Synthesis and Chemical Reactivity of Tetrahydro[60]fullerene Epoxides with Both Amino and Aryl Addends

Abstract

Tetrahydro[60]fullerene epoxides C60(O)Ar(n)(NR2)(4-n), n = 1, 2, have been prepared by treating 1,4-adducts C60(OH)Ph and C60(Tol)2 with cyclic secondary amines. The epoxy moieties in these mixed tetrahydro[60]fullerene epoxides were hydrolyzed into the corresponding diol derivatives, which were further oxidized into diketone open-cage fullerenes with a 10-membered orifice. A few other reactions also showed that the present tetrahydro[60]fullerene epoxides with both amino and aryl addends exhibit improved chemical reactivity over the tetraamino[60]fullerene epoxide without any aryl group.

Synthesis of Isomerically Pure Multi‐aniline C60 Adducts with Cyclopentadienyl Addition Pattern

“…As a result of the C 1 symmetry and the difficulty in separating the two isomers, conclusive structures could not be assigned for 2a / 2b by NMR spectroscopic means. To improve selectivity we treated compound 3 , which has two toluenyl addends, with toluidine in the presence of BiCl 3 . The reaction was much slower than the reaction of 1 (14 h versus 36 h).…”

“…To analyze the reactivity between cyclic and acyclic amino groups, we prepared compounds 6 and 7 by treating 1,4‐bistoluenyl adduct 5 with N ‐benzylmethylamine by following our previously reported method (Scheme ) . The higher yield of unsymmetrical product 7 suggests that the para ‐position of the initially added amino addend is more reactive towards further amination than the para ‐position of the toluenyl group.…”