Chemistry of hindered amines: synthesis and properties of di-t-butylamine and related compounds

Abstract

Di-t-butylamine was prepared from 2-methyl-2-nitropropane by an improved method in 54% yield, and was in turn converted into N-nitroso- and N-chloro-di-t-butylamine in yields of 89 and 90%, respectively. Di-t-butylamine is a non-nucleophilic base which is inert to benzoyl chloride. It reacts with acetyl chloride and with O-mesitylsulphonylhydroxylamine to form di-t-butylammonium chloride and mesitylenesulphonate rather than NN-di-t-butylacetamide and 1,1-di-t-butylhydrazine respectively. The N-chloro-amine was reduced to di-t-butylamine with sodium. The N-nitroso-amine reacted with methyl fluorosulphate to generate an unstable O-alkyl intermediate. The properties of tri-t-butylhydroxylamine, a by-product in the preparation of di-t-butylamine, are also described. Possible routes to tri-t-butylamine are discussed.