Azides, metal reactions with

The reaction of aminoguanidine bicarbonate (84) with sodium nitrite in the presence of excess acetic acid produces 1,3-ditetrazolyltriazine (89), another nitrogen-rich heterocycle (C2H3N11 = 85 % N) which readily forms explosive metal salts. The reaction of aminoguanidine bicarbonate (84) with sodium nitrite in the presence of mineral acid yields guanyl azide (90), of which, the perchlorate and picrate salts are primary explosives. Guanyl azide (90) reacts with sodium hydroxide to form sodium azide, whereas reaction with weak base or acid forms 5-aminotetrazole. ... 

AZIDA SODICA (Spanish) (26628-22-8) Reacts with hot water. Explosive decomposition in elevated temperatures above 525°F/274°C. Forms ultra-sensitive explosive compounds with heavy metals copper, copper alloys, lead, silver, mercury, carbon disulfide, trifluoroacryloyl fluoride. Violent reaction with acids, forming explosive hydrogen azide. Violent reaction with bromine, barium carbonate, chromyl chloride, dimethyl sulfate, dibromomalononitrile. Incompatible with caustics, cyanuric chloride, metal oxides, metal sulfides, methyl azide, phosgene. 

Its heat of combustion and heat of detonation are 631 and 368 cal/g, respectively (or 184 and 107 kcal/mol). The released gas volume is 308 cm /g at STP. It forms highly shock-sensitive copper and zinc azides when mixed with the solutions of copper and zinc salts. Its contact with these metals or then-alloys over a period of time results in the formation of their azides, too. Reaction with carbon disulfide is violently explosive. There is a report of an explosion resulting from the addition of calcium stearate in a lead azide preparation (MCA 1962). 

A number of studies have been reported concerning azide-isocyanide condensations to give tetrazoles. Early work by Beck and co-workers 18, 19) describes the addition of various isocyanides to metal azido species [Au(N3)4]", [Au(N3)2]", Au(PPh3)N3, and M(PPh3)2(N3)2, M = Pd, Pt, Hg. The products are carbon-bonded tetrazolato-metal complexes. It is not known whether metal isocyanide complexes are intermediates in these reactions. More recently inverse reactions with azide ion addition to metal isocyanide complexes were carried out, with similar results. From... 

The Ir(III,IV,IV) complex [Ir3N(S04)6(0H2)3]4 undergoes ligand substitution of the three H20 ligands with azide, Cl, Br, and NCS-. The three H20 ligands, one on each metal, are all equivalent towards substitution.103 The rate constant for the reaction with azide is 17.3 x 10-4 M 1s 1. 

Despite the volume of work concerned with metal-catalyzed decomposition of diazo compounds and carbenoid reactions 28>, relatively little work has been reported on the metal-catalyzed decomposition of sulphonyl azides. Some metal-aryl nitrene complexes have recently been isolated 29 31>. Nitro compounds have also been reduced to nitrene metal complexes with transition metal oxalates 32K... 

The importance of reactions with complex, metal hydrides in carbohydrate chemistry is well documented by a vast number of publications that deal mainly with reduction of carbonyl groups, N- and O-acyl functions, lactones, azides, and epoxides, as well as with reactions of sulfonic esters. With rare exceptions, lithium aluminum hydride and lithium, sodium, or potassium borohydride are the... 

Reaction of metal nitrosyls with azide ion proceeds with formation of N2 and N20 (56). This can be viewed as the result of a nitrene transfer reaction in analogy with the Curtius rearrangement (62) and its organome-tallic counterpart (63). 

Carbon disulfide is an extremely flammable liquid, the closed cup flash point being -22°F (-30°C). Its autoignition temperature is 90°C (194°F). Its vapors form explosive mixtures with air, within a wide range of 1.3 to 50.0% by volume in air. Reactions with certain substances can progress to explosive violence. They include finely divided metals, alkali metals, azides, fulminates, and nitrogen dioxide. 

Alkyl halides undergo Sn2 reactions with a variety of nucleophiles, e.g. metal hydroxides (NaOH or KOH), metal alkoxides (NaOR or KOR) or metal cyanides (NaCN or KCN), to produce alcohols, ethers or nitriles, respectively. They react with metal amides (NaNH2) or NH3, 1° amines and 2° amines to give 1°, 2° or 3° amines, respectively. Alkyl halides react with metal acetylides (R C=CNa), metal azides (NaN3) and metal carboxylate (R C02Na) to produce internal alkynes, azides and esters, respectively. Most of these transformations are limited to primary alkyl halides (see Section 5.5.2). Higher alkyl halides tend to react via elimination. 

Hydrazoic acid also reacts with copper, silver and mercury but in a different way it forms azides without loss of hydrogen and a considerable amount of hydrazoic acid is reduced to ammonia or hydrazine and free nitrogen. The reaction with copper recalls the action of nitric acid on this metal. 

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