High-density energetic mono- or bis(Oxy)-5-nitroiminotetrazoles

Article abstract of DOI:10.1002/anie.201003866

Making an impact: Oxy-5-aminotetrazoles, which were obtained from the reaction of cyanogen azide and alkyl oxy-amine in 100% nitric acid (see scheme), give a series of highly energetic oxy-5-nitroiminotetrazolates in good yield. These compounds exhibit good physical and detonation properties, such as moderate thermal stabilities, high densities, high endothermy, good detonation pressures P, and good detonation velocities D.

Full text of DOI:10.1002/anie.201003866

Communications
DOI: 10.1002/anie.201003866
Energetic Materials
High-Density Energetic Mono- or Bis(Oxy)-5-Nitroiminotetrazoles**
Young-Hyuk Joo and Jean’ne M. Shreeve*
Dedicated to Professor Malcolm M. Renfrew on the occasion of his 100th birthday
In the last decade, the investigation of energetic tetrazoles—
cyanotetrazole, aminotetrazole, azidotetrazole, nitrotetra-
zole, and nitroiminotetrazole—has led to major develop-
ments in the area of high-energetic materials by many
research groups.[1] Several exciting classes of 5-substituted
tetrazole moieties are introduced in the literature.[2]
substituted 5-aminotetrazoles from primary amines under
non-catalytic mild conditions. Nitration of these aminotetra-
zoles using 100% nitric acid has been shown to form mono-,
di-, or tri- substituted nitroiminotetrazole derivatives.[12] With
these features in mind, our group became interested in
examining the analogous chemistry using alkoxy amine
derivatives.
Here we describe the work leading to a series of nitro-
iminotetrazole derivatives of oxy nitroiminotetrazoles and
their salts, with potentially significant physical and energetic
properties. The aim of our study was to elucidate the
structures in the crystalline state using X-ray diffraction
analysis and to find new, potent oxygen- and nitrogen-rich
tetrazoles. Alkoxy 5-nitroiminotetrazolates may be of interest
as a new class of ionic energetic materials, which have good
thermal stabilities, high densities, good oxygen balance, and
high heats of formation and which are realizable in high yields
though straightforward routes.
Tetrazoles can be protonated to form tetrazolium salts[3]
or deprotonated to give tetrazolates.[4] While deprotonation
increases the thermal stability of tetrazoles, protonation can
lower the decomposition temperature.[5] These energetic
materials based on high nitrogen content are derived from
À
their high heats of formation due to the large number of N N
[6]
À
and C N bonds. The combination of a tetrazole ring with
energetic substituent groups containing oxygen atoms, such as
nitro groups, nitrate esters, or nitramine, is of interest leading
to excellent oxidizers. Current research issues in the field of
high energetic materials include increasing oxygen content,
which may result in the replacement of ammonium perchlo-
rate in an effort to decrease pollution. Organic 5-nitrotetra-
zole derivatives,[1k,7] especially for synthesis of the highly
energetic 1-methyl-5-nitrotetrazole, were synthesized in good
yields. These were calculated to be endothermic with heats of
formation of 2.16 kJgÀ1, which was assessed by means of
standard tests and quantum chemical calculations.[7] In
addition, the highly energetic, nitrogen-rich 1-methyl-5-nitro-
iminotetrazole[8] and its salts[8c] can easily be obtained by
nitration of aminotetrazole followed by metathesis reactions
using silver 1-methyl-5-nitroiminotetrazolate and the guani-
dinium family of chlorides in aqueous solution with high
yields. Although 5-nitroiminotetrazole derivatives and their
salts are energetic materials with high nitrogen content, they
show good stabilities towards friction and impact, and good
thermal stability.[8c,9] The development of new energetic
compounds with similar attractive properties exhibit signifi-
cant promise in optimizing environmentally benign replace-
ments for toxic materials.[10]
The synthesis of 1-methoxy-5-aminotetrazole (2) was
achieved from the reaction of cyanogen azide[11] with methoxy
amine (obtained by neutralization of 1 with sodium hydrox-
ide) (Scheme 1). At ambient temperature, nitration of amino-
Scheme 1. Synthesis and reaction of 3.
