Vous êtes sur la page 1sur 4

Propellants, Explosives, Pyrotechnics 19,145-148 (1994) 145 Review on Benzofuroxan System Compounds

Wang Naixing, Chen Boren, and Ou Yuxiang

Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China)

Überblick iiber Verbindungen des Benzofuroxan-Systems Récapitulatif sur les composés du système benzofuroxane
In dieser Arbeit werden Struktur, Darstellung und Entwicklung von Cette étude porte sur la structure, la description et le développement de
Verbindungen des Benzofuroxan-Systems besprochen. Der Ersatz von composés du système benzofuroxane. Le remplacement de groupes nitrés
Nitrogruppen durch Furoxan-Gruppen am aromatischen Ring kann die par des groupes furoxane dans le composé cyclique aromatique permet
Dichte, Detonationsgeschwindigkeit und den Energieinhalt von d'augmenter la densité, la vitesse de détonation et le contenu énergétique
Explosivstoffen vergrößern, so daß die Furoxanverbindungen und d'explosifs, ce qui explique le grand intérêt suscité par les composés de
benzofuroxane et certains matériaux énergétiques.
einige energetische Materialien große Beachtung gefunden haben.
Summary The main objection to the peroxide structure (2) was that
it is inconsistent with the chemical properties of furoxans in
This paper reviews on benzofuroxan system compounds about particular, their stability and their oxidizing power which is
structure, preparation and development. The replacement of nitro
not pronounced. Both of Wieland's formulas (1) and (3)
groups by furoxano groups on aromatic ring can increase density,
require that isomeric substances can exist when R I and R2 are
detonation velocity and energy of explosives, so benzofuroxan
system compounds and some energetic materials have aroused
not the same, but at the time of his proposal (1903) isomerism
much attention. had not been established. Although Wieland later believed
that he had isolated two isomers of monophenylfuroxan, the
first sound evidence came only in 1925, when Meisenheimer
1. Introduction et al.(9) showed that different isomers could be produced
The furoxan (furazan oxide, 1,2,5-oxadiazole-2-oxide) from different stereoisomers of p-methoxybenzil dioxime.
ring system has been the subject of much debate and Shortly afterward, isomers and their interconversions were
controversy since the first (unrecognized) preparation of a found in the aryl-alkyl series( 10- 12 )
compound of this type in 1850' s( l ) until almost the present
day. It is sufficient here to state that proton magnetic 0721-3115/94/0306-145 $5.00+.25/0
resonance spectroscopy resolved the benzofuroxan question 146 W. Naixing, C. Boren, and O. Yuxiang
at the beginning of the 1960's, while X-ray crystallography
cleared up all doubts that might have remained concerning This evidence led Beilstein's Handbuch( 13) recommend the
the unfused series in the latter half of that decade. furoxan structure (1). It was only in the mid-1960's that
NMR( 14 ) and X-ray( 15 ) evidences were obtained for the
2. Structure identity of both isomers of some pairs as furoxans (l), but by
that time the general consensus was that this was the case.
The earlier furoxans were produced from metal The benzofuroxans and naphthofuroxans presented an
fulminates. The dibromo compound, C2Br2N202, formed by apparently different problem, because the isomerism that
the action of bromine on mercury fulminate( l ), was for some might have been expected by analogy with the monocyclic
time believed to be dibromo nitroacetonitrile, until chemical series was not found. Although by the time of Beilstein's
investigation and an authentic synthesis forced that notion to second supplement (1929) the furoxan structure (5) was
be abandoned. In the meantime, other ways were found of considered the most likely, another symmetrical formula,
producing furoxans that provided more insight into their "Y-(pseudo) 0-dinitrosobenzene" (6), was put forward in
structures. Syntheses of furoxans from 1,2-dioximes 1955 by Boyer, whose review(4) is to a large extent colored
(glyoximes) by oxidation( 2 ) and by the action of by it. But in 1961, incontrovertible evidence for a rapidly
exchanging system( 16) led to a reinstatement of the
benzofuroxan formula (5), with the interconversion of
© VCH Verlagsgesellschaft, D-69451 Weinheim, 1994
isomers which had long previously been suggested by
nitrogen oxides on certain olefins( 3-4) showed the need for a
Hammick et al.( 17 ). X-ray crystallography almost
more symmetrical formula, and so the dioxadiazine, or
immediately confirmed this as correct( 18 )
glyoxime peroxide, structure (2) was put forward( 5 ). 3
Wieland(6-7 ) first proposed the oxadiazole-N-oxide formula
(1), although he later rejected it for a while in favor of the
bicyclic structure (3), which never gained wide currency.
Another bicyclic structure (4) enjoyed a brief popularity as it O
was capable of explaining the lack of isomerism in the (5) (6)
benzofuroxans (see below )(8).

