The Reaction of Fullerene C₆₀ with 4,6-Dimethyl-1,2,3-triazine:  Formation of an Open-Cage Fullerene Derivative

Abstract

A thermal reaction of fullerene C(60) with 4,6-dimethyl-1,2,3-triazine (4) in o-dichlorobenzene gave azacyclohexadiene-fused fullerene derivative 5, by the reaction with intermediate azete 11, and then, after flash chromatography over SiO(2), open-cage fullerene derivative 6 having an eight-membered ring orifice on the C(60) cage. Compound 6 is assumed to be formed via addition of diradical intermediate 13 to C(60). Compound 6 underwent a further photochemical reaction with singlet oxygen with the cleavage of one of the double bonds at the rim of the orifice to afford triketone derivative 8 having a 12-membered ring orifice.

Six‐Membered Heterocycles: Triazines, Tetrazines and Other Polyaza Systems

“…However, the reaction took place to give an azacyclohexadiene fused derivative such as 99 by extrusion of N 2 [134,135] Much detailed data on the structure of 1,2,4-triazine have been published. Two Kekul e structures can be drawn for this molecule (2a and 2b,Scheme 20.33).…”

Fullerene Reactivity – Fullerene Cations and Open‐Cage Fullerenes

“…9.2) [69][70][71][72][73][74]. These are nickel-promoted ene-diyne cycloaddition on C 60 [70], [4þ2] cycloaddition of palladacyclopentadiene with C 60 [71], and thermal reaction of C 60 with phthalazine [72] and a 1,2,3-triazine derivative [73].…”

“…9.2) [69][70][71][72][73][74]. These are nickel-promoted ene-diyne cycloaddition on C 60 [70], [4þ2] cycloaddition of palladacyclopentadiene with C 60 [71], and thermal reaction of C 60 with phthalazine [72] and a 1,2,3-triazine derivative [73]. The reaction of C 60 with a 1,2,4-triazine derivative gave a nitrogen-containing derivative 49, whose structure was clearly determined by X-ray crystallography showing that the eight-membered-ring orifice has a tub-form with the C1-C2-C3-C4 and C3-C4-C5-C6 dihedral angles being À39.0(4) and 38.8(4) o , respectively ( Fig.…”

“…9.4) [76]. Triketone 53 [73] and diketones 54 and 55 [74] were obtained in the same way. In these reactions, singlet oxygen generated by irradiation of visible light adds to one of the CbC bonds on the rim of the eight-membered-ring orifice, which is distorted and has the relatively large values for HOMO coefficients, to give dioxetane intermediate such as 50. This reaction is in contrast to the photooxygenation of pristine C 60 , which affords fullerene epoxide C 60 O [77].…”

The potential energy curve and Langmuir isotherm of hydrogen adsorption by a truncated carbon sphere

“…Carbon nanotubes are sonicated with acid to make the openings [22]. The opening on a C 60 molecule can be made by a chemical process [23], and the encapsulation of a hydrogen molecule by the opening has been clearly demonstrated [24]. Therefore, in this paper, we investigate the hydrogen adsorption by a truncated carbon sphere under finite temperatures and pressures based on the Langmuir isotherm derived from the adsorption potential curve.…”