In the past few years, the most convenient route to 1-
substituted 5-aminotetrazole is the addition of amine or
hydrazine to cyanogen azide,[11] which was found to be an
efficient reagent for the synthesis of readily purified 1-
tetrazole 2 using 100% nitric acid without solvent has been
shown to form 1-methoxy-5-nitroiminotetrazole (3) in good
yield. The new energetic salts 4 and 5 were easily obtained by
reacting 3 with a slight excess of 28% aqueous ammonia or
97% hydrazine hydrate in water, respectively. The structures
of methoxy nitroiminotetrazole and its salts are supported by
[*] Dr. Y.-H. Joo, Prof. Dr. J. M. Shreeve
Department of Chemistry, University of Idaho
Moscow, ID 83844-2343 (USA)
Fax: (+1)208-885-9146
1
IR, and H, 13C, and 15N NMR spectroscopic data as well as
elemental analysis. Structural confirmation of 3 and 5 by
single-crystal X-ray diffraction analyses is given in Figure 1a
for 3, and for 5 in the Supporting Information.[13]
E-mail: jshreeve@uidaho.edu
[**] The authors gratefully acknowledge the support of DTRA (HDTRA1-
07-1-0024) and ONR (N00014-10-1-0097).
Methylene bridged nitroiminotetrazoles are particularly
exciting molecules as high-energy density materials. We were
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201003866.
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The structures of 8, 9, and 10 are supported by IR, and 1H,
13C, and 15N NMR spectroscopic data as well as elemental
analysis. Structural confirmation of 9·2H2O by single-crystal
X-ray diffraction analyses is given in Figure 1b.[13] Com-
pounds 8 and 9 decomposed slowly in [D6]DMSO during
NMR measurements. While elemental analyses were success-
fully carried out for salts 9 and 10, an attempted elemental
analysis for neutral 8 resulted in a violent detonation in the
apparatus during the measurement. Although attempts to
remove the hydrazine and water molecules in the crystal of 10
to give 11 at 608C under high vacuum were unsuccessful, it
was possible to remove these species under the same
conditions from a solution in [D6]DMSO.
Next similar successful attempts were made to prepare 13
and 14 (I-10: Idaho) in good yield.[17] The energetic salts 15
and 16 were generally obtained by acid–base reactions with
14·3H2O and energetic bases (Scheme 3). Elemental analyses
attempted for neutral alkoxy-5-nitroiminotetrazoles 14·3H2O
and 14 resulted in violent detonations in the apparatus during
measurement.
Figure 1. a) Single-crystal X-ray structure and photograph of a crystal
of 3. The ruler scale is in mm. b) Single-crystal X-ray structure of
9·2H2O.
interested in utilizing our well-established 5-aminotetrazole
synthesis methodology with the highly sterically hindered
diaminomethane.[14] Unfortunately, addition of the methylene
diamine to cyanogen azide failed. However, it was possible to
prepare 7 by the analogous reaction of cyanogen azide with
the less sterically hindered methylene bis(oxyamine)[15]
(Scheme 2), and to investigate energetic ionic liquids based
on this bisoxyamine.[16] Nitration of 7 with 100% nitric acid
led to the extremely sensitive 8 (I-9: Idaho) that can be
converted to the more stable salts 9 and 10.
Scheme 3. Synthesis of 14 and its salts.
As expected and found in several structures of oxy-5-
nitroiminotetrazoles and their salts discussed here, the five-
membered ring is nearly planar, building an aromatic system,
which can be seen by the torsion angle N1-N2-N3-N4 of
between 0.09(10)8 and 0.10(17)8. The ring moieties of 3 and
9·2H2O are in agreement with the geometry observed for 5-
nitroiminotetrazoles and their salts.[5,8,9,12,18]
The tetrazole ring of 3 is nearly planar and four similar
bond lengths are observed (N1-N2 1.356 ꢀ, N3-N4 1.364 ꢀ,
N1-C5 1.351 ꢀ, N4-C5 1.342 ꢀ) (Figure 1a). These distances
À
are considerably longer than N2 N3 double bonds (1.279 ꢀ)
À
but significantly shorter than the O6 C7 single bond
(1.466 ꢀ). The nitroimine unit lies in the plane of the
tetrazole ring as clearly shown by the C5-N8-N9-O10 torsion
angle of À0.27(13)8 and C5-N8-N9-O11 torsion angle of
179.41(8)8, in which the oxygen atoms O10 and O11 are
slightly twisted out of the plane. The methoxy unit does not lie
in the plane of the tetrazole ring [torsion angle C5-N1-O6-C7
of 91.45(11)8]. The packing structure of 3 is strongly
influenced by strong hydrogen bonds. These extensive hydro-
Scheme 2. Synthesis of 8 and its salts.
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Table 1: Physical properties of oxy nitroiminotetrazoles, and their salts
compared with RDX and HMX.
gen bonding interactions between oxygen atom O11 from
nitro group and N4 [N4···O11 2.792(12)], can be seen in
Figure 1a) along the a axis.
