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Propellants, Explosives, Pyrotechnics 23, 142±149 (1998) 142

Dinitro Trifurazans with Oxy, Azo, and Azoxy Bridges


Aleksei B. Sheremetev*, Valentina O. Kulagina, Natalya S. Aleksandrova, Dmitrii E. Dmitriev,
and Yurii A. Strelenko

N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prosp. 47, Moscow 117913 (Russia)
Vyacheslav P. Lebedev and Yurii N. Matyushin

Institute of Chemical Physics, Russian Academy of Sciences, Kosygin Str. 7, Moscow 117977 (Russia)

Dinitrotrifurazane mit Oxy-, Azo- und Azoxy-BruÈcken Dinitrotrifurazane avec ponts Oxy-Azo et Azozy
Die Suche nach neuen niedrigschmelzenden energiereichen Mate- La recherche de nouvelles substances eÂnergeÂtiques aÁ base point de
rialien, welche die Leistung von TNAZ erreichen oder uÈbertreffen, ist fusion qui atteignent ou surpassent les performances de TNAZ est
zwingende Notwendigkeit. Die Synthesen von verschiedenen neuar- d'une absolue neÂcessiteÂ. Les syntheÁses de diffeÂrents heÂteÂrocycles
tigen nichtwasserstoff-, aber stickstoff- und sauerstoffreichen ener- eÂnergeÂtiques nouveaux contenant peu d'hydrogeÁne, mais beaucoup
getischen Heterocyclen, z.B. Nitrofurazane als BruÈckenglieder, d'azote et d'oxygeÁne, tels que le nitrofurazane comme eÂleÂments de
wurden durchgefuÈhrt zur PruÈfung der Hypothese, daû akkumulierte pont ont eÂte effectueÂes pour veÂri®er l'hypotheÁse selon laquelle les
Furazanringe in solchen MolekuÈlen wirksam sein koÈnnten fuÈr die anneaux accumuleÂs de furazane dans de telles moleÂcules pourraient
Konstruktion von energetisch wichtigen Materialien. Acht Dinitro- eÃtre ef®caces pour la formulation de substances eÂnergeÂtiquement
trifurazane wurden synthetisiert und getestet. Die Verbindungen importantes. Huit dinitrofurazanes ont eÂte syntheÂtiseÂs et testeÂs. Les
wurden dargestellt in drei bis fuÈnf Stufen aus 3,4-Diaminofurazan (10). combinaisons ont eÂte repreÂsenteÂes dans trois aÁ cinq eÂtages de 3,4-
OxybruÈcken wurden gebildet durch Verwendung des Hydroxyfurazans diaminofurazane (10). Des ponts oxydants ont eÂte formeÂs en utilisant
als nukleophile Komponente. AzobruÈcken wurden dargestellt durch l'hydroxyfurazane comme composant nucleÂophile. Des ponts azo ont
oxidierende Kupplung von Aminogruppen mit KMnO4 in saurem eÂte fabriqueÂs par couplage oxydant de groupes amino avec KMnO4 en
Medium. Die Umlagerung der AzobruÈcken in AzoxybruÈcken wurde milieu acide. La transformation des ponts azo en ponts azozy a eÂteÂ
erreicht mit einer Mischung aus Ammoniumpersulfat und Oleum. obtenue pour un meÂlange de persulfate d'ammonium et d'oleÂum. Cette
Diese Trifurazanreihe repraÈsentiert eine neuartige Klasse von nie- seÂrie trifurazane repreÂsente une classe nouvelle de substances eÂner-
drigschmelzenden Energiestoffen unter den bekannten wirksamsten geÂtiques aÁ bas point de fusion parmi les explosifs les plus ef®caces
Cx Hy Nz Ow -Explosivstoffen. Die isomeren Dioxyfurazane (28), (29), CxHyNzOw bien connus. Les dioxyfurazanes isomeÁres (28), (29), (30)
(30) unterscheiden sich grundlegend in ihren Eigenschaften. Die se distinguent fondamentalement dans leurs proprieÂteÂs. Le composeÂ
¯uÈssige Diazoxyverbindung (28) hat eine Dichte von 1,8 g/cm3 und diazoxy (28) a une densite de 1,8 g=cm3 et constitue un composeÂ
stellt eine Rekordverbindung fuÈr ein Cx Hy Nz Ow -O È 1 dar. record pour une huile CxHyNzOw.

