1
862
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 8, August, 2003
Korolev et al.
and the resulting product was dissolved in a sixfold (by weight)
Table 3. Crystallographic parameters of compounds 1 and 6
excess of water. The aqueous solution was extracted with Et O
2
(
50 mL×4) and the ethereal solution was dried with MgSO4.
Parameter
1
6
After removal of the solvent, compound 5 was obtained in a
yield of 26.8 g (43%), nD2 1.4934 (cf. lit. data : nD 1.4936).
Found (%): C, 26.58; H, 4,55; N, 12.30. C H N O . Calcuꢀ
0
12
20
Molecular formula
Molecular weight
C5H8N2O7
208.14
C5H9NO5
163.13
5
10
2
8
lated (%): C, 26.56; H, 4,46; N, 12.39. The aqueous solution
Space group
a/Å
b/Å
C2/c
P2 /n
1
was concentrated to dryness to prepare compound 4 in a yield of
15.020(2)
6.0553(9)
11.2392(16)
123.613(3)
851.3(2)
4*
8.285(9)
9.306(9)
9.259(6)
95.21(10)
710.8(11)
4
1
2
8
.1 g (16.2%), m.p. 78—79 °C (from DCE) (cf. lit. data : 79 °C).
Found (%): C, 33.21; H, 6,24; N, 7.65. C H NO . Calcuꢀ
c/Å
5
11
6
lated (%): C, 33.15; H, 6.12; N, 7.73. The neutralized aqueous
solution was concentrated to dryness, the residue was extracted
β/deg
V/Å3
Ζ
ρcalc/g cm
µ/mm–
with Me CO (25 mL×4), and the solution in acetone was dried
2
–
3
with MgSO . After removal of the solvent, compound 4 was
1.624
0.155
1.524
0.138
4
1
obtained in a yield of 4.1 g (8.2%), m.p. 78—79 °C (from DCE).
A mixture with a sample prepared as described above did not
give a melting point depression.
Radiation
MoꢀKα (λ = 0.71073 Å)
3.26—30.03
1048
θꢀ2θ Scan range/deg
Number of measured
reflections
Number of reflections
with I > 2σ(I )
R1
3.11—30.02
3
,3ꢀBis(hydroxymethyl)oxetane (3) was prepared from a soꢀ
lution of compound 4 (18.1 g, 100 mmol) and KOH (6.5 g,
15 mmol) in anhydrous EtOH according to a procedure deꢀ
3127
1496
1
873
1
1
scribed earlier. The yield was 8.25 g (70%), b.p. 132—134 °C
1
1
(
1 Torr) (cf. lit. data : 132—134 °C (1 Torr)).
,3ꢀBis(hydroxymethyl)oxetane mononitrate (6). A solution
7.9 mL) of KOH (0.6 g, 10.6 mmol) in anhydrous EtOH was
0.0693
0.1851
0.0601
0.1362
3
wR2
(
*
The molecule is located on a crystallographic twofold axis.
added with stirring to a solution of compound 5 (2.40 g,
0.6 mmol) in anhydrous EtOH (8 mL). The reaction mixture
1
was refluxed for 3 h, the precipitate that formed was filtered off,
the filtrate was concentrated, and the residue was fractionated.
Compound 6 was obtained in a yield of 0.96 g (55.5%), b.p.
stirred at ∼ 20 °C for 40 min, after which the reaction mixture
was diluted with CHCl (3 mL) and poured into ice water. The
3
organic layer was separated, washed with water, a 10% aqueous
1
17—119 °C (1 Torr), m.p. 39—40 °C. Found (%): C, 36.72;
NaHCO solution, and again with water, and then dried with
3
H, 5.69; N, 8.44. C H NO . Calculated (%): C, 36.81; H, 5.56;
5
9
5
MgSO . After removal of the solvent, compound 1 was obtained
4
–
1
N, 8.59. IR (capillary film), ν/cm : 3409, 1047 (OH); 1636,
in a yield of 525 mg (99%) as colorless crystals, m.p. 93.5—94 °C
(from DCE). A mixture with a sample prepared according to the
procedure A did not give a melting point depression. The IR
spectra of these samples are identical.
