Propellants, Explosives, Pyrotechnics 27, 1 6 (2002)

Octanitrocubane: A New Nitrocarbon

Philip E. Eaton* and Mao-Xi Zhang Department of Chemistry, The University of Chicago, Chicago, Illinois (USA) Richard Gilardi Laboratory for the Structure of Matter, Naval Research Laboratory, Washington, D.C. (USA) Nat Gelber, Sury Iyer, Rao Surapaneni US Army ARDEC, Picatinny Arsenal, New Jersey (USA) Dedicated to the memory of Everett E. Gilbert 1914 2000

Summary
Octanitrocubane, the first new nitrocarbon in 18 years, is introduced as a potential explosive of great power. Its synthesis and characterization are described.

1. Introduction
With few exceptions, e.g. the perchlorates, azides and peroxides, powerfully explosive, carbon-based molecules contain one or more nitro (NO2) groups. In the detonation of such an explosive the nitro group provides (at least in part) oxygen to convert the molecules hydrogen to water and its carbon to carbon dioxide or carbon monoxide. In a perfect explosion the nitrogen atom of the nitro group would be converted to dinitrogen. These products are gaseous and are released quickly, hot, and in voluminous amounts. A nitro group can be attached to a molecular skeleton in four quite different ways: 1) by a bond from its nitrogen to a carbon atom, as in TNT; 2) by a bond from its nitrogen to an oxygen part of the rest of the molecule, as in nitrate esters like nitroglycerin; 3) by a bond from its nitrogen to another nitrogen in the molecule, as in the nitramines HMX and CL20 or finally 4) by a bond from its oxygen to a carbon atom, as in nitrites like methyl nitrite (Figure 1). The bond strength of the weakest bond in these four quite different situations decreases in the order CNO2 > CNNO2 > CONO > CONO2 with bond dissociation energies of roughly 293,(1) 197, 184, and 167 kJ mol1,(2) respectively. It is not unlikely that the trigger for an explosive detonation is the rupture of one of these weak bonds; the rest of the molecule being made of CC, CH and CO bonds which are substantially stronger. It is much less sure, but probably not unrealistic, to say that an explosives ease of
* Corresponding author; e-mail: eaton@uchicago.edu

Figure 1. Nitro groups can be attached to a molecular skeleton in four quite different ways.

detonation (shock, impact, friction sensitivity, etc.) is related to the weakness of its weakest bond. Certainly, C-nitro explosives like TNT are rocks by comparison to O-nitro explosives like nitroglycerin. The first (though certainly deserving great respect) was once commonly used as an unknown in undergraduate qualitative organic analysis laboratories; the second was the stuff responsible for numerous disasters until Alfred Nobel calmed it with sawdust (as in dynamite). TNT was first made in 1863 and by the First World War was the explosive of choice (238,000 tons were produced in Britain alone)(3). However, through less sensitive to shock, TNT is not as powerful an explosive as the nitramines RDX and HMX. By the end of the Second World War these (sometimes in combination with TNT) became the explosifs ordinaires of military establishments world-wide, finding use as high power propellant ingredients for gun shells and rockets as well. In the late 1980s Nielson successfully synthesized the nitramine CL-20,(4) presently the best nextgeneration explosive(5).

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Propellants, Explosives, Pyrotechnics 27, 1 6 (2002)

