Polynitroaliphatic explosives

Polynitroaliphatic compounds have not found widespread use as either commercial or military explosives. This is perhaps surprising considering the high chemical and thermal stability of compounds containing internal em-dinitroaliphatic functionality. In fact, many polynitroaliphatic compounds are powerful explosives, for example, the explosive power of... 

Primary and secondary nitroalkanes, and substrates containing terminal em-dinitroaliphatic functionality, have one or more acidic a-protons, a consequence of inductive and resonance effects imposed by the nitro group. As a result, such compounds can behave like carbanions and participate in a number of addition and condensation reactions which are typical of substrates like ketones, aldehydes, and /S-ketoesters. Such reactions are extremely useful for the synthesis of functionalized polynitroaliphatic compounds which find potential use as explosives, energetic oligomers and plasticizers. 

Many of the nitronate salts of polynitroaliphatic compounds, particularly salts of gem-nitronitronates, exhibit properties similar to known primary explosives. Consequently, the storage of such salts is highly dangerous. Treatment of these nitronate salts with formaldehyde yields the corresponding methylol derivative via the Henry condensation. These methylol... 

A huge number of ester and carbonate derivatives of polynitroaliphatic alcohol have been synthesized driven by the search for new explosives and energetic plasticizers and oxidizers for propellant and explosive formulations. Most of these are derived from 2-fluoro-2,2-dinitroethanol and 2,2,2-trinitroethanol ° and have excellent oxygen balances. Some examples are illustrated above (168-174) but more comprehensive lists can be found in numerous reviews. " " Direct esterification of polynitroaliphatic alcohols with nitric acid, mixed acid, or acetic anhydride-nitric acid has been used as a route to mixed polynitroaliphatic-nitrate ester explosives. ... 

Formals and acetals prepared from the reaction of polynitroaliphatic alcohols with formaldehyde and acetaldehyde have found use as explosive plastisizers for nitrocellulose and in plastic bonded explosives (PBXs). Formals of polynitroaliphatic alcohols are commonly prepared via reaction with trioxane or paraformaldehyde in the presence of sulfuric acid as a condensing agent. Bis(2,2-dinitropropyl)formal (175) is prepared from the reaction of trioxane with 2,2-dinitropropanol (25). The reaction of 2,2,2-trinitroethanol (159) and 2,2-dinitro-l,3-propanediol (19) with formaldehyde in the presence of sulfu-... 

Polynitroaliphatic explosives containing at least one N-nitro linkage are more sensitiveas a class than nitroaliphaticexplosives containingonly C-nitro linkages. 

Kamlet, M.J. (1976) The relationship of impact sensitivity with structures of organic high explosives. I. Polynitroaliphatic explosives. Proc. 6th Symp. (Inti) on Detonation, San Diego, California, Aug. 24—27,1976, pp. 312-324. 

Kamlet, M. J. (1976) The Relationship of Impact Sensitivity with Structure of Organic High Explosives. I. Polynitroaliphatic Explosives, Proceedings 6th Symposium (International) on Detonation, San Diego, CA, Aug. 24-27, ONR Report ACR 221, p. 312. 

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