Dithiocarbonic azide

CHj),N-SCSN mw 192.32, N 29.13 wh crystalline tablets (from w), mp 95-8 (with color change to dk grn and then dec) very sol in w, sol in MeOH or acet si sol in eth and insol in CCl4, CSj chlf. It can be prepd by three methods a)neutralization of azido dithiocarbonic acid with aq tetramethylammonium hydroxide b)double decompn of Ba azidodithiocarbonate and tetramethylammonium sulfate and c)digestion of aq tetramethylammonium azide with a si excess of CS] as reqd by the equation... 

Treatment of thionhydrazides, RC(==S)—NH—NH2 with nitrous acid should lead to thiocarbonyl azides, RC(=S)—N3, and it seems likely that these azides are indeed formed as short-lived intermediates. The isolated products are 1,2,3,4-thiatriazoles. When thiosemi-carbazides are nitrosated, 5-amino-l,2,3,4-thiatriazoles or/and 5-mercaptotetrazoles are obtained. Freundformulated his products as such in 1895, while Oliveri-Mandala considered them thiocarbamoyl azides on the basis of some chemical evidence. Lieber resolved this controversy by recording the infrared spectra of the compounds and demonstrating the absence of an azide band . He did the same for the 5-alkylmercapto-l,2,3,4-thiatriazoles , which had earlier been reported as azido-dithiocarbonates , and for the products from azide ion and thiophosgene and carbon disulphide , all of which possess thiatriazole structures. Lieber also demon-... 

These similarities remove the dear distinction between the three dassic GRP systems (NMP, RAFT, and ATRP), particularly since ATRP can be conducted with an expanding range of radically transferable groups, initially exemplified by the use of azide" and thiocyanates" " as transferable groups, but now expanded to indude alkyl pseudohalides (APH) based on dithioesters, xanthates, dithiocarbonates, or trithiocarbo-... 

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