KHASANOVA et al.
1128
1.28 s (3H, CH3), 1.35 s (3H, CH3), 3.23 s (3H, OCH3),
3.32 s (3H, OCH3), 3.40 d.d (1H, H5, J 8.8, 10.8 Hz),
3.75 t (1H, H3, J 9.7 Hz), 3.86 s (3H, OCH3), 4.08 t (1H,
H2, J 9.5 Hz), 4.35 d.d (1H, H5, J 5.3, 11.57 Hz), 4.85 d
(1H, H1, J 9.5 Hz), 5.18 d.d.d (1H, H4, J 5.5, 8.7, 9.3 Hz),
6.91 d (2H, J 7.96 Hz), 7.95 d (2H, C6H4, J 7.96 Hz),
7.25–7.31 m (3H) and 7.52–7.55 m (2H, C6H5). 13C NMR
spectrum (CDCl3), δ, ppm: 17.35 (2 CH3), 47.55, 47.89
(OCH3), 55.19 (OCH3), 66.88 (C3), 67.95 (C5), 68.73
(C2), 71.27, (C4), 85.69 (C1), 99.44, 99.98 (C2’,3’), 113.52,
121.69, 127.27, 128.67, 131.53, 131.72, 132.99, 163.37
(Ar), 164.95 (C=O).
128.22, 128.91, 131.21, 133.22 (Ar). Found, %: C 56.98;
H 7.10; S 8.96. C17H24O6S. Calculated, %: C 57.28;
H 6.79; S 9.00.
Phenyl-2,3-O-(2',3'-dimethoxybutane-2',3'-diyl)-
1S-thio-D-xylopyranoside (V). Light-yellow needle
crystals, mp 136–138°C, [α]D20 –113.8° (C 2.15, CHCl3).
1H (CDCl3), δ, ppm: 1.34 s (3H, CH3), 1.35 s (3H, CH3),
2.55 br.s (1H, OH), 3.23 s (3H, OCH3), 3.30 s (3H,
OCH3), 3.61 t (1H, H3, J 9.6 Hz), 3.70 t (1H, H2, J 9.6 Hz),
3.82–3.91 m (1H, OCH2), 4.10 m (2H, H4, OCH2), 4.77 d
(1H, H1, J 9.6 Hz), 7.25–7.33 m (3H), 7.51–7.58 m
(2H, C6H5). 13C NMR spectrum (CDCl3), δ, ppm: 17.55
(2 CH3), 47.87, 48.08 (2 OCH3), 67.08 (C3), 67.91 (C2),
69.68 (C5), 74.83 (C4), 85.86 (C1), 99.54, 100.14 (C2’,3’),
127.37, 128.79, 131.66, 133.21 (Ar).
2-O-(4-Methoxybenzoyl)-3,4-O-(2’,3’-dimethoxy-
butane-2’,3’-diyl)-D-xylopyranosyltrichloro-acetimi-
date (IX). To a stirred solution of 2.0 g (5.60 mmol) of
compound VI in 10 ml of a mixture CH2Cl2–H2O, 8 : 1,
was added at room temperature 0.6 g (3.40 mmol) of
NBS. The reaction mixture was stirred at this tempera-
ture till complete consumption of the initial compound
(TLC monitoring), then saturated solution of Na2SO3 was
added. The reaction product was extracted into CH2Cl2
(3 × 10 ml), combined organic solutions were washed with
brine,dried with MgSO4, and evaporated. The residue
was purified by flash-chromatography on SiO2 (eluent
petroleum ether–ethyl acetate, 3:1), and the obtained
lactol VIII [0.94 g (82%), anomers mixture] was at once
brought into the next stage of imidation.
