Reaction of C₆₀ with Dimethyldioxirane—Formation of an Epoxide and a 1,3‐Dioxolane Derivative

Abstract

Not an oxygen‐bridged annulene (structural type 1) but rather an epoxide (structural type 2) is the product of the reaction of dimethyldioxirane with C60. In a competing reaction, a 1,3‐dioxolane (structural type 3) is formed—probably by a diradical mechanism. Cleavage of acetone from 3 leading to 2 was not observed at temperatures up to 110°C. Compound 3 could provide access to ring‐opened fullerenes.

Theoretical study of structure and stability of fullerene derivative: C50O

“…In 1992, Creegan et al [14] synthesized C 60 O by ultraviolet (UV)-induced oxidation of a C 60 in benzene and proposed a closed [6,6] epoxide structure for it. In the same year, Elemes et al [20] reported epoxidation of C 60 with dimethyldioxirane to generate the epoxide C 60 O. Moreover, there appeared to be some experimental evidence [21,22] for the formation of more than one C 60 O isomer, for instance, Hao et al [22] reported an observation of two C 60 O isomers ( [6,6] closed and [5,6] open) in the UV-vis spectra of products from ozonization of C 60 .…”

Ferric perchlorate-mediated radical reactions of [60]fullerene

“…Fe(ClO 4 ) 3 is an excellent reagent to promote free radical reactions of C 60 . In this article, radical reactions of C 60 promoted by Fe(ClO 4 ) 3 have been reviewed in detail.…”

“…Itami's group reported the functionalization of N-tosyl [1,2]aziridino [60]fullerene with p-tolylboronic acid in the presence of trifluoromethanesulfonic acid to afford the corresponding fullerenyl boronic esters [15]. This was the only known examples of fullerene-diol protected boronic ester.…”

“…It is obvious that the mechanisms for the reactions of C 60 with methyl ketones promoted by Fe(ClO 4 ) 3 and Mn(OAc) 3 /Cu(OAc) 2 are completely different. On the basis of the previously reported formation pathway of fullerooxazoles [54] in the reactions of C 60 with various nitriles promoted by Fe(ClO 4 ) 3 , we proposed a possible mechanism for the Fe(ClO 4 ) 3 -mediated reactions of C 60 with aldehydes/ ketones to afford C 60 nation with another molecule of Fe(ClO 4 ) 3 to give Fe(III)-complex 26, followed by intramolecular cyclization accompanied with the loss of a Fe(II) species to afford C 60 -fused 1,3-dioxolanes 22/23. The C 60 -fused 1,3-dioxolane derivatives are valuable precursors and can be utilized for further functionalizations.…”

“…Functionalization [15] of [60]fullerene (C 60 ) with various organic compounds is an important aspect in fullerene chemistry for further material and medicinal applications [69]. Diverse types of reactions of fullerenes have been developed to prepare a large number of fascinating fullerene derivatives [1018].…”