Nitration of primary aminofurazans with aqueous nitric acid

Article abstract of DOI:10.1007/s11172-011-0054-6

A convenient procedure for the synthesis of N-nitroaminofurazans by nitration of primary 3-amino-4-R-furazans (R = Me, NO₂, phenyl-, methyl-NNO-azoxy-, tert-butyl-NNO-azoxy-, tert-butyldiazenyl-, etc.) with 66-77% aqueous nitric acid was develo

Full text of DOI:10.1007/s11172-011-0054-6

Russian Chemical Bulletin, International Edition, Vol. 60, No. 2, pp. 334—338, February, 2011
334
Nitration of primary aminofurazans with aqueous nitric acid
V. P. Zelenova and A. A. Lobanovab
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: viczel2008@rambler.ru
bFederal Research and Production Center "Altay",
1 ul. Sotsialisticheskaya, 659322 Biysk, Altay territory, Russian Federation.
Fax: +7 (385 4) 30 5953. Eꢀmail: post@frpc.secna.ru
A convenient procedure for the synthesis of Nꢀnitroaminofurazans by nitration of primary
3ꢀaminoꢀ4ꢀRꢀfurazans (R = Me, NO2, phenylꢀ, methylꢀNNOꢀazoxyꢀ, tertꢀbutylꢀNNOꢀazoxyꢀ,
tertꢀbutyldiazenylꢀ, etc.) with 66—77% aqueous nitric acid was developed. Depending on the
concentration of HNO3, the reaction is carried out at a temperature from 18 to 55 °С, the yield
of the products is 80—99%. 3ꢀNitraminoꢀ4ꢀphenylfurazan with unsubstituted benzene ring was
obtained by nitration of 3ꢀaminoꢀ4ꢀphenylfurazan.
Key words: nitramines, primary aminofurazans, nitration, Nꢀnitroaminofurazans, nitric acid.
Scheme 2
Monosubstituted nitramines of the furazan series among
which compounds with high density are found attract
chemists´ attention as energetic compounds1—5 as well as
starting compounds in the synthesis of 1,2,3,4ꢀtetrazineꢀ
1,3ꢀdioxides,6—9 1,2,3ꢀtriazole Nꢀoxides,10 and furazanoꢀ
cinnoline Nꢀoxides.11
Several methods for synthesis of nitraminofurazans 1
are known. They can be obtained by either direct nitration
of primary aminofurazans 2a—с (see Refs 5—7, 10, 12 and
Scheme 1) or nitration of aminofurazan derivative 3 with
replacement of the leaving group R (see Ref. 3 and scheme 2),
or destructive nitrolysis.4
3ꢀAminoꢀ4ꢀRꢀfurazans 2 are weak bases, e.g., 3ꢀamiꢀ
noꢀ4ꢀnitrofurazan (pKBH = –4.4 (see Ref. 13)) is close
+
Scheme 1
R = SiMe3, BBu2
to dinitroaniline in basicity (pKBH+ = –5.39 (see Ref. 14)).
Therefore, in the nitration of aminofurazans 2 with nitric
acid or its mixtures the extent of protonation of the amino
group is low, which allows one to relatively easily obtain
3ꢀnitraminoꢀ4ꢀRꢀfurazans 1 using the majority of nitraꢀ
tion systems including acidic. Fuming nitric acid (d20
=
= 1.5 g cm–3), its solutions in organic solvents, mixtures with
H2SO4 or oleum, as well as mixtures of H2SO4 with
NaNO3 or KNO3, and mixtures of HNO3 with P2O5,
NO2BF4, N2O5 (see Refs 1—6, 11) are employed for Nꢀnitraꢀ
tion of primary aminofurazans. In most cases, nitraminoꢀ
furazans 1 are isolated in yields not exceeding 70—80%.
