 116.6, 116.5, 68.1, 67.7, 67.6, 55.3,
138.3, 138.0, 128.9, 128.3, 126.0, 124.8, 122.6, 122.5, 54.9, 52.9, 52.8.
120.0, 119.3, 119.0, 112.8, 112.6, 110.0, 109.6, 54.8,
3-О-{2-O-[N-(β-D-glucopyranosyluronoyl)-D-
54.1, 53.0, 52,4, 52.2, 36.5, 35.8.
valine methyl ester]-N-(β-D-glucopyranosyluronoyl)-
D-valine methyl ester}-(3β,20β)-11-oxo-30-(N-car-
3-О-{2-O-[N-(β-D-glucopyranosyluronoyl)-D-
bonyl-D-valine methyl ester)-30-norolean-12-ene
phenylalanine methyl ester]-N-(β-D-glucopyranosy-
(VIII). Yield 0.55 g (48%) (method B). Rf 0.47 (ben-
luronoyl)-D-phenylalanine methyl ester}-(3β,20β)-11-
zene–ethanol, 5 : 1).
+40 1° (с 0.04, EtOH).
[α]
20
oxo-30-(N-carbonyl-D-phenylalanine methyl ester)-
30-norolean-12-ene (VI). Yield 0.72 g (55%) (method
Found, %: C 60.75; H D7.70; N 3.50. C60H93N3O19.
А). R 0.45 (benzene–ethanol, 5 : 1).
+25 1° Calcd., %: C 60.96; H 7.46; N 3.61 (Мr 1162.43). IR
[α]D20
f
(с 0.06, EtOH). Found, %: С 65.86; H 7.22; N 3.14. (ν, cm–1): 3600–3200 (ОН, NH), 1739 (COOMe),
1
1662 (C11=O), 1528 (CONH). Н NMR (300 MHz,
C72H95N3O19. Calcd., %: C 66.19; H 7.33; N 3.22. (Мr
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 43 No. 4 2017