Alkyl halides Compounds with halogen ammonia

The reaction of ammonia with primary alkyl halides generally forms a mixture of primary, secondary, and tertiary amines and even a certain amount of the quaternary ammonium halide. Still, the method may be profitable for obtaining primary amines if the halogen compound is above C, and excess ammonia is employed, for then polyalkylation is less likely and the products, having widely different boiling points, are more readily separated. Thus w-butyl bromide and a large excess of ammonia in alcohol solution at room temperature give a 47% yield of w-butylamine. ... 

Synthesis.—We have shown that the alkyl halides are mono-substitution products of the hydrocarbons, i.e., one hydrogen of the hydrocarbon has been substituted by a halogen, e.g., methyl iodide, CH3—I. Now when methyl iodide is treated with ammonia a new compound is formed having the composition CHsN and the other product of the reaction is hydrogen iodide. 

Addition of primary aUcylmagnesium halides and alkyllithium compounds to nitroarenes leading to o -adducts is an irreversible process, and because of that, the Sj,jAr of halogens with these nucleophiles does not proceed. The o -adducts of these nucleophiles can be subsequently oxidized with a variety of oxidants [23]. The most convenient and efficient oxidant of these a"-adducts is a solution of KMnO in liquid ammonia added after formation of the adducts [24]. The reaction is a valuable method of nucleophilic alkylation of nitroarenes (Scheme 11.12). 

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