3. Preparation

O The previous reviews covered principal synthetic routes

(1) (2) (3) (4) to furoxans and benzofuroxans before 1960, and, apart from
occasional curiosities, none of the considerable number of
preparations since the time breaks significantly new ground( filtered and washed, the moist filter cake is transferred to a
). There are many synthetic routes, despite some of the large excess of propionic acid and heated to 140 D C. When
methods for furoxans and benzofuroxans are not applied nitrogen evolution, the reaction mixture is cooled to ambient
generally. The pyrolysis of o-nitrophenyl azides is the most and mixed slowly with an excess of water. The precipitated
reliable general method comparing with the considerable BTF is filtered and washed with water. The crude material
synthetic routes. The pyrolysis temperature is usually should be recrystallized in an excess of refluxing benzene. A
considêrably lower than is necessary to decompose mor p- BTF/benzene complex formed can be decomposed to obtain
nitrophenyl azides, and the nitro group is generally agreed to high-purity BTF by heating in vacuum above 80 c c.
take part in the displacement of the nitrogen(20). The Liao Zhiyuan and Chen Boren( 36 ) reported that the
mechanism of this and similar reactions has been the hydrogen-free compound 6,6-dinitro-
tetrafuroxano[b,d,b,d]biphenyl and hydrogen-few
subject of some discussion. There is a close parallel between compound 6-nitrotetrafuroxan[b,d,b,d]biphenyl are
nitroazide pyrolysis. Forming benzofuroxans, a simple synthesized from benzidine through nine or eight steps of
concerted cyclization and elimination was favored: reaction, i.e. acetylation, chlorination, deacetylation,
o- deamination, nitration, azidation, two-stage nitration and
pyrolysis. High-energy and low-sensitivity compound 5,7-
diamino-4,6-dinitrobenzofuroxan is synthesized from 1,3,5-
trichlorobenzene through five steps of reaction, i.e. nitration,
azidation, second nitration, pyrolysis and amination. It is
shown by HNMR decoupling experiments that 5-
Recently, Dyall has produced arguments, based on steric methylamino-4,6-dinitrobenzofuroxan and 5-methylamino-
effects of ortho substituents, challenging the mechanism of 2,4-dinitro azidobenzene exist as a pair of stereoisomeres.
other azide The molecular structure of 5-methylamino-4-
The azide pyrolysis route has been used in the preparation nitrofuroxano[4,3-h]benzofuroxan was determined by X-ray
of a wide variety of substituted benzofuroxans by diffraction. It is the first example of benzofuroxans that
Propellants, Explosives, Pyrotechnics 19, 145-148 (1994) exocyclic
Propellants, Explosives, Pyrotechnics 19, 145-148 (1994)
Ghosh and Whitehouse( 23 ), and it has been extensively
oxygen atoms of two furoxano groups on the same molecule
applied to the synthesis of specific examples, for instance,
are neighbouring each other.
the 5-carboxylic the 4-chloro-5-methyl
The binding energies of nitrogen atoms in benzofuroxans
compound(26) and others(27 ). It has been used to prepare
substituted by nitro groups are different and the difference of
heterocyclic-fused furoxans such as thieno[2,3-c]furoxan( 28
binding energies of two nitrogen atoms of furoxan is about
) some pyrido(29)-, pyrimido(30)-, and phoridazido(31 )
3.3 ev to 4.3 eV. Thus, ESCA can be used to determine
furoxans, and oxadiazolo( 32 )-, imidazo( 33 )-, and
structures of benzofuroxans together with IR, MS and NMR.
thiadiazolo( 34 )benzofuroxans. When the azido or nitro
The stability of similar compounds may be predicted by the
group is severely orthocrowded( 35), or when the azide group
amount of intramolecular charge-transfer (CT).
has to be disengaged from fusion into a tetrazole ring, more
The replacement of nitro groups by furoxano groups on
forcing conditions are sometime needed, and other methods
aromatic rings can increase density, detonation velocity and
may be found superior. On the other hand, some o-
energy of explosives; the introduction of imino groups will
nitroazides are so labile that it is not practicable to attempt
increase density and decrease drop-hammer sensitivity. In
to isolate them(36)
order to utilize these advantages, Wang Naixing(39) et al.
have has synthesized N,N'-bis(2-nitro-
4. Development benzodifuroxanyl)3,5-dinitro-2,6-diaminopyridine by
condensation reaction of trinitrotrichlorobenzene with 2,6-
R.R. McGuiva( 37 ) had reviewed the literature and diaminopyridine, then nitration, azidation and thermal
characterized benzotrifuroxan (B TF), a CO-balanced, degradation of N,N'bis(2,4,6-trinitro-3,5-diazidophenyl)-
hydrogenfree explosive that is sensitive to exploding 3,5-dinitro-2,6-diaminopyridine:
bridgewire initiation. It has performance parameters
equivalent to those of HMX-based explosive, but with a
different isentrope. The properties of BTF as an explosive
have been both exciting and perplexing. BTF was first
considered as a more thermally stable replacement for PETN
and EBW applications.
The synthesis of BTF generally starts with 1,3,5-
trichlorobenzene (TCB). This material can be nitrated to
2,4,6trichloro- (TCTNB) in one step
using either 100 % HN03 or NaN03 in 20 % - 30 % oleum
at 120 o c - 130 0 C. The TCTNB is then added in small
increments to a solution of NaN3 in 95 % ethanol while
maintaining the temperature at ambient to give 1,3,5-
triazido-2,4,6-trinitrobenzene. The reaction mixture is
02N 02N N02

