Hydrazoic acid and azides

Hydrazoic acids and azides Acetylenes, especially polyacetylenes... 

Chemical Properties of Hydrazoic Acid and Azide Salts... 

W. Gerhertz, ed., Ullmann s Encyclopedia of Industrial Chemistry , 7thedn., Wiley-VCH, Weinheim, 2003, chapters Ammonia Ammonium Compounds Hydrazoic Acid and Azides Hydrazine Hydroxylamine Nitrates and Nitrites Nitric Acid, Nitrous Acid and Nitrogen Oxides Nitrogen. 

Malonate and related activated methylene compounds have also been used as the nucleophile in conjugate addition/Michael reactions. Taylor and co-workers have developed a new methodology that utilizes (salen)aluminum complexes such as 43 as a catalyst to effect the enantioselective conjugate addition to a,p-unsaturated ketones by a variety of nucleophiles.25 For example, nitriles, nitroalkanes, hydrazoic acids, and azides have found utility in this reaction. Additionally, cyanoacetate (42) has been demonstrated to undergo a highly enantioselective conjugate addition to 41. The Krapcho decarboxylation is then necessary to produce cyanoketone 44, an intermediate in the synthesis of enantioenriched 2,4-cw-di substituted piperidine 45. 

Matheson, D. 1983. Hydrazoic acid and azide, in Encyclopedia of Health and Occupational Safety, 3rd ed. Vol. 1, L. Parmeggiani, ed. Geneva International Labor Office. 

HYDRAZOIC ACID AND AZIDES H. Hydrazoic Acid and Azides... 

By very careful hydrogenation (with stannous chloride in ethereal hydrogen chloride) phenyl azide has been converted into the exceedingly sensitive phenyltriazene (Dimroth), which, as has been shown, can be reconverted into the former by dehydrogenation. As in the case of the aliphatic diazo-compounds, an open chain structural formula has lately also been assigned to hydrazoic acid and its esters, so that the changes just mentioned may be formulated as follows ... 

Thiatriazole-5-thiol and its salts are readily obtained from the water-soluble alkali or alkaline earth azides with CS2 at 40 °C <64AHC(3)263>. However, these salts should be handled with extreme care as violent explosions have been reported when the alkali salts are spread on a porous plate or rubbed with a spatula. The slightly soluble heavy-metal salts are very sensitive to shock even under water. An improved method for the preparation and storage of sodium thiatriazole-5-thiolate has been reported. The free acid is obtained by addition of concentrated hydrochloric acid to a chilled solution of the sodium salt but can also be prepared from hydrazoic acid and carbon disulfide (Scheme 38). 

Sodium azide is used to make lead azide and hydrazoic acid, and as a propellant for automotive safety bags. It also is used as an antihypertensive agent to control blood pressure. 

Cadmium azide may also detonate spontaneously, but under different experimental conditions, i.e. when a rod of metallic cadmium is immersed in hydrazoic acid and cadmium azide is formed on the surface of the rod (A. T. Thomas [127]). 

Hydrazoic Acid and the Metal Azides (a literature survey)... 

Refs 1)E.Wiberg H.Michaud, ZNaturforsch 9b, 497-9(1954) CA 49, 767(1955) 2)H. Rosenwasser, USArmy EngrRes Develop LabsRpt 1551-TR, 48(1958), "Hydrazoic Acid and the Metal Azides" (a literature survey)... 

Rosenwasset, LSArmyEngrRes Develop LabsRpt 1551-TR, 27(1958), "Hydrazoic Acid and the Metal Azides (a literature survey)... 

Cupric Amminoazide (Ammoniate of Copper Azide), Diammine copper azide, [Cu(NHj)a] (Nj)a, mw 181.65, N 61.69% green crysrs, expl when heated or struck. Obtained by Dennis Isham (Ref 2) by shaking freshly pptd black cupric hydroxide, while still moist, with ao excess of hydrazoic acid, and washing and dissolving the ppt in aq ammonia. This compd was also prepd by Browne et al (Ref 6) and studied by Strecker Schwinn (Ref 8) and by Straumanis Cirulis (Ref 11) (See also Ref 21, p 149 and Table D under Ammines in this dictionary). Tetrammine copper azide, [Cu(NHs),](N3)a, mw 215.72, N 64.90%, blue crysts, expl at 202° and on impact. Prepd by Strecker Schwinn (Ref 8) and by Straumanis Cirulis (Ref 11) from cupric azide and NHS, (either liq or the dry gas). Only the di- and tetrammino- compds were prepd, (See also Ref 21, p 149 and Table D under Ammines)... 

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