SYNTHETIC GLYCOSIDES OF ent-CAURENE SERIES
2671
13-O-[β-D-soforosyl]-[4-N1(3,6-dimethyluracyl)-
butyl]-ent-cauren-19-oate (V). Needle-like crystals,
0.15 g (20%) were isolated, mp 115°C, Rf 0.4 Elution
with 10:2 chloroform-methanol, [α]D20 –35° (c 0.3,
MeOH). IR spectrum, ν, cm–1: 1714 (C=O), 1702
(C2=Ouracyl), 1662 (C=C), 1653 (C4=Ouracyl), 1614 (C–N).
1H NMR spectrum (pyridine-d5), δ, ppm, (J, Hz): 0.73
m (1H, C1H). 0.91 d (1H, C9H, J 6.1), 1.01 s (3H,
C20H3), 1.20 s 3H, C18H3), 1.4–2.23 m (14H,
aglycone), 2.14 s (3H, C6'uracylH3), 2.31 d (1H, C3H, J
13.7), 2.55 d (1H, C14H, J 11.2), 3.37 s (3H,
N3uracylH3), 3.78-4.51 m (12H, soforosyl), 3.87-3.9 m
[2H, C(O)-CH2], 5.09 s (1H, C17H2), 5.77 s (1H,
C17H2), 5.17 d (1H, C1'Hanomer, J 7.6), 5.29 d (1H,
C1'Hanomer, J 7.6), 5.68 s (1H, C5uracylH). Mass
spectrum. m/z (Irel, %): 860(100) [M + Na]+. Found, %:
C 56.51, H 7.98, N 3.04. C42H64O15N2·2H2O. Cal-
culated, %: C 56.62; H 7.93; N 3.14.
were prepared by the reaction of sodium 3,6-dimethyl-
uracyl with the 5-fold excess of 1,4- and 1,6-dibromo-
alkanes according to the reported procedures [13, 14].
General procedure for preparing compounds
III–VI. A mixture of 0.09 g of KOH and 20 ml of
DMSO was stirred for 1 h at 60–70°C, 0.5 g of
steviolobioside II was added, and the resulting mixture
was stirred for additional 30 min. After that 0.7 mmol
of the corresponding alkylating agent was added drop-
wise, and the mixture obtained was stirred for 10 h.
The reaction progress was monitored by TLC. After
the completion of the reaction the mixture was diluted
with water to 500 ml and extracted with butanol
(4×100 ml). Joined extracts were dried with magne-
sium sulfate and concentrated in a vacuum. After
chromatographing on silica gel (elution with chloro-
form–methanol) the products III–VI were obtained
and crystallized from methanol.
13-O-[β-D-soforosyl]-[6-N1(3,6-dimethyluracyl)-
hexyl]-ent-cauren-19-oate (VI). Needle-like crystals,
0.6 g (45%) were isolated, mp 132°C, Rf 0.38. Elution
with 10:5 chloroform-methanol. [α]D20 –44° (c 0.3,
MeOH). IR spectrum, ν, cm–1: 1718 (C=O), 1702
(C2=Ouracyl), 1670 (C4=Ouracyl). 1656 (C=C), 1615 (C–N).
1H NMR spectrum (pyridine-d5), δ, ppm (J, Hz): 0.74
m (1H, C1H, 0.89 d (1H, C9H, J 6.1), 1.02 s (3H,
C20H3), 1.19 s (3H, C18H3), 1.3–2.1 m (14H, aglycone),
2.11 s (3H, C6uracylH3), 2,31 d (1H, C3H, J 13.7), 2.54 d
(1H, C14H, J 11.2), 3.38 s (3H, N3uracylH), 3.30–3.79 m
[2H, C(O)–CH2), 3.94-4.51 m (12H, soforosyl), 5.08 s
(1H, C17H2), 5.75 s (1H, C5uracylH). Mass spectrum, m/z
(Irel, %): 888 (100) [M + Na]+. Found, %: C 56.63, H
8.12, N 3.07. C44H68O15N2. Calculated, %: C 56.38; H
8.19; N 2.98.
13-O-[β-D-soforosyl]-benzyl-ent-cauren-19-oate
(III). White powder, 0.18 g (32%) was isolated, mp
165°C, Rf 0.3. Elution with 10:3 chloroform-methanol.
[α]D20 –49° (c 0.3, MeOH). IR spectrum, ν, cm–1: 1718
(C=O), 1660 (C=C), 1630, 1550, 1450, 754, 698 (all
1
HPh). H NMR spectrum (pyridine-d5), δ, ppm (J, Hz):
0.71 m (1H, C1H), 0.87 d (1H, C9H, J 6.1), 0.97 s (3H,
C20H3), 1.17 s (3H, C18H3), 1.29-2.18 m (14H,
aglycone), 2.28 d (1H, C3H, J 13.7), 2.48 d (1H, C14H,
J 11.2), 3.81–4.53 m (12H, soforosyl), 5.08 s (1H,
C17H2), 5.74 s (1H, C17H2), 5.15–5.19 m [2H, C(O)–
CH2 ], 5.30 d (1H, C1'Hanomer, J 7.6), 5.35 d (1H,
C1'Hanomer. J 7.6), 7.3–7.6 m (5H, Ar). Found, %: C
63.75; H 7.78. C39H56O13. Calculated, %: C 63.90, H
7.71.
1,3-O-[β-D-soforosyl]-[2-(o-chlorophenoxy)ethyl]-
ent-cauren-19-oate (IV). White powder, 0.12 g (20%)
was isolated, mp 135°C. Rf 0.42. Elution with 10:2
chloroform–methanol. [α]D20 –36° (c 0.4, MeOH). IR
spectrum, ν, cm–1: 1718 (C=O), 1660 (C–C), 1590,
1465, 891, 749 (all HPh). 1H NMR spectrum (pyridine-
d5), δ, ppm (J, Hz): 0.69 m (1H, C1H), 0.85 d (1H,
C9H, J 6.1), 0.96 d (1H, C5H, J 12.2), 1.00 s (3H,
C20H3), 1.19 s (3H, C18H3), 1.27–2.1 m (14H,
aglycone), 2.27 d (1H, C3H, J 13.7), 2.50 d (1H, C14H
J 11.2), 3.74-4.66 m (12H, soforosyl), 4.6-4.7 m [2H,
C(O)CH2], 5.04 s (1H, C17H2), 5.7 s (1H, C17H2), 5.07
d (1H, C1'Hanomer, J 7.6), 5.15 d (1H, C1'Hanomer, J 7.6),
6.8–7.4 m (4H, Ar). Mass spectrum, m/z (Irel, %): 821
(100) [M + Na]+. Found, %: C 51.06; H 7.82; Cl 4.03.
C40H57O14Cl·8H2O. Calculated, %: C 51.02, H 7.83, Cl
3.76.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 12 2009