Azides preparation

Alkyl azides prepared by nucleophilic substitution of alkyl halides by sodium azide as shown m the first entry of Table 22 3 are reduced to alkylammes by a variety of reagents including lithium aluminum hydride... 

Alkyl azides prepared by nucleophilic substitution by azide ion in primary or secondary alkyl halides are reduced to primary alkylamines by lithium aluminum hydride or by catalytic hydrogenation... 

The Cunius degradation of acyl azides prepared either by treatment of acyl halides with sodium azide or trimethylsilyl azide [47] or by treatment of acyl hydrazides with nitrous acid [f J yields pnmarily alkyl isocyanates, which can be isolated when the reaction is earned out in aptotic solvents If alcohols are used as solvents, urethanes are formed Hydrolysis of the isocyanates and the urethanes yields primary amines. 

Germanes hydride, 2 76 reactivity of, 2 87 Germanium anionic cluster, 24 227 azides, preparation, 9 138 properties, 9 135-136, 139, 141 binary carbide not reported, 11 211 carbides, preparation of, 11 163 chalcogenide halides, 23 390 chlorides, mass spectra of, 18 248, 249 complexes, xenon fluoride reactions, 46 85 compounds, see also Organogermanium compounds... 

The addition of the pseudohalogen iodine azide (prepared from iodine monochloride and sodium azide in acetonitrile) to methyl 5,6-dideoxy-2,3-di-0-p-tolylsulfonyl-a -L-arabtno-hex-5-enofuranoside has also been achieved a crystalline /3-iodo azide was isolated, in 69% yield, that was stable in the dark, but became colored on exposure to light.130 Brimacombe and coworkers133 have reported the addition of iodine azide to 5,6-dideoxy-l,2-0-isopropylidene-o -D-xy/o-hex-5-enofuranose X-ray crystallographic analysis established that the product is 6-azido-5,6-dideoxy-5-iodo-l,2-0-isopropylidene-/3-L-idofuranose. 

An improved method of preparing alkyl azides has been reported wherein Carbitols are used as solvents for the interaction of an alkyl halide and commercial sodium azide [10]. The use of activated sodium azide [34] is not necessary. Sealed-tube reactions for alkyl azides are hazardous a violent explosion has been reported in an attempt to seal such a tube [35]. No reactions reported in this chapter involve sealed tubes. Table II describes the conditions and azides prepared using the Carbitol solvents. 

According to Sudo [96] lead azide prepared by the action of sodium azide on an aqueous solution of lead acetate has a lower ignition temperature (332-336°C) than that obtained by the action on a solution of lead nitrate (339-359°C). 

Study of the Explosive Characteristics of Lead Azide Prepared Commercially 2)Wm.H.Rinkenbach, USP 1,914, 530(1933) "Method of Producing Noncrystalline Explosive Azide 3)W.E.Garner A.S.Gomm, JCS 1931, 2123 34 (Thermal de-compn and deton of LA crysts) 4)F.D. 

Treatment of ethyl 2-(l-isoquinolylaminomethylene)cyanoacetate (238) with aluminum azide, prepared in situ from aluminum chloride and sodium azide, in boiling tetrahydrofuran gave 3-(l//-tetrazol-5-yl)-4//-pyrimido-[2,l-a]isoquinolin-4-one (239) (78USP4127720). The 8,9,10,11-tetrahydro derivative of compound 239 was similarly prepared (80USP4209620). 

Diazo transfer. Tosyl azide is the most commonly used reagent for diazo Irnnsfcr, even though it is now recognized as a potentially dangerous explosive. Merck chemists have examined a number of other organic azides of these the safest is p-dodccylhciizcncsulfonyl azide, prepared from a commercial sulfonic acid mixture. 

Sulfonyl azides 3 allow the introduction of an NH2+ synthon, and alkyl or aryl azides prepared with these reagents can be reduced or hydrolyzed to primary amines, [Id, 2],... 

Bromine azide, prepared by different methods, undergoes addition to alkenes stereoselectively by an ionic mechanism 33- 37 (Table 2). Improved yields are obtained by using azidotrimethyl-silane and A-bromosuccinimide (NBS) in the presence of Nafion-FI as catalyst33. Alternatively, A-bromosuccinimide may be added to the mixture of the alkene and sodium azide in dimeth-oxyethane/water34. Aziridines were prepared stereoselectively by reduction of (i-bromo azides with lithium aluminum hydride34. 

Azido-3a-iodo-5a-androstane (6) was obtained predominantly when iodine azide prepared in dichloromethane was used14. 

As part of a systematic search for benzodiazepines exhibiting unusual pharmacological properties, scientists at Hoffman-La Roche synthesized a number of novel azido-substituted benzodiazepine derivatives [291]. The introduction of an azido group in the 7-position of 5-phenyl-1,4-benzodiazepines afforded a series of compounds (225)-(231) which included the 7-azido analogues of diazepam and oxazepam (228) and (229). The azido pharmacophore endowed potency and a spectrum of biological activity comparable with the corresponding 7-halo and 7-nitro analogues, and far superior to the 7-amino derivatives. All of the azides prepared were... 

This azide, prepared by adding a solution of n-butyl bromide to a slurry of of sodium azide in water, cleaves ketones of the type ArCOCHjR in benzene or nitrobenzene at 70-90° in the presence of a catalytic amount of sulfuric acid to two carbonyl components. Acetophenone gives benzaldehyde (80%) and formaldehyde (83%) propiophenone gives benzaldehyde and acetaldehyde. The reaction is interpreted as involving combination of the azide with the coiyugate acid of the ketone, release of nitrogen from the diazonium cation with elimination of water, hydration, and cleavage. 

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