Hydrogen azide handling

Ray, P. C. et al., J. Chem. Soc., 1911, 99, 1470 1912, 101, 141, 216 Ammonium and substituted-ammonium nitrite salts exhibit a range of instability, and reaction mixtures which may be expected to yield these products should be handled with care. Ammonium nitrite will decompose explosively either as the solid, or in cone, aqueous solution when heated to 60-70°C. Presence of traces of acid lowers the decomposition temperature markedly. Hydroxylammo-nium nitrite appears to be so unstable that it decomposes immediately in solution. Hydrazinium(l+) nitrite is a solid which explodes violently on percussion, or less vigorously if heated rapidly, and hydrogen azide may be a product of decomposition [1], Mono- and di-alkylammonium nitrites decompose at temperatures below 60-70°C, but usually without violence [2], Individual entries are ... 

Caution Parts A and C of this procedure should be carried out in a well-ventilated hood since toxic hydrogen bromide and azidotrimethylsilane are handled and toxic hydrogen azide is liberated during the course of the reaction. 

Trimethylsilyl cyanide (TMSCN) and trimethylsilyl azide (TMSN3) are safe and convenient replacements for hydrogen cyanide and hydrogen azide, respectively, which are otherwise inconvenient or hazardous to handle. 

Nitrogen triiodide (black unstable crystals) explodes at the shghtest touch when dry. When handled, it is kept wet with ether. It is too sensitive to be used as an explosive, because it cannot be stored, handled, or transported. Azides, such as lead azide and hydrazoic azide, are highly unstable. Lead azide is a severe explosion risk and should be handled under water it is also a primary detonating compound. Hydrazoic acid or hydrogen azide is a dangerous explosion risk when shocked or heated. Metal fulminates, such as mercury fulminate, explode readily when dry. They are used in the manufacture of caps and detonators for producing explosions. 

The other /V tosylsulfoximines can be prepared by the tosylation of N-H sulfoximines with p-toluenesulfonyl chloride in the presence of base,. but the two most useful and general methods are the oxidation of /V tosylsulfilimines with basic hydrogen peroxide, m-chloroperbenzoic acid anion, sodium hypochlorite, or ruthe-nium(VIII) oxide/sodium metaperiodate and the copper powder-promoted reaction of sulfoxides with p-toluenesulfonyl azide Handling, Storage, and Precautions (1) is a highly crystalline compound with no known toxicity and unlimited shelf life. 

The major portion of this volume is taken up by hydrogen azide or hydrazoic acid, HN3, the first member in the series of trinitrogen compounds. Known to be highly explosive in pure form, it can be safely handled when diluted. Thus, a great deal of information is available mainly on its properties as a chemical reagent and its decomposition processes. 

A better method for preparing primary amines is to use the azide synthesis, in which azjde ion, N3, is used for SN2 reaction with a primary or secondary alkyl halide to give an alkyl azide, RN3. Because alkyl azides are not nucleophilic, overalkylation can t occur. Subsequent reduction of the alkyl azide, either by catalytic hydrogenation over a palladium catalyst or by reaction with LiAlK4. then leads to the desired primary amine. Although the method works well, low-molecular-weight alkyl azides are explosive and must be handled carefully. 

Sodium azide/hydrogen peroxide solution10 1 % (w/v) sodium azide in 0.3% (v/v) hydrogen peroxide This solution must be prepared m a fume cupboard and handled with care. 

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