What about new C-nitro explosives? These should be less shock sensitive than CL-20, but are there candidates that might be more powerful? Quantitative evaluation of the potential of a candidate explosive before synthesis would be a very valuable ability, but calculating such is very difficult and opens to much argument. It relies on the empiricallyderived Kamlet-Jacobs equations(6a) or, more recently, on sophisticated first principle techniques(6b) for an estimation of detonation velocity and detonation pressure, the key measures of the effectiveness of an explosive. In these equations, the explosives density, the heat released, the number of moles of gas produced, and the molecular weight of these gases are all critical factors. Estimations of the heat of formation(7) and of the density(8) of even very strange organic compounds are fairly straightforward. However, it is not possible to predict quantitatively the composition of the products unless one makes many assumptions about detonation efficiency: How much of the carbon goes to CO2 and/or CO rather than to soot, C60 and diamond? Is there complete equilibration amongst products? etc. None of this can be done with real confidence, and this has led to much discussion in the literature,(9) particularly in regard to explosives that have no hydrogen in their molecular makeup. Nonetheless, certain qualitative generalizations are reasonable. Of two molecules with the same formula, the one with the higher heat of formation will probably release more energy. The one with the higher density will probably be a superior explosive. Density affects an explosives detonation velocity, a specialized linear rate of reaction that relates to how fast the energy is released, and its maximum detonation pressure, a direct measure of the power of an explosive. The overall dependence of detonation pressure on density is greater than quadratic, so even a small increase in density can have a major impact on performance(10). At the start of our work only five fully nitrated organic compounds had ever been made and characterized. These, the nitrocarbons, are tetranitromethane, hexanitroethane, tetranitroethylene, hexanitrobenzene and decanitrobiphenyl. Their chemistry (and explosive properties) have been reviewed recently by Arnold Nielson,(11) one of the most notable contributors to the synthesis of high energy compounds. In the early 1980s Everett Gilbert of the U.S. Army Armament Research and Development Command (now ARDEC) pointed out that the nitrocarbon octanitrocubane (ONC), then unknown, has a perfect oxygen balance (see Figure 2), and in light of the properties of the parent hydrocarbon cubane (see below) should have a very high heat of formation per CNO2 unit and an exceptionally high density as well. His colleagues Jack Alster, Oscar Sandus and Norman Slagg at ARDEC provided theoretical support for Gilberts brilliant insight and estimated that ONC would have a detonation pressure significantly greater than HMX(12). Later, both statistical and computational approaches predicted a density of 2.1 2.2 g cm3 for octanitrocubane, greater than any other C, N, O compound(13). The most recently published calculated value for the heat of formation of solid ONC [(CNO2)8] is 594 kJ mol1,

Figure 2. Structure of octanitrocubane.

corresponding to 74 kJ per (CNO2)-mole(9b). The highest calculated heat of formation of solid hexanitrobenzene [(CNO2)6], one of the most energetic explosives known,(11) is about 200 kJ mol1,(9b,14) corresponding to 33 kJ per (CNO2)mole, less than half that of ONC. The energy content of hexanitrobenzene is lowered by the stabilizing resonance energy of the aromatic system. The energy content of octanitrocubane is increased by the strain energy of its unique carbon skeleton. The most recent theoretical estimate of the detonation velocity for ONC is 9.90 km sec1 (10). The experimental value for hexanitrobenzene is 9.5 km s1;(15) for HMX, 9.1 km s1;(16a) for CL-20, 9.2 km s1 (16b).

2. Cubane
Cubane, the hydrocarbon (CH)8, is named appropriately; its skeleton is in the shape of a cube.(17) At each corner of this cube there is a carbon atom (carrying a hydrogen) bound to three identical neighboring carbons. The internuclear CCC angles are 908, far off from the standard 109.58 typical of tetravalent, sp3-hybridized carbons like those in common hydrocarbons. This departure from normal is energetically expensive. Cubane is strained by about 695 kJ mol1 corresponding to a substantial weakening of its bonds. The large bond angle deformations in cubane make it a powerhouse of stored energy. Each strained bond is like the spring in a set mousetrap. It was once thought that cubane would be impossible to keep or even make. Neither proved to be the case. The cubane system and cubane itself were first synthesized in 1964 at The University of Chicago(17). It crystallizes as small rhombs and is one of the most dense hydrocarbons known, 1.29 g cm3. The measured heat of formation of solid cubane is 620 kJ mol1. This is a notably high value and quite unlike that of everyday hydrocarbons; these have negative heats of formation. The thermodynamic instability of cubane is not, however, accompanied by kinetic instability. Cubane and most of its derivatives are amazingly stable. The energy of activation for thermal decomposition of cubane in the gas phase is very large, about 180 kJ mol1 at 230 260 8C, so the molecule decomposes only slowly at such temperatures. The reason for this is that there are no kinetically viable paths along which cubane can

Propellants, Explosives, Pyrotechnics 27, 1 6 (2002)

