1686
PREDVODITELEV et al.
9
8
.14 Hz). 31P NMR spectrum (chloroform), d, ppm:
2.89 s. Found, %: C 34.71; H 5.39; P 10.12.
0.3 g (0.9 mmol) of cyclothionephosphate VII and 0.16 g
(2.7 mmol) of trimethylamine in 5 ml of anhydrous
benzene at 5560°C in 72 h. Yield 0.3 g (85%), mp 182
C H NO PS. Calculated, %: C 34.50; H 5.15; P 9.89.
9
16
7
M 313.27.
183°C (became moist at 165°C), R 0.00 (B), 0.15 (C),
f
1
0
.5 (D). H NMR spectrum (CDCl CD OD, 99:1),
2
-[(2,2-Dimethyl-5-nitro-1,3-dioxan-5-yl)-
3
3
d, ppm: 1.32 s, 1.39 s [6H, C(CH ) ], 2.02 m (2H,
methoxy]-2-thioxo-1,3,2-dioxaphosphorinane (VII)
was obtained in the same way as compound VI from 0.5
g (2.6 mmol) of compound II, 0.4 g (2.6 mmol) of 2-
chloro-1,3,2-dioxaphosphorinane (IIIb), 0.2 g (2.6 mmol)
of triethylamine, and 0.1 g (2.8 mmol) of sulfur in 20 ml
of anhydrous benzene. Phosphorinane V formation was
monitored by P NMR spectroscopy ( P NMR
spectrum, d, ppm: 129.56 s). The treatment with sulfur
was carried out at 8085°C for 3 h. Reaction product
VII was purified by chromatography on a column packed
with silica gel (15g) and filled with benzene. Compound
VII was eluted with 40 ml of benzenedioxane mixture,
3 2
+
+
POCH CH CH N ), 3.10 br.s [9H, N (CH ) ], 3.48 br.m
2
2
+
2
3 3
+ 3
(
1
1
2H, CH N ), 3.93 m (2H, OPOCH CH CH N , J
2 2 2 2 HP
2
1.00 Hz), 4.07 d (2H ) and 4.47 d (2H ) (CH OC, J
e a 2 a,e
3.43 Hz), 4.40 d (2H, CH OP, J 13.73 Hz). P NMR
3
31
2
HP
spectrum (chloroformmethanol, 99:1), d, ppm: 54.16 s.
Found, %: C 40.63; H 7.32; P 8.39. C H N O PS.
3
1
31
13 27
2
7
Calculated, %: C 40.41; H 7.04; P 8.02. M 386.41.
2-[(2-Nitro-3-palmitoyloxy-2-palmitoyl-
oxymethyl)propoxy]-2-thioxo-1,3,2-dioxaphos-
phorinane (X). To a solution of 0.1 g (0.3 mmol) of
thionephosphate VII in 5 ml of chloroform at 0°C was
added 0.008 g (0.08 mmol) of ZnCl ·1.5H O and 0.17 g
1
0:1. The solvent was removed in a vacuum, the residue
2
2
(
0.6 mmol) of palmitoyl chloride. The reaction mixture
was maintained for 2 h at 40°C and 1 mm Hg. Yield
1
was kept for 1 h at 0°C, then for 24 h at 2025°C.
Chloroform was removed in a vacuum. Compound X was
subjected to chromatography on a column packed with
silica gel (15 g) and filled with hexane, elution with 20 ml
of hexanedioxane mixture, 3:1. The solvent was
removed in a vacuum, and the residue was kept for 2 h
0
.64 g (75%), mp 98100°C, R 0.35 (A), 0.90 (B). H
f
NMR spectrum (CDCl ), d, ppm: 1.42 s, 1.43 s [6H,
3
C(CH ) ], 1.9 m (2H, OCH CH CH O), 4.08 d (2H )
3
2
2
2
2
e
2
and 4.47 d (2H ) (CH OC, J 11.60 Hz), 4.32 m (2H )
and 4.42 m (2H ) (OCH CHCH O, J 10.45 Hz),
a
2
a,e
e
3
a
2
2
HP
3
31
4
.50 m (2H, CH OP, J 8.98 Hz). P NMR spectrum
2 HP
at 40°C and 1 mm Hg, yield of amorphous compound
(
chloroform), d, ppm: 60.89 s. Found, %: C 36.59;
1
0
.14 g (60%), mp 5859°C, R 0.45 (A), 0.85 (B). H
f
H 5.34; P 9.71. C H NO PS. Calculated, %: C 36.70;
H 5.54; P 9.46. M 327.29.
