Diazobenzene nitrate

Berthelot and Vieille [1] examined the explosive properties of diazobenzene nitrate (C6H5N = N) NOf. Later Wohler and Matter [2] demonstrated that it is unsuitable for use as an initiator due to its very weak initiating properties and very high sensitiveness to friction and impact. Herz [3] suggested the use of m-nitrodiazobenzene perchlorate. This, however, is hygroscopic and insufficiently stable (it explodes at 154°C). 

Note According to Daniel(1902),pp 462-3, aniline nitrate served in France for the prepn of a primary compd, diazobenzene nitrate, known in France as aniline fulminmie. The reaction proceeded as follows ... 

Aniline fulminante (Fr). Diazobenzene Nitrate (See Note under Anilinonitrate on previous page)... 

Preparation 382.—Diazobenzene Nitrate (Benzene Diazonium Nitrate). C8H6.N( N).N03. C3H603N3. 167. 

Owing to the highly explosive nature of the diazobenzene nitrate, its preparation should never be undertaken except the compound is wanted for research or some special purpose. 20 gms. of aniline are placed in a beaker, well cooled, and boiled-out nitric acid, previously diluted with half its volume of water, oarefully added till the mixture sets to a thick crystalline paste—aniline nitrate. The crystalline mass is filtered off at the pump, and washed with a little cold water. 5 gms. of the moist salt are finely powdered and placed in a small flask with enough water just to cover the substance. The flask is now well cooled in ice-water, and nitrous fumes (for preparation, see p. 513) are led in with frequent agitation until all the aniline nitrate has disappeared. At no time must the temperature of the flask rise above 10°. Should there not be sufficient water to keep all the diazobenzene nitrate formed in solution, its crystalline form will easily enable it to be distinguished from the aniline salt. When the reaction is finished the contents of the flask are poured into 3 times their volume of absolute alcohol, and ether is added to this mixture as long as crystals separate. If too much water has been added to the aniline nitrate from the beginning, a thick aqueous solution of diazobenzene nitrate separates out in place of the crystals. If this occurs, the ether-alcohol is decanted off, and the residue redissolved in absolute alcohol, and reprecipitated with ether. On no account must... 

If a solution of diazobenzene nitrate be used, the liberated nitric acid acts on the phenol as it is formed, and nitrophenol is produced. 

The preparation of aniline nitrate is fully described on p. 375 under the preparation of diazobenzene nitrate. The crude product therein obtained is recrystallised by dissolving in a little absolute alcohol and precipitating therefrom with ether. The preparation and purification of aniline hydrochloride are exactly similar. 

The first volume of the Memorial des Poudres et Salpetres contains a report by Berthelot and Vieille04 on the properties of benzenediazonium nitrate (diazobenzene nitrate). They prepared the material by passing nitrous gas into a cooled aqueous solution of aniline nitrate, diluting with an equal volume of alcohol, and precipitating in the form of white, voluminous flocks by the addition of an excess of ether. 

Is prepared by treating diazobenzene nitrate with carbonate of barium, or by the action of the former on oxyazobenzene. 

Fischer discovered phenylhydrazine in 1875. Strecker by treating diazobenzene nitrate with excess of potassium hydrogen sulphite, obtained a salt... 

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