Synthesis of Nitro, Dinitro, and Polynitroalkylamino Derivatives of Trifurazanoxide

Article abstract of DOI:10.1002/jhet.2920

The synthesis and characterization of 3-chlorocarbohydroxymoyl-4-nitro-1,2,5-oxadiazole and its transformation to dinitro trifurazanoxide were described for the first time. Synthesis of new amino nitro and trinitroethylamino trifurazanoxide has been presented.

Full text of DOI:10.1002/jhet.2920

Month 2017
Synthesis of Nitro, Dinitro, and Polynitroalkylamino Derivatives of
Trifurazanoxide
Raja Duddu,a*
John Hoare, Peggy Sanchez, Reddy Damavarapu, * and Damon Parrish
a
b
b
c
a
Leidos, US Army ARDEC, Bldg-3028, Picatinny Arsenal, Morris County, NJ 07806, USA
b
US Army ARDEC, Bldg-3028, Picatinny Arsenal, Morris County, NJ 07806, USA
c
Naval Research Laboratory, 4555 Overlook Avenue, Washington, DC 20375, USA
*
E-mail: raja.g.duddu.ctr@mail.mil; reddy.s.damavarapu.civ@mail.mil
Received February 13, 2017
DOI 10.1002/jhet.2920
Published online 00 Month 2017 in Wiley Online Library (wileyonlinelibrary.com).
The synthesis and characterization of 3-chlorocarbohydroxymoyl-4-nitro-1,2,5-oxadiazole and its
transformation to dinitro trifurazanoxide were described for the first time. Synthesis of new amino nitro
and trinitroethylamino trifurazanoxide has been presented.
J. Heterocyclic Chem., 00, 00 (2017).
INTRODUCTION
RESULTS AND DISCUSSION
In continuation of efforts on the development of new
munitions systems for advanced applications, the
Department of Defense Agencies all over the world are
in search of materials that yield high energy output. In
order to meet increasing regulations, environmentally
benign high nitrogen-containing nitro and nitramino
heterocycles [1] with high densities having high positive
heat of formation are of great interest to the US
Department of Defense. Some nitro compounds of furazan
and its oxides (furoxans) are quite dense and highly
energetic [2]; thus, intense research is being carried out at
various laboratories with the aim of developing materials
that are thermally stable, insensitive to stimuli, and
providing energetic performance significantly greater than
in-service materials. A recently developed high-energy,
high-density melt-castable energetic material 3,4-bis(4-
nitro-1,2,5-oxadizaol-3-yl)-1,2,5-oxadiazole-N-oxide [3] (DNTF,
A careful analysis of literature reports revealed that, thus
far, all the synthetic approaches mainly involved oxidation
of amino groups of diamino furazanofuroxan (3, DAFF) to
prepare DNTF (5; Scheme 1). Herein is reported a novel
method for synthesis of DNTF in which no DAFF
preparation is required. Furthermore, the synthesis of two
new nitroenergetic materials, monoamino mononitro and
bistrinitroethylamino trifurazanoxides derived from
DAFF, is described.
Recently, Chinese scientists reported a procedure for
DAFF preparation using carboxamide oxime (1), using
sodium carbonate in solvent ether [5]. In-house attempts
to prepare DAFF by using this procedure resulted in
recovery of starting material. There was no formation of
DAFF. All other literature procedures utilized 3-amino-4-
chlorocarbohydroxymoyl-1,2,5-oxadiazole (ACOF, 2) as
starting material for DAFF preparation [3]. The methods
that utilized commonly used bases such as sodium
carbonate and potassium carbonate reported formation of
a mixture of DAFF and a six-member isomer of DAFF
(called iso-DAFF) in various ratios, thereby requiring
separations via crystallizations [3g]. In 2015, Tsyshevsky
and co-workers reported a procedure for exclusive
preparation [3k] of DAFF using a relatively expensive
base silver carbonate. Thus, an approach in which
preparation of DAFF is completely removed was
envisioned. Accordingly, it was planned to synthesize 3-
chlorocarbohydroxymoyl-4-nitro-1,2,5-oxadiazole (NCOF, 4)
from ACOF (2) and then transform 4 to DNTF (5).