Phenyl-2-O-(4-methoxybenzoyl)-3,4-O-(2',3'-di-
methoxybutane-2',3'-diyl)-1S-thio-D-xylopyranoside
(VI). To a solution of 0.32 g (0.89 mmol) of compound
IV in 10 ml of anhydrous CH2Cl2 was added 0.16 g
(1.07 mmol) of anise acid and 0.065 g (0.5 mmol) of
DMAP, the reaction mixture was cooled to 0°C and a solu-
tion of 0.218 g (1.07 mmol) of DCC in 3 ml CH2Cl2 was
added dropwise. The reaction mixture was stirred at room
temperature over 12 h, then it was washed in succession
with 10% solution of HCl and with a saturated solution
of NaHCO3. The organic layer was washed with brine,
dried with MgSO4, evaporated, the residue was subjected
to column chromatography on SiO2 (eluent petroleum
ether–ethyl acetate, 1 : 1). Yield 0.43 g (95%), colorless
crystals, mp 65–67°C, [α]D20 +146.0° (C 0.285, CHCl3).
1H NMR spectrum (CDCl3), δ, ppm: 1.22 s (3H, CH3),
1.27 s (3H, CH3), 3.17 s (3H, OCH3), 3.25 s (3H, OCH3),
3.49 m (1H, OCH), 3.87 s (3H, OCH3), 3.83–3.93 m (2H),
4.05 d.d (1H, OCH, OCH2, J 4.3, 11.5 Hz), 4.75 d (1H,
H1, J 9.6 Hz), 5.20 t (1H, H2, J 9.4 Hz), 6.94 d (2H, J 8.5
Hz), 8.03 d (2H, C6H4, J 8.8 Hz), 7.26–7.28 m (3H), 7.44–
7.46 m (2H, C6H5). 13C NMR spectrum (CDCl3), δ,
ppm: 17.39, 17.51 (CH3), 47.53, 47.82 (OCH3), 55.32
(OCH3), 65.66 (C3), 67.65 (C5), 69.48 (C2), 72.32
(C4), 87.51 (C1), 99.41, 99.83 (C2’,3’), 113.58, 122.09,
127.81, 128.77, 131.68, 132.51, 132.57, 163.43 (Ar),
164.48 (C=O). Found, %: C 60.95; H 5.85; S 6.69.
C12H18O2S. Calculated, %: C 61.21; H 6.16; S 6.54.
To a solution of 0.86 g (2.0 mmol) of compound
VIII in 7 ml of anhydrous CH2Cl2 was added 1 ml
(10.0 mmol) of CCl3CN and several drops of DBU, the
reaction mixture was stirred at room temperature for
4 h, then it was evaporated in a vacuum. The residue
was purified by flash-chromatography on SiO2 (eluent
petroleum ether–ethyl acetate, 1 : 1, containing 1% of
Et3N). Yield of anomeric mixture 0.54 g (57%). The
repeated chromatography of the anomers mixture on a
column packed with SiO2 furnished an analytically pure
sample of α-anomer IX. Oily substance, [α]D20 +143.3°
(C 2.038, CHCl3). 1H NMR spectrum (CDCl3), δ, ppm:
1.28 s (3H, CH3), 1.32 s (3H, CH3), 3.29 s (3H, OCH3),
3.31 s (3H, OCH3), 3.83 s (3H, OCH3), 3.80–4.05 m (3H,
H4, OCH2), 4.35 t (1H, H3, J 10.4 Hz), 5.27 d.d (1H, H2,
J 3.6, 10.6 Hz), 6.62 d (1H, H1, J 3.6 Hz), 6.89 d (2H,
J 8.8 Hz) and 7.96 d (2H, C6H4, J 8.80 Hz), 8.46 s (1H,
NH). 13C NMR spectrum (CDCl3), δ, ppm: 17.56, 17.70
(CH3), 47.70, 48.09 (OCH3), 55.44 (OCH3), 62.26 (C5),
65.77 (C3), 67.53 (C2), 69.79 (C4), 90.98 (CCl3), 94.10
(C1), 99.70, 100.0 (C2’,3’), 113.66, 121.72, 131.78, 163.62
Phenyl-4-O-(4-methoxybenzoyl)-2,3-O-(2',3'-
dimethoxybutane-2',3'-diyl)-1S-thio-D-xylopyran-
oside (VII) was obtained analogously. Yield 93%,
20
colorless crystals, mp 119–120°C, [α]D –150.9°
(C 0.555, CHCl3). 1H NMR spectrum (CDCl3), δ, ppm:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011