1
742
IL’YASOV et al.
of compound II was determined by spectrophotometry
precipitate was filtered off, washed with alcohol and
1
1
ether, and dried at room temperature. Yield 2.9 g
(
226 nm,
12530 l mol cm ). Yield 3.63 g
1
(
98%), mp 200 C. IR spectrum, , cm : 3040, 2985
(89%). The mixture was cooled to 20 C and extracted
(
%
CH ); 1570, 1270 (NNO ); 1440, 1210, 930. Found,
: C 16.2; H 2.70; N 37.2. CH N O . Calculated, %:
2 2 2
with ether (4 25 ml). The extract was dried over
2 2
MgSO and evaporated under reduced pressure. To the
4
C 16.22; H 2.70; N 37.84.
oily residue (2 g), 16 ml of 10% aqueous potassium
hydroxide and a mixture of 10 ml of ethanol and
Bis(hydroxymethyl)nitroamine (VI). Dinitrourea,
3 g (0.02 mol), was added under stirring at 5 to 0 C
to 6.0 g (0.08 mol) of a 40% formaldehyde solution.
The mixture was stirred for 3 h at 20 30 C and ex-
tracted with ether (5 10 ml). The extract was dried
1
0 ml of methanol were added. The precipitate was
filtered off, washed with alcohol and ether, and dried
for 24 h at room temperature. Yield 3.11 g (45%),
K [O NNCH NNO ] H O, mp 90 C (in a capillary).
2
2
2
2
2
1
IR spectrum, , cm : 3450 br (H O); 2950, 2850
over MgSO , and the solvent was distilled off under
2
4
(
(
CH ); 1640 w (H O); 1460, 1430, 1355, 1335
reduced pressure to obtain a yellowish oily substance.
Yield 2.92 g (60%). IR spectrum, , cm : 3500
2
2
+
1
NNO ). Found, %: K 34.63. CH K N O H O.
2
2
2
4
4
2
+
Calculated, %: K 33.91.
3400 br (OH); 2970, 2920, 2840 (CH ); 1560, 1295
2
(
NNO ). Found, %: C 19.7; H 5.0; N 22.0. C H N O .
b. The procedure was the same as above with the
difference that, after stirring for 20 min at 65 70 C,
the mixture was cooled to 20 C and 10% aqueous
potassium hydroxide was added to pH 7 8. A mixture
of 2.5 ml of ethanol and 2.5 ml of methanol was
added, the precipitate of K SO was filtered off, and
a mixture of 10 ml of ethanol and 10 ml of methanol
was added to the filtrate. The precipitate was filtered
off, washed with alcohol and ether, and dried for 24 h
at room temperature. The yield of salt III was the
same as in a.
2 2 6 2 4
Calculated, %: C 19.67; H 4.92; N 22.95.
1,3,5-Trinitrohexahydro-1,3,5-triazin-2-one
(VIII). Salt VII [1], 14.12 g (0.04 mol), was added
under stirring at 5 to 0 C to 24 ml of a mixture of
equal amounts (by weight) of H SO and HNO (d =
1.756 g/cm ). The mixture was stirred for 30 min at
20 C and poured into 40 g of an ice water mixture.
The precipitate was filtered off, washed with cold
water, alcohol, and ether, and dried at room tempera-
ture. Yield 8.4 g (89%), mp 170 180 C, 200 201 C
2
4
2
4
3
3
3
,7-Dinitro-1,5-dioxa-3,7-diazacyclooctane (IV).
A 5.7-g portion of N,N -dinitrourea (I) containing
.5 g (0.03 mol) of the main substance and 1.2 g
12.2 mmol) of H SO was added with stirring at
(from nitromethane, with decomposition). IR spec-
1
trum, , cm : 3040, 2980, 2910, 2840 (CH ); 1750
2
4
(
(C O); 1600, 1300, 1280 (NNO ); 1450, 1220, 1150,
2
1080, 1040, 920, 900, 880, 820, 790, 730, 705, 615,
560, 485, 460. Found, %: C 15.4; H 1.4; N 34.9.
C H N O . Calculated, %: C 15.25; H 1.69; N 35.59.
2
4
2
0 25 C to 5.63 g (0.06 mol) of a 32% formaldehyde
solution. The mixture was stirred for 20 min at 65
0 C, 20 ml of water was added, the mixture was
3
4
6
7
7
Dinitropentamethylenetetramine (IX). Urea, 5 g
cooled to 10 C, and the precipitate was filtered off,
washed with cold water, alcohol, and ether, and dried
at room temperature. Yield 0.1 g (1.6%), mp 260 C;
published data [10]: mp 263 264 C.
(0.0833 mol), was added under stirring at 5 to 0 C
to a mixture of 10 ml of 98% of nitric acid and 10 ml
of technical-grade oleum (20% SO ). The mixture was
3
stirred for 30 min at 0 5 C and poured into 30 g of
an ice water mixture, and 30 ml of a 37% formalde-
hyde solution was added at a temperature not exceed-
ing 20 C. The mixture was heated to 40 C, stirred
for 20 min, cooled, and neutralized to pH 6 with
25% aqueous ammonia at 20 25 C. It was then stirred
for 45 min at 20 C, and the precipitate was filtered
off, washed with water, and dried at room temperature
until constant weight. Yield 11 g (60%), mp 186
Poly(methylenenitroamine) (V). a. A 4.5-g
0.03-mol) portion of N,N -dinitrourea containing no
(
sulfuric acid (see method a in [2]) was added under
stirring at 20 25 C to 2.81 g (0.03 mol) of a 32%
formaldehyde solution. The cooling bath was re-
moved, and the mixture spontaneously warmed up to
1
05 C. It was cooled to 10 C, and the precipitate was
filtered off, washed with cold water, alcohol, and
ether, and dried at room temperature. Yield 1.11 g
190 C; published data [11]: mp 202 205 C. IR spec-
1
1
(
50%), mp 205 215 C. IR spectrum, , cm : 3040,
trum, , cm : 3000, 2925 (CH ); 1530, 1270, 1250
2
2
985 (CH ); 1570, 1270 (NNO ); 1440, 1210, 930.
(NNO ); 1500, 1440, 1400, 1335, 1205, 1190, 1080.
2
2
2
Found, %: C 16.0; H 2.75; N 36.2. CH N O . Cal-
Found, %: C 27.5; H 4.6; N 37.5. C H N O . Cal-
2
2
2
5
10
6
4
culated, %: C 16.22; H 2.70; N 37.84.
culated, %: C 27.5; H 4.6; N 38.5.
b. A 4.72-g (0.02-mol) portion of compound VIII
was added under stirring to 100 ml of DMF. The
mixture was stirred for 60 min at 80 85 C, and the
1,3,5-Trinitro-1,3,5-triazapentane (X). Urea, 5 g
(0.0833 mol), was added under stirring at 5 to 0 C
to 28.5 ml of a mixture of equal amounts (by weight)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 12 2002