However, Russian scientists reported that their attempts to
transform the amino group of ACOF (2) to the
corresponding nitro group in 4 were not successful [6]. This
5, also known as BNFF) has attracted the attention of
energetic material community. The reason for this is that
DNTF has a crystal density of 1.93 g/cc with a heat of
formation of 657 kJ/mol and a melting point of 108–110°C
[
3a]. Its decomposition temperature is 292°C, while its
energetic performance is 168% better than trinitrotoluene
3k]. All characteristics mentioned in the preceding texts
[
make DNTF a highly desirable energetic ingredient for
melt–pour formulations, and hence, it is currently being
investigated for its application in the development of
multipurpose energetic formulations. Our group has actively
been involved in the synthesis and development of novel
nitro heterocyclic energetic materials [4] for quite some
time. It is with this background that the development of
methods for preparation of DNTF was carried out.
©
2017. This article is a U.S. Government work and is in the public domain the USA.

R. Duddu, J. Hoare, P. Sanchez, R. Damavarapu, and D. Parrish
Vol 000
Scheme 1 [Color figure can be viewed at wileyonlinelibrary.com]
obtaining a mixed melting point and directly comparing the
data with an authentic DNTF sample prepared via oxidation
of DAFF [8]. This is a new synthesis method for DNTF
preparation.
The focus was changed to the partial oxidation of DAFF
(
3) to obtain monoamino mononitro trifurazanoxide, an
energetic material of interest for our applications
Scheme 2). Attempts to produce mononitro product
exclusively from DAFF with varying oxidation reagents
30–90% H O and H SO ) always resulted in DNTF or
(
(
2
2
2
4
in a complex mixtures of products with DNTF being a
major identifiable product. Finally, the desired
monoamino mononitro product(s) was obtained when
DAFF was reacted with 90% aqueous hydrogen peroxide
with disodium tungustate as catalyst in the reaction
medium under sonication conditions. Sonicating the
reaction mixture for 3.5 h, followed by an extractive
work-up, yielded a crude gooey material. The NMR
analysis of this crude product suggested that it is a
mixture of monoamino mononitro compounds 6 and 7
along with DNTF (5) and starting material. The crude
product was then subjected to Si-gel column
chromatography. The desired pure mononitro monoamine
products 6 and 7 were isolated in poor, 8.4% and 6.9%,
yields, respectively, as white solids along with DNTF in
14% yield.
report challenged us to investigate and develop a method for
synthesis of NCOF (4). The initial attempts to oxidize free
amino group of 1 with H O in presence of sulfuric acid
2
2
with or without catalyst yielded either a complex mixture of
products or decomposed materials. Many attempts to obtain
NCOF by using varying oxidation agent concentrations
were not successful. Finally, compound 2 was subjected to
oxidation by using aq. 70% H O in presence of tungsten-
2
2
based catalyst (Bmim) W O [7], initially by stirring the
4
10 23
reaction mixture at room temperature, and then heating it at
2°C for 4 h followed by an extractive work-up afforded
5
NCOF (4) as a pale yellow liquid. Carbon NMR analysis of
this liquid showed a resonance at 158.71 ppm as a triplet
due to coupling of the nitro group nitrogen with aromatic
ring carbon, suggesting the formation of the desired nitro
compound 4. In an effort to further confirm the identity of
this liquid, an ethereal solution of 4 was reacted with an aq.
potassium carbonate solution. Stirring the reaction mixture
at room temperature for 2 h followed by an extractive
workup and removal of solvent yielded the crude DNTF
Chung and co-workers [8] (Scheme 3) prepared an
amino nitro compound via nucleophilic displacement
reaction of ammonia on DNTF and assigned its structure
as ANFF (7), in which amino and N-oxide groups are on
the opposite sides.
The spectral and thermal data of one of our pure (6)
isolated compounds are in good agreement with that of
the values reported by Chung’s group, thereby allowing
us to initially believe that we also isolated the ANFF (7).