Xꢀray diffraction study. The Xꢀray diffraction data sets for
compounds 1 and 6 were collected on an automated Bruker AXS
SMART 1000 diffractometer equipped with a CCD detector
1
2
629, 1281, 872, 844 sh (ONO ); 980 (oxetane ring); 2960,
2
1
884, 1461, 1379 (CH ). H NMR (DMSOꢀd ), δ: 3.63 (s, 2 H,
2
6
2
CH OH); 4.35 (m, 4 H, OCH , AB, J ≈ 6.0; ∆νAВ ≈ 11.9 Hz);
2
2
AB
4
.71 (s, 2 H, CH ONO ); ∼ 5.00 (br.s, 1 H, OH).
2 2
3
,3ꢀBis(hydroxymethyl)oxetane dinitrate (1). A. A solution
of compound 3 (2.36 g, 20 mmol) in glacial AcOH (3.6 mL) was
added with stirring to a solution of a mixture of concentrated
(
graphite monochromator, 110 K, ω scanning technique, scan
2
0
HNO3 (d4 1.513) (3.2 mL, 80 mmol) and Ac O (4.7 mL,
2
step was 0.3°, frames were exposed for 30 s) according to a
5
0 mmol) in CHCl (20 mL) at –5—0 °C. The reaction mixture
20
3
standard procedure. The crystallographic parameters and deꢀ
was stirred for 20 min with a gradual increase in the temperature
to 18—20 °C and then stirred at ∼ 20 °C for 40 min, after which it
was poured into ice water. The organic layer was separated,
tails of the structure refinement of both structures are listed in
Table 3.
The structures of both compounds were solved by direct
methods and refined by the fullꢀmatrix leastꢀsquares method
with anisotropic thermal parameters for all nonhydrogen atoms.
The positions of the hydrogen atoms were calculated geometriꢀ
washed with water, a 10% aqueous NaHCO solution, and again
3
with water, and then dried with MgSO . After removal of the
4
solvent, compound 1 was obtained in a yield of 4.04 g (97%) as
colorless crystals, m.p. 93.5—94 °C (from 1,2ꢀdichloroethane)
cally and refined using the riding model. All calculations were
6
9,18,19
(
cf. lit. data: m.p. 89—911 и 90—92 °C
). Found (%):
21,22
carried out using the SHELX97 program package.
The seꢀ
C, 28.86; H, 4.02; N, 13.50. C H N O . Calculated (%):
5
8
2
7
lected geometric parameters of the compounds are given in
Tables 1 and 2.
–
1
C, 28.85; H, 3.87; N, 13.46. IR (KBr), ν/cm : 1645, 1638,
1
1
4
2
3
292, 1274, 848 (ONO ), 993 (oxetane ring); 2972, 2896, 1461,
2
1
382 (CH ). H NMR (CDCl ), δ: 4.54 (s, 4 H, OCH ); 4.75 (s,
2
3
2
We thank the Head and staff of the Center of Xꢀray
Diffraction Studies (A. N. Nesmeyanov Institute of
Organoelement Compounds, Russian Academy of Sciꢀ
ences) for giving us the possibility to collect the Xꢀray
data on a Smart diffractometer.
This study was financially supported by the Interꢀ
national Science and Technology Center (ISTC,
Grant 1550).
13
H, CH ONO ). C NMR (DMSOꢀd +CCl ), δ: 73.78 (s,
2
2
6
4
C(CH ONO or OCH )); 73.08 (s, 2 C(OCH or CH ONO ));
2
2
2
2
2
2
9.91 (s, 1 C (Cquat)).
B. A solution of compound 6 (417 mg, 2.55 mmol) in CHCl3
2.5 mL) was added with stirring to a mixture of concentrated
(
2
0
HNO (d4 1.513) (0.22 mL, 5.1 mmol) and Ac O (0.48 mL,
3
2
5
.1 mmol) at ∼ 0 °C. The reaction mixture was stirred for 20 min
with a gradual increase in the temperature to 20 °C and then