Examples of quantitative Nꢀnitration of aminofurꢀ
azans 2 using dinitrogen pentoxide or nitration systems
R = NO2 (a), Me (b),
(c), Ph (d),
(e),
(f),
(g)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 327—331, February, 2011.
1066ꢀ5285/11/6002ꢀ334 © 2011 Springer Science+Business Media, Inc.

Nitration of aminofurazans
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 2, February, 2011
335
Table 1. Nitration of 3ꢀaminoꢀ4ꢀRꢀfurazans 2a—g with aqueous nitric acid
Amine 2 Concentraꢀ
Amount of HNO3 (g)
T/°Ca
τ/minb
Yield of
compound 1
(%)
M.p. of nitramine 1/°Сс
The present study Literature
tion of HNO3 per 1 g of compound 2
(%)
a
b
71
77
71
77
76
70
77
71
71
10
6
8
8
4
10
10
6
30—33
20—23
22—24
15—18
20—24
20—24
20—22
40—42
40—44
120
60
60
25
15
120
15
40
70
83
72
92
99
90
81
92
95
48—54
55—56
40—42
47—484
(57, 60d)2
44—50 (51—52e)
103—107
88—893
102—1046
69—7111
—
c
d
e
f
gh
74—75
74—80 (80—81f)
85—90 (88—91g)
85—88.5
—
—
10
30
a Nitration temperature. b Nitration time. с In parentheses, melting point of a product following crystallization is given. d After twofold
f
recrystallization. e Nitramine 1b obtained was purified by twofold recrystallization from CH2Cl2—petroleum ether. From
CH2Cl2—petroleum ether mixture. g From aqueous MeOH. h Procedure for the synthesis of compound 2g (m.p. 94.5—95.5 °С) will be
published later.
based on it are known.2,3 In some cases,3 preliminary proꢀ
tection of the primary amino group (silylation, borylaꢀ
tion) followed by substitutive nitration of compound 3
with NO2BF4 affords ultimately the target product 1b in
85—93% yield (see Scheme 2).
In the present work, we studied nitration of primary
aminofurazans with nitric acid with different concentraꢀ
tions. Both the known nitramines 1a—d and new comꢀ
pounds 1e—g (see Scheme 1 and Table 1) were obtained.
3ꢀAminoꢀ4ꢀ(methylꢀNNOꢀazoxy)furazan (2e), which is
the starting compound for the synthesis of nitramine 1e,
was obtained according to the Kovacic procedure15 from
3ꢀaminoꢀ4ꢀnitrosofurazan (4) and N,Nꢀdibromomethylꢀ
amine (Scheme 3).
that is the nitrating agent in the Nꢀnitration, which subꢀ
stantially differs from fuming nitric acid. We have shown
that the concentrations of 66—71% (commercially availꢀ
able HNO3) or 76—77% (the solution prepared by diluꢀ
tion of more concentrated HNO3) are sufficient for the
preparation of nitramines 1 in high yields. This fact is
unexpected in the chemistry of aminofurazans in view of
low nitrating activity of aqueous nitric acid and reversibilꢀ
ity of Nꢀnitration.
The procedure is experimentally easy, affords high yield
of the product, and is free from expensive reagents. Nitraꢀ
tion is carried out at room temperature (in the case of
76—77% HNO3) or under moderate heating (in the case
of 70—71% HNO3). Nitramines 1c,d,f,g precipitate in
almost pure form upon completion of the reaction after
dilution of the nitration mixture. Nitramines 1a,b are isoꢀ
lated by extraction. It should be noted that the method
proposed allows successful access to 3ꢀnitraminoꢀ4ꢀ
phenylfurazan (1d) with the nonnitrated aromatic ring in
90% yield. It is known11 that the treatment of amine 2d
with a mixture H2SO4—KNO3 results only in compounds
with the nitrated benzene ring. Aryl substituents also unꢀ
dergo nitration in the reaction of phenylfurazans with an
H2SO4—HNO3 system.18
Scheme 3
The yield of nitramine 1а (83%) is close to that
achieved using the procedure described earlier2
(N2O5, CH2Cl2, –20—10 °С). The yield of nitramine 1b
(93%) significantly exceeds that attained in the nitration
of amine 2b with 100% HNO3 (22%) and is close to that
with the use of N2O5 or an HNO3—P2O5 system (96%)
(see Ref. 3).