Because Chung’s group made the structural assignment
based on the assumption of steric hindrance factors, it
was decided to determine the structure of this product
with no uncertainty. Hence, in an effort to establish the
structure of this product unambiguously and in order to
(5). Pure DNTF was obtained by triturating the crude with
diethyl ether and then separation of the formed solid via
filtration. The spectral and thermal data of the white solid
thus obtained matched with that of the literature reported
values, for DNTF (5). Further confirmation was obtained by
Scheme 2 [Color figure can be viewed at wileyonlinelibrary.com]
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2017
Synthesis of Nitro, Dinitro, and Polynitroalkylamino Derivatives of
Trifurazanoxide is Presented
Scheme 3 [Color figure can be viewed at wileyonlinelibrary.com]
obtain accurate experimental molecular density, a critically
required parameter in estimating the energetic performance
of new energetic materials, our material was subjected to
Because polynitroalkylamino furazan compounds are
also highly dense and energetic compounds of interest
[2q,2r], DAFF was subjected to Mannich condensation
reaction with trinitroethanol (Scheme 2). The reaction was
carried out in the presence of sodium acetate in dioxane-
water medium at 58°C for 2 h. The crude product was
purified via column chromatography to obtain bis
(trinitroethylamino)trifurazanoxide in 15% yield. The
structure of product 8 was further unambiguously
confirmed by single crystal X-ray crystallography (Fig. 1).
Selected [9] single crystal analysis details of compounds 6
and 8 are shown in Table 1.
In summary, for the first time, the synthesis of
3-chlorocarbohydroxymoyl-4-nitro-1,2,5-oxadiazole (4)
has been achieved and demonstrated its transformation to
DNTF (5), thus establishing a new method for the
synthesis of DNTF. Two energetic materials of interest 7
and 8 have been synthesized and characterized. Structures
of 6 and 8 have been established unambiguously via
single crystal X-ray crystallography. In this process,
literature-reported incorrect structural assignment for
ANFF (7) has been corrected.
single
crystal
X-ray
crystallographic
analysis.
Surprisingly, X-ray investigations (Fig. 1 and Table 1) [9]
revealed that this compound in fact possesses the
structure 6, in which amino and N-oxide groups are on
the same side, not the ANFF (7) structure (where amino
and N-oxide groups are on the opposite side), as
proposed by Chung’s group. Thus, based on our data
comparison and X-ray investigations, we conclude that
Chung and co-workers have indeed obtained 6 but
erroneously assigned their isolated compound’s structure
as ANFF (7).
We next paid attention on the characterization of the
other isolated new compound. While proton NMR
showed a singlet at 6.07 ppm for the amino group, the
carbon NMR spectrum of this compound consisted of six
carbon signals with carbon attached to the nitro group
resonating at 160.97 ppm as a typical triplet due to the
coupling of nitrogen of nitro group with aromatic ring
carbon. The experimentally determined elemental
composition of this compound is in good agreement with
that of the calculated values for the monoamino
mononitro trifurazanoxide, thereby allowing us to
conclude that it is the other monoamino mononitro
isomer, 7, where amino and N-oxide groups are on the
opposite sides. Our attempts to obtain suitable crystals for
single crystal X-ray crystallography investigations were
not successful.
EXPERIMENTAL
Melting points were obtained by using a Thomas
Hoover Uni-melt capillary melting point apparatus
(Arthur H. Thomas Company, Philadelphia, PA) and is
uncorrected. Differential scanning calorimetry (DSC)
Figure 1. ORTEP diagrams of compounds 6 and 8. [Color figure can be viewed at wileyonlinelibrary.com]
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

R. Duddu, J. Hoare, P. Sanchez, R. Damavarapu, and D. Parrish
Vol 000
Table 1
Single crystal X-ray analysis data of compounds 6 and 8.