02N 02N N02 N02


+ 6 NaCl

This compound has a density 1.91 g/cm3 (it was

determined preliminary by the method of the density bottle).
Review on Benzofuroxan System Compounds

Melting point 231.5 oc (dec), detonation velocity 8626 m/s

(calculated). Compared with a moderately powerful heat
resisting explosive 2,6-bis (picrylamino)-3,5-
dinitropyridine(40), this compound displays both a higher 148 W. Naixing, C. Boren, and O. Yuxiang
density and detonation velocity.
High energy and low-sensitivity compound N,N', N" This compound has a molecular formula C21H3N21018,
tri(2-nitro-benzodifuroxanyl)-melamine(41 ) is synthesized molecular weight 837, density 1.90 g/cm3 (density bottle),
as follows: melting point 316 o c (dec), detonation velocity 8696.5 m/s
(calculated). This compound has very low hydrogen content,
high nitrogen content, high density and good heat resistance.
In addition, N,N'-bis(2,4-dinitrobenzofuroxanyl)-
l,3,5trinitro-2,6-diaminobenzene which cost is relative low
due to the inexpensive raw materials has been reported( 42):
This compound is a yellow solid, it decomposes at 209.3
c and has a density of 1.92 g/cm 3 , detonation velocity of
8573.6 m/s, no massloss at 100 o c for 48 h.
In search of new high-energy and low-sensitivity
explosives we have tried to introduce amino groups to
multicircle benzofuroxan system so that densities increase
and heat resistance of explosive molecules improves. We
believe, many new and better benzofuroxan system will be


