DIPENTAERETHRITE IN THE SYNTHESIS
1053
0.35 g of phosphorous hexaethyltriamide and 0.1 g of
selenium. The selenium excess was filtered off and
dioxane was removed in a vacuum. Diamidodiseleno-
nediphosphate VI was purified by chromatography on
a column with silica gel (5 g) filled with hexane.
Compound VI was eluded with 25 ml of hexane di-
oxane mixture 6:1, solvents were removed in a
vacuum and residue was kept for 2 h at 40 C (1 mm
Hg). Yield of compound VI 0.4 g (59%), 1.5429, Rf
tion mixture was then cooled to room temperature,
diluted with equal volume of water (4 ml) and washed
with hexane (2 10 ml) to transparency of aqueous
layer. Water was removed in a vacuum and residue
was kept for 3 h at 80 C (1 mm Hg). Yield of com-
pound I 0.1 g (88%), mp 220 223 C (crude), 223
1
225 C (from H2O), Rf 0.00 (B). H NMR spectrum
[(CD3)2SO], , ppm: 3.28 br.s (4H, CH2OCH2), 4.19 d
3
(12H, CH2OH, JHH 5.50 Hz), 4.08 t (6H, CH2OH,
1
0.90 (A), 0.47 (B). H NMR spectrum (CDCl3), ,
3JHH 5.49 Hz). Found, %: C 47.41; H 8.95. C10H22O7.
Calculated, %: C 47.23; H 8.72. M 254.
3
ppm: 1.11 t (24H, NCH2CH3, JHH 6.10 Hz), 3.09 q
3
(16H, NCH2CH3, JHP 12.29 Hz), 3.36 s, 3.46 s,
2 ,2 ,6 ,6 -Tetra-O-acetyl-1,7-tetraethyldiamido-
thionophosphate-2 ,2 ,6 ,6 -tetra(hydroxymethyl)-4-
oxa-1,7-heptanediol (VIII). Diphosphotetraol VII,
0.2 g, was dissolved at heating (50 C) in 5 ml of
pyridine. To the solution cooled to room temperature
was added 0.15 g of freshly distilled acetic anhydride
and mixture was stirred for 48 h. Solution was then
poured to cold water (0 1 C) the oil dropped was
decanted, washed with cold water (2 10 ml), dis-
solved in chloroform and solution was dried over
anhydrous K2CO3 for 3 h. Solvent was removed in a
vacuum and compound VIII obtained was purified on
a column with silica gel (5 g) filled with hexane.
Compound VIII was eluded with 20 ml using hexane
dioxane 1:1 system. Solvents were removed in a va-
cuum and residue was kept for 2 h at 40 C (1 mm Hg).
Yield of compound VIII 0.2 g (78%), 1.5513, Rf 0.78
3.54 s (4H, CH2OCH2), 3.89 m (4He) and 4.27 m
2
(4Ha) (CH2OCH, J(HaHe) 11.90 Hz), 4.14 m (4H,
CH2OP, 3JHP 11.95 Hz), 5.35 br.s (2H, CHC6H5), 7.36
br.s (6H, -m, -p) and 7.46 br.s (4H, -o) (C6H5). 31P
NMR spectrum (dioxane), P, ppm: 80.92 br.s. and
1
two broaden satellites, J(31P 77Se)837.06 Hz. Found,
%: C 51.41; H 7.44; P 6.79. C40H68N4O7P2Se2. Cal-
culated, %: C 51.28; H 7.32; P 6.61. M 937.