[a]
Compd Tdec.
[8C]
d[b]
DHf8[c]
P[d]
D[e]
IS[f] OB[g]
[gcmÀ3
]
[kJgÀ1
]
[GPa] [msÀ1
]
[J]
[%]
The unit cell of 9·2H2O, which crystallizes with a
calculated density [1.610 gcmÀ3, 296(2) K] in the monoclinic
space group P21/n, contains four formula moieties. Between
the oxy nitroiminotetrazole, a torsion angle N1-O10-C11-O12
of 78.73(13)8 is observed. (Figure 1b). The packing of 9·2H2O
is also characterized by a three-dimensional network (Sup-
porting Information), whereby several strong hydrogen bonds
are formed between the nitrogen atom of the ammonium
cation and the nitrogen atom of the tetrazolate anion N4 and
N16.
3
4
5
8
9
14
15
16
116
184
156
157
167
134
202
169
230
287
1.66
1.55
1.63
1.90
1.71
1.81
1.72
1.73
1.82
1.91
3.15[h]
2.40
31.5
27.7
32.3
46.7
33.9
38.4
33.3
35.5
35.2
39.6
8660
8448
9036
9867
8984
9200
9014
9305
8977
9320
5
1.5
4
1
1
1.5
2
1.5
7.4
7.4
À30
À41
À42
À11
À24
À25
À36
À38
À22
À22
2.98
3.58[h]
2.38
3.47[h]
2.24
2.92
0.42
0.35
RDX[i]
HMX[i]
The 15N NMR spectra of alkoxy nitroiminotetrazole and
its salts were measured in [D6]DMSO and chemical shifts are
given with respect to CH3NO2 as external standard. In
Figure 2, selected 15N NMR spectra of 4, 11, and 14 are
[a] Thermal decomposition temperature under nitrogen gas (DSC,
58CminÀ1); no melting points are observed. [b] From gas pycnometer
(258C). [c] Heat of formation (calculated with Gaussian 03). [d] Calcu-
lated detonation pressure (Cheetah 5.0). [e] Calculated detonation
velocity (Cheetah 5.0). [f] Impact sensitivity (BAM drophammer).
[g] OB=Oxygen balance (%) for CaHbOcNd: 1600ꢀ(c À 2a À b/2)/Mw
(Mw =molecular weight of salt). [h] Solid state. [i] Ref. [19].
lower nitrogen content has a high positive heat of formation
with a value of 2.24 kJgÀ1.
Impact sensitivity measurements were made using stan-
dard BAM Fallhammer techniques.[20] Listed in Table 1 are
impact sensitivities ranging from those of the relatively less
sensitive 3 and 5 to the very sensitive compounds 4, 8, 9, and
14–16 between 1 J and 3 J. Thermal stabilities of the energetic
compounds were studied with differential scanning calorim-
etry (DSC). All oxy nitroiminotetrazoles decomposed
between 116 and 2028C without melting. In the case of
ammonium salt 15, decomposition occurred at the highest
temperature at 2028C, while Tdec = 1348C is observed for
neutral 14 as the least thermally stable species.
Figure 2. 15N NMR spectra of oxy-5-nitroiminotetrazole and selected
By using the calculated values of the heats of formation
and the experimental values for the densities (gas pycnometer
values, 258C) of the new highly energetic oxy nitroiminote-
trazoles, and their salts, the detonation pressures (P) and
detonation velocities (D) were calculated based on traditional
Chapman–Jouget thermodynamic detonation theory using
Cheetah 5.0 (Table 1).[21] The calculated detonation pressures
of oxy nitroiminotetrazoles and their salts lie in the range
between P = 27.7 and P = 46.7 GPa (comparable to RDX
35.2 GPa and HMX 39.6 GPa). Detonation velocities lie
between D = 8448 and D = 9867 msÀ1 (comparable to RDX
8977 msÀ1, HMX 9320 msÀ1). These properties coupled with
the rather high thermal and hydrolytic stabilities make these
high-nitrogen materials attractive candidates for energetic
applications. The relatively good oxygen balances of 8, 9, and
14 are À11%, À24%, and À25%, respectively, which are
comparable with those of RDX (À22%) and HMX (À22%).