Synthesis of compound 1e is the only case where the
yield of nitraminofurazan formed upon nitration with fumꢀ
ing HNO3 (94%) is higher than that with aqueous nitric
acid (yield 81%) (see Table 1).
We established that aqueous nitric acid is applicable
for the nitration of 3ꢀaminoꢀ4ꢀRꢀfurazans 2a—g. NꢀNitraꢀ
tion is known to be the reversible process,14,16 dilution of
nitric acid reduces the rate of nitration and increases the
rate of denitration.14 The decrease in the rate constant for
nitration is caused by a decrease in the nitronium cation
activity due to its hydration. Presumably, 80% HNO3 exꢀ
ists in the form of hydrate HNO3•H2O, whereas 60%
HNO3 exists in the form of dihydrate HNO3•2H2O (see
Ref. 17). Intrinsically, it is aqueous nitric acid (60—80%)

336
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 2, February, 2011
Zelenov and Lobanova
CDCl3 and DMSOꢀd6 using signals of the residual protons of the
Nitration of aminofurazans with 76—77% HNO3 genꢀ
solvent (1H, 13C) and MeNO2 14N) as the internal standards.
(
erally takes 15—25 min at nearly room temperatures. It is
necessary to increase nitration time to 1 h in the case of
furazans 2а,d, which is probably caused by electronꢀwithꢀ
drawing properties of the substituent adjacent to the amino
group thus decreasing the amine basicity. The use of more
The IR spectra were recorded on a Perkin—Elmer 684 instruꢀ
ment. The course of the reactions was monitored, and the purity
of the compounds was checked, by TLC on Silica gel 60 F254
(Merсk). Mass spectra were obtained on a Kratos MSꢀ300 mass
spectrometer (EI, 70 eV). Aminofurazans 2a,19 2b,20 2c,6 2d,21
2f,22 and 423 were prepared according to the known procedures.
N,NꢀDibromomethylamine. Bromine (22.7 mL, 0.44 mol) was
added dropwise to aqueous solution of NaOH (40 g (1 mol) of
NaOH in 95 mL of water) over a period of 0.5 h maintaining the
temperature at 0 3 °С. Then 35% aqueous solution of MeNH2
(19.4 mL, 0.21 mol) in CH2Cl2 (80 mL) was added dropwise
over a period of 20 min at 0 3 °С to the obtained solution of
sodium hypobromite and the reaction mixture was stirred at
0—5 °С for 5 h. Dark red organic layer was separated and aqueꢀ
ous layer was extracted with CH2Cl2 (2×50 mL). The combined
organic extracts were dried with MgSO4. The solvent was
removed in vacuo at the temperature not exceeding 30 °С.
N,NꢀDibromomethylamine was obtained as a dark red liquid
with characteristic odor in a yield of 29.7 g (79%) (cf. Ref. 24:
m.p. 10—11 °С). The substance is unstable and possesses explosive
properties.
