Improved synthesis of cubane-1,2,4,7-tetracarboxylic acid

Bottaro, Jeffrey C.; Penwell, Paul E.; Schmitt, Robert J.

doi:10.1021/jo00003a071

Cited by 23 publications

(23 citation statements)

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“…The non-selective nitration by N 2 O 5 in acidic medium can be exploited to nitrate deactivated precursors [6][7][8] while nitration by N 2 O 5 dissolved in an organic solvent (especially chlorinated hydrocarbons) is an effective means for selective nitration of substrates where there is more than one possible nitration site in the molecule. This unique dichotomy of dinitrogen pentoxide chemistry may lead to a wide variety of products of interest to energetic materials community and has accelerated R&D efforts towards utilizing the potential of dinitrogen pentoxide as nitrating agent.…”

Section: Introductionmentioning

confidence: 99%

Establishment of process technology for the manufacture of dinitrogen pentoxide and its utility for the synthesis of most powerful explosive of today—CL-20

Talawar

Sivabalan

Polke

et al. 2005

Journal of Hazardous Materials

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Section: Introductionmentioning

confidence: 99%

Establishment of process technology for the manufacture of dinitrogen pentoxide and its utility for the synthesis of most powerful explosive of today—CL-20

Talawar

Sivabalan

Polke

et al. 2005

Journal of Hazardous Materials

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“…The latter spectrum is identical to a pure NH 4 N0 3 absorption spectrum, whereas the spectrum displayed in Figure 4 is a composite of NH4NO 3 with a small amount of NH 3 (note the bending mode at 958 cm-1 ). Conspicuously absent from the lower temperature spectrum in Figure 4, however, is any indication of the presence of HNO 3 , which would manifest itself through the very intense absorption at 1710 cmr-I and 870 cm- 1 . We conclude that, in the temperature range from -188' to -50 0 C, NH 3 evaporates, after which pure NI-14N0 3 remains.…”

Section: Resultsmentioning

confidence: 92%

“…Our results delineate the possible pathways in the thermal decomposition of those energetic materials as well as some similarities between them and thus provide a guide to future experiments in the more relevant high heating rate regime Bottaro and Schmitt of SRI's Chemistry Laboratory recently synthesized for the first time 1 several examples in a family of novel energetic materials, namely, salts of the previously unknown compound dinitramide acid HN(NO2)2. A typical member of the family is the ammonium dinitramide, NH 4 N(NO 2 ) 2 ("SRI-12"or ADN).…”

Section: Introductionmentioning

confidence: 76%

See 1 more Smart Citation

Low Pressure Thermal Decomposition Studies Selected Nitramine and Dinitramine Energetic Materials

Rossi¹,

McMillen²,

Golden³

1992

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Vice PresidentPt.t2 ibut '-@/ Physical Sciences Division . Brief studies were also performed with RDX and with AgN(N0 2 )CH2CN, which was tested as a potential source of the suspected RDX intermediate CH 2 = NNO 2 . The former portion of the work has resulted in a manuscript, which is being submitted for publication and is included as an appendix to this final report. A summary of the work and its principal findings is given below, beginning with the results for ADN itself.Pyrolysis of ADN under low pressure showed acid-base dissociation like AN, but it also resulted in some decomposition to N20, NO, and water. The onset of evolution of these species was at 90'C, and as in the case of AN, an "explosive" event w.s noted at 174*C, which is about 80'C higher than the melting point of ADN and 15'C higher than thermal decomposition in a DSC. When the cryostat window was left at ambient temperature, only dinitramine, HDN, condensed on it, along with some water as determined by FTIR. However, if the window was cooled to -190 0 C, ADN was formed again.The experiment with the cryostat at ambient temperature provided us the oppo-tunity to examine the properties of the acid component of ADN, namely HDN, which has not been previously obtained in the pure form. FTIR of the film showed the characteristic N-H stretch at 3250 cm-1 . Also some of the other major bands were shifted from the corresponding bands in ADN, a result that is consistent with the formation of the free acid. Interestingly enough, when we bled ammonia into the system containing HDN, we did not observe the formation of the salt. This result is puzzling and should be pursued in a future research effort.To test whether the decomposition products seen in ADN pyrolysis were a result of HDN decomposition, we subjected the HDN film to thermal stress. HDN decomposed very readily, the i gentlest of warming (cryostat temperature >60'C) produced peaks corresponding to H20, NO, and N 2 0. Most significantly, no peaks were observed at rn/z 46 or 62 (ion fragments of HDN), which implies that the HDN film decomposed but did not evaporate. Using FTIR, we determined that the HDN was completely depleted from the KC1 window by 140'C. The finding that no HDN evaporated intact from the HDN film even at temperatures as low as 701C means that HDN in the bulk condensed state is much less stable than that formed as an isolated species during ADN pyrolysis. This finding is significant and suggests that care should be exercised to avoid buildup of HDN during storage of ADN. Furthermore, we speculate that the decomposition of condensed phase HDN occurs more rapidly than that of various dinitramide salts because the very high acidity of HDN makes an acid-catalyzed, self-protonation pathway readily accessible. This conclusion is consistent with the recent finding that acids destabilize ADN.Slow heating of ammonium nitrate (AN) in our system produced only ammonia and nitric acid-an acid-base dissociation-and no nitrous oxide. The sample was completely depleted by the time it was heated t...