Octanitrocubane: A New Nitrocarbon

rearrange thermally. On one hand, orbital symmetry considerations raise the energy of concerted two-bond ring opening reactions. On the other, there is little to be gained by breaking just one bond, as there is only a small concomitant change in geometry and thus the resulting biradical is still very strained.(17)

3. Synthesis of Nitrocubanes
Like cubane once, octanitrocubane was first thought to be impossible to keep and maybe even impossible to make. How might one approach the synthesis of octanitrocubane? Nitrations (i.e., replacing a hydrogen by a nitro group) of aromatics and other unsaturated systems are well-known reactions. However, this approach is inapplicable to the cubane system, as it has no unsaturated carbons. In most cases, nitro groups on saturated systems are introduced by functional group transformations. The most standard is the sequence of introducing a carboxylic acid substituent (COOH) in place of hydrogen, changing it to an amine (NH2) by one version or another of the classic Curtius rearrangement, and then oxidizing the amine to the desired nitro group. Simple enough. But at the time this project was started there was no way of introducing carboxylic acid groups directly onto the cubane skeleton. Indeed, methodology for systematic substitution on strained systems was almost unknown. It was finally worked out at Chicago, in the quest for ONC; the details are described fully elsewhere(18). It is rewarding to report that this new methodology, developed specially for the synthesis of one of the most unusual organic compounds, now finds wide use for introducing substituents in place of hydrogen on common systems like cyclopropanes and aromatics (18b, 19). Once made,(20) cubane-1,3,5,7-tetracarboxylic acid was converted to the corresponding tetranitrocubane (TNC) by a much modernized version (Scheme 1) of the classic COOH 3 NO2 functional group manipulation mentioned

Scheme 1.

above(20a, d). TNC is an extraordinary material. It is a crystalline solid with a very high density (1.814 g cm3), quite up to prediction. Although a thermodynamic powerhouse, it is kinetically quite stable, not melting until 270 8C, and then with decomposition, not detonation. Tiny samples on the lab bench stone top survive hammer blows. Detonation has been achieved purposefully under controlled conditions at ARDEC; the explosive energy release exceeded expectation, but the quantitative results are not yet available openly. Calculations indicate that TNC may well prove to be a better monopropellant than ONC(21). How about the synthesis of more highly nitrated cubanes? It is easy enough to use the methodology developed at Chicago to introduce more than four carboxylic acid groups onto cubane (indeed the full complement of eight have been put on). But, as soon as there are more than four carboxylic acid groups on cubane at least two must be adjacent. Conversion of adjacent acid groups to adjacent nitro groups necessarily involves adjacent amine groups (cf. Scheme 1). There is nothing wrong with this, even on the cubane skeleton; 1,2-diaminocubanes have been made. They are relatively stable compounds, but ring cleavage reactions intervene during attempted oxidation to the corresponding 1,2-dinitrocubane. This sort of skeletal cleavage always happens when attempts are made to place an electrondonating group (e.g. NH2) on a cubane carbon adjacent to one bearing an electron-withdrawing substituent (e.g. NO2). It is unavoidable and is one of the very few limitations imposed on manipulation of substitution/substitution pattern in the cubanes(17). Putting more than four nitro groups onto cubane required learning how to directly nitrate tetranitrocubane. Chemically the most exciting thing about TNC is its Brnsted acidity. The measured pKa is $ 21, at least 20 powers of ten more acidic than cubane itself(20d). Much of this enhanced acidity must be the result of the tremendous inductive electron withdrawing power of the nitro groups stabilizing the anion. Salts of TNC are readily formed. Reaction of these with different electrophiles has been used with great success to add one to four additional substituents (e.g. methyl, carboxyl, trimethyltin) to the carbon skeleton of tetranitrocubane(20d, 22). Unfortunately, it is not nearly so simple to introduce additional nitro groups. Before the present work nitration of an undelocalized anion was impossible to achieve in useful yield. For example, reaction under various conditions of phenyllithium with any of numerous nitrating agents (N2O4, NO2BF4, N2O5, etc.) gives, if anything, complex mixtures containing little nitrobenzene. The same is true for aliphatic organometallics. However, interfacial nitration, a new nitration process discovered serendipitously at Chicago goes a long way toward solving this old problem(23). In this approach, a solution of an anion salt is frozen to a glass and solid N2O4 is deposited on its surface. The reactants come into productive combination when the glass is allowed to melt. So, for example, reaction of phenyllithium in frozen tetrahydrofuran with N2O4 on its surface proceeds successfully as melting occurs (ca. 115 8C). This gives nitrobenzene in good yield,

