176
GUR’EVA et al.
1
'
1
–1
H , J 8.0 Hz), 4.51–4.53 t (2H, H , J 7.4 Hz), 4.46–
(mull in mineral oil), cm : 3390 (OH), 3290 (NH), 2960,
1
,2
1,2
6
'
2
2'
4
5
5
.53 m (2H, H ), 4.85–4.99 m (2H, H , H ), 5.10–
.22 m (2H, H , H ), 5.36–5.39 m (2H, H , H ), 5.89–
.92 t (1H, NH).
1465,1375, 715 (CH), 1730, 1720 (C=O), 1640 (C=O,
NH), 1389 (C–N). H NMR spectrum (CDCl ), δ, ppm:
0.83–0.92 t (6H, CH ), 1.15–1.40 s (44H, CH ), 1.50–
3
4'
3'
4
1
3
3
2
N-{2-[4-O-(β-D-Galactopyranosyl)-β-D-glyco-
1.70 m (4H, β-CH2CH2OCO), 2.35–2.42 m (2H, β-CH2),
2.62–2.77 m (2H, δ-CH ), 3.59–3.70 m (4H, CH CO),
pyranosido]ethyl}dodecylamide (VII). To a solution
of 0.3 g of compound VI in 3 ml of methanol was added
at room temperature while stirring 0.75 ml of freshly
obtained 0.1 M solution of sodium methylate in methanol
till pH 8. After 20 min the solution was treated with ion-
exchange resin KU-2 till pH 7, the resin was filtered off,
the solvent was distilled off in a vacuum. Yield 0.2 g
2
2
4.03–4.08 t (2H, α-CH OCO), 4.10–4.15 t (2H, α-
2
CH OCO), 4.57–4.64 m (1H, CH).
2
N-[4-O-(2,3,4,6-Tetra-O-acetyl-β-D-galacto-
pyranosyl)-2,3,6-tri-O-acetyl-β -D-glyco-
pyranosido]succinimide (XIV). To a solution of 5 g
(
7.4 mmol) of octaacetyl-β-D-lactose (V) in 22 ml of
(
(
(
94%), R 0.45 (eluent system A), mp 146–147°C
f
anhydrous dichloromethane was added 1 ml (8.1 mmol)
of boron trifluoride etherate. After 15 min the reaction
mixture was treated with 0.93 g (8.1 mmol) of N-hy-
droxysuccinimide and left standing for 12 h at room
temperature. On completion of the reaction the mixture
was neutralized with 25% ammonia solution till pH 7
and washed with water (5 × 100 ml). The organic layer
was dried, the solvent was distilled off in a vacuum, the
residue was subjected to column chromatography (eluent
-1
MeOH). IR spectrum (mull in mineral oil), cm : 3280
NH), 3250 (OH), 1630 (C=O), 1560 (NH), 2890, 1324,
7
00 (CH), 1210–1060 (4 bands, carbohydrate skeleton).
+
Mass spectrum, m/z (I , %): 589.2 (4.2) [M] , 399.2
rel
(
1
(
18.9), 280.1 (19.9), 279.1 (100), 206.1 (25), 191.2 (70),
63.2 (23.8), 147.1 (39.8), 111.1 (44.5), 85.1 (57.9), 71.0
68), 57.1 (89.1).
Ditetradecyl L-glutamate (XI). A mixture of 2.3 g
15.6 mmol) of L-glutamic acid (VIII), 10 g (46.9 mmol)
(
system J). Yield 2.4 g (43%), colorless crystals, R 0.42
f
of tetradecanol (IX), and 4.15 g (15.6 mmol) finely
dispersed in a mortar p-toluenesulfonic acid was heated
on an oil bath at 110°C for 1.5 h. The completion of the
reaction was determined by the disappearance of the
L-glutamic acid; then the reaction mixture was cooled to
room temperature and recrystallized from acetone. The
precipitate was filtered off, dissolved in 100 ml of
chloroform, washed with 5% solution of sodium hydrogen
carbonate (5×35 ml), with water till pH 7, and dried with
sodium sulfate. The solvent was removed in a vacuum.
(
[
eluent system B), mp 90–91°C (EtOH) (92.5–93.7°C
1
17]). H NMR spectrum (CDCl ), δ, ppm: 1.90 s,
3
1
2
3
4
4
.99 s, 2.00 s, 2.02 s, 2.04 s, 2.06 s, 2.09 s (21H, COCH ),
3
5
.73 s (4H, CH CH ), 3.72–3.78 m (1H, H ), 3.86–
.91 m (1H, H ), 4.05–4.23 m (4H, H , H ), 4.41–
2
2
5
'
6
6'
4
1'
.45 d.d (1H, H ), 4.53–4.56 d (1H, H , J 7.9 Hz),
1,2
3
'
1
.94–4.98 d.d (1H, H ), 5.06–5.10 d (1H, H ,
2
2'
3
J1,2 6.3 Hz), 5.14–5.22 m (2H, H , H , H ), 5.33–5.35 d.d
(
C H NO . Calculated, %: C 49.12; H 5.36; N 1.91.
4
’
1H, H ). Found, %: C 48.97; H 5.43; N 2.09.
Yield 10 g (96%), colorless amorphous substance, R 0.53
30 39
20
f
(
eluent system E). IR spectrum (mull in mineral oil),
[4-O-(β-D-Galactopyranosyl)-β-D-glycopyrano-
syl]oxyamine (XV). To a solution of 100 mg (0.1 mmol)
of compound XIV in 15 ml of ethanol was added 1.65 ml
(0.95 mmol) of hydrazine hydrate. The mixture was left
standing at room temperature for 24 h. The reaction
progress was monitored by TLC (eluent system K). On
completion of the reaction the excess hydrazine hydrate
and the solvent were removed in a vacuum. The reaction
product was purified by recrystallization from ethanol.
Yield 0.03 g (33%), Rf 0.6 (eluent system K), mp 138–
–1
cm : 3450 (NH), 2926, 2904, 1450, 1375, 700 (CH), 1736
(
C=O), 1172 (C–N), 1145, 1028 (C–O).
The obtained chromatographically pure compound XI
without further purification was used in the next reaction
stage.
3
-[1,3-Di(tetradecyloxycarbonyl)propylcar-
bamoyl]propanoic acid (XIII). To a solution of 1.53 g
2.8 mmol) of ester XI in 20 ml of toluene was added
.29 g (2.8 mmol) of succinic anhydride XII, and the
(
0
–1
mixture was stirred for 12 h at room temperature. Toluene
was distilled off in a vacuum, the residue was dissolved
in 50 ml of chloroform, washed with 0.1 N HCl, with
water till pH 7, and dried. The solvent was removed in
139°C (EtOH). IR spectrum (mull in mineral oil), cm :
3340 (OH), 3320 (NH), 2920 (CH), 1638 (NH), 1435,1356
(CH), 1212 (C–O), 1114–1035 (C–O, 4 bands, carbo-
1
hydrate skeleton). H NMR spectrum (D O), δ, ppm:
2
3
2
2'
3'
a vacuum. Yield 1.6 g (91%), colorless crystals, R 0.4
3.41 d.d (1H, H ), 3.53–3.69 m (3H, H , H , H ), 3.76–
3.81 m (1H, H , H ), 3.88 d (1H, H ), 4.07–4.18 m (2H,
f
6
6'
4'
(eluent system C), mp 33–34°C (CH C H ). IR spectrum
3
6
5
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 2 2009