Ammonium nitrate formation from nitric acid reaction

Qualitative. The classic method for the quaUtative determination of silver ia solution is precipitation as silver chloride with dilute nitric acid and chloride ion. The silver chloride can be differentiated from lead or mercurous chlorides, which also may precipitate, by the fact that lead chloride is soluble ia hot water but not ia ammonium hydroxide, whereas mercurous chloride turns black ia ammonium hydroxide. Silver chloride dissolves ia ammonium hydroxide because of the formation of soluble silver—ammonia complexes. A number of selective spot tests (24) iaclude reactions with /)-dimethy1amino-henz1idenerhodanine, ceric ammonium nitrate, or bromopyrogaHol red [16574-43-9]. Silver is detected by x-ray fluorescence and arc-emission spectrometry. Two sensitive arc-emission lines for silver occur at 328.1 and 338.3 nm. 

RDX. Gilpin Winkler (Ref 38b) measured a heat of nitration of — 88.0kcal/mole of hexa-mine for the reaction of hexamine with 97.5% nitric acid. They also obtained a value of — 140kcal/mole of hexamine for the formation of RDX from hexamine and Bachmann reagents (acetic anhydride, acetic acid, ammonium nitrate and nitric acid). Incidentally, Gilpin Winkler interpret their results to mean that hexamine dinitrate is an intermediate in the direct nitrolysis of hexamine to give RDX, while hexamine mononitrate is an intermediate in the Bachmann process of producing RDX... 

Nichols and co-workersstudied the formation of j8-hydroxy nitrate esters via the acid-catalyzed ring-opening of epoxides with nitrate anion. Reactions were conducted in aqueous media using solutions of ammonium nitrate is nitric acid and under nonaqueous conditions using solutions of pure nitric acid in chloroform. 2-Nitratoethanol (32) is formed in 58 % yield from ethylene oxide (30) using either of these methods. ... 

The most important nitrolysis reaction to date is the formation of RDX (3) and HMX (4) from the caged methylenediamine known as hexamine (104). These important military explosives were first mass manufactured by this route towards the end of the Second World War and they are still prepared by this route today. The process uses a mixture of acetic anhydride, ammonium nitrate and nitric acid. The nitrolysis of hexamine is one of the most widely studied reactions in the history of explosives. Many other cyclic and linear polynitramines have been isolated from these reactions and this rich chemistry is discussed in more detail in Section 5.15. 

The chemistry of l,5-dinitroendomethylene-l,3,5,7-tetraazacyclooctane (239) (DPT) is interesting in the context of the nitramine products which can be obtained from its nitrolysis under different reaction conditions. The nitrolysis of DPT (239) with acetic anhydride-nitric acid mixtures in the presence of ammonium nitrate is an important route to HMX (4) and this has been discussed in Section 5.15.2. The nitrolysis of DPT (239) in the absence of ammonium nitrate leads to the formation of l,9-diacetoxy-2,4,6,8-tetranitro-2,4,6,8-tetraazanonane (248) the latter has found use in the synthesis of energetic polymers. 

The particularly good activity against protein kinases of a-aminoquinazoline derivatives is borne out by their activity against both in vitro and in vivo models of human tumors. The examples that follow are but two of a number of compounds from this structural class that have emerged from the focus that has been devoted to this stmctural class. Nitration of the benzoate (78-1) with nitric acid affords the nitro derivative. Hydrogenation converts this to the anthrandate (78-2). In one of the standard conditions for forming quinazolones, that intermediate is then treated with ammonium formate to yield the heterocycle (78-3). Reaction of this last product with phosphorus oxychloride leads to the corresponding enol chloride (78-4). Condensation of this last intermediate with meta-iodoanUine (78-5) leads to displacement of chlorine and the consequent formation of the aminoquinazoline... 

Summary beta-HMX can be prepared by reacting hexamine with ammonium nitrate and nitric acid in the presence of excess glacial acetic acid and acetic anhydride. The rate of additions is crucial to ensure proper HMX formation. After the reaction is complete, the alpha-HMX is refluxed with water to ensure quality and purification. The resulting water insoluble product is then filtered-off, and then recrystallized from acetone to produce excellent crystals of beta-HMX. Commercial Industrial note For related, or similar information, see Serial No. 696,888, November 15th, 1957, by The United States Army, to Jean P. Picard, Morristown, NJ. Part or parts of this laboratory process may be protected by international, and/or commercial/industrial processes. Before using this process to legally manufacture the mentioned explosive, with intent to sell, consult any protected commercial or industrial processes related to, similar to, or additional to, the process discussed in this procedure. This process may be used to legally prepare the mentioned explosive for laboratory, educational, or research purposes. 

With regard to preparation of the compound, apart from the straiglu forward formation from rnethylamine and nitric acid (66%) (as described in Vol. II) another method based on the Fldchl reaction, by reacting ammonium nitrate with formaldehyde at 80-100 C, as was suggested by the author of this book [39] and brought to industrial application ... 

Although the discovery of ionic liquids can be dated back to 1914 when Walden reported the formation of ethyl ammonium nitrate (m.p. 12 C) from the reaction of ethylamine with concentrated nitric acid, no interest in these compounds was shown at the time. Over the last few years however, ionic liquids are emerging as an attractive... 

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