Chemical Reactivity of Adamantane and Related Compounds

The chemical reactivity of hydrogens in adamantane and substituted adamantanes has been calculated. The results of calculation have shown that the bridgehead hydrogens are most reactive toward electrophilic reagents or radicals. The chemical reactivity of hydrogens in diamantane, triamantane, and tetramantane has also been predicted. A discussion has been made of the stable configuration of the 1-adamantyl cation, radical, and anion and of the nature of the back-side conjugation between the two tertiary carbons in these species. A mode of the electrocyclic polymerization of p-quinodimethane to form polyamantane has been predicted on the basis of the symmetry properties of the frontier orbitals in the pi and sigma parts of p-quinodimethane.