434
NIFANT’EV et al.
3
spectrum (C6D6), , ppm: 1.99 t (6H, NCH2CH3, JHH
purified on a column with silica gel (5 g) willed with
benzene. Compound XIV was elued with 40 ml of
benzene. The solvent was removed in a vacuum and
residue was kept for 5 h at 80 C (1 mm Hg). After
2 weeks keeping at 25 C compound has crystallized.
Yield of XIV 0.13 g (52%), n2D01 1.5693, mp 159
161 C, Rf 0.72 (A), 0.44 (B). H NMR spectrum
3
7.31 Hz), 3.01 q (4H, NCH2CH3, JHP 13.68 Hz),
3.17 s (4H, CH2OCH2), 3.39 d (4Ha) and 4.08 d (4He)
[CH2OC, 2JH H 5.57 Hz], 3.68 d.d (4H, CH2OP, 3JHP
a
e
2
12.79 Hz), 4.47 s and 4.65 d.d (4H, OCH2O, JHH
6.32 Hz, JHH 1.87 Hz). 31P NMR spectrum (dioxane),
4
P, ppm: 77.78 br.s. Found, %: C 46.82; H 7.40; P
7.61. C16H30NO7PS. Calculated, %: C 46.70; H 7.35;
P 7.53. M 411.45. Found, M (12C): 411.62. Calculated,
M (12C): 411.29.
3
(CDCl3), , ppm: 1.15 t (12H, NCH2CH3, JHH
3
7.15 Hz), 3.17 q (8H, NCH2CH3, JHP 13.79 Hz),
3.50 m (4Ha) and 4.12 m (4He) (8H, CH2OC), 3.69 s
and 3.81 s (8H, CH2OCH2), 3.75 m (4Ha) and 4.33 m
(4He) (CH2OCH), 4.19 m (8H, CH2OP), 4.57 d and
1,7-Bis(tetraethyldiamido)-2 ,2 ; 6 ,6 -di-O-
methylene-2 ,2 ;6 ,6 -tetra(hydroxymethyl)-4-oxa-
heptan-1,7-diol (X). 0.2 g dimethylenedipentaerytri-
tiol (III) and 0.36 g of phosphorous hexaethyltriamide
VIII (molar ratio 1:2) in 3 ml of anhydrous dioxane
was stirred for 48 h at 25 C. Formation of amidphos-
phite IX was monitored by means of 31P NMR spec-
2
4.76 s (4H, OCH2O, JHH 6.72 Hz), 5.41 br.s (2H,
CHC6H5), 7.37 br.s (6H, m-, p-) and 7.47 br.s (4H, o-)
(C6H5). 31P NMR spectrum (dioxane), P, ppm:
76.64 br.s. Found, %: C 54.23; H 7.18; P 6.41.
C44H68N2O14P2S2. Calculated, %: C 54.19; H 7.03;
P 6.35. M 975.08. Found, M (12C): 974.24. Calculated
M (12C): 974.64.
troscopy. 31P NMR spectrum (dioxane),
P, ppm:
135.40 br.s. To the reaction mixture was then added
0.07 g of sulfur at room temperature and mixture was
kept at 40 C for 3 h. Sulfur excess was filtered off,
dioxane was removed in a vacuum. Diamidodithiono-
diphosphate X was purified on a column with silica
gel (5 g) filled with hexane. Compound X was elued
with 30 ml of hexane dioxane 3:1 mixture. Solvents
were then removed in a vacuum and residue was kept
for 2 h at 40 C (1 mm Hg). Yield of compound X
ACKNOWLEDGMENTS
This work was financially supported by Foundation
of the President of Russian Federation for supporting
advanced scientific schools of Russian Federation
(grant no. NSh-5515.2006.3).
0.3 g (60%), n2D0 1.5284, Rf 0.80 (A), 0.55 (B). H
1
NMR spectrum (C6D6), , ppm: 0.98 t (24H, NCH2
CH3, JHH 6.94 Hz), 2.99 q (16H, NCH2CH3, JHP
REFERENCES
3
3
12.06 Hz), 3.16 s, 3.50 s (4H, CH2OCH2), 3.37 d
1. Nifant’ev, E.E., Maslennikova, V.I., and Rasadki-
na, E.N., Zh. Obshch, Khim., 1999, vol. 69, no. 11,
p. 1813.
2
(4Ha) and 4.05 d (4He) [CH2OC, JH H 6.99 Hz],
a
e
3
3.68 d.d (4H, CH2OP, JHP 11.69 Hz), 4.46 s and
2
4
4.67 d.d (4H, OCH2O, JHH 6.22 Hz, JHH 1.46 Hz).
31P NMR spectrum (dioxane), P, ppm: 79.55 br.s.
Found, %: C 48.81; H 8.90; P 9.03. C28H60N4O7P2S2.
Calculated, %: C 48.67; H 8.75; P 8.97. M 690.87.
2. Bauer, I., Khabikher, V.D., Antipin, I.S., and Sinya-
shin, O.G., Izv. Ross. Akad. Nauk, Ser. Khim., 2004,
no. 7, p. 1348.
20-Membered diamidocyclodithionodiphosphate
(XIV). 0.3 g of mixture of dibenzylidenedipentaery-
tritiols I and 0.35 g of phosphorous hexaethyltriamide
VIII (molar ratio 1:2) in 5 ml of anhydrous dioxane
was stirred for 12 h at 25 C. Formation of bisdiami-
dophosphite XIII was monitored by means of 31P
3. Uroguchi, D. and Terada, M., J. Am. Chem. Soc.,
2004, vol. 126, no. 17, p. 5356.
4. Predvoditelev, D.A., Malenkovskaya, M.A., and Ni-
fant’ev, E.E., Zh. Obshch. Khim., 2006, vol. 76, no. 8,
p. 1254.
NMR spectroscopy. 31P NMR spectrum (dioxane),
,
P
5. Predvoditelev, D.A., Malenkovskaya, M.A., Streb-
kova, E.V., and Nifant’ev, E.E., Zh. Obshch. Khim.,
2006, vol. 76, no. 7, p. 1095.
ppm: 135.20 br.s. Then to the reaction mixture was
added equimolar amount (0.19 g) of dimethylenedi-
pentaerytritiol III and the mixture was kept at 85 C
for 40 h. Formation of cyclophosphite XII was
6. Yanovskaya, L.A., Yufit, S.S., and Kucherov, V.F.,
Khimiya acetalei (Cheistry of Acetals), Moscow:
Nauka, 1973.
monitored by 31P NMR spectroscopy:
147.68 ppm,
P
br.s. Then to the mixture was added 0.13 g of sulfur at
room temperature and the mixture was kept at 40 C
for 1 h. The sulfur excess was filtered off and dioxane
was removed in a vacuum. Compound XIV was
7. Kukharev, B.F., Stakevich, V.K., and Kukhareva, V.A.,
Zh. Org. Khim., 2003, vol. 39, no. 5, p. 668.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 3 2007