FIRST CONJUGATE OF GLUCURONIC ACID
581
Scheme 4.
AcO
OCH3
O
AcO
4
'
3
'
5'
3
0
2'
1'
O
20
AcO
2
9
21
H
19
TBAB
O
7
+ 5
1
7
1
1
1
8
2
CH Cl2
O
O
2
5
26
H O
2
2
8
1
5
O
1
9
3
5
7
27
AcO
24
23
8
3
1
8.4, 40.9, 42.9, 44.5, 46.6, 48.2, 50.0, 55.3, 63.3, 81.0,
65.25; H 8.17. C H O . Calculated, %: C 65.17; H
36 58 6
8.26.
71.1, 172.4, 177.4. Mass spectrum (ESI), m/z: 609.6
+
[
M + Na] . Found, %: C 73.75; H 9.90. C H O . Cal-
1
13
3
6
58
6
H and C NMR spectra were recorded on an
Avance-400 and Avance-600 spectrometers (Bruker,
Germany). Mass spectra (MALDI) were obtained on a
time-of-flight mass spectrometer UltraFlex III TOF/
TOF (Bruker Daltonik GmbH, Germany) in a linear
mode (Nd:YAG laser, λ 355 nm). Data was processed
using the FlexAnalysis 3.0 program (Bruker Daltonik
GmbH, Germany). The measurements were carried out
in the range of m/z 200–6000. Positively charged ions
were registered. 2,5-Dihydroxybenzoic acid and
p-nitroaniline were used as a matrix. Electrospray
ionization mass spectra (ESI) were obtained on an
AmazonX mass spectrometer (Bruker Daltonik GmbH,
Germany). The measurements were carried out in the
m/z range from 100 to 2800 recording the positively
charged ions (the capillary voltage 4500 V). Nitrogen
at a temperature of 250°C and a flow rate of 8 L/min
was used as the gas drier. A methanol–water solution
(70 : 30) was used as the eluent, and the eluent flow
rate was 0.2 mL/min. The completeness of the
reactions and the purity of the substances were
monitored by thin layer chromatography on Sorbfil
plates (Imid, Russia), the substances were detected by
plate treatment with a 5% solution of sulfuric acid
followed by heating to 120°C. Specific rotation was
measured on a Model 341 polarimeter (Perkin Elmer
Inc., USA) in a temperature-controlled cell at 20°C
and at 589 nm. Melting points were measured on a
Boetius instrument.
culated, %: C 73.68; H 9.96.
3
β-O-Acetyl-28-O-succinyl-(2,3,4-tri-O-acetyl-5-
methoxycarbonyl-β-D-glucopyranosyl)dihydrobetulin
8). To a solution of 0.185 g (0.32 mmol) of terpenoid
and 0.15 g (0.38 mmol) of bromide 5 in 10 mL of
CH Cl was added a solution of 0.11 g (0.80 mmol) of
(
7
2
2
K CO and 0.02 g (0.06 mmol) of t-butylammonium
2
3
bromide (TBAB) in 1 mL of H O while stirring under
argon. The reaction mixture was refluxed for 10 h,
2
then diluted with CHCl , washed with water, and dried
3
with MgSO . The solvent was removed at a reduced
4
pressure, and the residue was recrystallized from
MeOH. Yield 0.12 g (42.9%), white amorphous powder,
2
0
1
mp 173–175°C, [α]D –4.8° (с 1.53, CH Cl ). H NMR
2
2
spectrum (400 MHz, CDCl ), δ, ppm: 0.80–1.90 m
3
2
9(30)
3
(
26H, triterpenoid skeleton), 0.77 d [3H, H
, J =
3
0(29) 3
6
0
2
.8 Hz], 0.83 d [3H, H
.86 s, 0.94 s, 1.03 s (5×3H, H
.04 s, 2.06 s [4×3H, CH C(О)], 2.60–2.74 m [4H,
, J = 6.8 Hz]; 0.84 s, 0.85 s,
2
3–27
); 2.031 s, 2.035 s,
3
(
(
4
1
О)CCH CH C(O)], 3.74 s [3H, CH ОC(О)], 3.84 d
2 2 3
2
8
3
5' 3
1H, HА , J = 11.3 Hz), 4.17 d (1H, H , J = 9.5 Hz ),
2
8
3
3' 3
.28 d (1H, HB , J = 11.3 Hz), 4.48 d.d (1H, H , J =
2
' 3
0.3, 5.7 Hz), 5.15 t (1H, H , J = 9.9 Hz), 5.24 t (1H,
4
'
3
3' 3
H , J = 9.4 Hz), 5.31 t (1H, H , J = 9.2 Hz), 5.79 d
(
1
'
3
13
1H, H , J = 7.6 Hz). C NMR spectrum (400 MHz,
CDCl ), δ , ppm: 13.7, 14.6, 14.9, 16.0, 16.1, 16.5,
3
C
1
2
3
6
1
8.2, 20.4, 20.5, 20.8, 21.3, 21.6, 22.9, 23.7, 26.8, 26.9,
7.9, 28.7, 29.0, 29.4, 29.8, 34.2, 34.6, 37.0, 37.2, 37.8,
8.4, 40.9, 42.9, 44.5, 46.6, 48.1, 49.9, 53.0, 55.3, 63.2,
9.0, 70.0, 71.8, 73.1, 80.9, 91.5, 166.7, 169.2, 169.3,
69.8, 170.4, 171.0, 172.1. Mass spectrum (MALDI),
ACKNOWLEDGMENTS
This work was supported by the Russian Science
Foundation (grant no. 14-50-00014).
+
+
m/z: 925.9 [M + Na] , 941.9 [M + K] . Found, %: C
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 3 2017