Summary energetic compounds have been reviewed by Sheremetev(2).


Although nitrofurazans have been studied for many years, a
The search of the new low-melting high energetic materials, which relatively small set of high energetic furazans possessing as
match the performance of TNAZ and more available, is the barest
a rule one or two furazan rings was published. 3,4-Dini-
necessity. The syntheses of several novel zero-hydrogen but nitrogen and
oxygen rich high energetic heterocycles, such as bridged nitrofurazans, trofurazan (1),(3) 3-cyano-4-nitrofurazan (2),(3) 5-(3-nitro-
were undertaken to test the hypothesis that accumulate furazan ring in furazan-4-yl)-1H-[1,2,3]triazolo[4,5-c]-furazan inner salt
such molecule could effectively serve in construction of energetically (3)(4,5), 4,4-dinitrobifurazan (4)(1,3,6), 4,4-dinitrodifurazalyl
interesting materials. Eight dinitro trifurazans were synthesized and
tested. The series of compounds was prepared in three±®ve stages from
ether (5)(7), 4,4-dinitrodifurazalyl sul®de and S-oxides
the 3,4-diaminofurazan (10). Oxy bridge was formed by utilizing (6a-c)(8), 4,40 dinitroazo-(7)(3,9) and -azoxyfurazan
(3,10,11)
hydroxyfurazans as nucleophiles. Azo bridge was prepared by oxidizing (8) , methylene-bis(3-nitroamino-4-nitrofurazan)
coupling of amino groups with KMnO4 in acid medium. Transformation (9)(12,13) are examples of the compounds.
of azo bridge to azoxy one was accomplished by mixture of (NH4)2S2O8
and oleum. The set of trifurazans represents a new class of low-melting
high energetic materials which are among the most potent CxHyNzOw-
explosives known. The isomeric diazoxyfurazans, (28), (29), and (30),
differ dramatically in their properties. Liquid diazoxy compound (28) has
density of 1.8 g/cm3 and is reach a record ®gure for CxHyNzOw-oil known.

1. Introduction

Since the ®rst mention in open literature(1) of the idea of


an explosive possessing a nitrofurazan (nitro-1,2,5-oxadia-
zole) moiety, the synthesis of the compounds has been
achieved and carried out successfully exploiting a variety of
methodology. Recently, methods of synthesis of these high

# WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998 0721-3115/98/0306±0142 $17.50‡:50=0


Propellants, Explosives, Pyrotechnics 23, 142±149 (1998) Dinitro Trifurazans with Oxy, Azo, and Azoxy Bridges 143

In our laboratory investigation of nitrofurazans has been


carried out for about two decades.(5,14,15) The use of the
furazan ring as key building block was not accidental in this
work. At ®rst, aromaticity of the ring increased thermal
stability to its derivatives, and planarity of the ring usually
provided them with higher density. Secondly, in contrast to
other oxygen heterocycles furazan possesses the ``working''
oxygen atom, that is not bonded with carbon or with
hydrogen, and therefore able to oxidize these atoms in the
combustion or explosive degradation of the compounds. Scheme I
The development of energetic materials that accumulate
similar energetic blocks, such as polynitrophenyl, was (Scheme 1). Using column chromatography, the mixture
previously receiving much attention, and a few excellent was completely separated and the structures of the ethers
reviews on both the synthesis and properties of the com- were determined. The trifurazan (13) has been characterized
pounds were published(16,17). The previous studies have all by IR spectroscopy, mass spectrometry, and 14N- and 13C-
concentrated upon the construction of the energetic phenyl NMR spectroscopy (see, Table 1) and elemental analyses.
derivatives. Following up on the early works, we were For example, pertinent features of the IR spectrum include a
interested in the synthesis of energetic compounds posses- sharp ether-O-stretch at 1210±1170 cmÿ1 and a NO2 stretch
sing several similar heterocyclic building blocks, such as at 1320±1365 cmÿ1 and 1525±1560 cmÿ1. Compound (13)
furazan ring. is thermally stable up to 220 C and can be stored at room
Here, we report a new type of zero-hydrogen nitrofur- temperature for a long time without decomposion (also see,
azans, in which two nitrofurazan moieties are linked via Table 2).
oxy, azo, and/or azoxy bridges to a single central furazan When a mixture of (12) and 3-cyano-4-nitrofurazan (2)(3)
ring, producing a trifurazan structure. These compounds in was subjected to the similar conditions, the diether (15) was
accordance with the computer prediction showed very the sole isolable product (89% yield). Analytical and
attractive energetic properties(18). spectral data are in full agreement with structure (15) (see
Experimental Section).