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Propellants, Explosives, Pyrotechnics 27, 1 6 (2002)

whereas little nitrobenzene is formed when N2O4 is reacted with phenyllithium in a very cold fluid solution of THF just above its melting point. It is not understood why interfacial nitration works so well. Whatever the explanation, the method is widely successful and has been used to convert the sodium salt of TNC to pentanitrocubane (PNC). PNC is about a thousand times more acidic than TNC, and its sodium salt was converted in turn by interfacial nitration to hexanitrocubane (HNC), a still more acidic material. Both PNC and HNC are stable, crystalline materials of high density (Figure 3)(20d, 22). PNC is the first example of a nitrocubane with nitro groups on adjacent carbons. X-ray single crystal analysis at the Naval Research Laboratory showed, contrary to the worries of some, that no significant distortion within the nitro groups, or in the N to C bonds, or in the cubane core are necessary to accommodate a nitro group surrounded entirely by other nitro groups. Bond angles and lengths in PNC and HNC are little different from those in TNC(24). As good as the interfacial nitration process is, it proved deficient for further nitration of hexanitrocubane. Different experimental methodology had to be developed to make heptanitrocubane (HpNC)(25). In this procedure TNC was treated with at least 4 equiv. of the base NaN(TMS)2 at

Figure 3. Structure of pentanitrocubane (left) and hexanitrocubane (right).

78 8C in 1 : 1 THF/a-methyl THF. After the mono-sodium salt formed, the solution was cooled to between 125 and 130 8C giving a clear, but very viscous fluid. This was stirred vigorously as excess N2O4 in cold isopentane was added. After one minute the base was quenched with nitric acid in cold ether, and then the whole mixture was added to water. This resulted reproducibly in almost complete conversion of TNC (1 gram scale) to HpNC (95% by NMR), isolated crystalline in 74% yield. When lesser amounts of base were used the conversion could be controlled to give predominantly penta- or hexanitrocubane. For the conversions of TNC to HpNC to have happened, many sequential reactions (Scheme 2) must have occurred very rapidly in the viscous solvent at about 125 8C. That all these come about so quickly is truly remarkable and testimony to the extraordinary power of this new methodology; the reaction of an anion with N2O4 at very low temperature is a very effective nitration procedure. The sequence of Scheme 2 ends (prior to quenching) with formation of the salt of HpNC. This salt is quite a powerful nucleophile as shown by its reaction at 125 8C with methyl triflate to give methylheptanitrocubane. Nonetheless, even when an excess of a nitrating agent (N2O4 or many others) was substituted for methyl triflate, no indication of any formation of octanitrocubane was ever seen. That ONC is not formed was very strange and very frustrating. Maybe some of the more pessimistic theorists had been right, and there was something wrong with ONC. This notion was soon discarded in favor of the idea that the anion of HpNC is too stabilized for nitration with N2O4 (HpNC is much more acidic than HNC). This concept led to the use of the more powerful oxidant nitrosyl chloride. Addition of excess NOCl to a solution of the lithium salt of HpNC in dichloromethane at 78 8C followed by ozonation

Scheme 2.

Propellants, Explosives, Pyrotechnics 27, 1 6 (2002)

Octanitrocubane: A New Nitrocarbon

at 78 8C gave the long-sought ONC in 45 55% isolated yield(25). Octanitrocubane is the sixth known nitrocarbon and the first new one to be made in the last 18 years.

