Synthesis and properties of 3-azido-4-(2H-tetrazol-5-yl)furazan

Article abstract of DOI:10.1007/s10593-017-2123-8

[Figure not available: see fulltext.] We describe an effective scheme for the synthesis of a new energetic compound – 3-azido-4-(2H-tetrazol-5-yl)furazan from 4-amino-N'-hydroxyfurazan-3-carboximidamide. The structure of 3-azido-4-(2H-tetrazol-5-yl)furazan was proved by ¹Н and ¹³С NMR spectroscopy, mass spectrometry, and X-ray structural analysis. 3-Azido-4-(2H-tetrazol-5-yl)furazan crystallized in monoclinic syngony, space group Р2₁/n, monocrystal density d 1.953 g·cm^–3 (100 K). According to differential scanning calorimetry data, 3-azido-4-(2Htetrazol-5-yl)furazan melts at 103.3°С, while the maximum of thermal decomposition exotherm was observed at 185.6°С. The sensitivity of 3-azido-4-(2H-tetrazol-5-yl)furazan to impact (2 kg, 25 cm, 36% explosion frequency) and to friction (1450 kg·cm–3 lower limit) was at the level of pentaerythritol tetranitrate. The salts of 3-azido-4-(2H-tetrazol-5-yl)furazan with ammonia and guanylurea were also obtained and characterized.

Full text of DOI:10.1007/s10593-017-2123-8

DOI 10.1007/s10593-017-2123-8
Chemistry of Heterocyclic Compounds 2017, 53(6/7), 779–785
Synthesis and properties of 3-azido-4-(2H-tetrazol-5-yl)furazan
Andrei I. Stepanov1*, Vladimir S. Sannikov1, Dmitry V. Dashko1,
Aleksey G. Roslyakov1, Alexander A. Astrat'yev1, Elena V. Stepanova2,
Zainutdin G. Aliev3, Tel'man K. Goncharov3, Sergei M. Aldoshin3
1 Special Engineering and Design Bureau "Technolog",
33-А Sovetsky Ave., Saint Petersburg 192076, Russia; е-mail: stepanoffai@yandex.ru
2 Russian State Hydrometeorological University,
98 Malookhtinsky Ave., Saint Petersburg 195196, Russia; е-mail: stepanoffev@yandex.ru
3 Institute of Problems of Chemical Physics, Russian Academy of Sciences,
1 Akademika Semenova Ave., Chernogolovka 142432, Russia; e-mail: aliev@icp.ac.ru
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2017, 53(6/7), 779–785
Submitted December 30, 2016
Accepted after revision March 1, 2017
We describe an effective scheme for the synthesis of a new energetic compound – 3-azido-4-(2H-tetrazol-5-yl)furazan from 4-amino-
N'-hydroxyfurazan-3-carboximidamide. The structure of 3-azido-4-(2H-tetrazol-5-yl)furazan was proved by 1Н and 13С NMR
spectroscopy, mass spectrometry, and X-ray structural analysis. 3-Azido-4-(2H-tetrazol-5-yl)furazan crystallized in monoclinic syngony,
space group Р21/n, monocrystal density d 1.953 g·cm–3 (100 K). According to differential scanning calorimetry data, 3-azido-4-(2H-
tetrazol-5-yl)furazan melts at 103.3°С, while the maximum of thermal decomposition exotherm was observed at 185.6°С. The sensitivity of
3-azido-4-(2H-tetrazol-5-yl)furazan to impact (2 kg, 25 cm, 36% explosion frequency) and to friction (1450 kg·cm–3 lower limit) was at
the level of pentaerythritol tetranitrate. The salts of 3-azido-4-(2H-tetrazol-5-yl)furazan with ammonia and guanylurea were also obtained
and characterized.
Keywords: amidrazone, azidofurazan, nitrofurazan, 1,2,5-oxadiazole, tetrazole.
Azoles (oxadiazoles, triazoles, tetrazoles, and others),
especially derivatives containing explosophoric substi-
tuents (nitro, azo, azoxy, and azido groups) represent
promising objects for the synthesis of new energetic
compounds.1 In contrast to the usual aromatic systems,
azoles are characterized by high positive enthalpies of
formation, which is an essential property of energetic
compounds.2 The combination of several azole rings in one
molecule of energetic compound,3,4 in particular tetrazole5
and furazan (1,2,5-oxadiazole) rings,6 provides an approach
for the design of compounds that simultaneously have the
high energy characteristics of tetrazoles and the good
thermal stability of furazans.