2. Results and Discussion

The target compounds listed in the paper were synthe-


sized from a common precursor, namely 3,4-diaminofur-
azan (10). This compound (10) was previously synthesized
by some laboratories(1,19±22) by multi-step procedures; We have also prepared a trifurazan involving both oxy
however, these approaches provided low and capricious and azo bridges as outlined in Scheme II. 4-Hydroxy-40 -
yields, and necessary isolation of the intermediates added a nitroazofurazan (16) was synthesized in low (18%) yield by
great many problems. We recently(5) reported an alternate treatment with NaOH in the mixture of hydrogen peroxide
one-pot synthesis of (10) starting from commercially and acetonitrile of the nitrocompound (7), which is readily
available chemicals. The synthetic routes were convenient prepared in two-step procedure from (10)(3). Many varia-
for large-scale preparation of (10), required for the synthesis tions in the reaction conditions with aprotic and protic
of the desired compounds. solvents, the use of varying amount of different bases such
We used the hydrogen peroxide procedure developed as KOH, LiOH, triethylamine, and pyridine, and inverse
earlier(3) for oxidizing of compound (10) to (1), which was addition of reactants were explored, but in every case was a
hydrolyzed in aqueous acetronitrile alkali followed by complete mixture of products, when (16) was a minor
acidi®cation with hydrochloric acid to the 3,4-dihydroxy- product. Treatment of (16) with sodium ethoxide in ether at
furazan (11)(23) using a reported procedure(24) (Scheme 1). 0±5 C gave salt (17) in 43% yield. Reaction of (17) with (1)
The resulting acid (11) was then converted to the bisalt (12) in diglym provided the nucleophilic displacement product
in 92% yield by treatment with sodium ethoxide in ether. (18). A byproduct identi®ed as the corresponding ether (5)
Several methods for preparation of (13) were examined. was also obtained. Column chromatography afforded a
Recently, a very facile and straightforward phase transfer modest yield of the azo ether (18) whose red-orange colour
approaches, to closely related furazanoxy compounds, have was characteristic of azofurazans. Compound (5) was the
been reported(23,25±28), and we chose these routes for the predominant product if the reaction was run in acetonitrile.
synthesis of the difurazanyl ether moiety. Unfortunately, Attempts to synthesize (18) from (7) and (19), which is
these methods failed for conversion of the dinitro derivative readily prepared in 87% yield from more available
(1) into the corresponding diether (13). However, we have 3-hydroxy-4-nitrofurazan(3,24), were unsuccessful.
found that the reaction between (1) and (12) in glyme at We then explored the possible oxidation of (18) in an
30 C produced the desired trifurazan (13) (43%) along with attempt to generate corresponding azoxy derivatives. Per-
ether (5) (10%) and very volatile tricycle (14) (12%) acides oxidation is a well-established synthetic procedure in
144 Sheremetev, Kulagina, Aleksandrova, Dmitriev, Strelenko, Lebedev, Matyushin Propellants, Explosives, Pyrotechnics 23, 142±149 (1998)

Table 1. NMR Spectra of Dinitro Trifurazans


13 14
Compounds Structural Formula C chemical shifts (ppm) N chemical shifts (ppm)
…Dn1=2 ; Hz†

C (1) C (2) C (3) C (4) C (5) C (6) NO2 N ! O…1†

13 153.6 156.3 154.2 Ð Ð Ð ÿ38.4 Ð


(10)

18 153.0 154.9 154.2 158.6 157.4 156.2 ÿ39.9, ÿ41.4 Ð


(15)

20 153.6 156.7 155.9 153.1 149.7 157.2 ÿ39.0, ÿ37.2 ÿ68.1


(30) (60)

24 156.1 157.6 158.9 Ð Ð Ð ÿ38.1 Ð


(40)