6
8
Empirical formula
Formula weight
Temperature
C
6
H
2
N
8
O
6
10 6 14 16
C H N O
578.29
100(2) K
282.16
296(2) K
Wavelength
Crystal system
Space group
0.71073 Å
Monoclinic
0.71073 Å
Monoclinic
P2 /c
1
P2
1
/n
Unit cell dimensions
a = 7.6896(6) Å, α = 90°
a = 12.172(3) Å, α = 90°
b = 18.806(5) Å, β = 111.780(3)°
c = 9.889(2) Å, γ = 90°
b = 13.1271(11) Å, β = 103.608(2)°
c = 10.3101(8) Å, γ = 90°
3
3
Volume
1011.51(14) Å
2102.2(9) Å
Z
4
4
—
3
Density (À123°C)
1.853 Mg/m
1.807 Mg/m
0.167 mm
568
3
3
Density (20°C)
1.827 Mg/m
0.174 mm
1168
À1
À1
Absorption coefficient
F(000)
Crystal size
3
3
0.75 × 0.31 × 0.28 mm
0.35 × 0.07 × 0.05 mm
Theta range for data collection
Index ranges
2.56 to 26.43°
1.80 to 26.83°
À9 ≤ h ≤ 9, À15 ≤ k ≤ 16, À12 ≤ l ≤ 12
À15 ≤ h ≤ 15, À23 ≤ k ≤ 23, À12 ≤ l ≤ 12
Reflections collected
Independent reflections
Completeness to theta = 26.43°
Absorption correction
Max. and min. transmissions
Refinement method
Data/restraints/parameters
9492
18,294
2076 [Rint = 0.0207]
99.9%
Semiempirical from equivalents
0.9548 and 0.8850
Full-matrix least squares on F
2076/0/187
4392 [Rint = 0.0637]
97.1%
Semiempirical from equivalents
0.9914 and 0.9417
Full-matrix least squares on F
4392/3/365
2
2
2
Goodness-of-fit on F
1.047
1.039
Final R indices [I > 2sigma(I)]
R indices (all data)
Largest diff. peak and hole
R
R
1
= 0.0325, wR
= 0.0352, wR
2
= 0.0811
R
R
1
= 0.0529, wR
= 0.0882, wR
2
= 0.1238
1
2
= 0.0832
1
2
= 0.1410
À3
À3
0.782 and À0.496 Å
0.782 and À0.496 Å
measurement was recorded by using a Perkin Elmer
brine (1 × 50 mL), dried (Na SO ), and filtered. The
filtrate was evaporated on a rotary evaporator under
2
4
1
DSC-4000 (Perkin Elmer, Waltham, MA). H-NMR and
1
3
C-NMR spectra were recorded on a Bruker Avance
00-MHz NMR spectrometer (Billerica, MA) with
vacuum at room temperature to dryness, to obtain product
1
4
4 (0.32 g, 67% yield) as a colorless liquid. H-NMR
13
acetone-d6 as solvent. Chemical shift (δ) values are
reported in ppm relative to TMS as an internal
standard. Column chromatography was performed on
Sigma-Aldrich (St. Louis, MO) 70-230 mesh silica gel
(acetone-d ): 13.03 (br S); C-NMR (acetone-d ): 123.74,
6
6
145.38, and 158.719 (t). Anal. Calcd. for C HClN O : C,
3
4 4
18.72; H, 0.52; N 29.10; Cl, 18.42. Found C, 18.91; H,
0.58; N, 29. 06; Cl, 18.29.
(
St. Louis, MO). ACOF and DAFF were prepared by
The nitro compound 4 thus obtained in the preceding
texts (0.32 g, 1.66 mmol) was dissolved in diethyl ether
(5 mL). A solution of potassium carbonate (166 mg,
1.2 mmol) was added in water (3 mL) at room
temperature dropwise. The reaction mixture was then
stirred at room temperature for 2 h. Ether layer was
separated, and the aqueous layer was extracted with
diethyl ether (2 × 5 mL). The combined organic layer was
then washed with water (1 × 5 mL) and brine (1 × 5 mL),
dried (Na SO ), and filtered. The organic solution was
using literature procedures [3g,3k].