An important structural feature of furazan ring is the
presence of "active oxygen" atom, which has no direct
covalent bonds to carbon atoms and thus can provide
energy via oxidation of carbon-containing moieties. The
second carbon atom of furazan ring can be decorated with
an explosophoric group, while the presence of an acidic
proton in the structure of tetrazole moiety can be exploited
for the preparation of various energetic salts either with
metals or with various inorganic and organic nitrogenous
bases.2 In particular, such compounds as 4-(2H-tetrazol-
5-yl)furazan-3-amine7–10 (1), 5-(4-nitrofurazan-3-yl)-2H-tetra-
zole9 (2), N-[4-(2H-tetrazol-5-yl)furazan-3-yl]nitramine11 (3),
3,4-bis(2H-tetrazol-5-yl)furazan12 (4), 1,2-bis[4-(2H-tetrazol-5-yl)-
furazan-3-yl]diazene9,13,14 (5), 4,4'-oxybis[3-(2H-tetrazol-
5-yl)furazan]15–18 (6) are known in the series of 3-substi-
tuted 4-(tetrazol-5-yl)furazan derivatives (Fig. 1). The
energetic characteristics of their salts are presented in
Table 1. Compound 3 has been used as ligand in penta-
aminecobalt(III) complexes.19
In this work, we describe the synthesis of a new
energetic compound, 3-azido-4-(2H-tetrazol-5-yl)furazan (7).
The synthesis of compound 7 can be accomplished by
starting from 4-amino-N'-hydroxyfurazan-3-carboximidamide
(8)20,21 according to Scheme 1. The azido group can be
introduced into furazan ring by nucleophilic substitution of
nitro group in compound 2 with sodium azide,22,23 or by
reaction of diazonium salt 10 with sodium azide.24
It should be noted that the synthesis of compound 7
according to Scheme 1 includes some problematic and
0009-3122/17/53(6/7)-0779©2017 Springer Science+Business Media New York
779

Chemistry of Heterocyclic Compounds 2017, 53(6/7), 779–785
Figure 1. Energetic derivatives of 4-(tetrazol-5-yl)furazan.
Table 1. Energetic characteristics of salts obtained from
dangerous procedures. Thus, the methods for the
preparation of intermediate 4-aminofurazan-3-carbonitrile
(9)7 and nitro compound 29 are quite laborious.
Furthermore, the literature procedure9 for the isolation of
compound 2 from reaction mixture by extraction with
dichloromethane could not be reproduced. We were able to
achieve full extraction of nitro compound 2 from the
reaction mixture with ethyl acetate only after its partial
neutralization by addition of crystalline Na3PO4 (see
Experimental). According to the known reactivity of
aminofurazans,25 diazotation of amine 1 can be performed
with nitrosylsulfuric acid in concentrated H2SO4 medium.
The azidation of diazonium salt 10 involves the use of an
4-(tetrazol-5-yl)furazan derivatives
ρ,
ΔHf°298
,
VD, m·s–
Compound
g·cm–3
kJ·mol–1
1
3 (salt with biguanidine)2
1.770
441
8670
3 (salt with NH2OH)11
514
1.815
1.747
1.75
1.86
1.80
426
1117
1371
585
93
8830
7730
8620
8320
8778
6 (salt with triaminoguanidine)15
6 (salt with carbodihydrazide)15
Hexogen (RDX)15
excess of aqueous sodium azide solution in an acidic
reaction mixture, which invariably leads to the liberation of
toxic and explosive HN3.24
Scheme 1
Scheme 2 shows an alternative route proposed by us for
the synthesis of azide 7. We used amidoxime 8 as precursor,
the condensation of which with triethyl orthoformate26 in the
presence of BF3·Et2O provided 4-(1,2,4-oxadiazol-3-yl)-
furazan-3-amine (11) in up to 90% yield when using the
optimized procedure.27 Nitrofurazan 12 was obtained in
84% yield by oxidation of compound 11 with a mixture of
aqueous 36% H2O2 solution and concentrated H2SO4 at
elevated temperature.27 The synthesis of the key
intermediate 13 was based on a reductive opening of the
1,2,4-oxadiazole ring with hydrazine.27 Thus, the treatment
of compound 12 with an excess of hydrazine hydrate in
MeCN at room temperature resulted both in the opening of
1,2,4-oxadiazole ring and the substitution of nitro group
with a hydrazinyl moiety, leading to the formation of
compound 13. The treatment of the latter with aqueous NaNO2
solution in acetic acid medium while cooling gave the
target azidotetrazole 7 in 75% yield. The overall yield of
tetrazole 7, as calculated from amidoxime 8, was
approximately 50%.
