Efficient Acetalization of Epoxy Rings on a Fullerene Cage

Abstract

Fullerene epoxides react with benzaldehyde derivatives in the presence of a pyridinium hexafluoroantimonate to give corresponding 1,3-dioxolane derivatives of [60]fullerene in excellent yields. The activation energy for the reaction of fullerene monoepoxide with benzaldehyde was determined to be 112.7 kJ mol−1. This result shows that fullerene epoxides undergo the stepwise SN1-like acetalization reaction.

Chemistry of Fullerene Epoxides: Synthesis, Structure, and Nucleophilic Substitution-Addition Reactivity

“…Under reaction conditions similar to those for mono-epoxide 1a , the fullerene di-epoxides 1b and 1c were also subjected to acetalization with benzaldehyde derivatives to give bis-1,3-dioxolanes 5a and 5b , respectivelyinhigh yields ( Table 3 ) [ 9 , 21 ]. The visible absorption spectra of 5a and 5b show the bands characteristic to those of the di-epoxides 1b and 1c , respectively, that is, 5a showed a sharp band at 423 nm, which is the characteristic band for the cis -isomer 1b [ 11 , 15 ]. This fact suggests that during the acetalization reaction, no migration of the carbocation on the fullerene moiety occurs and that the acetalization reaction of the fullerene di-epoxide proceeds while the rearrangement of the two epoxy rings on the fullerene cage is conserved.…”

“…However, the chemical transformations of fullerene epoxides have been studied sparingly, despite the general recognition that they could serve as convenient starting materials for the synthesis of functionalized fullerene derivatives [ 10 ]. We first succeeded in converting fullerene epoxide stoichiometrically into a 1,3-dioxolane derivative [ 11 ]. Reaction of C 60 O with benzaldehyde in the presence of a Lewis acid led to the formation of a 1,3-dioxolane derivative of C 60 in high yield.…”

Boron-Doped C24 Fullerenes for Alkyl Functionalization or Potential Polymerization

“…The inherent stability of fullerenes makes them difficult to functionalize. Although there exists rich fullerene chemistry, most functionalization of these compounds comes from adding a cyclic group such as diepoxide or pyrrolidine over a CC moiety within the structure. − This disrupts the overall π cloud, resulting in a destabilization of the system. While such functionalization can have varied applications, even in the creation of veritable molecular submarines for delivering atomic cargoes for medical applications, other means of allowing buckyballs to bond to other species could have wide-ranging applications, opening up these molecules to more of their potential uses across the chemical spectrum.…”

Highly efficient synthesis of [60]fullerene oxides by plasma jet

“…In addition, the formation of C 60 O and C 60 O n (n ≥ 2) was identified by mass spectroscopy or high-performance liquid chromatography (HPLC), yet no isolated yields were reported in the oxidation of electrochemically generated anionic C 60 [15] and ozonolysis of C 60 [16][17][18]. Interestingly, C 60 O has been employed as the precursor for further functionalizations, leading to the formation of C 120 O [19], 1,3-dioxolane derivatives of C 60 [20], indoline derivatives of C 60 [21], and 1,2-perfluorophenylfullerenol [22]. Similarly, the cis-1 isomer of C 60 O 2 has been used as the precursor for bis-1,3-dioxolane derivatives of C 60 [20].…”

“…Interestingly, C 60 O has been employed as the precursor for further functionalizations, leading to the formation of C 120 O [19], 1,3-dioxolane derivatives of C 60 [20], indoline derivatives of C 60 [21], and 1,2-perfluorophenylfullerenol [22]. Similarly, the cis-1 isomer of C 60 O 2 has been used as the precursor for bis-1,3-dioxolane derivatives of C 60 [20]. Despite these achievements, new approach to obtain C 60 O and C 60 O 2 in higher yields is still highly demanding.…”