3ꢀAminoꢀ4ꢀ(methylꢀNNOꢀazoxy)furazan (2e). N,NꢀDibromoꢀ
methylamine (6.5 g, 30 mmol) in CH2Cl2 (20 mL) was added
to a stirred solution of 3ꢀaminoꢀ4ꢀnitrosofurazan (4) (3.0 g,
26 mmol) in MeCN (40 mL) at 10—20 °С, the reaction mixture
was stirred at 20—25 °С for 1 h. The solvents and bromine evolved
were removed in vacuo, 1,2ꢀdichloroethane or the mixture of
CCl4—CH2Cl2 (1 : 1) (50 mL) was added to the residue, and the
solution was concentrated in vacuo. Such a treatment was reꢀ
peated twice. Product 2e (3.0 g, 80%) was filtered off, colorless
crystals of 2e were obtained by crystallization from acetone in
a yield of 2.1 g (56%). M.p. 124—126.5 °С. Found (%): C, 25.22;
H, 3.50; N, 48.80. C3H5N5O2. Calculated (%): C, 25.18; H, 3.52;
N, 48.94. MS, m/z: 143 [M]+. IR (KBr), ν/сm–1: 3420, 3320,
3250, 3200, 3030, 2920, 1640, 1515, 1485, 1440, 1380, 1355,
1200, 1140, 1045, 985. 1H NMR (DMSOꢀd6, 200 MHz), δ: 3.44
(s, 3 Н, CH3); 6.70 (s, 2 Н, NH2). 1H NMR (CDCl3, 200 MHz),
δ: 3.55 (s, 3 Н, CH3); 5.25 (s, 2 Н, NH2). 13C NMR (DMSOꢀd6,
75 MHz), δ: 39.5 (CH3); 150.9 (br. С=N). 14N NMR
(CDCl3, 22 MHz), δ: –63.1 ((N→O), Δν0.5 = 40 Hz). 14N NMR
(DMSOꢀd6), δ: –63.1 ((N→O), Δν0.5 = 140 Hz).
dilute HNO3, viz., 68—71% (d20 = 1.396—1.418 g cm–3
in most cases requires heating to 30—55 °С.
)
The influence of reaction conditions (concentration of
HNO3, temperature, percentage of N2O4) on the yield of
product 1с was studied by the example of nitration of
amine 2c. The nitration temperature depends on the conꢀ
centration of HNO3. After five minutes of nitration of
amine 2c with fuming HNO3 (d20 = 1.5 g cm–3, 4 g of
HNO3 per 1 g of 2a, 0.3% N2O4, temperature interval
–
–
15— 10 °С), product 1с was isolated in 90% yield. Exꢀ
tension of the nitration time leads to the reduction of the
yield: after 20 min the yield is 87%, but after 120 min the
yield is 78%.
Product 1c was isolated in 92—94% yield in all the
cases using 66—76% aqueous acid. The optimal concenꢀ
tration of HNO3 in the case of nitration of amine 2c at
room temperature (18—25 °С) is 74—76%, the yield of 2c
being virtually quantitative under these conditions (see
Table 1). Nitration of amine 2c with 66—68% aqueous
nitric acid at 55 °С for 30 min resulted in the product 1c in
92—94% yield. The quality of nitramine is much worse
when using nitric acid of lower concentration; therefore, it
is not useful for nitration. The amount of HNO3 in
the interval from 4 to 10 g per 1 g of 2c does not influence
the yield.
Earlier,3 it has been noted that the increase in the N2O4
percentage in fuming nitric acid in the case of nitration of
3ꢀaminoꢀ4ꢀmethylfurazan (2b) considerably reduces the
yield and the quality of compound 1b. The negative influꢀ
ence of nitric oxides on nitration of primary aminofuraꢀ
zans was demonstrated by the example of aqueous nitric
acid. Nitration of amine 2c with 76% HNO3 prepared on
the basis of fresh distilled nitric acid (d20 = 1.5 g cm–3),
which was free of N2O4, resulted in 99% yield of 1c (m.p.
103—107 °С (see Table 1)). If percentage of N2O4 is 1.8%,
nitramine 2c is isolated in a yield of 89% under the same
conditions, but the melting point of the product obtained
was significantly lower (94—101 °С).