Scheme 2
780

Chemistry of Heterocyclic Compounds 2017, 53(6/7), 779–785
Table 2. The spectral characteristics of 3-R-4-(tetrazol-5-yl)furazans 2, 7, 14, and 15
13С NMR spectrum, δ, ppm
Com-
pound
1H NMR spectrum,
Mass spectrum,
m/z (Irel, %)
IR spectrum, ν, cm–1
Furazan
δ, ppm
Tetrazole Cation
С-3
С-4
3223 (NH), 1620 (C=N), 1568 (NO2), 1397, 1386
(NO2), 1329, 1305, 1144, 1115, 1030, 999, 825, 429
10.40–8.80
160.0 141.3
147.4
–
183 [M]+ (0.2), 78 (20), 46
(20), 30 [NO]+ (100), 29
(50)
2
7
(1H, br. s, NH)
3048, 3006, 2934, 2857, 2836, 2766, 2719, 2663,
2591, 2142 (N3), 1544, 1493, 1396, 1315, 1273,
1237, 1184, 1149, 1049, 1029, 1021, 998, 935, 906,
883, 782, 581, 530, 488, 432
3290, 3154, 3017, 2984, 2839, 2284, 2229, 2166 7.24 (4H, s, NH4 )
(N3), 2152 (N3), 2139 (N3), 1899, 1809, 1688, 1535,
1466, 1433, 1395, 1217, 1173, 1145, 1033, 910, 887,
786, 589, 531, 491, 435, 407
12.00–9.0
(1Н, br. s, NH)
153.3 140.0
152.8 143.6
148.0
–
179 [M]+ (1), 151 [M–N2]+
(8), 67 (11), 30 [NO]+ (100),
29 (33)
+
148.7
148.8
–
–
14
15
3412, 3362, 3191, 2180 (N3), 2141 (N3), 1745, 1704, 9.76 (1H, br. s, NH); 155.9 143.6
1608, 1528, 1400, 1352, 1231, 1189, 1119, 998, 941, 8.14 (4H, br. s, 2NH2);
908, 888, 781, 770, 719, 695, 590, 492, 454
154.8;
152.8
–
7.18 (2H, br. s, NH2)
According to the results of potentiometric titration, azide 7
was a stronger NH acid (рKа 2.32) than amine 1 (рKа 2.53),
but weaker than nitro analog 2 (pKa 2.22). Similarly to
compounds 1 and 2, azide 7 formed hydrolytically stable
salts with metal cations and nitrogenous bases. From
practical point of view, the salts easiest to isolate were
ammonium salt 14 and the salt with guanylurea 15, which
was sparingly soluble in water (Scheme 2).
The salts of compound
7 with hydrazine and
hydroxylamine could not be obtained, because the addition
of hydrazine or hydroxylamine to azide 7 caused its
vigorous decomposition. The spectral characteristics of
3-azido-4-(2H-tetrazol-5-yl)furazan (7) and salts 14, 15 are
presented in Table 2.
Figure 2. The molecular structure of 3-azido-4-(2H-tetrazol-5-yl)-
furazan (7) with atoms represented by thermal vibration ellipsoids
of 50% probability.
Since compounds 2 and 7 are strong NH acids, the
proton signals in 1Н NMR spectra were observed as
significantly broadened singlets in the downfield region.
The replacement of nitro group with azide group resulted in
4.1–7.2 ppm upfield shift of 13С NMR signal for the
furazan ring carbon atom bearing the azido group.
Deprotonation of the tetrazole ring in salts 14 and 15 did
not substantially affect the positions of 13C NMR signals
due to the furazan and tetrazole ring carbon atoms.
Monocrystals of compound 7 that were suitable for
X-ray structural analysis were obtained by slow
evaporation of its solution in water. The colorless, well-
faceted crystals of compound 7 belonged to monoclinic
syngony. The molecule of compound 7 was practically
planar: the torsion angle N(1)–C(1)–C(2)–C(3) was equal to
6.3° (Fig. 2). The bond lengths and valence angles in
furazan ring containing localized C=N double bonds were
in good agreement with the literature data.28–32 In general,
with the exception of known differences between the bond
lengths and angles in furazans and furoxans,33 the
molecular geometry of compound 7 was similar to the
structure of its closest structural analog, 3-azido-4-(1H-
tetrazol-5-yl)furoxan.34 All three N–N bonds in the
tetrazole ring had similar lengths, providing evidence of
significant delocalization of the double bonds.
The molecules related by the symmetry of second order
screw axis were linked into infinite chains by relatively
strong N(3)–H(3)···N(1) hydrogen bonds with 2.829 Å
length. The H(3)···N(1) distance was equal to 1.945 Å,
while the angle at hydrogen atom was 164.5°. An illustra-
tion of a fragment of the chain is provided in Figure 3.
The crystal lattice of compound 7 had a layered
structure. The crystal packing in projection along the
monoclinic axis is shown in Figure 4. All of the molecules
forming the crystal were located in the (1 0 3) plane with an
interlayer distance of 3.15 Å. An analogous layered structure
was noted also for the closest structural analog of
compound 7 – the ammonium salt of 3-azido-4-(1H-tetrazol-
5-yl)furoxan,34 where planar anions were also located in the
(1 0 3) plane of crystal, while the hydrogen atoms of
ammonium ion provided hydrogen bonds that formed a
three-dimensional framework. The hydrogen bond lengths
were in the range of 3.03–3.06 Å.