fuming HN03
02N N02

N02 H2S04
02N 02N N02 (26) A.S. Angeioni, D. Dal Monte, E. Sandri, and G. Scapini,
Tetrahedron 30, 3849 (1974).
(27) P. Grieco and J.P. Mason, J. Chem. Eng. Data 12, 623
(28) C. Paulmier, G. Ah-Kow, and P. Pastour, Bull. Soc. Chim.
02N N02 Fr., 1437 (1975).
(29) J.H. Boyer, DI. McLane, w.l. McCarville, and A.T. Tweedie, J.
Am. Chem. soc. 75, 5298 (1953).
02N 02N N02
(30) C. Temple, CL. Kussner, and J.A. Montgomery, J. Org.
Chem. 33, 2086 (1968).
(31) A. Karklina and E. Gudriniece, Latv. SPR Zinat. Akad.
Vestis, Khim. ser., 718 (1972), [CA 78, 72037 (1973)].
02N (32) P.B. Ghosh and B.J. Everitt, J. Med. Chem. 17, 203 (1974).
(33) R.C. Perera, RK. Smalley, and L.G. Rogerson, J. Chem.
Soc. C, 1348 (1971).
(34) P.B. Ghosh, Tetrahedron Lett., 2999 (1971).
(35) A.J. Boulton and P.B. Ghosh, Adv. Heterocycl. Chem. 10, 10,
.14 (1969).
(36) P.B. Ghosh and M.W. Whitehouse, J. Med. Chem. 12, 505
(1969). (37)R.R. McGuiva, UCRL-52353, Oct 27, (1977).
(38)Chen Boren and Liao Zhiyua, Propellants, Explos., Pyrotech.
02N N02 15 (3), 97 (1990).
(V) (39)Wang Naixing, Chen Boren, and Ou Yuxiang, J. Energetic
Materials, to be published.
(40)F.M. Hudson, Eur. Pat. 104717 (1984), [CA 101, 1 10736 (1984)].
5. References (41)Wang Naixing, Synthesis of N,N' ,N"-tri(2-nitro-
benzodifuroxanyl)-melamine, Proceedings of China
(l) A. Kekule, Justus Liebigs Ann. Chem. 101, 200 (1857); 105, 279
Association for Science and Technology First Academic
Annual Meeting of Youths, Part of Engineering Course (Il),
Propellants, Explosives, Pyrotechnics 19, 145-148 (1994)
160, Beijing, (1992).
(42)Wang Naixing, "Synthesis of N,N'-bis(2,4-
(2) R. Koreff, Ber. Dtsch. Chem. Ges. 19, 176 (1886).
dinitrobenzofuroxanyl)-l,3,5-trinitro-2,6-diaminobenzene", in:
(3) P. Tonnies, Ber. Dtsch. Chem. Ges. 13, 1845 (1880).
(4) A. Angeli, Ber. Dtsch. Chem. Ges. 26, 593 (1893).
Ou Yuxiang (ed.) Proceedings of the 17th International
(5) R. Koreff, Ber. Dtsch. Chem. Ges. 19, 176 (1886). Pyrotechnics Seminar Combined with the 2nd Beijing
(6) H. Wieland, Justus Liebigs Ann. Chem. 329, 225 (1903). International Symposium on Pyrotechnics and Explosives,
(7) H. Wieland and L. Semper, Justus Liebigs Ann. Chem. 358, 36 Beijing, 1991, Beijing Institute of Technology Press, 1991, pp.
( 1907). 235-237.
(8) A.G. Green and F.M. Rowe, J. Chem. soc. 103, 897 (1913). (Received October 5, 1992; Ms 59/92)
(9) J. Meisenheimer, H. Lange, and W. Lamparter, Justus Liebigs
Ann. Chem. 444, 94 (1925).
(10) G. Ponzio, Gazz. China. Ital. 58, 329 (1928); Ber. Dtsch. Chem.
Ges. 61, 1316 (1928).
(11) G. Ponzio and G. Carta-Satta, Gazz. Chim. Ital. 60, 150 (1930).
(12) G.f Ponzio, Gazz. Chim. Ital. 59, 713 (1929).
(13) "Beilstein's Handbuch der Organischen Chemie", Hauptwerk,
4th ed., Springer-Verlag, Berlin, New York, 1937, Vol. 27, p.
(14) F.B. Mallory and A. Gammarata, J. Am. Chem. Soc. 88, 61
(15) M. Calleri, G. Ferraris, and D. Viterbo, Tetrahedron Lett. 4549
(16) A.J. Boulton and P.B. Ghosh, Adv. Heterocycl. Chem. 10, 8
(17) D.L. Hammick, W.A.M. Edwardes, and E.R. Steiner, J. Chem.
soc. 3308 (1931).
(18) R. Hulme, Chem. Ind. (London), 42 (1962); D. Britton and W.E.
Noland, ibid., 562 (1962).
(19) A. Gasco and A.J. Boulton, "Furoxans and Benzofuroxans",
"Advances in Heterocyclic Chemistry" 29, 270 (1981).
(20)L.K. Dyall and J.E. Kemp, J. Chem. soc. B, 976 (1968).
(21 )L.K. Dyall, Aust. J. Chem. 28, 2147 (1975).
(22) L.K. Dyall, Aust. J. Chem. 30, 2669 (1977).
(23) P.B. Ghosh and M.W. Whitehouse, J. Med. Chem. 11 , 305
(24) T. Nishikubo and T. Takaoka, Nippon Kagaku Kaishi, 327
(1975), [CA 82, 156762 (1975)].
(25) T. Nishikubo, Japanese Patent 76/04, 982 (1976), [CA 85,
160104 (1976)].