26 157.0 149.5 154.8 158.0 157.5 156.1 ÿ38.1 ÿ66.1


(40) (200)

28 157.3 149.8 156.3 149.8 153.6 154.9 ÿ38.7 [N1], ÿ65.1 [N2],
ÿ44.2 [N4] ÿ70.2 [N3]
(20) (80)

29 155.2 153.4 150.7 Ð Ð Ð ÿ43.2 ÿ69.7


(30) (100)

30 156.9 149.5 153.8 Ð Ð Ð ÿ37.6 ÿ69.9


(15) (100)

doubts in synthesizing this very compound. An analytical


sample of (20) is colourless stable solid. However the pre-
sence of minor impurities causes it to become viscous oil.

Scheme III
Scheme II
When KMnO4 was added to a hydrochloric acid sus-
pension of (22) and (23), that are readily prepared from
chemistry of azoxy compounds(29). However after treatment (10)(3), the oxidative coupling was complete in less than 3 h
of (18) with such common oxidants as peracetic acid, tri- at 45±50 C, and the products, (7), (24), and (25), were
¯uoroperacetic acid, and performic acid, the compound was chromatographed on silica gel (Scheme IV). Three clean
recovered without any changes. Successful oxidation of fractions were obtained. The red-orange desired trifurazan
(18) was ®nally achieved utilizing ammonium persulfate in (24)(30) was obtained as the second fraction in 18% yield.
oleum at 70 C until the mixture became colourless from Compound (24) is a solid at ÿ20 C, but it is a liquid at
conversion of the azo group to azoxy group; the colour room temperature. Additional puri®cation can be achieved
acted as an indicator for the completion of the reaction by sublimation or distillation. At 230 C it decomposes with
(Scheme III). We observed that under these conditions the release of NxOy.
greater amount of (20) was formed with a very slight Finally, oxidation of azo bridge to azoxy one was per-
amount of (21). The products were isolated by silica gel formed. The reaction between oxidative mixture and di-azo
chromatography using mixture of CH2Cl2 and pentane as compound (24) proceeds via nonselective attack at each
eluants. The amount of (21) was not enough for the com- nitrogen atoms of both azo bridges to produce a mixture of
plete assignment. Yet, the speci®c mass spectrum leaves no positional isomers. Thus, treatment of (24) with ammonium
Propellants, Explosives, Pyrotechnics 23, 142±149 (1998) Dinitro Trifurazans with Oxy, Azo, and Azoxy Bridges 145

Table 2. Physical and Explosive Properties of Dinitro Trifurazans and Some Analogs
Melting Heat of Heat of Formation
Compounds Structural Formula Empirical Molecular Oxygen Nitrogen point, Density Combustion DHf (kcal/mol)
Formula weight Balance Content, Mp d ÿDHc
OB100 %N ( C) (g/cm3) (kcal/mol) Observe Calculated

4 C4N6O6 228.08 1.75 36.85 85 1.85 477.2  0.5 101.0 98.8

5 C4N6O7 244.08 2.46 34.43 63±64 1.907 449.3  0.8 73.1 73.8

7 C4N8O6 256.09 1.56 43.75 56 1.73 544.6  1.0 168.4 166.9

8 C4N8O7 272.09 2.21 41.18 112 1.82 530.9  1.6 154.7 152.8

13 C6N8O9 328.11 1.83 34.15 38±40 Ð Ð 95.3

18 C6N10O8 340.13 1.18 41.18 oil Ð Ð 190.6

20 C6N10O9 356.13 1.68 39.33 41±42 Ð Ð 175.4

24 C6N12O7 352.14 0.57 47.73 oil 1.71 Ð Ð 285.9

26 C6N12O8 368.14 1.09 45.66 70±72 1.79 Ð Ð 276.5

28 C6N12O9 384.14 1.56 43.75 oil 1.8 825.6  0.9 261.13 260.5

29 C6N12O9 384.14 1.56 43.75 115 Ð Ð 260.5

30 C6N12O9 384.14 1.56 43.75 85 1.89 Ð Ð 260.5

NG C3H5N3O9 227.09 3.08 18.50 oil 1.59 ÿ83.9(37)

TNM C(NO2)4 CN4O8 196.03 7.14 28.58 oil 1.64 12.3(37)


