534
KHODAREV et al.
(
(
CHCl ), , ppm: 37.3, 37.7 s. 13C NMR spectrum
0.32 g of phosphorous tetramethyldiamide and puri-
fied by column chromatography, eluent D. Yield
3
CDCl ), , ppm: 15.7 s (SCH CH ), 23.4 d (SCH
3
2
3
2
2
31
CH , J < 2 Hz), 23.2 24.5, 34.9 36.2 s (cyclo-
hexylidene protections), 37.3 d (NCH , J 6.8 Hz),
5
0.25 g (12%), colorless oil, R 0.41 (D). P NMR
3
PC
f
2
spectrum (C H ), , ppm: 7.1 d.d ( J 721.1 Hz, 2J
10.1 Hz). H NMR spectrum (C D ), , ppm: 1.05
6 6
1
3
PC
6
6
PH
PH
6
1
4
3
1
9.9 s (C ), 71.0 s (C ), 73.0 d (C , J < 2 Hz),
PC
5
3
2
2
4
6
7
4.9 s (C ), 77.1 d (C , J 9.8 Hz), 103.0 d (C ,
PC
1.34 s (24H, 4C(CH ) ), 4.0 m (4H, H , H , the coupl-
3 2
3
JPC < 2 Hz), 109.5 s and 111.9 s (Cquat). Found, %:
ing constant was not determined due to overlap of
5
6
C 53.90; H 7.50, P 6.10. C H NO PS. Calculated,
%
signals), 4.3 m (4H, H , H , the coupling constant was
not determined due to overlap of signals), 4.8 d.d (2H,
2
2
38
7
: C 53.75; H 7.79; P 6.30.
Cyclohexyl phosphite (XVII). To a solution of
.59 g of cyclohexanol in 3 ml of dioxane, 1.04 g of
2
3
3
H , J
2
1
3.4 Hz, J
2
3
was not determined due to
H H
H H
3
2
overlap of signals), 5.2 d (2H, H , J
.8, 5.9 d (2H, J
H3P
10.1 Hz),
0
3
1
5
1
2
3.4 Hz), 7.0 d (1H, PH, J
H H PH
phosphorous tetramethyldiamide was added. The
mixture was heated at 60 C for 3 h and cooled to
room temperature. Water, 0.11 g, in 2 ml of dioxane
was added, and the mixture was left for 24 h. The
solvent was evaporated, and the residue was subjected
to column chromatography, eluent A, R 0.15 (A).
NMR spectrum (CHCl ), , ppm: 4.6 d ( J
7
21.1 Hz). Found, %: C 50.30; P 4.91. C H O P.
24 39 13
Calculated, %: C 50.88; P 5.47.
Bis(2,3-O-isopropylidene- -L-methylramnopyra-
noside) 4,4 -phosphite (XX) was prepared 1.11 g of
3
1
2
,3-O-isopropylidene- -L-methylramnopyranoside
P
f
1
and 0.44 g of phoshorous tetramethyldiamide and
purified by column chromatography, system E.
3
PH
1
6
80.7 Hz). H NMR spectrum (C D ) , , ppm: 1.0 m
6 6
Colorless oily substance. Yield 0.60 g (24%), color-
4
3
2
(2H, H ), 1.5 m (2H, H ), 1.8 m (2H, H ), 3.9 br.s
31
less oil, R 0.37 (E). P NMR spectrum (C H ), ,
1
2
3
f
6
6
(
7
4
1H, POH), 4.4 d.d (1H, H , J 15.3 Hz, J
1 2
PH
H H
ppm: 7.1 d.d ( J 713.8 Hz, 2J 10.5 Hz). H NMR
1
1
1
PH PH
.3 Hz), 6.9 d (1H, PH, JPH 680.7 Hz). Found, %: C
4.15; P 18.60. C H O P. Calculated, %: C 43.90;
spectrum (C D ), , ppm: 1.2 s (6H, 26CH ); 1.4 1.6
6
6
3
6
13
3
(
s, 12H, 2C(CH ) ); 3.03, 3.05 s (6H, 2OCH ); 3.7 m
3 2 3
P 18.87.