According to calculations,35 the anion of compound 7,
its triaminoguanidine salt, and ammonium salt 14 had high
positive enthalpies of formation (682, 1089, and 799 kJ·mol–1,
respectively). As shown in Table 3, the target compound,
azide 7, and its salts were characterized by relatively good
thermal stability. The sensitivity of compounds 7 and 14 to
781

Chemistry of Heterocyclic Compounds 2017, 53(6/7), 779–785
Table 3. Physicochemical properties of
3-R-4-(tetrazol-5-yl)furazans 2, 7, 14, and 15
Starting tempe-
rature of vigor- Oxygen
Sensitivity
Compound Mp, °С ous decomposi- balance,
impact*, friction**,
tion,
%
%
kg·cm–2
°С
29
7
123–124
102.5–103.5
–
–
–30.6
–49.1
–57.1
20
36
24
3100
1450
1900
185.6
185.2
14
(32,
10 kg)
–
206.0
–65.4
3400
15
PETN
141.3
121.9
140–145
–10.1
–45.4
20–36
1500
4500
Picric acid
(25,
10 kg)
* Fall hammer apparatus K-44-II (apparatus No. 1, hammer mass 2 kg at
drop height 25 cm), explosion frequency, %.
** Apparatus K-44-III (lower limit).
Figure 3. A fragment from the infinite chain formed by
molecules of compound 7.
MAT Incos 50 instrument (EI ionization, 70 eV).
Elemental analysis was performed on a PerkinElmer 2400
elemental analyzer. The dissociation constants for com-
pounds 1, 2, and 7 were determined by method of potentio-
metric titration in aqueous solutions with 0.1 N NaOH
solution. Calorimetric studies were performed in aluminum
crucible under argon flow (100 ml/min) at the heating rate
of 5 K/min, using a Netzsch TG 209 F1 Libra analyzer.
The sensitivity to mechanical stimuli was determined
according to GOST 4545-88 and GOST R 50835-95
standards.36 Melting points were determined in capillary
tubes. The reaction progress and the purity of the obtained
compounds were controlled on a Shimadzu Series 20
HPLC instrument with a diode matrix detector. The
following analytical conditions were used: Luna С18(2)
250 × 4.6 mm column, 5 µm Phenomenex stationary phase.
The mobile phase was MeOH–H2O–CF3CO2H at the
volume ratio of 74.95:24.95:0.10. The thermostat and
detector temperatures were set at 40°С. Detection was
performed at 209, 230, and 254 nm wavelengths. The
retention time of compound 7 was 4.2 min at 0.8 ml/min
flow rate.
Figure 4. The structure of compound 7 projected along the b axis
of unit cell.
The synthesis of compound 1 was performed as described
previously,27 the synthesis of amidoxime 8 – according to
another publication.21 The synthesis of 4-(1,2,4-oxadiazol-
3-yl)furazan-3-amine (11) was accomplished according to
optimized literature procedure.26
mechanical stimuli was at the level of pentaerythritol
tetranitrate (PETN), while the guanylammonium salt 15 in
this regard was similar to picric acid.
The proposed scheme for the synthesis of 3-azido-4-(2H-
tetrazol-5-yl)furazan is suitable for scale-up, thus enabling
further practical studies of this compound and a series of its
salts as nitrogen-rich components of energetic composi-
tions.
5-(4-Nitrofurazan-3-yl)-2H-tetrazole (2). Concd H2SO4
(40.0 ml, 73.6 g, 0.72 mol, d 1.84 g/cm3) was added
dropwise to a vigorously stirred and externally cooled 30%
aqueous H2O2 solution (32.6 ml, 36.3 g, 0.32 mol), while
maintaining the temperature in the solution below 50–55°C.
Compound 1 (12.2 g, 0.08 mol) was then added in 2–3 g
portions, while maintaining the temperature of reaction
mixture in the range of 50–55°С. After completing the
addition of compound 1, the mixture was stirred for 1 h at
50–55°С, cooled to room temperature, and poured into a
mixture of ice and water (50 ml). The quenched mixture was
partially neutralized by adding crystalline sodium
orthophosphate (100 g, approximately 0.26 mol) and then
Experimental
IR spectra were recorded on an FSM-1201 FT-IR
spectrometer in KBr pellets. 1Н and 13С NMR spectra were
acquired in DMSO-d6 solutions on a Bruker DRX 400
spectrometer (400 and 100 MHz, respectively). The
chemical shifts of 1Н and 13С nuclei were determined
relative to the solvent signals (2.51 and 40.0 ppm,
respectively). Mass spectra were recorded on a Finnigan
782

Chemistry of Heterocyclic Compounds 2017, 53(6/7), 779–785
extracted with ethyl acetate (4×30 ml). The combined organic
157 [M]+ (100), 140 (11), 111 (15), 85 (37), 68 (19), 67
(12), 58 (12), 53 (16), 43 (32), 42 (12), 32 (29), 31 (23), 30
(28), 29 (17).
layers were washed with water (2×10 ml) and dried over
anhydrous MgSO4. The solvent was evaporated at reduced
pressure, the oily residue was crystallized from 1,1,1-trichloro-
ethane. Yield 12.4 g (85%), yellow, needle-shaped crystals,
mp 123–124°С (MeCCl3) (mp 123–124°С (EtOAc)9).