PETN C5H8N4O12 316.14 1.90 17.72 141 1.76 ÿ120.1(37)

TNT C7H5N3O6 227.13 ÿ3.08 18.50 80.8 1.65 ÿ10(37)

TNAZ C3H4N4O6 192.09 1.04 29.17 104 1.84 6.9(38)

persulfate in oleum at 80±90 C gave three isomeric di- also was formed, although the compound was never suc-
N,N0 -oxides, (28), (29), and (30), which were separated by cessfully isolated.
¯ash chromatography in 15%, 8%, and 34% yields, The novel compounds gave satisfactory elemental
respectively (Scheme V). The reaction produced a very analyses and had been fully characterized by 13C- and 14N-
small amount of an additional product which was success- NMR, IR and mass spectrometry, and size exclusion chro-
fully isolated by ¯ash chromatography. Mass spectral and matography. In the 13C-NMR spectra the carbon signals of
NMR analysis showed this product to be a mono-N-oxide the C-NO2 moiety appeared at around 153 and 157 ppm.
(26). Additionally, in situ GC-MS analysis of the reaction The typical ranges for the carbons of the C-O moiety are
mixture indicated that a minor isomeric mono-N-oxide (27), 154±156 ppm. The signals of the carbons bonded with
146 Sheremetev, Kulagina, Aleksandrova, Dmitriev, Strelenko, Lebedev, Matyushin Propellants, Explosives, Pyrotechnics 23, 142±149 (1998)

fragments generating as a result of C-N and N-N bonds


break in C-N(O)=N moiety were observed for the products
with azoxy bridges. The fragmentation was an additional
support for this series of structures. The product ion peaks
useful for structure assignment are listed in the experi-
mental sections.
The trifurazans (13), (20), (26), (29), and (30) are
colourless crystalline compounds, whereas orange dinitro
derivatives (18), (24), and colourless compound (28) are
high density liquids (Table 2), have no solubility in water,
and are not hydroscopic. The compounds are well soluble in
common organic solvents such as CH2Cl2, CHCl3, CH3CN,
acetone, benzene, and DMF, have little solubility in hexane
and pentane, and they are stable to solvolysis by EtOH in
CH2Cl2 at room temperature over a period of 20 h. The
Scheme IV
series dinitro trifurazans was found to be thermally stable
up to 210±230 C.
The heat of formation DHf is much determining of the
performance. Here DHf were calculated from the heat of
combustion DHc using the Institute Chemical Physics (ICP)
Code adapted for furazan series(34). Determination of DHc
was carried out in calorimetric bomb at large excess of
oxygen (at constant pressure) using automatic hermetic
semimicrocalorimeter constructed by ICP(35). Since the
furazan derivatives are technologically complicated for the
investigation we used a specially developed method for
study of analogous compounds(36). The heats of formation
calculated by ICP Code have been found to be very close
(within 97±99%) to those received on the basis of experi-
mental DHc. Table 2 summarizes some physical and
explosive properties of these compounds.
It cannot be too highly stressed that the dinitro trifurazans
Scheme V
are zero-hydrogen compounds and nitrogen percent in them
are 39.3±47.7, with the heats of formation are 290±812 cal/
g, that lacks analogy among the known low-melting high
azoxy moiety are in the range 149±158 ppm. In the 14N- energetic materials, with the performance better than that of
NMR spectra there are narrow signals due to the N(O) atom TNAZ. Liquid dinitro trifurazans, (18), (24), and (28), are
of the azoxy group (d ÿ66 to ÿ70 ppm, Dn1=2 ˆ 60±200 Hz) high dense oils, which are very high compared to the other
and the nitrogen atom of the nitro group (d ÿ37 to liquids composed of C, N, H, and O atoms, in particular to
ÿ44 ppm, Dn1=2 ˆ 10±40 Hz). Signals of the carbon atoms such common high energetic liquid materials as NG or
bonded with nitro and azoxy groups were broadened by TNM.
13
C-14N coupling. Identi®cation of N-oxide isomers was
made through selective 13 C-f14 Ng double heteronuclear
resonance (Table 1). The high symmetry of (13), (24), (30)
makes structural veri®cation by NMR spectroscopy very
simple. The combinations of 13C- and 14N-NMR and 3. Conclusion
comparison with th established literature data(6±8,11,31±33)
were useful for the identi®cation of the compounds. The preparation of these dinitro trifurazans illustrates the
The electrospray mass spectra showed, for all these high synthetic potential of the construction sequence. The
compounds, expected molecular ion peak together with the simplicity and availability of the starting materials makes
typical fragmentation. Peculiarity of this group of com- this strategy a powerful method for high energetic material
pounds are peaks corresponding to the loss of one and/or construction. We specially emphasize the fact of possible
two nitro moieties, giving rise to signals with m/z values for achievement of various properties by synthesis of isomeric
(M-NO2)‡ and/or (M-2NO2)‡. In the case of the azoxy compounds with the same empirical formula. We believe
compounds, these products showed a peak the spectra 16 this ®nding represents not only scienti®c signi®cance, but
mass units lower than the respective starting material, cor- also interesting practical perspectives. Therefore, some tri-
responding to the loss of the oxygen atom (from azoxy furazans may be important candidates for further study and
group). In addition, an abundant peaks corresponding to the potential applications.
Propellants, Explosives, Pyrotechnics 23, 142±149 (1998) Dinitro Trifurazans with Oxy, Azo, and Azoxy Bridges 147