Caution: Although no incidents were encountered with
these materials, energetic materials presented in this
article are sensitive toward shock and friction. Thus,
proper safety precautions (such as wearing safety glasses,
face shield, and conductive shoes) must be taken while
synthesizing and handling these compounds.
3,4-Bis(4-nitro-1,2,5-oxadizaol-3-yl)-1,2,5-oxadiazole-N-oxide
(5,DNTF).
A heterogeneous mixture of 3-amino-4-
chlorohydroximoyl 1-2,4-oxadiazole [3g] (0.4 g,
.47 mmol) in 70% H O (10 mL) and (Bmim) W O
10 23
2
4
evaporated under vacuum at room temperature on a rotary
evaporator. The pale yellow crude solid residue thus
obtained was triturated with ether (1 mL). The white
solid was separated via filtration and air dried. Yield:
68 mg (27% from nitro derivative) mp 107–108°C (lit mp
2
2
2
4
catalyst (200 mg, 0.072 mmol) was stirred at room
temperature for 16 h and then kept at 52°C for 4 h. The
reaction mixture was diluted with water (100 mL) and
extracted with ethylacetate (3 × 30 mL). The combined
organic layer was washed with water (2 × 50 mL) and
13
108–110°C) [3g]. C-NMR (acetone-d ): 104.45, 138.20,
6
140.55, 143.83, 160.82 (2 C).
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2017
Synthesis of Nitro, Dinitro, and Polynitroalkylamino Derivatives of
Trifurazanoxide is Presented
1
4
-Amino-1,2,5-oxadiazole-3yl-4-nitro-1,2,5-oxadiazole-4yl-
decomposition onset): 168°C. H-NMR (acetone-d6):
5.48 (d, J = 8.0 Hz, 2H), 5.58 (d, J = 8.0 Hz, 2H), 6.74
(br t, J = 8.0 Hz, 1H), 6.94 (br t, J = 8.0 Hz, 1H).
1
,2,5-oxadiazole-N-oxide and its isomer (6 and 7).
WO .2H O (0.69 g, 2.1 mmol) was added to a
suspension of DAFF (0.48 g, 1.9 mmol) in 10 mL of
0% H O equipped with a thermocouple and magnetic
Na2
4
2
13
C-NMR (acetone-d ): 48.99, 49.21, 105.33, 126.86,
6
132.73, 134.00, 136.91, 147.26, 156.22, and 157.06.
9
2
2
stirring bead over a period of several minutes while
maintaining the temperature at 15–20°C. The reaction
mixture was sonicated for 3.5 h, and the aqueous
solution was extracted with 30 mL of ethyl acetate. The
ethyl acetate solution was washed with water
Anal. Calcd. for C H N O : C, 20.77; H, 1.05; N,
33.91. Found: C, 20.82; H, 1.03; N 33.98.
10 6 14 16
REFERENCES AND NOTES
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7 mg (6.9%); mp 115.8°C. DSC decomposition (5°C/min,
3
1
decomposition peak): 233.5°C H-NMR (acetone-d6):
13
6
.07 (s, 2H). C-NMR (acetone-d ): 108.73, 134.50,
6
2
1
40.74, 143.94, 156.48, 160.97(t). Anal. Calcd. for
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6
2 8 6
(
(
H, 0.68; N 38.76.
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8
(
lit. 106°C). DSC (5°C/min, decomposition peak): 247°
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13
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0
acetone-d ): 102.48, 137.11, 138.40, 147.19, 156.06,
6
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4 × 25 mL). The combined yellow organic layer was
sequentially washed with water (2 × 50 mL) and brine
1 × 50 mL). The organic layer was dried over Na SO ,
filtered, and evaporated under vacuum to yield a yellow
syrupy liquid. This liquid was subjected to column
chromatography (Si-gel, 10–20% ethyl acetate–hexanes).
The relevant fractions were concentrated to yield pure
product 7 (78 mg, 15%) as a white solid. A crystalline
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obtained from chloroform–ethyl acetate (1:1) solvent
recrystallization. mp 159–160°C; DSC (5°C/min,
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet