C8(NO2)8

Nitrocubanes

Octanitrocubane: A New Nitrocarbon, P.E. Eaton, M.-X. Zhang, Propellants, Explosives, Pyrotechnics 27, 2002, p.1-6.

CAGED STRUCTURES AS ENERGETIC MATERIALS

Many explosives use today derive their energy solely from the heat released on the combustion of the carbon skeleton. Efforts have focused on synthesizing explosives containing strained or caged structures which derive their energy from both the heat of combustion of the carbon skeleton and the relief of molecular strain. Energetic materials with caged structures also benefit from a decrease in molecular motion which leads to higher crystal density and increase in explosive performance. Of equal importance is the thermal and chemical stability of these new explosives.

Caged skeletons
These compounds derive their energy from both the release of molecular strain and the combustion of the carbon skeleton.

nitramine CL-20 was made by NIELSON

Energetic materials with strained or caged structures are often much more difficult to synthesize compared to their open chain counterparts.

Skeletons often lead to an increase in crystal density relative to the open chain compounds - this usually results in higher explosive performance. For example compounds containing strained or caged skeletons in conjunction with N-nitro functionality are some of the most powerful explosives available

CAGED-STRUCTURES ADAMANTANES
The highly rigid skeleton of adamantane results in much higher crystal densities compared to its open chain counterparts, and hence, higher performance for its nitro derivatives. BUT the adamantane core shows little to almost no strain.

2,2,6,6-tetranitroadamantane

1,4,6,9-tetranitrodiamantane

Of the various caged structures investigated for the synthesis of energetic compounds some have more internal strain than others. The cubane skeleton is highly energetic (Hf = 620 KJ/mol) and shows a high degree of molecular strain. Consequently, the nitro derivatives of cubane exhibit much higher performance than those of adamantane, which show little to no molecular strain.

The nitro derivatives of cubane are generally thermally stable. Additionally, the higher decomposition temperatures of some nitro derivatives of cubane, as compared to cubane itself, could infer that the electron-withdrawing nitro groups stabilize the cubane system and enhance thermal stability

Cubane (C8H8)

Cubane, the hydrocarbon (CH)8 - its skeleton is in the shape of a cube. At each corner of this cube there is a carbon atom bound to three identical carbons. The internuclear C-C-C angles are 90O far off from the standard 109.5O 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/mol 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.

The cubane system and cubane itself were first synthesized in 1964 at The University of Chicago. It crystallizes as small rhombs and is one of the most dense hydrocarbons known, 1.29 g/cm3. The heat of formation of solid cubane is 620 kJ/mol. This is a high value and quite unlike that of hydrocarbons; these have negative heats of formation. The thermodynamic instability of cubane is not, 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/mol at 230260 OC

The nitrocarbons CX(NO2)Y are: tetranitromethane, hexanitroethane, hexanitrobenzene and decanitrobiphenyl

O 2N O 2N NO 2 NO 2 NO 2 NO 2 O 2N NO 2 NO 2 NO 2

NO 2 O 2N NO 2 O 2N O 2N NO 2 NO 2

O 2N

NO 2 O2N

NO 2

NO 2

O 2N

NO 2 O2N

NO 2

Octanitrocubane ONC: A New Nitrocarbon C8(NO2)8 no hydrogen !!!

O 2N O 2N O 2N O 2N
C8(NO 2)8

NO2 NO2 NO2 NO2

+
4N2

8CO2
Energy release: 3475 kJ/mol

Philip E. Eaton

The calculated value for the heat of formation of solid ONC [(CNO2)8] is 594 kJ /mol

Computational approaches predicted a density of 2.12.2 g/cm3

The energy content of octanitrocubane is increased by the strain energy of its unique carbon skeleton. The theoretical estimate of the detonation velocity for ONC is

9.90 km/sec

Octanitrocubane (ONC) has a density of

1.979 g/cm3, a calculated heat of formation of 594 kJ/mol, and a decomposition temperature above 200 C. The explosive performance of octanitrocubane from theoretical calculations is predicted to be extremely high.

The most recent theoretical estimate of VOD is 9900 m/s, making this compound one of the most powerful explosives synthesized to date. Surprisingly, the density of heptanitrocubane (2.028 g/cm3) is higher than octanitrocubane, and so this compound, which is easier to synthesize, may prove a more powerful explosive than the latter from the point of view of application.

Octanitrocubane was first synthesized by Philip Eaton (who was also the first to synthesize cubane in 1964) and M. Zhang at the University of Chicago in 1999

Small amounts have been synthesized in the laboratory, but not enough for performance testing as an explosive
ONC OXYGEN BALANCE = 0

C8(NO2)8 8CO2 + 4N2

Properties of Hepta- and Octanitrocubane

Both hepta- and octanitrocubane have decomposition points well above 200 C. Octanitrocubane sublimes unchanged at atmospheric pressure at 200 C.

Octanitrocubane is a white solid, somewhat soluble in hexane and readily soluble in polar organics.
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 (2.028 g/cm3)

It is quite reasonable to expect that oxidative coupling of HpNC would produce tetradecanitrobicubyl (14 nitro groups)

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

SYNTHESIS of ONC

1,4-Dinitrocubane (28) has been synthesized by Eaton and co-workers via two routes both starting from cubane-1,4-dicarboxylic acid (25).