4. Experimental Section Bis-3,4-(3-cyanofurazan-4-oxy)furazan (15). The com-


pound (15) was synthesized according to mentioned above
CAUTION! The compounds are high explosives and may procedure starting from 3-cyano-4-nitrofurazan (2) and salt
be sensitive to shock, friction or heating and must be han- (12); yield 89%; m.p. 70±72 C; IR 2210, 1615, 1590, 1575,
dled with appropriate precautions. The most hazardous are 1510, 1470, 1410, 1290, 1270, 1240, 1035 [cmÿ1]; 13C-
hydroxyfurazan salts that explode at slight touch. NMR (CDCl3): d ˆ 162.1 (NC-C-C), 153.8 (O-C-C-O),
Melting points were determined on a Ko¯er hot-stage 128.7 (NC-C), 106.3 (CN).-MS m/z 288 (M‡), 258 (M‡-
microscope and are uncorrected. IR spectra were NO). Anal. Calcd for C8N8O5 (288.14): C, 33.35; N, 38.89.
recorded using a Perkin-Elmer 577 spectrometer as thin Found: C, 33.21; N 38.76 [%].
®lms on KBr disks. Mass-spectra were obtained on a 4-Hydroxy-40 -nitroazofurazan (16). A solution of
Varian MAT-311A instrument. 13C- and 14N-NMR sodium hydroxide (0.8 g, 20 mmol) in 30% H2O2 (15 ml)
spectra were recorded on a Brucker AM-300 instrument at was added dropwise with stirring at 0 C to a solution of (7)
75 and 21.68 MHz, respectively. The chemical shift values (2.56 g, 10 mmol) in acetonitrile (15 ml). This was followed
are expressed in d values (ppm) relative to the chemical by addition of precooled (nearly 0 C) water (50 ml) and
shift of the solvent-d. Analytical TLC was conducted on extracted with Et2O/CH2Cl2 (3620 ml). The aqueous phase
precoated silica gel plates (Silufol F254). The plates were was strongly acidi®ed with H2SO4 and extracted with Et2O
visualized under UV after development followed by (4620 ml). The combined ether extracts were dried
spraying with DPA reagent (5% diphenylamine in hexane) (MgSO4) and ®ltered. The solvent was removed by rotary
and heating the plate at 150±180 C for about 2±5 min in an evaporation, and the residue was separated by silica gel
oven. column chromatography using CH2Cl2/ether as eluent.
Di-Na-salt of (11), (12). To a solution of (11) (5.1 g, The product (16) was obtained in 18% as yellow oil: MS
50 mmol) in ether (80 ml) was added dropwise with stirring m/z 227 (M‡), 199 (M‡-N2), 169 (M‡-N2-NO), 140
a solution of Na (2.30 g) in ethanol at 10±15 C, and the (nitrofurazanCN‡), 113 (hydroxyfurazanNN‡), 90, 69, 68,
resulting mixture was stirred at ambient temperature for 1 h. 60, 57, 54, 44, 30, 28; IR 3200±2700, 1605, 1545, 1505,
During this time, a colourless solid precipitated from the 1465, 1325, 1280, 1050, 960, 890, 820 [cmÿ1]; Anal. Calcd
solution. This solid was collected by ®ltration, and the for C4H1N7O5 (227.10): C, 21.16; H, 0.44; N, 43.17. Found:
residue was washed with Et2O (50 ml). The residue was C, 21.07; H, 1.01; N, 43.06 [%].
dried, thereby affording 6.7 g (92%) of salt (12). It was used Na-Salt 4-Hydroxy-40 -nitroazofurazan (17). To a
as obtained in the next step without puri®cation. solution of (16) (2.27 g, 10 mmol) in ether (70 ml) was
Bis-3,4-(3-nitrofurazan-4-oxy)furazan (13): To solu- added dropwise with stirring a solution of Na (0.25 g) in