1,7-Tetraethyldiamidothionophosphate-2 ,2 ,6 ,
6 -tetra(hydroxymethyl)-4-oxa-1,7-heptanediol
2,2 -[Oxa(methylene)-di(2-methoxytetraethyldi-
amidothionophosphate-1,3-propandyl] (VII). Ami-
dodithionodiphosphate V, 0.15 g, was placed to a
round-bottom flask, 3 ml of 75% acetic acid was
added and the mixture was heated with a reflux con-
denser at vigorous stirring for 13 h at 100 110 C to
complete dissolving of compound V. Reaction mix-
ture was then cooled to room temperature and diluted
with equal amount of water (3 ml). The oil dropped
was separated, washed with water (2 3 ml), dissolved
in 5 ml of chloroform and dried over anhydrous
K2CO3. After filtration, the solvent was removed in a
vacuum and residue was kept for 3 h at 80 oC (1 mm
Hg). Yield of compound VII 0.1 g (75%), 1.5490, Rf
(A), 0.49 (B). 1H NMR spectrum (C6D6), , ppm: 1.02
3
t (24H, NCH2CH3, JHH 6.94 Hz), 1.78 s [12H,
3
CH3(O)], 3.03 q (16H, NCH2CH3 , JHP 12.19 Hz),
3.35 s, 3.42 s (4H, CH2OCH2), 4.28 d (4H, CH2OP,
3JHP 12.06 Hz), 4.30 s [8H, CCH2OC(O)]. 31P NMR
spectrum (chloroform), P, ppm: 79.84 br.s. Found,
%: C 48.78; H 8.01; P 7.38. C34H68N4O11P2S2. Cal-
culated, %: C 48.90; H 8.21; P 7.42. M 835.
1
0.10 (B), 0.75 (B). H NMR spectrum (CDCl3), ,
1,2 ,2 ,6 ,6 ,7-Hexa-O-acetyl -2 ,2 ,6 ,6 -tetra(-
hydroxymethyl)-4-oxa-1,7-heptanediol (IX) is pre-
pared similarly to compound VIII from 0.15 g of
pentaeritritol I and 0.25 g of acetic anhydride in the
presence of 3 ml of pyridine in 12 h. The precipitate
dropped at pouring to water was filtered off, washed
with cold water (3 10 ml) and dried for 3 h at 80 C
(1 mm Hg). Yield of compound IX 0.3 g (90%), mp
ppm: 1.07 t (24H, NCH2CH3, 3JHH 7.02 Hz), 2.02 br.s
3
(4H, OH), 3.05 q (16H, NCH2CH3, JHP 12.20 Hz),
3.35 br.s (8H, CH2OH), 3.54 s (4H, CH2OCH2), 3.86
3
m (4H, CH2OP, JHP 6.41 Hz). 31P NMR spectrum
(chloroform), P, ppm: 80.10 br.s. Found, %: C 46.47;
H 9.28; P 9.16. C26H60N4O7P2S2. Calculated, %: C
46.83; H 9.05; P 9.29. M 667. Phosphotetraol VII
after drying of its solution in chloroform can be ad-
ditionally purified on a column with silica gel (10 g)
filled with hexane. Compound VII was eluded with
20 ml of hexane dioxane mixture 3:1.
1
71 73 C, Rf 0.85 (A), 0.50 (B). H NMR spectrum
(CDCl3), , ppm: 2.05 s [18H, CH3(O)], 3.18 s (4H,
CH2OCH2), 4.14 s [12H, CCH2OC(O)]. Found, %: C
52.23; H 6.84. C22H34O13. Calculated, %: C 52.17; H
6.77. M 507.
Preparation of 2 ,2 ,6 ,6 -tetra(hydroxymethyl)-
4-oxa-1,7-heptanediol (I) from dibenzylidenedi-
pentaerythritol III. Diacetal III, 0.2 g, was sus-
pended in 4 ml of 75% acetic acid and heated with
reflux condenser at vigorous stirring for 1.5 h at 85
90 C to complete dissolution of compound III. Reac-
2 ,6 -Dipalmoyl-1,7-tetraethyldiamidothiono-
phosphate-2 ,6 -di(hydroxymethyl)-4-oxa-1,7-hep-
tanediol (X) is prepared similarly to compound VIII
from 0.1 g of diphosphotetraol VII and 0.2 g of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 7 2006