4. Properties of Hepta- and Octanitrocubane

Both hepta- and octanitrocubane have decomposition points well above 200 8C. Octanitrocubane sublimes unchanged at atmospheric pressure at 200 8C. Samples were not detonated by hammer taps. Little is yet known about long term storage behavior, but at least one sample of ONC sealed in a glass tube has survived unchanged for 14 months. Heptanitrocubane forms beautiful, colorless crystals when its solution in fuming nitric acid is diluted with sulfuric acid. Single crystal X-ray analysis at the Naval Research Laboratory confirmed the assigned structure and provided an accurate density at 21 8C of 2.028 g cm3, impressively high for a C,H,N,O compound. There are only two or three other known compounds composed of these elements that (perhaps) have higher densities(26). Although ONC catches the imagination with its symmetry, HpNC currently is significantly easier to make than ONC. It may prove to be a more powerful explosive and/or monopropellant as it is more dense, has a calculated(9b) heat of formation only about 6% less than ONC, and will produce some lighter gaseous products as it is not perfectly oxygen balanced. It is quite reasonable to expect that oxidative coupling of HpNC would produce tetradecanitrobicubyl (14 nitro groups, Figure 4). Early estimates(27) put its heat of formation at 1013 kJ mol1. Its parent (in a formal sense), the hydrocarbon bicubyl, is already known; it has a density of 1.336 g cm3, significantly higher than cubane (1.29 g cm3). Other polycubyls are known and together make an interesting set of stable rigid rod rulers to which each cubyl unit adds 0.42 nm to the length of the rod(28). Nitro derivatives of these are not yet known. Octanitrocubane is a white solid, somewhat soluble in hexane and readily soluble in polar organics. Solvent-free crystals for X-ray analysis were obtained from trifluoroacetic acid, from fuming nitric acid/sulfuric acid, or from scrupulously dried cyclohexane. X-ray structural analysis

showed, as with HpNC, that the intramolecular bond lengths and angles are not unusual for cubanes (Figure 5)(24). The D4 symmetric equilibrium conformation of isolated ONC, computed by Hrovat, Kahr and Borden,(29) is essentially the same as the conformation found in the crystalline state. This effectively interdigitates the eight nitro substituents on the cubane skeleton, thereby avoiding close intramolecular O..O contacts. These remain very small throughout 1808 rotations about the CNO2 bonds, proceeding by nearly barrierless, correlated disrotation of all eight nitro groups through a D2d transition state; two tetrahedral subsets of four nitro groups turn in opposite directions. This threshold mechanism provides for enantiomerization of the chiral equilibrium conformation. The density of the one ONC polymorph now in hand is very high, 1.979 g cm3, but still lower than that calculated. Even a simple extrapolation from the observed X-ray densities of the other nitrocubanes leads to an expected value of 2.06 g cm3. The latest and most sophisticated calculation, using all the available data from polynitrocubane X-ray crystal structures, predicts a density above 2.1 g cm3 for the most stable polymorph of ONC.(13, 30) This encourages belief in the existence of a crystal form of ONC much more dense than the one now in hand. Many nitro compounds, e.g. HMX and CL-20, have multiple polymorphs of remarkably different density. The four known polymorphs of CL-20 have densities ranging from 1.91 to 2.044 g cm3 (4). There is no magic recipe for obtaining the most dense polymorph. Typically, the search is done by trying different crystallization solvents, temperatures, etc. This work is underway. Although the first signs are good ONC exists and is stable significant quantities must still be made for the exploration of its properties as an explosive and/or propellant. Presently, ONC is an expensive compound to make. Research is now focused on finding an economical synthesis. Fortunately, there are many possibilities. One particularly enticing approach recognizes that four molecules of dinitroacetylene are a stoichiometric (atom-by-atom) equivalent of one molecule of ONC. Perhaps ONC can be made directly by tetramerization of dinitroacetylene. Politzer has applied the state-of-the-art theoretical calculations to this

Figure 4. Structure of tetradecanitrobicubyl and polycubyl.

Figure 5. The molecular structure of octanitrocubane as it occurs in the crystal. The ellipsoids represent the magnitudes of atomic displacements that are primarily due to harmonic vibrations.