1
0
18
7
NMR spectrum (CDCl ), d, ppm: 0.89 t (6H, CH CH ,
3
3
2
3
JHH 6.7 Hz), 1.26 m [48H, CH (CH ) ], 1.61 m [4H,
3
2 12
O-[(2,2-Dimethyl-5-nitro-1,3-dioxan-5-yl)-
methyl]thionephosphocholine (VIII). Asealed ampule
containing a solution of 0.2 g (0.64 mmol) of thione-
phosphate VI and 0.11 g (1.9 mmol) of trimethylamine in
CH CH C(O)], 1.98 br.m (2H, OCH CH CH O), 2.34
2
2
2
2
2
m [4H, CH CH C(O)], 4.02 br.m (2H ) and 4.40 br.m
2
2
e
(
2H ) (OCH CH CH O), 4.04 d (2H, CH OP,
a 2 2 2 2
3
OCH CH CH O, JHP 12.51 Hz), 4.60 C [4H,
CH OC(O)]. P NMR spectrum (chloroform), d, ppm:
6
2
2
2
31
5
ml of anhydrous benzene was maintained at 3035°C
2
for 80 h. The solvent was removed in a vacuum, the oily
residue was washed with benzene (2´5 ml), hexane
1.56 s. Found, %: C 61.56; H 10.01; P 4.31.
C H NO PS. Calculated, %: C 61.31; H 9.76; P 4.05.
3
9
74
9
(2´5 ml), and dried for 2 h at 40°C and 1 mm Hg. Yield
M 764.023.
0
.13 g (55%), mp 145147°C (became moist at 99°C),
O-[(2-Nitro-3-palmitoyloxy-2-palmitoyloxy-
methyl)propyl]thionephosphohomocholine (XI) was
obtained in the same way as phosphocholine VIII from
1
R 0.00 (B), 0.45 (D). H NMR spectrum (CDCl ), d,
f
3
ppm: 1.25 s, 1.41 s [6H, C(CH ) ], 2.82 br.s [9H,
3
2
+
+
N (CH ) ], 3.74 m (2H, CH N ), 3.98 d (2H ) and 4.38
3
3
2
e
0
.1 g (0.13 mmol) of cyclothionephosphate X and 0.03 g
2
d (2H ) (CH OC, J 12.65 Hz), 4.06 m (2H,
a
2
a,e
(
0.52 mmol) of trimethylamine in 5 ml of anhydrous
+
3
3
POCH CH N , J 11.68 Hz), 4.40 d (2H, CH OP, J
HP
2
2
HP
2
benzene at 7075°C in 10 h. Yield 0.04 g (35%), mp
3
1
1
5
0.03 Hz). P NMR spectrum (chloroform), d, ppm:
5.50 s. Found, %: C 38.59; H 6.93; P 8.61.
1
1
90192°C (became moist at 150°C), R 0.35 (C). H
f
NMR spectrum NMR spectrum (CDCl ), d, ppm: 0.88 t
3
C H N O PS. Calculated, %: C 38.70; H 6.78; P 8.32.
1
2
25
2
7
3
(
6H, CH CH J 6.74 Hz), 1.26 m [48H, CH (CH ) ],
3
2, HH
3
2 12
M 372.39.
1
.60 m [4H, CH CH C(O)], 2.14 br.m (2H,
2 2
O-[(2,2-Dimethyl-5-nitro-1,3-dioxan-5-yl)-
methyl]thionephosphohomocholine (IX) was
obtained in the same way as phosphocholine VIII from
POCH CH CH N+), 2.34 m [4H, CH CH C(O)], 3.17 br.s
2
2
2
2
2
[9H, N+(CH ) ], 4.04 d (2H, CH OP, 3J 12.20 Hz),
4.07 m (2H, POCH CH CH N+), 4.12 m (2H,
3
3
2
HP
2
2
2
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004