612
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 3, March, 2019
Korepin et al.
in an air stream to give 2.05 g (84%) of the product with m.p.
1
44—150 °C. Recrystallization from a mixture of CCl (8 mL)
4
and CHCl (36 mL) (reflux, hot filtration, stepwise cooling to
3
–
1
(
15 °C for 4 days) afforded 1.6 g (66%) of compound 1 with m.p.
–
1
59—160 °C (decomp.). IR, ν/cm : 1612 sh., 1591, 1584, 814 sh.
triazine ring); 1500, 1330, 806 (NO ); 3415, 3426 (NH); 2958,
2
1
2
894, 1437 (CH ). H NMR (DMSO-d ), a mixture of two
2
6
conformers (I : II ≈ 3 : 2), the signals partially overlap, δ: 5.19
and 5.29 (both br.d, 3.6 H and 2.4 H, CH NH); 8.01 and 8.08
2
1
(
both br.t, 3 H, CH NH). H NMR (acetone-d ), a mixture of
2
6
two conformers (I : II ≈ 1 : 1.2), the signals partially overlap,
δ: 5.45 (br.s, 6 H, CH NH); 7.49, 7.43, and 7.27 (all br.s, 3 H,
2
13
1
CH NH). C{ H} NMR, δ: 166.9 and 166.5 (ring, symm. and
2
unsymm. CNHCH ); 125.5 (br.s, C(NO ) ); 44.5 (br.s, CH NH).
2
2 3
2
14
N NMR, δ: –31.9 (C(NO ) ). Found (%): C, 17.56; H, 1.46;
2
3
O, 47.11. C H N O . Calculated (%): C, 17.57; H, 1.47; O, 46.81.
9
9
15 18
2
,4,6-Tris(2,2,2-trinitroethylnitramino)-1,3,5-triazine (5).
To a stirred mixture of compound 3 (0.185 g, 0.3 mmol) and
CF CO) O (1.8 mL, 12.7 mmol), HNO (0.9 mL, 21.6 mmol)
(
Fig. 1. Structures of symmetrical (I) and unsymmetrical (II)
3
2
3
was added dropwise over 30 min at 1—2 °C (ice bath). The mix-
ture was stirred for 5 h at room temperature (18—20 °C) and
poured onto crashed ice. After 15 min, the precipitate formed
was collected by filtration, washed with water, and dried under
conformers of compounds 1 (R = H) and 5 (R = NO ).
2
Experimental
water-jet vacuum over P O . Recrystallization from CHCl gave
2
5
3
0
.18 g of colorless product with m.p. 121—123 °C (decomp.).
IR spectra were recorded with a Bruker ALPHA FTIR
According to NMR spectroscopy, this product is a ~1 : 3 mixture
of 4-(2,2,2-trinitroethylamino)-2,6-bis(2,2,2-trinitroethylnitr-
amino)-1,3,5-triazine (4) and 2,4,6-tris(2,2,2-trinitroethyl-
nitramino)-1,3,5-triazine (5). NMR spectra of the mixture are
superpositions of the spectra of compounds 4 and 5. The signals
of the individual compounds 4 and 5 were identified in the spec-
1
13
14
spectrometer in KBr pellets. H, C, and N NMR spectra were
run on a Bruker AVANCE III 500 instrument (working frequen-
1
13
14
cies of 500 ( H), 127.75 ( C), and 36.14 MHz ( N)) in (CD ) CO
3
2
(
if not stated otherwise) using the same sample for recording
1
13
NMR spectra for all nuclei. The H and C NMR shifts are
14
given relative to Me Si (internal standard), the N NMR shifts
4
tra. Both compounds exist as conformers I (NMR data).
are given relative the signal of nitromethane. NMR signals were
assigned based on the chemical shift values, shapes of the
multiplets, a comparison of integral intensities of the signals, and
1
Compound 5. H NMR (acetone-d ), δ: 6.57 (s, 6 H,
6
13
1
CH N(NO )). C{ H} NMR, δ: 166.52 (ring); 123.92 (br.,
2
2
14
C(NO ) ); 50.53 (s, CH N(NO )). N NMR, δ: –54.07 (N(NO )).