Eaton, Zhang, Gilardi, Gelber, Iyer, Surapaneni

Propellants, Explosives, Pyrotechnics 27, 1 6 (2002) (16) a) As formulated in LX-14 (95.5% HMX), see Ref. 5. b) As formulated in RX-39-AB (95.5% e-CL-20), see Ref. 5. (17) For a review and references to the synthesis, properties and chemistry of the cubane system see P. E. Eaton, Angew. Chem. Int. Ed. Engl. 104, 1447 1462 (1992). (18) a) P. E. Eaton, G. Castaldi, J. Am. Chem. Soc. 107, 724 (1985). b) P. E. Eaton, C.-H. Lee, and Y. Xiong, J. Am. Chem. Soc. 111, 8016 8018 (1989). c) P. E. Eaton, Y. Xiong, and C.-H. Lee, J. Chinese Chem. Soc. (Taiwan) 38, 303 306 (1991). (19) a) P. E. Eaton, R. G. Daniels, D. Casucci, G. T. Cunkle, and P. Engel, J. Org. Chem. 52, 2100 2102 (1987). b) P. E. Eaton, K. Lukin, J. Am. Chem. Soc. 115, 11370 11375 (1993). (20) a) P. E. Eaton, Y. Xiong, and R. Gilardi, J. Am. Chem. Soc. 115, 10195 10202 (1993). b) A. Bashir-Hashemi, Angew. Chemie Int. Ed. Engl. 32, 612 613 (1993). c) A. Bashir-Hashemi, J. Li, N. Gelber, and H. Ammon, J. Org. Chem. 60, 698 702 (1995). d) K. A. Lukin, J. Li, P. E. Eaton, N. Kanomata, J. Hain, E. Punzalan, and R. Gilardi, J. Am. Chem. Soc. 119, 9591 9602 (1997). (21) P. Politzer, J. S. Murray, M. E. Grice, P. Sjoberg in: G. A. Olah, D. A. Squire, (eds), Chemistry of Energetic Materials, Academic Press, San Diego 1991, p 89. (22) K. A. Lukin, J. Li, P. E. Eaton, and R. Gilardi, J. Org. Chem. 62, 8490 8496 (1997). (23) K. Tani, K. Lukin, and P. E. Eaton, J. Am. Chem. Soc. 119, 1476 1477 (1997). (24) Details of the X-ray crystallographic structures for all the nitrocubanes reported in this paper can be obtained on request from the Director, Cambridge X-Ray Crystallographic Data Centre. (25) M. X. Zhang, P. E. Eaton, and R. Gilardi, Angew. Chemie Int. Ed. Engl. 39, 401 404 (2000). (26) The only certain example is the epsilon polymorph of CL-20 with an X-ray structure density of 2.044 g cm3 at room temperature(4). Hexanitroethanes density is reported to be 2.075 g cm3 by X-ray analysis, but this is at 128 8C. Its density at room temperature is controversial, with reports ranging from 1.88 to 2.25 g cm3, none backed up by an Xray structure analysis. Tetranitroglycolurile has a reported density of 2.01 g cm3, but this was not determined by X-ray analysis. See: R. Meyer, Explosives Verlag Chemie, New York 1977. (27) B. Rice, private communication, July 24, 2001. (28) P. E. Eaton, K. Pramod, T. Emrick, and R. Gilardi J. Am. Chem. Soc. 121, 4111 4123 (1999). (29) a) D. A. Hrovat, W. T. Borden, P. E. Eaton, and B. Kahr, J. Am. Chem. Soc. 123, 1289 1293 (2001). b) The correlated motion can be viewed on the net at http:// depts.washington.edu/chemfac/kahr_movie.html (30) The packing of ONC in the crystal is described in P. E. Eaton, M.-X. Zhang, and R. Gilardi, Adv. Mat. 12, 1143 1148 (2000). (31) P. Politzer, P. Lane, and J. J. M. Wiener in: K. Laali (ed.), Carbocyclic and Heterocyclic Cage Compounds and Their Building Blocks, JAI Press, Stamford, CN, 1999, p 73 85.

possibility(31). His conclusion is spectacular: the free energy change for dinitroacetylene to octanitrocubane is thermodynamically downhill by nearly 417 kJ mol1. Of course, these calculations do not address the kinetics of the tetramerization or provide a clue as to how to make it happen. But it is time to open the investigation. Unfortunately, dinitroacetylene is not yet a known compound. The acidity of acetylene, its hydrocarbon parent, is not unlike that of tetranitrocubane, whose anion has been nitrated with great success (see above). Perhaps a similar approach will provide for the simple conversion of acetylene, a cheap starting material, to dinitroacetylene and thence to octanitrocubane.