Eaton and co-workers also reported the synthesis of 1,3,5-trinitrocubane and 1,3,5,7-tetranitrocubane
The synthesis of precursors like cubane-1,3,5,7tetracarboxylic acid was long and inefficient by EATONS method and required the synthesis of toxic organomercury intermediates. BashirHashemi reported an route to cubane-1,3,5,7tetracarboxylic acid chloride (35) involving photochemical chlorocarbonylation of cubane carboxylic acid chloride (34) with a mercury lamp and excess oxalyl chloride.

Under optimum conditions this reaction is reported to give a 70:8:22 isomeric mixture of 35:36:37 respectively.

Eaton and co-workers used cubane-1,3,5,7tetracarboxylic acid chloride (35) as a precursor to 1,3,5,7-tetranitrocubane (39) (TNC).

Once made, cubane-1,3,5,7-tetracarboxylic acid was converted to the corresponding tetranitrocubane (TNC)

Treatment of cubane-1,3,5,7-tetracarboxylic acid chloride (35) with trimethylsilyl azide gave the dangerously explosive tetraacylazide, which generates the tetraisocyanate (38) on heating in chloroform at reflux. Eaton found that acylazide isolation was not necessary if azide formation was preformed with trimethylsilyl azide in the presence of a catalytic amount of 2,6-di-tertbutylpyridine hydrochloride. Under these conditions Curtius rearrangement to the tetraisocyanate (38) can be conducted in situ.

Oxidation of the tetraisocyanate (38) with dimethyldioxirane in wet acetone gives 1,3,5,7tetranitrocubane (39) in 47% yield overall yield from the acid chloride (35). 1,3,5,7-Tetranitrocubane has a density of 1.814 g/cm3, is highly energetic, and doesnt melt until 270 OC.

Anion formation requires the use of a relatively strong base - sodium hexamethyldisilazide, a consequence of proton removal from a carbon to the nitro group. This is not normally possible, but in this special case three electron-withdrawing nitro groups flank each -proton and the strained cubane core causes deviation from sp3 hybridization towards sp2 character.

Treating 1,3,5,7-tetranitrocubane (39) with four equivalents of base, followed by reaction with frozen N2O4 in tetrahydrofuranpentane, gives heptanitrocubane (40) in 74% yield. Further nitration to octanitrocubane (41) (ONC) required the anion of (40) to be treated with nitrosyl chloride followed by oxidation with ozone.

Interfacial nitration
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 oC).

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

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)

For the conversions of TNC to HpNC many sequential reactions must have occurred very rapidly in the viscous solvent at about -125oC. The reaction of an anion with N2O4 at very low temperature is a very effective nitration procedure.

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 C followed by ozonation at -78 C gave the long-sought ONC in 45- 55% isolated yield

Theoretical synthesis of ONC

O 2N

NO2 NO2 NO2 NO2

O2N

NO2

O 2N O 2N O 2N

Polymerisation to ONC

HOMOCUBANES
The D3-trishomocubane (pentacyclo[6.3.0.02,6.03,10.05,9]unde cane) and bishomocubane skeletons are less strained than cubane and so their polynitro derivatives are less energetic but generally show higher thermal stability.

A widely used strategy for the synthesis of polynitropolycyclic caged compounds is to first synthesize the appropriate caged polycycle to contain either di- or tri-ketone functionality, which can subsequently be transformed into nitro or gem-dinitro functionality via the oxime. The methods available for oxime to nitro group conversion are usually robust. Direct oxidation of an oxime to a nitro group can be achieved with varying success using peroxyacids

Marchand and co-workers synthesis of 5,5,9,9tetranitropentacyclo[5.3.0.02,6.03,10.04,8]decane (52) required the dioxime of pentacyclo[5.3.0.02,6.03,10.04,8]decane-5,9-dione (49) for the incorporation of the four nitro groups. Synthesis of the diketone precursor (48) was achieved in only five steps from cyclopentanone. Thus, acetal protection of cyclopentanone with ethylene glycol, followed by -bromination, and dehydrobromination with sodium in methanol, yielded the reactive intermediate (45), which underwent a spontaneous DielsAlder cycloaddition to give (46). Selective acetal deprotection of (46) was followed by a photo-initiated intramolecular cyclization and final acetal deprotection with aqueous mineral acid to give the diketone (48). Derivatization of the diketone (48) to the corresponding dioxime (49) was followed by conversion of the oxime groups to gem-dinitro functionality using standard literature procedures.

D3-hexanitrotrishomocubane

Tests on D3-hexanitrotrishomocubane show it to be both less sensitive and significantly more powerful than TNT whilst exhibiting high thermal stability.

CUBANEBASED NITRAMINES
The incorporation of the nitramino group into the core of cubane has not yet been achieved. However, a number of cubane-based energetic nitramines and nitramides have been synthesized.

Eaton and co-workers synthesized the cubane-based dinitrourea (42) via N-nitration of the cyclic urea (41) with nitric acidacetic anhydride.

Cubane-based nitramide (43) is prepared from the N-nitration of the corresponding bis-amide with acetic anhydridenitric acid. Bisnitramine (44) is prepared from the N-nitration of the corresponding diamine with TFAAnitric acid