Nitraminofurazans 1a—g (general procedure). A. Aminofurꢀ
azan 2 (10 mmol) was added with stirring to aqueous nitric acid
(76—77%, d20 = 1.438—1.442 g cm–3) at room temperature
(18—25 °С) (4—10 g of HNO3 per 1 g of 2), the reaction mixture
was stirred at the temperature indicated in Table 1, then poured
onto ice (3—4 g per 1 g of HNO3) and stirred. In the case of
compounds 1c,d,f,g, the precipitate that formed was filtered off,
washed with ice water three times (1—3 mL per 1 g of the
product), and dried on air. Waterꢀsoluble compounds 1a,b,e
were isolated by extraction of the aqueous solution with diethyl
ether (10—15 mL of ether per 1 g of the product), the organic
extracts were dried with MgSO4, and the solvent was removed
in vacuo.
Structure of all new compounds was confirmed by the
combination of physicochemical methods.
Thus, a convenient oneꢀstep procedure for the synꢀ
thesis of monosubstituted nitramines of the furazan series 1
based on nitration of primary aminofurazans 2 with aqueꢀ
ous nitric acid is developed.
B. Aminofurazan 2a—g was added with stirring to aqueous
nitric acid (70—71%, d20 = 1.413—1.420 g cm–3) at 30—40 °С
(5—10 g of HNO3 per 1 g of 2), the reaction mixture was stirred
at this temperature. Subsequent workꢀup was analogous to that
in the method А.
Experimental
1
H, 13C, and 14N NMR spectra were recorded on Bruker
АM 200, Bruker AM 300, and Bruker DRX 500 spectrometers in

Nitration of aminofurazans
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 2, February, 2011
337
3ꢀNitraminoꢀ4ꢀnitrofurazan (1a). Dichloromethane (two
drops) and CCl4 (1 mL) was added to the residue obtained after
removal of diethyl ether, this mixture was kept at –20 °С for
6—12 h. Crystalline product 1a was filtered off, washed with
cold CCl4 (2×5 mL). 3ꢀNitraminoꢀ4ꢀnitrofurazan (1a) was obꢀ
tained in yields of 83% (method А) and 70% (method B), m.p.
The yield of compound 1e prepared according to the method
А was 81%, m.p. 74—80 °C.
4ꢀ(tertꢀButyldiazenyl)ꢀ3ꢀnitraminofurazan (1f) was prepared
according to the method B. Found (%): C, 33.82; H, 4.66;
N, 39.08. C6H10N6O3. Calculated (%): C, 33.65; H, 4.71;
N, 39.24. MS, m/z: 214 [M]+. IR (KBr), ν/сm–1: 3256, 2980,
2936, 2872, 1612, 1584, 1524, 1492, 1476, 1448, 1364, 1348,
1308, 1200. 1H NMR (CDCl3, 300 MHz), δ: 1.44 (s, 3 Н, CH3);
11.31 (s, 1 Н, NH). 13C NMR (CDCl3, 75 MHz), δ: 26.6
(C—CH3); 72.29 (C—CH3); 142.5 (СNH); 152.7 (С—N=N).
14N NMR (CDCl3, 22 MHz), δ: –47.2 (NO2, Δν0.5 = 35 Hz).
4ꢀ(tertꢀButylꢀNNOꢀazoxyfurazanyldiazenyl)ꢀ3ꢀnitraminofurꢀ
azan (1g) was prepared according to the method B. Found (%):
C, 29.47; H, 3.13; N, 42.78. C8H10N10O5. Calculated (%):
C, 29.45; H, 3.09; N, 42.94. IR (KBr), ν/сm–1: 3232, 2980,
2940, 1612, 1476, 1460, 1444, 1384, 1316, 1288, 1204. 1H NMR
(CDCl3, 300 MHz), δ: 1.40 (s, 3 Н, CH3); 10.09 (s, 1 Н, NH).
13C NMR (CDCl3, 75 MHz), δ: 25.2 (C—CH3); 62.4 (C—CH3);
141.6 (СNH); 151.9 (С—N(O)); 155.5, 155.9 (С—N=N).
