Synthesis of N-trinitroethyl derivatives of linear and heterocyclic nitrogen-containing compounds

Article abstract of DOI:10.1007/s11172-005-0408-z

Earlier unknown N-trinitroethyl derivatives of acetylhydrazine, 4-amino-1,2,4-triazole, and 2,4,6-triamino-1,3,5-triazine, which are potential components for gas-generating formulations, were synthesized.

Full text of DOI:10.1007/s11172-005-0408-z

1346
Russian Chemical Bulletin, International Edition, Vol. 54, No. 5, pp. 1346—1349, May, 2005
Synthesis of Nꢀtrinitroethyl derivatives of linear
and heterocyclic nitrogenꢀcontaining compounds*
ꢀ
I. V. Ovchinnikov, A. S. Kulikov, M. A. Epishina, N. N. Makhova, and V. A. Tartakovsky
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
4
7 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5328. Eꢀmail: mnn@ioc.ac.ru
Earlier unknown Nꢀtrinitroethyl derivatives of acetylhydrazine, 4ꢀaminoꢀ1,2,4ꢀtriazole,
and 2,4,6ꢀtriaminoꢀ1,3,5ꢀtriazine, which are potential components for gasꢀgenerating formuꢀ
lations, were synthesized.
Key words: Nꢀtrinitroethyl derivatives, heterocyclic and linear amino derivatives,
trinitroethanol, trinitromethane.
Compounds containing linear or heterocyclic Nꢀtriꢀ
pends on the basicity of the starting amino derivative. In
nitroethyl fragments (NꢀTNE) are of interest as compoꢀ
nents for gasꢀgenerating formulations. Some of them have
particular, urea or its Nꢀmonoꢀ and N,N´ꢀbis(hydroxyꢀ
1
3
methyl) derivatives easily form the corresponding monoꢀ
4
sufficiently long been known; however, relevant data were
published mainly in the patent literature, often without
reporting synthetic procedures or specifying the physicoꢀ
chemical (except for some explosive) characteristics of
the compounds obtained. The goal of the present work
was to study the possibility of preparing NꢀTNE derivaꢀ
tives of heterocyclic and linear nitrogenꢀcontaining comꢀ
pounds with a primary or secondary amino group.
Two known2 basic approaches to the synthesis of
NꢀTNE derivatives are condensation of the starting amino
derivative with trinitroethanol (pathway a) and condenꢀ
sation of a hydroxymethyl intermediate (prepared by a
reaction with formaldehyde) with trinitromethane (pathꢀ
way b) (Scheme 1).
or bis(NꢀTNE) derivatives, depending on the ratio of the
reagents. Nitroguanidine undergoes no condensation with
trinitroethanol; its NꢀTNE derivative is obtained only
through a monohydroxymethyl intermediate (pathway b).5
Unfortunately, a number of amino derivatives of linear
and heterocyclic nitrogenꢀcontaining compounds have
not been studied as possible precursors for the synthesis of
NꢀTNE derivatives. In the present work, we investigated
the following precursors: oxamide 1, biuret 2, cyanuric
acid 3, 1,2,4ꢀtriazolꢀ5ꢀone (4), 3ꢀnitroꢀ1,2,4ꢀtriazolꢀ5ꢀ
one (5), 4ꢀaminoꢀ1,2,4ꢀtriazole (6), 2,4,6ꢀtriaminoꢀ1,3,5ꢀ
triazine (melamine, 7), and acetylhydrazine 8.
Taking into account a positive experience of the synꢀ
thesis of NꢀTNE derivatives of urea, we used compounds
structurally close to urea as starting material: oxamide 1,
biuret 2, and cyanuric acid 3. However, the reactions of
these compounds in both pathways a and b gave no target
NꢀTNE derivatives, although their hydroxymethyl derivaꢀ
tives were documented.6 Nor were attempts at obtainꢀ
ing NꢀTNE derivatives successful when 1,2,4ꢀtriazolꢀ5ꢀ
one 4 and 3ꢀnitroꢀ1,2,4ꢀtriazolꢀ5ꢀone 5 were used, the
syntheses of their Nꢀhydroxymethyl derivatives being also
reported9 (Scheme 2).
Scheme 1
—8
,10
Apparently, the low basicities of the starting reagents
1
1
11
12
(
pK = 13.2, 6.5, and 9.1 for compounds 2, 3, and 4,
a
respectively) prevent a very important step of the process
from occurring under the conditions studied. The step
1
3
The efficiency of either approach, as well as the funꢀ
damental possibility of obtaining NꢀTNE derivatives, deꢀ
involves the Mannich reaction, i.e., the formation of
immonium ion 9, which then reacts with trinitromethane
(
Scheme 3).
In the only available publication14 devoted to
*
Dedicated to Academician N. K. Kochetkov on the occasion
of his 90th birthday.
2,4,6ꢀtris(2,2,2ꢀtrinitroethylamino)ꢀ1,3,5ꢀtriazine (10),
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1306—1309, May, 2005.
066ꢀ5285/05/5405ꢀ1346 © 2005 Springer Science+Business Media, Inc.
1

