Nitrocyanamide

Harris [25] isolated this substance by the action of anhydrous hydrogen chloride on the solution of the silver salt of nitrocyanamide in acetonitrile. It has explosive properties but it is of no practical value due to the difficulty of preparing it. On the other hand its salts may be of practical value. These salts and their preparation will be discussed in the chapters dealing with initiating explosives (p. 211). 

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When the reagent is the thiocyanate ion, S-alkylation is an important side reaction (10-43), but the cyanate ion practically always gives exclusive N-alkylation. ° Primary alkyl halides have been converted to isocyanates by treatment with sodium nitrocyanamide (NaNCNN02) and m-chloroperoxybenzoic acid, followed by heating of the initially produced RN(N02)CN. ° When alkyl halides are treated with NCO in the presence of ethanol, carbamates can be prepared directly (see 16-7). ° Acyl halides give the corresponding acyl isocyanates and isothiocyanates. For the formation of isocyanides, see 10-111. 

Hydrolysis of N -nitro-N-methylnitroguanidine (101) and Al-nitroso-N-methylnitrogu-anidine (102) with aqueous potassium hydroxide results in the formation of potassium nitrocyanamide. Addition of acidic silver nitrate solution to these reaction mixtures leads to... 

In the presence of primary aliphatic amines in aqueous solution nitroguanidine undergoes decomposition according to equation (22). Ammonia is then evolved, and nitrocyanamide combines with the amine to form alkylnitroguanidine, e.g. N-methyl-N -nitroguanidine ... 

The explosive properties of the potassium salt of nitrocyanamide first attracted McKay s [37] attention. He separated this potassium salt as a by-product from the preparation of aliphatic diazo compounds by the hydrolysis of N-alkyl-N-nitroso-N -nitroguanidines with an aqueous solution of sodium hydroxide at temperatures from 0°C to room temperature ... 

The same author et al. (McKay, Hatton, G. W. Taylor [38]) prepared a number of nitrocyanamide salts by the action of the chlorides of various metals on the silver salt in suitable solvents or the by reaction of the carbonates of various metals with a solution of nitrocyanamide in acetonitrile, and found that some of these salts have initiating properties. The majority, however, cannot be recommended for practical use, their sensitiveness to impact being too low (they are not exploded by a 5 kg weight falling from a height of 300 cm). 

Harris [39] reports that only the following nitrocyanamide salts possess greater sensitiveness and may be considered to be of practical use potassium, tin, lead, barium and silver nitrocyanamides. 

Comparing with the experiments of Grant and Tiffany [40] Harris states that silver and barium nitrocyanamides show an initiation capacity the same as that of an 80 20 mixture of mercury fulminate and potassium chlorate, but weaker than that of a mixture of lead azide and lead styphnate. This can be seen from Table 38 quoted by Harris ... 

In spite of their fairly promising initiating properties, nitrocyanamide salts are of no practical use due to their high hygroscopicity. 

This compd was rapidly cleaved by dil KOH to yield K nitrocyanamide n-butylnitramine, isolated as the monohydrate of the Ba salt. 

The prepn props of Silver Nitrocyanamide, NCN.NOzAg, are given by Okazaki et al (Ref... 

In the absence of ammonia and in the presence of a primary aliphatic amine, nitroguanidine in aqueous solution dearranges in the second of the above-indicated modes, ammonia is liberated, and the nitrocyanamide combines with the amine to form an alkylnitroguanidine. 

Silver Nitrocyanamide. See under Cyanamide and Derivatives in Vol 3, C581-L, plus the following addnl material ... 

Finally, alkyl halides are readily converted into isocyanates, in very good yields, by reaction with the silver salt of nitrocyanamide (equation 52)404. This is the first reported reaction for the preparation of isocyanates, from alkyl halides, that is of a general nature. The direct reaction of halides with metal cyanates gives very erratic results. 

The impact friction sensitivity props are similar to those of LSt DADNPh. When used in caps, Ag Nitrocyanamide initiates Tetryl TNT but not as satisfactorily as... 

Other reactions of aminoguanidine with nitrous acid Cyanamide salts Silver cyanamide Nitrocyanamide salts Nitrophenol salts Lead picrate Lead styphenate Lead stypheratc manufacture... 

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