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Hepta- and Octanitrocubanes** Mocubenes, Cubene, Cubyl Carbinyl Radical, Cubyl Cation, Cubanediyl, and the [N]Cubyls.[6] Mao-Xi Zhang, Philip E

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Hepta- and Octanitrocubanes** Mocubenes, Cubene, Cubyl Carbinyl Radical, Cubyl Cation, Cubanediyl, and the [N]Cubyls.[6] Mao-Xi Zhang, Philip E COMMUNICATIONS Hepta- and Octanitrocubanes** mocubenes, cubene, cubyl carbinyl radical, cubyl cation, cubanediyl, and the [n]cubyls.[6] Mao-Xi Zhang, Philip E. Eaton,* and Richard Gilardi As we have reported previously,[7] 1,3,5,7-tetranitrocubane (1) can be made by dimethyldioxirane oxidation of the Highly nitrated cubanes are predicted to be shock-insensi- tetraamine derived from Curtius-type transformations of the tive, very dense, high-energy compounds with great potential corresponding tetraacid, itself made either from ortho-metal- as explosives and propellants.[1] Application of the Kamlett ± ation of amide-activated cubanes[7a] or from photochlorocar- Jacobs equations[2] to octanitrocubane using predicted values bonylation of cubane monoacid.[7b, 8] More highly nitrated for density (1.9 ± 2.2 gcm3)[3] and DH (81 ± 144 kcal mol1)[4] f cubanes cannot be made similarly from more highly carboxy- leads to calculated detonation velocities and pressures much lated cubanes, as the conversion would proceed through higher than that of the classic C-nitro explosive TNT, 15 ± intermediates that contain an electron-donating group vicinal 30% greater than that of the N-nitro compound HMX, to a group that is electron-withdrawing; this situation results presently the most energetic of standard military explosives, unavoidably in cleavage of the highly strained cubane cage.[7b] and perhaps even better than that of the experimental As shown earlier,[7b, 9] 1 is quite acidic (pK 21). Nitration polycyclic nitramine CL-20, arguably the most powerful a of its anion (e.g., as the sodium salt) at the melting (approx. nonnuclear explosive known.[5] 1058C) interface between frozen THF and N2O4 gave 1,2,3,5,7-pentanitrocubane (2), the first nitrocubane with NO2 CH3 NO2 [10] NO2 adjacent nitro groups. Similarly, ªinterfacial nitrationº of NO NO N N N 2 2 NO2 NO N 2 NO the salt of this even more acidic nitrocubane gave 1,2,3,4,5,7- N N 2 N hexanitrocubane (3). As expected the anion of hexanitrocu- N N NO2 N NO2 bane is readily formed, but the use of different experimental NO2 NO2 NO2 methodology, as indicated in Scheme 1, proved to be essential TNT HMX CL-20 Successful methodology for the synthesis of highly nitrated cu- banes is far less predictable. Al- H NO2 though nitration is one of the H NO2 x equiv ratio oldest reactions in organic chem- NaN(TMS)2 (by NMR) H NO2 1 2 3 4 istry, it is little understood outside NO NO2 2 classical electrophilic nitration of 2 1.5 12 70 18 - p systems. Systematic polynitra- 1. monoanion formation: NO2 H x equiv of NaN(TMS) H tion of saturated systems is gen- H 2 NO2 NO2 in THF/MeTHF at –78 °C NO erally unknown. Indeed, general- NO2 2 H NO2 11 3 57 29 ly speaking, systematic substitu- 2. cool to ca. –130 °C H NO2 3.0 H 5 38 34 23 NO2 3. add N O NO tion of any kind on strained 2 4 NO2 2 systems like cubane and cyclo- 1 in cold isopentane 4. quench with H+ 3 propanes is difficult. It is primar- in cold Et O H 2 NO2 ily for these reasons that we NO2 NO2 4.0 - - 5 95 undertook the challenge of de- NO2 NO2 veloping a rational synthesis for NO NO2 2 octanitrocubane. In the process, 4 we were rewarded by many dis- coveries of new chemistry includ- Scheme 1. Sequential nitration of polynitrocubyl anions, and product distribution as a function of the molar 1,9 ing ortho-magnesiation, D -ho- ratio of 1 to NaN(TMS)2 . for its successful conversion into heptanitrocubane (4), and [*] Prof. Dr. P. E. Eaton, Dr. M.-X. Zhang this provided as well for better yield, more reproducible, Department of Chemistry, The University of Chicago larger scale preparations of 2 and 3. 5735 South Ellis Avenue, Chicago, IL 60637 (USA) 1,3,5,7-Tetranitrocubane (1) was treated with 1.5 equiv of Fax : ( 1) 773-702-2053 E-mail: [email protected] NaN(TMS)2 (TMS trimethylsilyl) at 788C in tetrahydro- Dr. R. Gilardi furan/a-methyltetrahydrofuran (1/1). After the monoanion Laboratory for the Structure of Matter had formed, the solution was cooled to between 125 and The Naval Research Laboratory, Washington, DC 20375 (USA) 1308C, giving a clear, but very viscous fluid. This was stirred [**] This work was supported at Chicago by the University of Chicago and vigorously as excess N2O4 in cold isopentane was added. After by the United States Army Armament Research and Development one minute nitric acid in cold ( 308C) diethyl ether was Center (ARDEC) and at NRL by the Office of Naval Research, added, and then the whole mixture was added to water. Mechanics