tion of salt (12) (2.92 g, 20 mmol) in glyme (25 ml) was ethanol at 5±10 C, and the resulting mixture was stirred at
added solution of (1) (1.6 g, 10 mmol) in glyme (25 ml) ambient temperature for 1 h. During this time, a yellow
under a dry atmosphere at 30 C. The resulting mixture was solid precipitated from the solution. This solid was collected
stirred 0.5±1 h at 30 C. The progress of the reaction was by ®ltration, and the residue was washed with Et2O (50 ml).
monitored by TLC. The reaction was cooled. After addition The residue was dried, thereby affording 1.1 g (43%) salt
of CH2Cl2 (250 ml), the resulting mixture was washed (17). It was used as obtained in the next step without pur-
(H2O), dried (MgSO4), ®ltered, and evaporated. The residue i®cation.
was a mixture of (5), (13) and (14). The products were 3-(3-Nitrofurazan-4-azo)-4-(3-nitrofurazan-4-oxy)fur-
separated by silica gel ¯ash chromatograpy using CH2Cl2/ azan (18): To solution of salt (17) (2.49 g, 10 mmol) in
pentane as eluent. diglyme (30 ml) was added solution of (1) (1.6 g, 10 mmol)
The ®rst fraction, difurazano[3,4-b;30 ,40 -e]dioxine in glym (15 ml) under a dry atmosphere at 50 C. The
(14)(39) was obtained as very volatile oil (12%); sublimation resulting mixture was stirred 3±4 h at 70 C. The progress of
gave analytically pure (14) as colourless needles, m.p. the reaction was monitored by TLC. The reaction was
16 C; IR 1615, 1510, 1440, 1320, 1280, 1115, 985, 935 cooled. After addition of CH2Cl2 (350 ml), the resulting
[cmÿ1]. 13C-NMR (CDCl3) 156.3; MS m/z 168 (M‡), 138 mixture was washed (H2O), dried (MgSO4), ®ltered, and
(M‡-NO), 108 (M‡-2NO). Anal. Calcd for C4N4O4 evaporated. The residue was a mixture of (18) and (5). The
(168.07): C, 28.59, N, 33.34. Found: C, 28.16, N, 33.11 [%]. products were separated by silica gel ¯ash chromatography
The second fraction, 3,3-dinitrodifurazanyl ether (5) using CH2Cl2/CCL4 (1:1) as eluent.
was obtained as colourless crystals, mp 63±64 C (Ref. 7, The ®rst fraction, 3,3-dinitrodifurazanyl ether (5) was
64 C, mixed m.p. 63±64 C) on the basis of IR obtained as colourless crystals, mp 63±64 C.
spectroscopy, MS and TLC, the substance corresponded The second fraction gave an orange oil of (18) (51%);
in all the respects with the compound described MS m/z 340 (M‡), 294 (M‡-NO2); IR 1650, 1585, 1340,
earlier.(7) 1315, 1210, 1010, 980 [cmÿ1]; Anal. Calcd for C6N10O8
The third fraction gave 1.41 g (43%) of colourless crys- (340.13): C, 21.19; N, 41.18. Found: C, 21.26; N, 41.05
tals of (13): mp 38±40 C; IR 1600, 1560, 1490, 1365, 1265, [%].
1205, 1190, 1040 [cmÿ1]. MS m/z 328 (M‡), 206 (M‡- 3-(3-Nitrofurazan-4-NNO-azoxy-4-(3-nitrofurazan-4-
2NO2-NO), 68. Anal. Calcd for C6N8O9 (328.11): C, 21.96; oxy)furazan (20): To mixture of (NH4)2S2O8 (11.4 g,
N, 34.15. Found: C, 21.89; N, 34.09 [%]. 50 mmol) and 20% oleum (30 ml) was added (18) (0.34 g,
148 Sheremetev, Kulagina, Aleksandrova, Dmitriev, Strelenko, Lebedev, Matyushin Propellants, Explosives, Pyrotechnics 23, 142±149 (1998)