Preparation of ammonium 5-(4-azidofurazan-3-yl)-
tetrazolide (14). Amidrazone 13 (3.14 g, 20 mmol) was
added to acetic acid (20 ml). The reaction mixture was
cooled to 5°С, vigorously stirred at 5–10°С and treated by
dropwise addition of NaNO2 (3.0 g, 43.5 mmol) in water
(10 ml). After completing the addition of NaNO2, the
reaction mixture was stirred for 30 min at 10–15°С, then
acidified with concd HCl to рН 1. The solvent was
evaporated at reduced pressure, water (20 ml) was added to
the residue and the oil that separated was extracted with
CH2Cl2 (2×20 ml). The combined organic layers were
washed with water (2×20 ml) and extracted with 10%
aqueous ammonia solution (20 ml). The aqueous layer was
separated, evaporated under vacuum, and the residue was
dissolved in anhydrous 2-PrOH (50 ml). The obtained
solution was evaporated at atmospheric pressure to 20 ml
volume, cooled, and the precipitate that formed was
separated. An analytical sample of salt 14 was obtained by
recrystallization from anhydrous EtOH. Yield 2.9 g (75%),
colorless, fine agglomerates of needle-shaped crystals,
mp 184°С (decomp.) (EtОН). Found, %: C 18.11; H 2.27;
N 71.65. C3H4N10O. Calculated, %: C 18.37; H 2.06;
N 71.42.
Amino(carbamoylamino)methanaminium 5-(4-azido-
furazan-3-yl)tetrazolide (15). Method I (from reaction
mixture after diazotation of amidrazone 13). After the
diazotation reaction of amidrazone 13 with NaNO2
solution, followed by maintaining for 30 min at 10–15°С,
the reaction mixture was basified to рН 7.0–7.5 by the
addition of 25% aqueous ammonia solution (20–25 ml).
The obtained solution was heated to reflux and treated by
adding a hot solution of guanylurea sulfate (2.26 g,
15 mmol) in water (25 ml). The solution was cooled to
room temperature, the precipitate that formed was filtered
off, washed with ethanol (20 ml), and the product was
recrystallized from water. The yield of salt 15 was 3.9 g
(70%), agglomerates of fine, colorless irregularly shaped
crystals, mp 206°С (decomp.). Found, %: C 21.22; H 2.68;
N 64.88. C5H7N13O2. Calculated, %: C 21.36; H 2.51;
N 64.75.
Method II (from ammonium salt 14). Compound 14
(1 g, 5 mmol) was dissolved in water (5 ml), and the
solution was treated with a hot solution of guanylurea (0.75 g,
5 mmol) in water (5 ml). The precipitate that formed after
cooling to room temperature was filtered off and washed
with cold water. The guanylammonium salt 15 was isolated
in 1.33 g (95%) yield as agglomerates of fine, needle-
shaped crystals.
3-Azido-4-(2H-tetrazol-5-yl)furazan (7). Method I
(from 5-(4-nitrofurazan-3-yl)-2H-tetrazole (2)). NaN3 (1.62 g,
25 mmol) was added to a solution of compound 2 (1.83 g,
10 mmol) in acetonitrile (15 ml). The reaction mixture was
stirred for 5 h at 55–60°С. The solvent was evaporated at
reduced pressure, the residue was dissolved in water
(10 ml), acidified with concd HCl to рН 1 and cooled to
0°С. The precipitate that formed was filtered off and
4-(1,2,4-Oxadiazol-3-yl)furazan-3-amine (11). Com-
pound 8 (143 g, 1.00 mol) was added with vigorous stirring
to (EtO)3CH (160 g, 1.08 mol), followed by the addition of
BF3·Et2O (1 ml, 8.00 mmol). The stirred mixture was
slowly heated to reflux temperature and was refluxed for 1 h.
The mixture was then diluted with an equal volume of hot
water, again heated to reflux, and then allowed to slowly
crystallize. The precipitate was filtered off and re-
crystallized from 2-PrOH. Yield 138 g (90%), white, fine
crystalline powder, mp 126–127°С (Н2О) (mp 126–127°С
(Н2О)26). IR spectrum, ν, cm–1: 3480, 3320 (NH2), 3120
1
(CH), 1647 (NH2), 1014 (oxadiazole). H NMR spectrum,
δ, ppm: 10.00 (1H, s, CH); 6.50 (2H, s, NH2). 13C NMR
spectrum, δ, ppm: 168.7; 158.6; 156.0; 137.4. Mass
spectrum, m/z (Irel, %): 154 [M+H]+ (2.5), 153 [M]+ (100),
123 [M‒NO]+ (23), 96 (94), 69 (20), 58 (91), 54 (13), 53
(28), 42 (15), 30 [NO]+ (55), 29 [CHO]+ (41).