3
,10
2 3
2
2
2
the published data
for the related compounds. Elemental
1
Compound 4. H NMR (acetone-d ), δ: 5.64 (m, 2 H,
6
analysis was carried out with an Elementar vario EL cube
CHNO analyzer (Germany). Melting points were measured us-
ing a Boetius apparatus heating near the melting point at a rate
13
1
CH NH); 6.50, 6.44 (both s, 2 H each, CH N(NO )). C{ H}
ab
2
2
NMR, δ: 167.60 and 154.82 (ring); 123.92 (br., C(NO ) ); 44.26
2
3
14
(
(
br., CH NH). N NMR δ: –34.8 (C(NO ) ); –53.5 (br.,
–
1
2
2
3
of 4 deg min . Density of compound 5 was measured by a pycno-
N(NO )).
1
1
2
meter method.
Melamine 2 (99%) was purchased from Aldrich.
,4,6-Tris(2,2,2-trinitroethylamino)-1,3,5-triazine (1).
A mixture of melamine 2 (0.5 g, 4 mmol), DMSO (8 mL), and
5% aqueous formaldehyde (2 mL, 17 mmol) was stirred at room
To a mixture of compounds 4 and 5 (0.22 g), dichloroethane
(
1
1 mL) was added followed by addition of HNO3 (0.5 mL,
2
2.6 mmol) under stirring and cooling to 1—2 °C. The resulting
solution was treated dropwise with (CF CO) O (1 mL, 7.1 mmol)
3
2
2
at 1—2 °C. The mixture was stirred at 18—20 °C for 4 h and
temperature for 30 min. Then the stirred mixture was treated
dropwise with a solution of NaOH (0.02 g, 0.5 mmol) in water
4
0 min, treated dropwise with CCl4 (2 mL), and stirring was
continued for 20 min. The mixture was poured onto crashed ice,
the precipitate formed was collected by filtration, washed with
(
3 mL). The obtained solution was stirred for 2 h, cooled to 10 °C,
and a solution of H SO (0.033 g, 0.34 mmol) in water (2 mL)
2
4
water, and dried under water-jet vacuum over P O . Recryst-
2
5
was added dropwise. Cooling was removed and after warming up
allization from CHCl afforded 0.095 g (34% based on the start-
3
to 17 °C a solution of trinitromethane (3.6 g, 24 mmol) in water
ing triazine 3) of compound 5 with m.p. 128—129 °C (decomp.).
(
12 mL) was added dropwise. Addition of trinitromethane was
–
1
IR, ν/cm : 1613, 1608 sh., 1592 (triazine ring); 1640, 1259, 851
exothermic causing the rise of the reaction temperature up to
3—25 °C and turning the mixture cloudy. The mixture was stirred
(
NNO ); 1560, 1337, 1296 (NO ), 2972, 2888, 1424, 1386 (CH ).
2 2 2
H NMR (acetone-d ), δ: 6.57 (s, 6 H, CH N(NO )). C{ H}
2
1
13
1
6
2
2
at 25 °C for 2 h and then at 60 °C for 5 h. After spontaneous
cooling to room temperature, the precipitate formed was col-
lected by filtration, washed with water, and dried in an air stream
to give 2.42 g of the yellow product. The obtained product was
dissolved in propan-2-ol (35 mL), the resulting solution was
filtered, the filtrate was diluted with water (400 mL), and the
obtained mixture was stirred for 2.5 h. The colorless precipitate
formed was filtered off, washed with water (150 mL), and dried
NMR, δ: 165.25 (ring); 123.91 (br., C(NO ) ); 50.53 (s,
2
3
14
CH N(NO )). N NMR, δ: –34.9 (C(NO ) ); –53.5 (br.,
2
2
2 3
N(NO ). Found (%): C, 14.90; H, 0.83; O, 50.93. C H N O24.
2
9
6
18
Calculated (%): C, 14.41; H, 0.81; O, 51.18.
This work was performed using the equipment of the
Analytical Center for Collective use of the Institute of