Division. We are grateful to Nat Gelber of ARDEC for preparing all the tetranitrocubane used in this work and to Art Bates Standard workup (CH2Cl2 extraction) and NMR analysis for his advice and assistance with the NMR studies. showed (for a typical run) that the product mixture contained Angew. Chem. Int. Ed. 2000, 39, No. 2 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 0570-0833/00/3902-0401 $ 17.50+.50/0 401 COMMUNICATIONS principally pentanitrocubane (2, 53% isolated), a little start- CD3OD was used, exchange was quick and deuterioheptani- ing material, and some hexanitrocubane (3). When the trocubane was produced. Addition of iodine to the methanol [14] quantity of NaN(TMS)2 was increased to 3 equiv the distri- solution gave iodoheptanitrocubane (6; Scheme 2); this butions of products in seemingly similar runs were quite formed more rapidly if a little NaF was added as base. Clearly variable (Scheme 1), but always there was a significant 4 is acidic, reflecting very substantial delocalization of charge amount of hexanitrocubane formed along with some heptani- in its anion. Heptanitrocubane is sensitive to base. NaF alone trocubane (4).[11] A further increase in base to 4.0 equiv in methanol catalyzed its decomposition, as did amines like resulted reproducibly in almost complete conversion of 1 (1- 2,2,6,6-tetramethylpiperidine. Powerful deflagration occurred gram scale) into heptanitrocubane (95% by NMR), isolated when a microdrop of pyridine was added to the dry solid. crystalline in 74% yield! For this to have happened, many Alkali metal salts of 4 were prepared at low temperature in sequential conversions must have occurred very rapidly in the inert solvents by reaction with appropriate bases like viscous solvent at about 1258C. Nitration of the anion of 1 NaN(TMS)2 or LiN(TMS)2 . Such salts in THF decomposed (!2), anion formation from 2, nitration (!3), anion forma- fairly quickly at 1008C, but in CH2Cl2 they were relatively tion from 3, and nitration (!4) are all required. (That all this stable to about 508C. Reaction with powerful electrophiles comes about so quickly is all the more remarkable considering like methyl triflate and iodine gave 5 and 6, respectively, in the fact that the first anion, 1, does not form at a useful rate high yield (Scheme 2). below 788C.) The sequence ends with formation of the Despite the reactivity of heptanitrocubyl anion towards anion of 4 as shown by high-yield production of methylhep- these electrophiles, we could find no indication for any tanitrocubane (5; Scheme 2)[12] on quenching with methyl formation of octanitrocubane from reactions of various triflate rather than acid. Nonetheless, even on addition of heptanitrocubane salts with NO2BF4 , NO2PF6, acetyl excess N2O4, no octanitrocubane was formed. nitrate, methyl nitrate, isoamyl nitrate, CF3CH2ONO2 , or CF3SO2ONO2 . Indeed, although it is not well-known, such ªobviously electrophilicº reagents are generally useless for nitrations of non-resonance-delocalized anions.[10] Although CH NO2 3 N O and (to a degree) NO Cl do nitrate some nitrocubyl NO NO 2 4 2 2 2 anions,[7b, 9] both failed to give any octanitrocubane on NO NO2 [7b] H 2 reaction with salts of 4. As we have speculated previously, NO2 NO CH3OTf NO2 2 nitration with these reagents may proceed by oxidation of the NO2 NO2 NaN(TMS)2 5 carbanion to the corresponding radical; perhaps the anion of 4 NO NO2 2 I NO 2 is too stabilized for this to occur. NO2 2 I NO2 We now report that addition of excess nitrosyl chloride 4 NO2 NO2 (NOCl) to a solution of the lithium salt of heptanitrocubane NO2 NO2 (from 4 and LiN(TMS)2) in CH2Cl2 at 78 8C followed by NO NO2 2 ozonation at 788C until the solution was blue gave, after 6 standard workup, the long-sought octanitrocubane (7; Scheme 2. Preparation of methyl (5) and iodo derivatives (6) of heptani- Scheme 3) in 45 ± 55% yield on millimole scale. The inter- trocubane (4). Tf trifluoromethanesulfonyl. mediate product prior to oxidation was unstable; we suspect that it might be nitrosoheptanitrocubane.[15] Heptanitrocubane is easily soluble in polar solvents, for example, acetone, THF, and CH Cl . Beautiful, colorless, H NO 2 2 NO2 NO2 2 solvent-free crystals formed when its solution in fuming nitric NO NO 2 2 1. LiN(TMS)2 NO2 NO2 acid was diluted with sulfuric acid. Single-crystal X-ray 2. NOCl NO2 NO2 NO2 NO2 analysis confirmed the assigned structure and provided an NO2 3. O3 NO NO2 NO2 2 3 accurate density at 218C of 2.028 gcm , impressively high for 4 7 a C,H,N,O compound. The crystal structure of 4 shows many Scheme 3. ªNitrationº of heptanitrocubane (4). Synthesis of octanitro- intermolecular contacts about each molecule that are shorter cubane (7). than the sum of the van der Waals radii;[13] 21 between oxygen atoms and 12 between an oxygen and a C, N, or H atom.
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