3-(4-Nitrofurazan-3-yl)-1,2,4-oxadiazole (12). Com-
pound 11 (76.5 g, 0.5 mol) was added to a vigorously
stirred mixture that was prepared from 36% H2O2 solution
(105 ml) and 94–96% H2SO4 (107 ml), while maintaining
the temperature in reaction mixture in the range of 50–55°С.
After the exothermic effect ceased, the mixture was
maintained for 30 min at 50–55°С, cooled to room tempe-
rature, diluted with water (400 ml), and extracted with
CH2Cl2 (2×100 ml). The organic layers were washed with
water, evaporated under vacuum, the solid residue was
recrystallized from methanol. Yield 76.9
g (84%),
colorless, round crystals, mp 54–55°С (CCl4). IR spectrum,
ν, cm–1: 3430, 3138, 1609, 1564, 1539, 1505, 1422, 1408,
1307, 1270, 1116, 1035, 965, 910, 883, 823, 773, 742, 616,
586, 475, 418, 404. 1H NMR spectrum, δ, ppm: 10.08 (1H,
s, CH). 13C NMR spectrum, δ, ppm: 169.2 (CH); 160.0
(CNO2); 156.5; 141.1. Mass spectrum, m/z (Irel, %): 183
[M]+ (1.2), 137 [M–NO2]+ (1.6), 77 (22), 46 (100), 38 (13),
30 [NO]+ (99).
4-Hydrazinylfurazan-3-carbohydrazonamide (13). A
solution of compound 12 (10 g, 0.055 mol) in acetonitrile
(50 ml) was vigorously stirred and maintained at 20–25°С,
while 100% hydrazine hydrate (11 ml, 0.22 mol) was added
dropwise over 10 min. After the exothermic effect and gas
evolution ceased, the obtained suspension was stirred for
1 h at 40°С. The reaction mixture was then worked up by
diluting with water (100 ml), cooling to room temperature,
and collecting the precipitate by filtration. The precipitate
was washed with water and recrystallized from a 1:1
mixture of DMF–МеОН. Yield 6.2 g (72%), light-beige
amorphous powder, mp 204–205°С (CCl4). IR spectrum,
ν, cm–1: 3380, 3336, 3154, 1664, 1605, 1572, 1544, 1322,
1
1289, 1193, 1102, 953, 856, 650, 417. H NMR spectrum,
δ, ppm: 7.24 (1H, s, NH); 5.84 (2H, s, NH2); 4.74 (4H,
br. s, 2NH2). 13C NMR spectrum, δ, ppm: 158.9 (C-3);
140.5; 136.8. Mass spectrum, m/z (Irel, %): 158 [M+H]+ (7.7),
783

Chemistry of Heterocyclic Compounds 2017, 53(6/7), 779–785
recrystallized from water. Yield 1.1 g (62%), white
prismatic crystals, mp 102–103°С (Н2О).
The complete crystallographic dataset for compound 7 was
deposited at the Cambridge Crystallographic Data Center
(deposit CCDC 1038997).
Method II (through the diazonium salt 10).
Aminofurazan 1 (3.06 g, 0.02 mol) was dissolved in concd
H2SO4 (30 ml, 55.2 g, 0.56 mol, d 1.84 g/cm3). The
obtained solution was treated at a temperature not
exceeding 5°С by dropwise addition of nitrosylsulfuric acid
solution, which was prepared by dissolving finely ground
NaNO2 (1.66 g, 0.024 mol) in concd H2SO4 (25 ml, 46 g,
0.47 mol, d 1.84 g/cm3) at 0–5°С. After the addition was
complete, the reaction mixture was stirred for 3 h at 0–5°С.
The obtained solution of 4-(2Н-tetrazol-5-yl)-furazan-
3-diazonium hydrogen sulfate (10) was vigorously stirred
with cooling and treated by dropwise addition of NaN3
(3.25 g, 0.05 mol) that was dissolved in a minimum amount
of water, while maintaining the reaction mixture tempera-
ture at 5–10°С (Caution: evolution of HN3!). After
completing the addition, the mixture was stirred for 1 h at
room temperature and poured onto crushed ice (150 g). The
mixture was extracted with CH2Cl2 (2×30 ml). The organic
layers were combined and washed with water (20 ml). The
solvent was evaporated at reduced pressure. The residue
was dissolved in hot water (5 ml), treated with activated
carbon (0.1 g), filtered, and the obtained filtrate was cooled
to 0°С. The precipitate that formed was filtered off. Yield
0.97 g (27%), beige prismatic crystals, mp 100–101°С.