Nitroformꢀderivative explosives
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 5, May, 2005
1347
Scheme 2
hydrazine 8 (pKa = –0.5 16) with trinitroethanol
Scheme 3
(
Scheme 6). The yield of product 14 was 56%.
The structures of compounds 10 and 12—14 were deꢀ
termined from elemental analysis and spectroscopic data.
1
It should be noted that their H NMR spectra in soluꢀ
tion suggest an equilibrium between the final products
(
Mannich bases) and the starting reagents (amino derivaꢀ
tives and trinitroethanol), which is always substantially
shifted to the former (> 95%). However, in the solid state
all the compounds obtained are authentic NꢀTNE derivaꢀ
tives with elemental analysis data matching the structures
proposed. The yields, physicochemical parameters, and
spectroscopic characteristics of all the new compounds
are given in Tables 1 and 2.
this compound was obtained by condensation of melamine
7
with trinitroethanol (pathway a). However, the detailed
synthetic route to compound 10 was unavailable and its
selected explosive characteristics were reported only. Our
1
1
attempted condensation of melamine 7 (pK = 5.1
)
a
with trinitroethanol (pathway a) in water at different temꢀ
peratures failed. Pathway b proved to be more effective.
Preparation of 2,4,6ꢀtris(hydroxymethylamino)ꢀ1,3,5ꢀtriꢀ
azine (11) followed by its condensation with trinitroꢀ
methane gave the target product 10 in 81% yield. Hydroxyꢀ
methyl intermediate 11 was not isolated; its aqueous soluꢀ
tion was used in situ in the reaction with trinitromethane
Scheme 4
(
Scheme 4).
ꢀ(2,2,2ꢀTrinitroethylamino)ꢀ1,2,4ꢀtriazole (12)
was successfully synthesized from aminotriazole 6
4
1
5
(
pK = 0.6 ) in both pathways a and b. The yield of
a
product 12 was 93%. Our attempts to introduce two
trinitroethyl fragments into the amino group of the startꢀ
ing aminotriazole 6 failed; the sufficiently high basicity of
compound 12 made it possible to obtain its nitrate 13
(
Scheme 5).
ꢀAcetylꢀ2ꢀ(2,2,2ꢀtrinitroethyl)hydrazine (14) was
synthesized only in pathway a by condensation of acetylꢀ
1
Scheme 5