1 mmol) in one portion with stirring. The resulting orange (M‡-O-nitrofurazanyl), 238 (M‡-2O-nitrofurazanyl), 226,
suspension was stirred at 70 C for 2 h, cooled to 0 C, and 210, 196, 180, 162, 158 (nitrofurazanNNO‡), 144, 142
poured over crushed ice. It was extracted with CH2Cl2 (nitrofurazanNN‡), 122, 68; IR 1580, 1510, 1350, 1300,
(4625 ml), and the combined organic layers were washed 1215, 1160, 1130, 1030, 980, 940, 820 [cmÿ1]; Anal. Calcd
(H2O), dried (MgSO4), and concentrated. The residual oil for C6N12O9 (384.14): C, 18.76; N, 43.75. Found: C, 18.77;
was recrystallized from hexane to give 0.29 g (82%) of (20): N, 43.66 [%].
mp 41±42 C; MS m/z 356 (M‡), 340 (M‡-O), 310 (M‡- The third fraction, 3,4-bis(4-nitrofurazan-3-NNO-
NO2), 294 (M‡-O-NO2); IR 1650, 1585, 1340, 1315, 1210, azoxy)-furazan (30): mp 85 C; MS m/z 384 (M‡), 338
1010, 980 [cmÿ1]; Anal. Calcd for C6N10O9 (356.13): C, (M‡-NO2), 276 (M‡-O-2NO2), 254 (M‡-O-nitrofurazanyl),
20.24; N, 39.33. Found: C, 20.30; N, 39.19 [%]. 238 (M‡-2O-nitrofurazanyl), 217, 212, 162, 158
3,4-Bis(3-nitrofurazan-4-azo-)furazan (24): To a sus- (nitrofurazanNNO‡), 142 (nitrofurazanNN‡), 84, 68; IR
pension of (22) (1.3 g, 10 mmol) and (23) (2.26 g, 10 mmol) 1580, 1505, 1490, 1350, 1295, 1150, 1020, 940, 880, 810
in conc. hydrochloric acid (50 ml) was added dropwise with [cmÿ1]; Anal. Calcd for C6N12O9 (384.14): C, 18.76; N,
stirring 0.1N aqueous solution of KMnO4 (250 ml) at 45± 43.75. Found: C, 18.71; N, 43.69.
50 C, and the resulting mixture was stirred for 2 h. The The fourth fraction, 3,4-bis(4-nitrofurazan-3-ONN-
resulting black suspension was extracted with CHCl3 azoxy)-furazan (29): mp 115 C; MS n/z 384 (M‡), 368
(4625 ml), and the combined orange organic layers were (M‡-O), 308 (M‡-NO-NO2), 278, 256, 254 (M‡-O-nitro-
washed (H2O), dried (MgSO4), and concentrated. The furazanyl), 234 (M‡-O-NO-nitrofurazanyl), 210, 182, 166,
residue was a mixture of (24) with (7) and (25). The pro- 144, 142 (nitrofurazanNN‡), 108, 94, 84, 68; IR 1590,
ducts were separated by silica gel ¯ash chromatography 1565, 1510, 1480, 1445, 1365, 1310, 1210, 1150, 1040, 855
using CH2Cl2/pentane as eluent. [cmÿ1]; Anal. Calcd for C6N12O9 (384.14): C, 18.76; N,
The ®rst fraction, 4,40 -dinitroazofurazan (7) was 43.75. Found: C, 18.74; N, 43.71 [%].
obtained as red-orange crystals, mp 56 C (Ref. 3: 56 C,
mixed m.p. 56 C) on the basis of IR spectroscopy, MS and
TLC, the substance corresponded in all respects with the
compound described earlier(3). 5. References
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