Synthesis and Reactivity of Amines Containing Several Cage-like Fragments

By reaction of bicyclo[2.2.1]hept-5-en-exo- and endo-2-ylmethylamine, exo-5,6-epoxybicyclo[2.2.1]hept-exo-2-ylmethylamine and benzylamine with 1-adamantanecarbonyl chloride, 1,3-adamantanedicarbonyl dichloride, and 1,3-adamantanediacetyl dichloride amides were obtained with one, two, and three cage-like fragments that were reduced to amines by lithium aluminum hydride. The reactivity of the amines was evaluated with the use of semiempirical quantum-chemical method PM3. Derivatives of the amines were prepared by reactions with arene-sulfonyl chlorides, p-nitrobenzoyl chloride, succinic and endic anhydrides, p-toluenesulfonyl and m-tolyl isocyanates, phenyl isothiocyanate, and p-nitrophenyloxirane. The structure of the new compounds was supported by analysis of their IR and 1H NMR spectra. The dependence of some reaction conditions was observed on the number and remoteness of the cage-like fragments from the reaction centers of the amines.