Method III (isolation from ammonium salt 14). The
ammonium salt 14 (10 g, 50 mmol) was dissolved in water
(25 ml), then NaCl (4 g) was added, the solution was cooled
to 10–15°С, vigorously stirred, and acidified with concd
HCl to рН 1. The precipitate that formed was filtered off.
Azide 7 was isolated as agglomerates of white, prismatic
crystals. Yield 8.5 g (95%), mp 102.5–103.5°С (Н2О). Found,
%: C 19.94; H 0.93; N 70.13. C3HN9O. Calculated, %:
C 20.12; H 0.56; N 70.39.
References
1. Yin, P.; Shreeve, J. M. Adv. Heterocycl. Chem. 2017, 121, 89.
2. Gao, H.; Shreeve, J. M. Chem. Rev. 2011, 111, 7377.
3. Ghule, V. D.; Sarangapani, R.; Jadhav, P. M.; Tewari, S. P.
J. Mol. Model. 2011, 17, 1507.
4. Wei, H.; He, C.; Zhang, J.; Shreeve, J. M. Angew. Chem., Int.
Ed. 2015, 54, 9367.
5. Ostrovskii, V. A.; Koldobskii, G. I.; Trifonov, R. E. In
Comprehensive Heterocyclic Chemistry III; Katritzky, A. R.;
Ramsden, C. A.; Scriven, E. F. V.; Taylor, R. J. K., Eds.;
Elsevier: Amsterdam, 2008, Vol. 6, p. 257.
6. Fershtat, L. L.; Makhova, N. N. Russ. Chem. Rev. 2016, 85,
1097. [Usp. Khim. 2016, 85, 1097.]
7. Andrianov, V. G.; Eremeev, A. V. Chem. Heterocycl. Compd.
1994, 30, 608. [Khim. Geterotsikl. Soedin. 1994, 693.]
8. Wang, R.; Guo, Y.; Zeng, Z.; Twamley, B.; Shreeve, J. M.
Chem.–Eur. J. 2009, 15, 2625.
9. Wang, B.; Zhang, G.; Huo, H.; Fan, Y.; Fan, X. Chin. J.
Chem. 2011, 29, 919.
10. Wang, J.-Y.; Liang, J.; Wu, B.-D.; An, C.-W. Main Group
Chem. 2016, 15, 325.
11. Huang, H.; Shi, Y.; Li, Y.; Liu, Y.; Yang, J. RSC Adv. 2016,
6, 64568.
12. Godovikova, T.; Vorontsova, S.; Konyushkin, L.; Firgang, S.;
Rakitin, O. Russ. Chem. Bull., Int. Ed. 2009, 58, 406. [Izv.
Akad. Nauk, Ser. Khim. 2009, 400.]
13. Li, H.; Yu, Q.; Wang, B.; Lai, W.; Ge, Z.; Li, Y.; Liu, N.
Hanneng Cailiao 2013, 21, 821.
14. Leonard, P. W.; Chavez, D. E.; Pagoria, P. F.; Parrish, D. L.
Propellants, Explos., Pyrotech. 2011, 36, 233.
15. Liang, L.; Huang, H.; Wang, K.; Bian, C.; Song, J.; Ling, L.;
Zhao, F.; Zhou, Z. J. Mater. Chem. 2012, 22, 21954.
16. Li, H.; Wang, B.-Z.; Yu, Q.-Q.; Li, Y.-N.; Shang, Y.
Hanneng Cailiao 2012, 20, 18.
X-ray structural study of compound 7 was performed
on an Oxford Diffraction Xсalibur CCD diffractometer
with an EOS detector (Agilent Technologies UK, Ltd.),
using a crystal with dimensions of 0.25 × 0.20 × 0.16 mm.
The data collection was performed at 100(1) K. The data
processing, solving and refinement of unit cell parameters
were performed with the CrysAlis PRO program (Agilent
Technologies UK, Ltd., 2011). A total of 5280 reflections
were collected, of which 1769 were independent (Rint
0.0359). The structure was solved by direct method using the
SIR9237 program, followed by a series of electron density
map calculations. The hydrogen atom positions were
determined objectively from the difference electron density
synthesis and refined in isotropic approximation. The full-
matrix anisotropic refinement of non-hydrogen atoms by
method of least squares was performed with the SHELXL-97
program38 at R1 0.0596, wR2 0.1759 by 1436 reflections
with I > 2σ(I) and R1 0.0712, wR2 0.1871 by all 1769
reflections. GООF 1.110. The number of refined
parameters was 122. The maximum electron density from
the difference electron density synthesis maps was equal to
0.408 е/Å3. The main crystallographic parameters: space
group Р21/n; a 6.9664(11), b 9.3410(11), c 10.2002(15) Å;
β 90.27°; V 663.75(16) Å3; Z 4; d 1.953 g/cm3; μ 0.167 mm–1.