In summary, compounds 8, 14, and 16 exhibit good
physical and detonation properties, such as moderate thermal
stabilities, high densities, highly endothermic, good detona-
tion pressures and good detonation velocities. Calculated
detonation values of these compounds are comparable to
those of explosives such as HMX (P = 39.63 GPa, D =
9320 msÀ1). However, they are very impact sensitive with
salts.
shown. The spectrum of 14 (bottom) is depicted with six
signals at À154.7 (N5), À124.3 (N4), À117.0 (N1), À24.5 (N3),
À17.8 (N6), and À10.6 ppm (N2). The signals for N1, which
has oxygen as a neighbor in the tetrazole ring appear as
expected at lower field (117.0 ppm) compared with the N1
position (170.6 ppm) of 1,1’-ethylenebis(5-nitroiminotetra-
zole).[12] The assignments are based on the literature values
of the remainder of the peaks which are essentially unchanged
for the nitroiminotetrazole group. The ammonium or hydra-
zinium nitrogen atoms of salts 4 or 11 are observed as an
intense signal at d = À350.9 or À324.1 ppm, respectively,
similar to other salts.[18]
In Table 1 it is shown that all alkoxy nitroiminotetrazoles
and their salts are highly endothermic compounds. The
enthalpies of energetic materials depend on the molecular
structure of the compounds. Consequently, heterocycles with
higher nitrogen content, especially tetrazole, show higher
heats of formation (see Supporting Information). All of the
compounds exhibit positive heats of formation with 8 having
the highest value of 3.58 kJgÀ1. Compound 15 in spite of the
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14; b) T. M. Klapꢁtke, J. Stierstorfer, Eur. J. Inorg. Chem. 2008,
4055 – 4062; c) H. Xue, H. Gao, B. Twamley, J. M. Shreeve,
Chem. Mater. 2007, 19, 1731 – 1739.
values between 1 and 1.5 J. The impact sensitivity of these
compounds could be reduced by combination with a less
sensitive oxidizer, e.g., ammonium nitrate.
[7] T. M. Klapꢁtke, C. M. Sabate, J. Stierstorfer, New J. Chem. 2009,
33, 136 – 147, and references therein.
Received: June 24, 2010
Published online: August 25, 2010
[8] a) T. M. Klapꢁtke, J. Stierstorfer, Helv. Chim. Acta 2007, 90,
2132 – 2150; b) G. Geisberger, T. M. Klapꢁtke, J. Stierstorfer,
Eur. J. Inorg. Chem. 2007, 4743 – 4750; c) T. M. Klapꢁtke, J.
Stierstorfer, A. U. Wallek, Chem. Mater. 2008, 20, 4519 – 4530.
[9] H. Gao, Y. Huang, C. Ye, B. Twamley, J. M. Shreeve, Chem. Eur.
J. 2008, 14, 5596 – 5603.
[10] T. M. Klapꢁtke, J. Stierstorfer, New Trends in Research of
Energetic Materials, Proceedings of the Seminar, 12th, Pardubice,
Czech Republic, April 1–3, 2009, 825 – 831.
[11] a) F. D. Marsh, M. E. Hermes, J. Am. Chem. Soc. 1964, 86, 4506 –
4507; b) Y.-H. Joo, J. M. Shreeve, Org. Lett. 2008, 10, 4665 – 4667;
c) Y.-H. Joo, B. Twamley, S. Garg, J. M. Shreeve, Angew. Chem.
2008, 120, 6332 – 6335; Angew. Chem. Int. Ed. 2008, 47, 6236 –
6239.
Keywords: detonation properties · energetic materials ·
.
tetrazole
[1] a) G. Steinhauser, T. M. Klapꢁtke, Angew. Chem. 2008, 120,
3376 – 3394; Angew. Chem. Int. Ed. 2008, 47, 3330 – 3347; b) R. P.
Singh, R. D. Verma, D. T. Meshri, J. M. Shreeve, Angew. Chem.
2006, 118, 3664 – 3682; Angew. Chem. Int. Ed. 2006, 45, 3584 –
3601; c) J. Sauer, G. R. Pabst, U. Holland, H.-S. Kim, S.
Loebbecke, Eur. J. Org. Chem. 2001, 697 – 706; d) M. Gꢁbel,
T. M. Klapꢁtke, Adv. Funct. Mater. 2009, 19, 347 – 365; e) T. M.
Klapꢁtke, P. Mayer, A. Schulz, J. J. Weigand, J. Am. Chem. Soc.
2005, 127, 2032 – 2033; f) H. V. Huynh, M. A. Hiskey, T. J.
Meyer, M. Wetzler, Proc. Natl. Acad. Sci. USA 2006, 103,
5409 – 5412; g) A. Hammerl, M. A. Hiskey, G. Holl, T. M.
Klapꢁtke, K. Polborn, J. Stierstorfer, J. J. Weigand, Chem.
