Nitric acid ammonium formate, reaction with

NITRIC ACID, AMMONIUM SALT (6484-52-2) A strong oxidizer. An ingredient in dynamite. Violent reaction and/or the formation of explosive mixtures with hot water, reducing agents, combustible materials, organic materials, ammonium dichromate, barium chloride, barium nitrate, charcoal, cyanoguanidine, phosphorus, potassium chromate, potassium dichromate, potassium nitrate, potassium permanganate, sodium chloride, finely divided metals. Forms explosive or heat- and shock-sensitive compounds with acetic acid, alkali metals (potassium, sodium, etc.), ammonia, nitric acid, sodium hypochlorite, sulfur, urea. At elevated temperatures, contained or confined material may explode violently. 

The earlier process for making RDX consisted of reacting hexamine (hexamethylenetetramine) or its dinitrate salt with 98-100 per cent nitric acid. The yields of this method are not good because the formation of RDX is accompanied by the formation of formaldehyde, which is oxidized by the nitric acid. Greatly improved yields (70-80 per cent) can be obtained by means of the Bachman process, which employs hexamine, 98 per cent nitric acid, ammonium nitrate, and acetic anhydride. In the Bachman process a by-product having the structure I is also formed in yields up to 10 per cent. The mechanism of these reactions is not thoroughly understood. 

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 above observations allow the selective formation of RDX, HMX or the two linear nitramines (247) and (248) by choosing the right reaction conditions. For the synthesis of the linear nitramine (247), with its three amino nitrogens, we would need high reaction acidity, but in the absence of ammonium nitrate. These conditions are achieved by adding a solution of hexamine in acetic acid to a solution of nitric acid in acetic anhydride and this leads to the isolation of (247) in 51 % yield. Bachmann and co-workers also noted that (247) was formed if the hexamine nitrolysis reaction was conducted at 0 °C even in the presence of ammonium nitrate. This result is because ammonium nitrate is essentially insoluble in the nitrolysis mixture at this temperature and, hence, the reaction is essentially between the hexamine and nitric acid-acetic anhydride. If we desire to form linear nitramine (248) the absence of ammonium nitrate should be coupled with low acidity. These conditions are satisfied by the simultaneous addition of a solution of hexamine in acetic acid and a solution of nitric acid in acetic anhydride, into a reactor vessel containing acetic acid. 

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... 

When an excess of nitric acid of 10-50 per cent, strength is treated in the cold with stannous salt soln., hydroxylamine salts are the primary end-product of the reaction, but when the conditions of temp, and cone, are such that the nitric acid and the hydroxylamine salts react, then nitrous oxide is the. chief product together with small amounts of nitHe oxide, nitrogen and traces of nitrogen peroxide. No ammonium salts are formed. When stannous salts are used in excess over the nitric acid, the reaction takes place with hydroxylamine and ammonium salts as the products either in hot or cold soln., but the reaction is very slow in the latter case. When an excess of nitric acid is treated with titanous salt soln., the reaction takes place very rapidly with the formation of nitric oxide as the chief... 

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. 

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