polarimeter. IR spectra were recorded on a UB-20 spectrometer. N1VIR spectra were measured in CD3CN on
a Varian XL-100 spectrometer at 100 MHz using TMS as an internal standard.
Benzyl-2-acetamido-3,4-di-O-acetyl-2-didesoxy-6-O-tosyl-~-D-glucopyranoside (II). Compound (I) (3
g) [5] and tosyl chloride (2 g) were dissolved in abs. pyridine (50 ml) and the mixture was left standing over-
night at 5°C. (CH3COs)20 (10 ml) was added and after 3-4 hthe mixture was poured onto ice (100 g). The
aqueous layer was extracted with CHCIs (3 × 50 ml), the chloroform extract was washed with water, 10~
NaHCOs, and water and then dried over MgSO4. CHCI3 was evaporated and the residue was crystallized from
MeOH -- ether mi~ure to give 3.5 g (55%) of (II), mp 125-127°C, [~]D20 + 69° (C 0.8 CHCI3). Found: C 56.61;
H 5.49; N 2.49; S 5.71%. C2e~I31Ot~. Calculated: C 56.83; H 5.65; N 2.55; S 5.83.
Benzyl-2-acetamido-2,6-didesoxy-6-iodo-~-D-glucopyranoslde (HI). A mixture of (II) (3.4 g) and KI
(2.5 g) in DMF was refluxed for 30 min (the progress of the reaction checked by TLC, system A), then cooled
to about 20"C and poured into water; the aqueous l a y e r was extracted with C6H6--CHCI3 1:1 mixture (3 x 50
ml), the organic layer was successively washed with water, 270 Na~2C~, and water, dried over MgSO4 and
evaporated. The residue was treated with 0.01 N MeONa in abs. MeOH to give 1.6 g (62%) of (III), mp 196-
197"C (from MeOH--ether, with decoml~osition), [~]DZZ + 14.6~ (C 0.7 MeOH). Found: C 42.58; H 4.86;
29.88; N 3.29%. ClsHz0IC~N. Calculated: C 42.76; H 4.75; I 30.17; N 3.32%.
I
Benzyl-2-acetamid6-2,6-didesoxy-~-D-glucop~rranoside
(IV). Compound (III) (1.5 g) was hydrogenated
in MeOH (10 ml) i n t h e presence of 20~ Pd/C (1.5 g) and AcONa .3H20 (4.5 g) for 16-20 h. The catalyst was
then filtered off, the filtrate was evaporated to dryness and the residue, was chromatographed on silica gel
using the system C (80 ml) to give (IV) in 99% yield (0.9 g), mp 200-201"C (from alcohol--ether), [r,]D~ +
18.9 ° (C 1.6, MeOH). Found: C 61.20; H 7.08; N 4 . 8 0 ~ . ClsHnOsN. Calculated: C 61.02; H 7.12; N4.75%.
2-Acetamldo-2,6--didesoxy-D-~lucopyranose
(V). A quantity (0.86 g) of (IV) was hydrogenated in MeOH
h(1o0l)m, l[)']l~nothe presence of fresh 29% Pd/C (1.5 g) for 16 h to give 0.6 g of (V) (73~), mp 209-210°C (from alco-
+ 26- (c 0.8, H~O); (cf. [3]).
Benzyl-2-acetamido-3,6-di-O-acetyl-2-desoxy-4-O-tosyl-~-D-glucopyranoside (VII). A solution of
(VI) (9.5 g) [6] and tosyl chloride (24 g)in pyridine (50 ml) was kept for 3 days at about 20~C; the solvent was
then evaporated, the residue was extracted with CHCI~, the chloroform layer was washed with water, 10~
NaHCO3, water and then dried over MgSO4 before evaporating to dryness. The yield of (VII) was 11 g (83%),
mp 114-115°C (from ether), [a~)~ + 56° (C 1.0, CHCI3). Found: C 56.50; H 5.55; N 2.35; S 5.75%. C2sHsl-
Ot01~. Calculated: C 56.83; H 5.65; N 2.55; S 5.83~.
Benzyl-2-acetamido-~,4-didesoxy-u-D-xylohexopyranoside
(VIII). A solution of (VII) (10.9 g) and KI
(9 g) i n D M F (50 ml) was refluxed for 30 rain and the reaction mixture was worked up as for (liD. The product
was deacetylated with 0.01 N MeONa in aim. MeOH; the resulting solution was then neutralized using the H+
form of KU-2 cationic-exchange resin, and then hydrngenated on 20~-Pd/C (3.0 g) in the presence of AcONa •
3 H20 (4 g) for 16-20 h to give 3.2 g (54%) of (VIII), mp 168-169°C; (cf. [3]).
2-Acetamido-2,4-<lidesoxy-D-xylohexopyranose
(IX). A quantity (3.1 g) of (VIII) were hydrogennted in
the presence of a freshly prepared Pd/C (2.5 g) as for (IV). A quantity (1.8 g) (84%) of a viscous liquid (IX)
were obtained, [u~)2a + 80° (C 0.6, HzO); (cf. [3]).
Phenyl-2-acetamido-4,6-O-benzylidlne-2,3-dldesoxy-3-chloro-~-D-aUopyranoside
(XI). This compound
was prepared according to [3] in 42% yield, mp 183-184°C (from CH3CN, with decomposition), lug)20-- 25° (C
0.6, CHCIs).
Phen~l-2-acetamido-2,3-didesoxy-3-chloro-~-D-allopyranoside (XII). A quantity (3 g) of (XI) in 80~
AcOH (70 ml) were refluxed for 10-15 mln (checked by TLC, system B), the solution was then evaporated to
dryness and the residue was crystallized from an alcohol-- ether mixture. Further recrystallization from
alcohol gave 1 g (43%) of (XII), mp 163-164°C, [ ~ ) z 0 _ 56° (C 0.7, MeOH). Found: C 53.09; H 5.79; CI,
11.00; N4.26%. CI4HteCIOsN. Calculated: C 53.25; H 5.71; C111.25; N4.44%.
Phen~l-2-acetamido-2,3-didesoxy-~-D-ribohexopyranoside
(XIV). To a mixture of Na (0.2 g) in i-C3H7-
OH (5 ml) was added 0.4 g of (XII) at 55-60"C. The mixture was cooled, the resulting solid was dissolved in
MeOH (5 ml) and acidified with 1~ AcOH to pH 7-8. The volatile components were evaporated under vacuum,
the residue was dissolved in the solvent system B and then passed through charcoal and silica gel. The fil-
trate was evaporated to give 0.13 g (28%) of
phenyl-2-acetamldo-2-desoxy-~-D-erythrohex-2-enopyranoside
(XIII) as a viscous liquid. NMR spectrum (5, ppm): 6.52 d(H3), J =4 Hz; 5.85 s(Hi); 4.20tCr14). IR spec-
trum (~, cm-i): 1665 and 1550 (amide I and H). 0A g of (XIII) was hydrogenated with I g of 20~ Pd/C for 3
2178
Kolesnikov et al.
