Ammonium Nitrourethane

In a 1-1. beaker immersed in an ice-salt bath, 500 ml. of concentrated sulfuric acid is cooled to 0°C. One hundred grams of ethyl carbamate is added, and the mixture stirred until a homogeneous solution is obtained. 

The solution is cooled to — 5°C., and 110 g. (100 ml.) of ethyl nitrate is added. The mixture, is agitated for 1) hours. It is then poured slowly over 1.5 kg. of cracked ice, being stirred continuously. The solution is extracted six times with 200-ml. portions of U.S.P. ethyl ether in a large separatory funnel. The ethereal solution contains the nitrourethane together with a considerable quantity of impurities. 

One hundred milliliters concentrated ammonium hydroxide is diluted with 200 ml. water, and 100 g. finely cracked ice is added. The combined ethereal extracts are poured over this mixture slowly with continuous stirring. The aqueous layer, which must be alkaline to litmus, is drawn 

A mixture of 100 ml. of concentrated sulfuric acid and 300 g. of cracked ice is now added to the foregoing ammoni-acal solution the resultant solution must be acid to Congo red. It is extracted six times with 200-ml. portions of alcohol-free ether, and the combined ethereal extracts are dried over anhydrous calcium chloride. This operation further purifies the nitrourethane which is then again converted to the ammonium salt. 

The ether solution of nitrourethane is filtered into a 4-1. flask or beaker and is diluted to 3 1. with anhydrous alcohol-free ether. The solution is then saturated with dry ammonia gas or treated with an excess of liquid ammonia, thereby precipitating ammonium nitrourethane. The product is filtered on a large Buchner funnel, washed with a small quantity of alcohol-free ether, f and dried by drawing air through the filter cake. Theoretical yield 170 g. actual yield 80 to 95 g. (47 to 55 per cent of theory). 

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Ammonium nitrourethane is a white, crystalline solid and is quite stable in air. It may, therefore, be prepared in large quantity and stored at room temperature in an ordinary bottle. 

Fifty grams of powdered ammonium nitrourethane is added to a mixture of 100 ml. of water and 100 ml. of... 

Acetic acid-acetic anhydride, 85 Alkali azides, 79 Alkaline earth azides, 79 Alumino-oxalates, 36 Amalgams, 5 concentration of, 17 preparation of, 6 rare earth metal, 15 Ammonium nitrourethane, 69 Ammonium perrhenate, 177 Antimony oxyiodide, 105 Antimony triiodide, 104 Aquopentammino cobalti bromide, 187, 188... 

The SRI researchers later introduced an approach whereby ammonium nitrourethane can be nitrated with N2O5 or NO2BF4 to give dinitrourethane. In a subsequent step, the urethane is cleaved with ammonia resulting in ADN. This route has been used in the US in scaled-up... 

N 36.83%, OB to C02 -42.1% colorless needles from ether nip 38° d 1.243 at 49/4° RI 1.4616 at 48,6°. V sol in cold w, ale, chlf and benz less sol in eth and still less sol in petr eth. Can be prepd by nitrating n-methyl-urethane with abs nitric acid. The resulting soln of methyl nitrourethane is drowned in w, neutralized with Na carbonate, and extrd with eth to remove methyl nitrourethane. On passing ammonia gas thru the eth extract, a white ppt of the ammonium salt of methylnitramine is deposited and sepd by filtration. It is disd in ale and boiled to drive off the ammonia, and... 

A practical application of dinitrogen pentoxide in methylene chloride reagent involves the nitration of either ammonium carbamate or nitrourethane, followed by ammonolysis to yield ammonium dinitramide, an energetic oxidizer with enormous potential for use in future high performance propellant compositions. This important reaction is discussed in more detail in Chapter 9. 

Neodymium amalgam, 15 Neodymium chloride, anhydrous, 32 Nitramide, 68, 72 Nitrocarbamate, potassium, 70 Nitrocarbamates, 68 Nitrogen, pure, 79 Nitrogen trichloride, 65 analysis of, 67 Nitrosyl chloride, 55 analysis of, 57 Nitrosylsulfuric acid, 55 Nitrourethane, 69 ammonium, 69... 

Nitrosylpentamminecobalt(III) chloride, pink, 4 168 [shown to be chloropentamminecobalt-(III) chloride], 6 185 Nitrosyls, nomenclature of, 2 264 Nitrosylsulfuric acid, 1 55 Nitrourethan, and ammonium salt, 1 69... 

N02N(NH4)C02C2H6 Ammonium salt of nitrourethan, 1 69 N03H Nitric acid, 3 13 4 52 N(S03K)s Potassium nitridotri-sulfate, 2 182... 

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