1348
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 5, May, 2005
Ovchinnikov et al.
Scheme 6
Table 2. IR and NMR spectra of the compounds obtained
Comꢀ
pound
IR,
ν/cm
NMR (acetoneꢀd ),
6
–
1
δ
1Н
14N
1
1
0
2
3440, 3004, 2952, 2888,
5.10 (d, 6 H,
–30.4
1
1
8
588, 1504, 1440, 1328,
304, 1184, 1088, 1020,
76, 856, 808, 784
CH ); 5.83
(NO )*
2
2
(s, 3 H, NH)**
Experimental
3240, 3156, 3128, 3100,
5.36 (d, 2 Н,
–30.8
(NO2)
IR spectra were recorded on a URꢀ20 spectrometer (pellets
3
1
1
1
9
7
044, 2988, 2940, 2892,
616, 1604, 1588, 1504,
420, 1352, 1304, 1200,
128, 1072, 960, 940,
08, 880, 848, 804,
CH , J =
2
1
with KBr). H NMR spectra were recorded on a Bruker WMꢀ250
spectrometer (250 MHz). 13C and N NMR spectra were reꢀ
corded on a Bruker AMꢀ300 spectrometer (75.5 and 21.5 MHz,
respectively). Chemical shifts are given on the δ scale relative to
6 Hz); 7.80 (t,
1 Н, NH);
8.70 (s, 2 H,
CH in the ring)
14
1
13
14
Me Si ( H and C) and MeNO2 ( N). Melting points were
4
72, 716, 684, 624
determined on a Boetius RNMK 05 instrument.
1
1
3
4
3244, 3128, 3000, 1608,
5.25 (s, 2 Н,
–9.6***
2
,4,6ꢀTris(2,2,2ꢀtrinitroethylamino)ꢀ1,3,5ꢀtriazine (10).
–
1
1
1
8
7
588, 1432, 1400, 1340,
300, 1212, 1172, 1120,
080, 1048, 1024, 916,
84, 856, 820, 804, 780,
24, 700, 664, 628
СН ); 9.47
(NO3 );
2
A mixture of 2,4,6ꢀtriaminoꢀ1,3,5ꢀtriazine 7 (0.82 g, 6.5 mmol)
and 30% aqueous formalin (2.0 g, 20 mmol) in water (2 mL) was
heated in a water bath to 70 °C and stirred until compound 7
was completely dissolved. The stirred resulting solution of
tris(hydroxymethyl) derivative 11 was diluted with water (11 mL)
and cooled to 20 °C. Trinitromethane (3.02 g, 20 mmol) was
added and the mixture was kept at 15 to 20 °C. The yellow oil
that formed after ∼ 0.5 h completely solidified after ∼ 3 days. The
precipitate was carefully triturated under a layer of the mother
liquor, filtered off, thoroughly washed with water, and dried in a
vacuum desiccator over KOH and P O to give compound 10
(s, 2 Н, СН
in the ring)
–30.8***
(NO2)
3322, 3288, 3000, 2976,
1.90 (s, 3 H,
Me); 5.00 (s,
–30.2
(NO2)
2
1
1
1
8
960, 2920, 2884, 1660,
604, 1584, 1528, 1408,
372, 1336, 1312, 1164,
136, 1112, 1008, 876,
56, 792, 764
2 H, CH );
2
8.75, 9.05
(both br.s,
1 H each, NH)
2
5
* 13C NMR (acetoneꢀd ), δ: 45.4 (CH ); 126.3 (C(NO ) ); 167.2
6 2 2 3
(ring C).
** H NMR (DMSOꢀd ), δ: 5.25 (s, 6 H, CH ); 8.05 (s,
6 2
3 H, NH). H NMR (CDCl ), δ: 5.40 (s, 6 H, CH ); 7.40
(
3.23 g, 81%).
ꢀ(2,2,2ꢀTrinitroethylamino)ꢀ1,2,4ꢀtriazole (12). A mixture
of 4ꢀaminoꢀ1,2,4ꢀtriazole 6 (1.36 g, 16.2 mmol) and a 86%
4
1
1
aqueous solution of trinitroethanol (3.41 g, 16.2 mmol) in water
3
2
(
10 mL) was stirred at room temperature for 2 h. The precipitate
(s, 3 H, NH).
was filtered off, washed with water (2×5 mL), and dried in a
vacuum desiccator over P O to give product 12 (3.73 g, 93.3%).
*** In CD OD.
3
2
5
4
ꢀ(2,2,2ꢀTrinitroethylamino)ꢀ1,2,4ꢀtriazole, nitrate (13).
thoroughly squashed on the filter for 1 h, and dried in a
Compound 12 (3.73 g, 15.1 mmol) was added to stirred HNO
d = 1.358 g cm ) (6.6 mL). The reaction mixture was heated
to 55 °C to complete homogenization. The resulting solution
was slowly cooled and the precipitate of the salt was filtered off,
3
vacuum desiccator over P O5 and KOH to give product 13
2
–
3
(
(
3.76 g, 80.4%).
ꢀAcetylꢀ2ꢀ(2,2,2ꢀtrinitroethyl)hydrazine (14). A mixture of
1
acetylhydrazine 8 (1.0 g, 13.5 mmol) and a 86% aqueous soluꢀ
tion of trinitroethanol (2.84 g, 13.5 mmol) in water (9 mL) was
stirred at 20 °C for 1 h. The precipitate that formed was filtered
off, washed with water (2×5 mL), and dried in a vacuum desicꢀ
cator over P O to give product 16 (1.78 g, 56%).
Table 1. Yields and physicochemical characteristics of the comꢀ
pounds obtained
2
5
Comꢀ Yield
pound (%)
M.p.
/°C
Found
Calculated
Molecular
formula
(
%)
This work was financially supported by the Internaꢀ
tional Scientific and Technical Center (Grant 1882).
C
H
N
1
1
1
0
2
3
81
55—57 17.59 1.58 33.89 C H N O
15 18
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1
Received December 20, 2004;
in revised form March 30, 2005
3