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“…Dieser (als den kann [28], als aktivierende Gruppe bei der ortho-Metallierung ein. Daraufhin beobachteten wir, daI3 die tert-Butylgruppe schon im schwach Sauren entfernt werden kann und daI3 man das resultierende Amid (bei unseren Untersuchungen das Methylamid) mit saure-oder besser noch basenkatalysierter Hydrolyse in die freie Carbonsaure umwandeln kann.…”

Section: Die Rucktransmetallierungunclassified

Cubane: Ausgangsverbindungen für die Chemie der neunziger Jahre und des nächsten Jahrhunderts

Eaton

1992

Angewandte Chemie

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Die Untersuchung von Verbindungen, die in der Natur nicht vorkommen, hat vie1 zum Verstandnis der Bindungsverhaltnisse und der Reaktivitat in der Organischen Chemie beigetragen. Oft erhielt man im Laufe dieser Untersuchungen Substanzen, die man fur undenkbar gehalten hatte. Das Cuban, ein Meilenstein in der Welt ,,unmoglicher" Verbindungen, zeigt eine reichhaltige Chemie voller unerwarteter Aspekte. Die vor kurzem begonnene Renaissance der Cubanchemie, die durch mogliche Anwendungen von Cubanverbindungen -beispielsweise als sehr energiereiche Treibstoffe -ausgelost wurde, hat zu vielen neuen Erkenntnissen gefiihrt. So wurde z. B. die erste Methode zur systematischen Substitution gespannter gesattigter Verbindungen und ein neuer Reaktionstyp der Metallierung von Arenen, der orthoMagnesiierung, entwickelt. Reaktive Zwischenprodukte mit auBergewohnlichen Bindungsparametern wurden charakterisiert : I (9)-Homocuben, das Olefin mit der starksten Verdrillung; Cuben, das Olefin, mit der starksten Pyramidalisierung; das Cubyl-Kation, das einmal als das am wenigsten wahrscheinliche Kation gegolten hatte; das Cubylmethylradikal, ein gesattigtes Radikal, das sich innerhalb von Picosekunden umlagert, und viele andere auBergewohnliche Verbindungen. Sicherlich werden zukunftige Arbeiten auf dem Cubangebiet mindestens genauso viele -wahrscheinlich sogar mehr -Ergebnisse hervorbringen und zu einem tieferen Verstandnis der Chemie beitragen.

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Improved synthesis of cubane-1,2,4,7-tetracarboxylic acid

Cited by 23 publications

References 1 publication

Establishment of process technology for the manufacture of dinitrogen pentoxide and its utility for the synthesis of most powerful explosive of today—CL-20

Establishment of process technology for the manufacture of dinitrogen pentoxide and its utility for the synthesis of most powerful explosive of today—CL-20

Low Pressure Thermal Decomposition Studies Selected Nitramine and Dinitramine Energetic Materials

Cubane: Ausgangsverbindungen für die Chemie der neunziger Jahre und des nächsten Jahrhunderts

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