1
55—56 °С. MS, m/z: 175 [M]+. H, 13C, and 14N NMR spectra
of compound 1a are identical to those reported in the literature.2,4
3ꢀNitraminoꢀ4ꢀmethylfurazan (1b). Na2CO3 (4.4 g) was addꢀ
ed portionwise to the reaction mixture poured onto ice. The
solution obtained was extracted with diethyl ether, the organic
extracts were dried, solvent was removed in vacuo. Three drops
of CF3COOH were added to the residue and the mixture obꢀ
tained was kept at –20 °C for 6—12 h, then CCl4 (1 mL) was
added and crystalline product was filtered off. Nitramine 1b was
obtained in yields of 92% (method А) and 72% (method B),
m.p. 44—50 °С (decomp.). MS, m/z: 144 [M]+. 1H, 13C, and
14N NMR spectra of compound 1b are identical to those reportꢀ
ed in the literature.25
4ꢀ(tertꢀButylꢀNNOꢀazoxy)ꢀ3ꢀnitraminofurazan (1c). 3ꢀAmiꢀ
noꢀ4ꢀ(tertꢀbutylꢀNNOꢀazoxy)furazan (2c) (18.5 g, 0.1 mol) was
added portionwise to 98.5% HNO3 (55.5 g, d20 = 1.5 g cm–3) at
–17 °С in such a way that the temperature of the reaction mixꢀ
ture did not exceed –10 °С, the reaction mixture was stirred
maintaining the temperature at –10 to –12 °С for 10 min and
poured onto ice (300 g), stirred and kept for 0.5 h. The precipiꢀ
tate of nitramine 1c was filtered off, washed with ice water
(2×50 mL), and dried. Compound 1c was obtained in a yield of
21.4 g (93%), m.p. 104—106 °С (decomp.). 1H, 13C, and
14N NMR spectra of compound 1c are identical to those reportꢀ
ed in the literature.6 IR (KBr), ν/сm–1: 3290, 3000, 2870, 1620,
1590, 1510, 1490, 1480, 1460, 1450, 1370, 1315, 1300, 1270,
1240, 1160, 860, 820, 740.
14N NMR (CDCl3, 22 MHz), δ: –48.5 (NO2, Δν = 90 Hz);
0.5
–75.7 ((N→O), Δν0.5 = 210 Hz).
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)
over 2—3 min in such a way that temperature of the reaction
mixture did not exceed –10 °С. The reaction mixture was stirred
at –15 3 °С for 5 min and poured onto ice (55 g). The precipiꢀ
tate that formed was filtered off and washed with cold water
(5 mL), 4ꢀ(methylꢀNNOꢀazoxy)ꢀ3ꢀnitraminofurazan (1e) was
obtained in a yield of 2.89 г (62%), m.p. 80—81 °С (decomp.).
The mother liquor was extracted with CH2Cl2 (3×50 mL), exꢀ
tracts were dried with MgSO4, the solvent was removed in vacuo.
An additional portion (1.46 g) of nitramine 1e was obtained. The
overall yield was 94%, m.p. 80—81 °С (decomp.). Found (%):
C, 19.20; H, 2.18; N, 44.39. C3H4N6O4. Calculated (%): C, 19.16;
H, 2.14; N, 44.68. MS, m/z: 188 [M]+. IR (KBr), ν/сm–1: 3260,
3040, 2950, 2920, 1615, 1580, 1510, 1500, 1450, 1430, 1375,
1315, 1270, 1190. 1H NMR (DMSOꢀd6, 200 MHz), δ: 3.38
(s, 3 Н, CH3); 10.6 (s, 1 Н, NH). 1H NMR (CDCl3, 200 MHz),
δ: 3.65 (s, 3 Н, CH3); 11.38 (s, 1 Н, NH). 13C NMR (DMSOꢀd6,
75 MHz), δ: 40.0 (CH3); 149.5 (C—NH); 155.0 (br. C—N→O).
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Received April 6, 2010;
in revised form January 11, 2011