17. Li, X.; Liu, X.; Zhang, S.; Wu, H.; Wang, B.; Yang, Q.; Wei, Q.;
Xie, G.; Chen, S.; Gao, S. J. Chem. Eng. Data 2016, 61, 207.
18. Li, X.-H.; Mei, Z.; Zhang, R.-Z.; Zhang, X.-Z. Mol. Phys.
2016, vol. 114, 23, 3437.
19. Ilyushin, M. A.; Shugaley, I. V.; Tselinskii, I. V.;
Garabadzhiu, A. V. Russ. J. Gen. Chem. 2013, 83, 2624.
[Ekol. Khimiya 2012, 21, 154.]
20. Ichikawa, T.; Kato, T.; Takenishi, T. J. Heterocycl. Chem.
1965, 2, 253.
21. Stepanov, A. I.; Sannikov, V. S.; Dashko, D. V.;
Astrat'yev, А. А. Izv. SPbGTI (TU) 2014, 25, 32.
22. Stepanova, E. V.; Stepanov, A. I.; Stepanov, V. A. In: Science
Today: Proceedings of the International Scientific-practical
Conference, Vologda, October 24, 2014 [in Russian]; Izdat.
Dom Vologzhanin: Vologda, 2014, part 1, p. 14.
23. Rozhkov, V. Yu.; Batog, L. V.; Struchkova, M. I. Russ.
Chem. Bull., Int. Ed. 2005, 54, 1923. [Izv. Akad. Nauk, Ser.
Khim. 2005, 1866.]
24. Rakitin, O. A.; Zalesova, O. A.; Kulikov, A. S.; Makhova, N. N.;
Godovikova, T. I.; Khmel'nitskii, L. I. Russ. Chem. Bull.
1993, 42, 1865. [Izv. Akad. Nauk, Ser. Khim. 1993, 1949.]
25. Andrianov, V. G.; Eremeev, A. V. Chem. Heterocycl. Compd.
1984, 20, 937. [Khim. Geterotsikl. Soedin. 1984, 1155.]
26. Andrianov, V. G.; Rozhkov, E. N.; Eremeev, A. V. Chem.
Heterocycl. Compd. 1994, 30, 470. [Khim. Geterotsikl.
Soedin. 1994, 534.]
784

Chemistry of Heterocyclic Compounds 2017, 53(6/7), 779–785
27. Stepanov, A. I.; Sannikov, V. S.; Dashko, D. V.;
32. Allen, F. H.; Kennard, O.; Watson, D. V.; Brammer, L.;
Orpen, A. G.; Taylor, R. J. Chem. Soc., Perkin Trans. 2 1987, S1.
33. Khmelnitskii, L. I.; Novikov, S. S.; Godovikova, T. I.
Chemistry of Furoxans: Structure and Synthesis [in Russian];
Nauka: Moscow, 1996, p. 43.
Roslyakov, A. G.; Astrat'ev, A. A.; Stepanova, E. V. Chem.
Heterocycl. Compd. 2015, 51, 350. [Khim. Geterotsikl.
Soedin. 2015, 51, 350.]
28. Li, H.-Z.; Huang, M.; Li, J.-S.; Cheng, B.-B.; Zhou, X.-Q.
Hecheng Huaxue 2007, 15, 710.
34. Fershtat, L. L.; Epishina, M. A.; Kulikov, A. S.; Ovchinnikov, I. V.;
Ananyev, I. V.; Makhova, N. N. Tetrahedron 2015, 71, 6764.
35. Shao, Y.; Zhu, W.; Xiao, H. J. Mol. Graphics Modell. 2013,
40, 54.
29. Zhou, Y.; Wang, B.; Zhou, C.; Li, J.; Chen, Z.; Lian, P.;
Zhang, Z. Youji Huaxue 2010, 30, 1044.
30. Sheremetev, A. B.; Palysaeva, N. V.; Struchkova, M. I.;
Suponitsky, K. Yu.; Antipin, M. Yu. Eur. J. Org. Chem.
2012, 11, 2266.
36. Fizika vzryva [in Russian]; Orlenko, L. P., Ed.; Fizmatlit:
Moscow, 2002, 3rd ed., Vol. 1, p. 204.
31. Sheremetev, A. B.; Lyalin, B. V.; Kozeev, A. M.;
Palysaeva, N. V.; Struchkova, M. I.; Suponitsky, K. Yu. RSC
Adv. 2015, 5, 37617.
37. Altomare, A.; Cascarno, G.; Giacovazzo, C.; Guagliardi, A.;
Burla, M. C. J. Appl. Crystallogr. 1993, 26, 343.
38. Sheldrick, G. M. SHELXL 97; University of Göttingen, 1998.
785