5. References
(1) This value pertains to nitro attached to sp2 unsaturated carbon as in nitroaromatics. The C-NO2 bond in nitrocubanes is very much like that in nitroaromatics. The bond strength is less, $ 250 kJ mol1, for a nitro group on an unstrained saturated carbon.(3) (2) C. F. Melius in: S. N. Bulusu (ed), Chemistry and Physics of Energetic Materials, Kluwer Academic Publishers 1990, pp 30 32. (3) A. Bailey, S. G. Murray, Explosives, Propellants & Pyrotechnics, Brassey (UK), London 1989, pp 6 7. (4) A. T. Nielsen, A. P. Chafin, S. L. Christian, D. W. Moore, M. P. Nadler, R. A. Nissan, D. J. Vanderah, R. D. Gilardi, C. F. George, and J. L. Flippen-Anderson, Tetrahedron 54, 11793 11812 (1998). (5) R. L. Simpson, P. A. Urtiew, D. L. Ornellas, G. L. Moody, K. J. Scribner, and D. M. Hoffman, Propellants, Explosives, Pyrotechnics 22, 249 255 (1997). (6) a) M. J. Kamlet, S. J. Jacobs, J. Chem. Phys. 48, 23 35 (1968). b) For example, the CHEETAH code; see, L. E. Fried, M. R. Manaa, P. F. Pagoria, and R. L. Simpson, Ann. Rev. Mater. Res. 31, 291 321 (2001). (7) See, for example and comparison of methods: T. Matsunaga, Y. Nakyama, M. Iida, S. Oinuma, N. Ishikawa, and K. Tanaka, Propellants, Explosives, Pyrotechnics 17, 63 69 (1992). (8) For an overview: J. R. Holden, Z. Du, and H. L. Ammon, J. Comput. Chem. 13, 422 437 (1993). (9) a) L. T. Eremenko, D. A. Nesterenko, Chem. Phys. Reports 16, 1675 1683 (1997). b) A. M. Astakhov, R. S. Stepanov, and A. Yu. Babushkin, Combustion, Explosion, and Shock Waves 34, 85 87 (1998); cf. J. Zhang, H. Xiao, and X. Gong, J. Phys. Org. Chem. 14, 583 588 (2001). c) C. L. Mader, Numerical Modeling of Explosives and Propellants, 2nd ed., CRC Press, New York 1998. (10) R. D. Gilardi, J. Karle in: G. A. Olah, D. A. Squire (eds.), Chemistry of Energetic Materials, Academic Press, San Diego 1991, p 2. (11) A. T. Nielson (ed.), Nitrocarbons, VCH-Verlagsgesellschaft, Weinheim 1995. (12) a) J. Alster, O. Sandus, R. Gentner, N. Slagg, J. P. Ritchie, and M. J. S. Dewar, Calculation of Molecular Properties for Polynitrohedranes Molecules, Working Group Meeting on High-Energy Compounds, Hilton Head, SC, 1981. b) J. Alster, S. Iyer, O. Sandus in Ref. 2, pp 641 652. c) G. P. Sollott, J. Alster, E. E. Gilbert, and N. Slagg, J. Energ. Mat. 4, 5 28 (1986). (13) H. Ammon, Private Communication, June 10, 1999. (14) A much lower value (95 kJ mol1) is given in Ref. 7. (15) Ref. 11, Table 7, p 97.

Acknowledgements
This work was supported at Chicago by the United States Army Armament Research Development and Engineering Center (ARDEC) and at the Naval Research Laboratory (NRL) by the Office of Naval Research, Mechanics Division. We are grateful to Bransby Bushey and Joseph Lannon of ARDEC for their continuing interest and encouragement.

(Received September 26, 2001; Ms 2001/019)