Azidodithiocarbonic acid

A few salts of azidodithiocarbonic acid were first prepared by Sommer1 by the reaction of azides (trinitrides) with carbon disulfide  

These studies have been extended by A. W. Browne and his coworkers,2 6 so that our knowledge of the chemistry of azidodithiocarbonic acid and the halogenoid azidocarbondisulphide is more complete than for most halogenoid compounds. The highly explosive character of the free halogenoid and of most of the anhydrous salts, particularly those of the heavy metals, makes them very dangerous and extremely difficult to handle. 

Recrystallized sodium azide (12 g.) is dissolved in 50 ml. of water, and 12 ml. of carbon disulfide is added. The mixture is placed in a small flask fitted with a reflux condenser and kept at a temperature of about 40°C. for approximately 48 hours. If carbon disulfide is lost by volatilization, more is added from time to time. The resulting solution of sodium azidodithiocarbonate is filtered, chilled in an ice bath, and treated with chilled concentrated hydrochloric acid. The white, crystalline precipitate is washed twice by decantation with ice water, separated by filtration on a Buchner funnel, dried on a porous plate or between filter paper, preserved in a desiccator protected from the light, and kept at a temperature below 10°C. (In this way, azidodithiocarbonic acid may be kept for 24 to 48 hours without appreciable decomposition.) 

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No other compounds which were considered to be thiatriazoles had been prepared at this time. However, one other thoroughly investigated compound, the reaction product of carbon disulfide and sodium azide, which had generally been considered as azidodithiocarbonic acid, was shown by Lieber et al. to be a thiatriazole. 

Seel and Nogradi were probably the first to suspect that the formulation of the thiol as azidodithiocarbonic acid was incorrect. In a study of the reaction of nitrosyl chloride with azides they found that... 

Thio-l,2,3,4-thiatriazole was originally thought to have an open structure, azidodithiocarbonic acid, but Lieber et al. concluded from infrared spectroscopic measurements that it aetually possesses the closed 1,2,3,4-thiatriazole structure <57JOC1750>. 

Many derivs and salts of azidodithiocarbonic acid are known some of which are expl (see below)... 

Guanidine Azidodithiocarbonate, HNC(NH2)2 HSCSNj, mw 178.25, N 47.15% col prisms, mp 88-90° (dec) readily sol in w or acet, sol in ale and almost insol in eth. It was prepd by interacting aq guanidine carbonate with freshly prepd solid azidodithiocarbonic acid or by reacting aq guanidine azide, HNC(NHa) -HNS, with purified CSa... 

Heavy Metal Salts of Azidodithiocarbonic Acid. Some heavy metal salts of azidodithiocarbonic acid, such as Ag, Cu++, Hg+, Hg++, Cd, Bi, Fe+++ Zn, were prepd and... 

Carbon disulfide and derivs 2 C60-C61 carbon disulfide monoazide 2 C61 see Azidodithiocarbonic acid 1 A632... 

It reacts with caustic potash in much the same manner as a halogen, forming the potassium salts of azidodithiocarbonic acid and azido-oxydithiocarbonic acid ... 

Carbon Disulfide Monoozide, N3.CS2H. This compd is described in Vol l,p A632- L as Azidodithiocarbonic Acid, Lieber et al (Ref 2) assigned to it(based on IR spectra), the thiatriazole structure, HjjJ—N, naming it... 

H-SC -N=NsN, mw 119.17, N 35.27% wh or si yel cryst, mp 50-65° (dec), explodes at 70° sol in ale, methanol, eth, benz AcOH and fairly sol in w. It was first prepd by Sommer (Ref 2) by treatment of a cold coned so In of Na azidodithiocarboxylic acid with coned HCi, but no evidence was offered to identify the compd. It s prepn has been described by Oliveri-Mandala (Ref 3), Smith et al (Refs 4 9), Audrieth (Ref 8) and others. Azidodithiocarbonic Acid can be prepd, according to Smith et al (Refs 4 9), by refluxing for 48 hrs at 40° pure CS and a coned aq soln of recrystd NaNj, filtering the soln, washing the crysts with chilled coned... 

Dry azidodithiocarbonic acid is very sensitive to expln by friction, impact or heat. It detonates with a puff on contact with a hot wire below red heat. It is easily oxidized by various reagents to a more expl solid, (SCSNj)j, azidocarbondisidfide (Ref 4)... 

Alkali and Alkaline Earth Salts of Azidodithiocarbonic Acid... 

Heavy Metal-Salts of Azidodithiocarbonic Acid A636-R... 

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