Mater. 2005, 17, 3784 – 3793; h) T. Abe, G.-H. Tao, Y.-H. Joo,
Y. Huang, B. Twamley, J. M. Shreeve, Angew. Chem. 2008, 120,
7195 – 7198; Angew. Chem. Int. Ed. 2008, 47, 7087 – 7090; i) T. M.
Klapꢁtke, J. Stierstorfer, J. Am. Chem. Soc. 2009, 131, 1122 –
1134, and references therein; j) T. M. Klapꢁtke, C. M. Sabate, M.
Rasp, J. Mater. Chem. 2009, 19, 2240 – 2252, and references
therein; k) T. M. Klapꢁtke, B. Krumm, M. Scherr, F. X. Stee-
mann, K. Banert, Y.-H. Joo, Chem. Eur. J. 2009, 15, 11341 –
11345; l) A. R. Katritzky, G. L. Sommen, A. V. Gromova,
R. M. Witek, P. J. Steel, R. Damavarapu, Chem. Heterocycl.
Compd. 2005, 41, 111 – 118.
[12] Y.-H. Joo, J. M. Shreeve, Angew. Chem. 2009, 121, 572 – 575;
Angew. Chem. Int. Ed. 2009, 48, 564 – 567.
[13] CCDC 782054 (3), 782055 (5), and 782056 (9·2H2O) contain the
supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[14] R. Ohme, E. Schmitz, Chem. Ber. 1964, 97, 297 – 298.
[15] a) C. S. McDowell, M. W. Barnes, U. S. Patent 3709920, 1973;
b) C. S. McDowell, C. Merrill, U. S. Patent 3714200, 1973;
c) C. S. McDowell, C. Merrill, U. S. Patent 3714199, 1973;
d) D. V. Davydov, I. P. Beletskaya, Russ. J. Org. Chem. 2004, 40,
124 – 126.
[16] a) K. Tollison, G. Drake, T. Hawkins, A. Brand, M. McKay, I.
Ismail, C. Merrill, J. Energ. Mater. 2001, 19, 277 – 303; b) T.
Hawkins, L. Hall, K. Tollison, A. Brand, M. McKay, Propellants
Explos. Pyrotech. 2006, 31, 196 – 204.
[17] Synthesis of 12: D. W. Dixon, R. H. Weiss, J. Org. Chem. 1984,
49, 4487 – 4494.
[18] Y.-H. Joo, J. M. Shreeve, Chem. Eur. J. 2009, 15, 3198 – 3203.
[19] H. H. Krause in Energetic Materials (Ed.: U. Teipel), VCH,
Weinheim, 2005, pp. 1 – 25.
[20] a) www.bam.de. b) A portion of 20 mg of alkoxy nitroiminote-
trazole and their salts was subjected to a drop-hammer test using
a 5 or 10 kg weight dropped. The range in impact sensitivities
according to the UN Recommendations is: insensitive > 40 J;
less sensitive ꢀ 35 J; sensitive ꢀ 4 J; very sensitive ꢁ 3 J.
[21] S. Bastea, L. E. Fried, K. R. Glaesemann, W. M. Howard, P. C.
Souers, P. A. Vitello, CHEETAH 5.0 Userꢀs Manual, Lawrence
Livermore National Laboratory, 2007.
[2] a) R. J. Spear, Aust. J. Chem. 1984, 37, 2453 – 2468; b) T. M.
Klapꢁtke in High Energy Density Materials (Ed.: T. M. Kla-
pꢁtke), Springer, Berlin, 2007, pp. 85 – 122.
[3] a) H. Xue, B. Twamley, J. M. Shreeve, Inorg. Chem. 2004, 43,
7972 – 7977; b) J. C. Gꢂlvez-Ruiz, G. Holl, K. Karaghiosoff, T. M.
Klapꢁtke, K. Lꢁhnwitz, P. Mayer, H. Nꢁth, K. Polborn, C. J.
Rohbogner, M. Suter, J. J. Weigand, Inorg. Chem. 2005, 44,
4237 – 4253.
[4] C. Ye, J.-C. Xiao, B. Twamley, J. M. Shreeve, Chem. Commun.
2005, 2750 – 2752.
[5] T. M. Klapꢁtke, H. Radies, J. Stierstorfer, Z. Naturforsch. B
2007, 62, 1343 – 1352.
[6] a) M. A. Hiskey, D. E. Chavez, D. L. Naud, S. F. Son, H. L.
Berghout, C. A. Bolme, Proc. Int. Pyrotech. Semin. 2000, 27, 3 –
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