5
(2H, H , the coupling constant was not determined
2
,3-O-Isopropylidene- -L-methylramnopyrano-
side 4-(butyl phosphite) (XVIII). To a solution of
.93 g of compound XI in 5 ml of dioxane, 0.24 g of
butanol was added. The mixture was heated for 5 at
0 C, the solvent was evaporated, and the residue was
purified by column chromatography, eluent A. Yield
3
3
due to overlap of signals), 4.1 d.d (2H, H , J
3 2
H H
3
2 3
5
.5 Hz, J
3
4
4.3 Hz), 4.2 d.d (2H, H , J
2
1
6.1 Hz,
0
H H
H H
3
4
2
3
J
2
3
5.5 Hz), 4.4 m (2H, H , J
H4P
10.5 Hz, J
4 5
H H
H H
3
1
3
5
7.3 Hz, J
4
3
4.3 Hz), 4.8 d (2H, H , J
1
2
6.1 Hz),
H H
H H
1
7.4 d (1H, PH, J 713.8 Hz). Found, %: C 51.0;
PH
3
1
0
.20 g (20.1%), mobile yellow oil, R 0.53 (A).
P
P 6.91. C H O P. Calculated, %: C 49.79; P 6.42.
f
20 35 11
1
NMR spectrum (CHCl ), , ppm: 6.93 d, 8.04 d ( J
6
3
PH
1
13
REFERENCES
83.5 Hz, J 692.6 Hz). C NMR spectrum (C D ),
PH 6 6
,
ppm: 14.1
s
(OCH CH CH CH ), 17.8
s
2
2
2
3
1. Nifant’ev, E.E. and Grachev, M.K., Usp. Khim., 1994,
6
(
(
OCH CH CH CH ), 19.4 s (C ), 27.0 s and 28.5 s
C(CH ) ), 33.1 d (OCH CH CH CH , J 5.8 Hz),
vol. 63, no. 7, p. 602.
2
2
2
3
3
3 2 2 2 2 3 PC
2. Nifant’ev, E.E., Khimiya gidrofosforilnykh soedinenii
(The Chemistry of Hydrophosphoryl Compounds),
Moscow: Nauka, 1983.
2
5
9
5.0 s (OCH ), 64.8 d (OCH CH CH CH , JPC
3 2 2 2 3
.6 Hz), 65.6 d (C , J 5.3 Hz) 77.2 s (C ), 77.7 d
5
3
2
PC
3
3
4
2
(
(
C , J 5.3 Hz), 79.6 d (C , J 8.4 Hz), 98.7 s
PC PC
1
3. Zhukova, N.A., Koroteev, M.P., Vasyanina, L.K., and
Nifant’ev, E.E., Russ. J. Gen. Chem., 2003, vol. 73,
no. 9, p. 1371.
C ), 110.3 s and 110.7 s (C(CH ) ). Found, %: C
3 2
4
9
6.8; P 9.83. C H O P. Calculated, %: C 49.7; P
14 27 7
.15.
Diglycophosphites XIX and XX (general proce-
dure). To a solution of 2 equiv of monosaccharide in
ml of dioxane, 1.3 equiv of phosphorous tetramethyl-
4
5
6
7
. Abramov, V.S., Il’ina, N.A., and Yuldasheva, I.N.,
Zh. Obshch. Khim., 1969, vol. 39, no. 10, p. 2237.
. Shilov, I.V. and Nifant’ev, E.E., Zh. Prikl. Khim., 1971,
vol. 44, no. 11, p. 2581.
. Zwierzak, A. and Koziara, A., Tetrahedron, 1967,
vol. 23, no. 5, p. 2243.
3
diamide was added. The mixture was heated for 6 h
at 60 C, the solvent was evaporated, and the residue
was purified by column chromatography.
. Hoegberg, E.J. and Cassaday, J.T., J. Am. Chem. Soc.,
1951, vol. 73, p. 557.
Bis(1,2:5,6-di-O-isopropylidene- -D-glucofura-
nose) 3,3 -phosphite (XIX) was prepared from 0.94 g
of 1,2:5,6-di-O-isopropylidene- -D-glucofuranose and
8. Nifant’ev, E.E. and Shilov, I.V., Zh. Obshch. Khim.,
1972, vol. 42, no. 9, p. 1936.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 4 2006