Phenyl azide-Aluminum chloride

Addition of nitrogen to form aziridines Phenyl azide-Aluminum chloride,... 

Phenyl azide-Aluminum chloride, 240 Haloboration Boron tribromide, 43 Halogenation Boron tribromide, 43 Tetrabutylammonium tribromide, 287 Hydroacylation Dicarbonyl(nitrosyl)triphenyl-phosphinecobalt, 101 Hydrofluorination... 

Diethoxytriphenylphosphorane, 109 Diphosphorus tetraiodide, 127 Phenyl azide-Aluminum chloride, 240 Triphenylphosphine-Diethyl azodicar-boxylate, 332... 

Lithium diisopropylamide, 163 Phenyl azide-Aluminum chloride, 240 Halo carbonyl compounds (see also Unsaturated carbonyl compounds) a-Chloro acids Sodium nitrite, 282 a-Halo aldehydes and ketones... 

Phenyl azide-Aluminum chloride, 240 Potassium fluoride-Alumina, 15, 254, 256... 

Butyl alcohol in synthesis of phenyl 1-butyl ether, 46, 89 1-Butyl azidoacetate, 46, 47 hydrogenation of, 46, 47 1-Butyl chloroacetate, reaction with sodium azide, 46, 47 lre l-4-i-BUTYLCYCLOHEXANOL, 47,16 4-(-Butylcyclohexanonc, reduction with lithium aluminum hydride and aluminum chloride, 47, 17 1-Butyl hypochlorite, reaction with cy-clohexylamine, 46,17 l-Butylthiourea, 46, 72... 

In the presence of gallium chloride, aluminum bromide, aluminum chloride, and ferric chloride, benzoyl azide is decomposed according to eq 2. Here complex formation is very fast, and the decomposition of the complex is the ratedetermining step. The halides do not complex with the phenyl isocyanate formed and, as a consequence, they are not consumed in the reaction. As long as benzoyl azide is in excess, the concentration of the complex is equal to the halide concentration and remains constant. The experimentally determined pseudo-zero-order rate constant depends therefore upon the first power of the initial halide concentration. When, however, the reaction is at a stage where the azide is no longer in excess, the rate of the reaction becomes first order with respect to benzoyl azide and zero order with respect to halide. PhCONj + AlBr, -r - PhCONrAlBr, r+-... 

This reaction may involve stepwise addition of the two equivalents of PhNCS via a 3-membered ring intermediate, RN—S—C=NPh.66 A thia-ziridine was also suggested by Borsche67 to explain the formation of 4-phenyl-5-phenylimino-l,2,4-dithiazolidine-3-thione from the aluminum chloride-catalyzed decomposition of phenyl azide in carbon disulfide. If a 4-substituted thiatriazoline is formed from phenyl isothiocyanate and the alkyl azide, the reaction may then be formulated as indicated in Eq. (21). This scheme is supported by the recent findings of Neidlein and... 

The primary adducts from the reaction of tetrachlorocyclopropene and azides yield chlorinated azabutadienes.170b The triazoline derived from Dewar benzene and phenyl azide, when heated in the presence of aluminum chloride, yields unique ring-enlarged heterocycles (Scheme 168).484... 

On decomposition of the 1 1 adduct of phenyl azide with both alkyl aluminum chlorides, the main reaction is A-ethylation with the formation of IV-ethylanilides 100). 

ALUMINUM CHLORIDE (7446-70-0) Contact with moist air or water produces hydrogen chloride and heat. Contact with water, alcohol, alkenes. bases, epichlorohydrin, ethylene oxide can result in violent polymerization. Incompatible with butyl nitrate, glycidol, methyl chloride, organic material, oxygen difluoride, phenyl azide. Forms shock-sensitive or explosive compounds with ammonium nitrate, nitrobenzene. Attacks metals including 316 stainless steel in the presence of moisture. 

In 1956, Hattori and co-workers estabUshed that aluminum azide adds to alkyl isocyanates or acid chlorides in tetrahydrofuran to afford l-aUcyl-A -tetrazoline-5-ones in excellent yields [ 101 ]. Three years later, Horwitz and coworkers reported on the synthesis of l-aryl-A -tetrazoline-5-ones by reaction of aryl isocyanates with a mixture of sodium azide and aluminum chloride in tetrahydrofiuan at reflux temperature [102]. The in situ produced aluminum azide adds to the N=C-bond of the corresponding isocyanate 122 and yields the 1-substituted A -tetrazoHne-5-one 124. According to this method, different 1-substituted A -tetrazoUne-5-ones 124 were synthesized by reaction of phenyl isocyanate and further 1-p-substituted phenyl isocyanates with aluminum azide. In addition, acyl halides 123, like acetyl chloride and benzoyl chloride, were converted to 1-methyl and 1-phenyl-A -tetrazoline-5-one with aluminum azide under the same conditions (Scheme 28A). It is assumed that in the initial step of the reaction, aluminum azide is able to coordinate to the aryl isocyanate by foiu pathways, forming an aluminum salt 129. The first two possibilities (Scheme 28B 125 and 126) require the separation of an azide ion from the complex, recombination at the electrophihc carbon atom followed... 

Decomposition of aryl azides in the presence of Lewis acids does not involve arylnitrenes arylnitrenium-Lewis acid complexes are much more likely intermediates. The reaction of phenyl azide with aluminum chloride and aromatic substrates gives fair yields of diarylamines. This reaction is not undergone by phenyl azide alone on thermolysis or photolysis in aromatic solvents (Section II.l.A) ... 

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