Aza-aziridinofullerene: Interconversion between Aza-aziridinofullerene and Bisazafulleroid

Abstract

The synthesis and spectroscopic characterization of a novel bisazafulleroid (12) and aza-aziridinofulleroid (13) are described. Treatment of C 60 fullerene with the C 2 -chiral bisazide 11 in refluxing chlorobenzene afforded bisazafulleroid 12 in 20 % yield. When a solution of 12 was exposed to ambient light a quantitative conversion to the more polar 13, in which the two imino groups add at both [5,6] and [6,6]-ring junctions, was observed. The two compounds exhibited characteristic absorption profiles in the electronic spectra and also showed distinct CD curves. Further, thermolysis of 13 in refluxing toluene resulted in a clean conversion to 12 within 10 min.15 N-labeled 12 and 13 were synthesized to establish the structures. These observations provide the first example of an interconversion between an azaand an aziridinofulleroid.

[2+1] Cycloaddition of Nitrene onto C60 Revisited: Interconversion between an Aziridinofullerene and an Azafulleroid

“…In the course of our study on the development of synthetic methodology for the preparation of [1,2]aziridinofullerene,2 we carried out the photoreaction of C 60 with an N ‐ p ‐toluenesulfonylsulfilimine7 having a dibenzothiophene structure ( 3 ; Scheme ) to accomplish the regioselective synthesis of N ‐tosyl[1,2]aziridinofullerene ([6,6]‐closed C 60 NTs, 4 ). It is well known that 1,6‐azafulleroids 1 readily cyclize thermally and photochemically to afford [1,2]aziridinofullerenes 2 , while the reverse reaction hardly occurs 8. This finding may indicate that 2 is more thermally stable than 1 .…”

Isolation and Characterization of All Eight Bisadducts of Fulleropyrrolidine Derivatives

“…By controlling the length and geometry of the tether, either equatorial , or cis-2 , or even trans-2 and trans-1 , structures could be almost exclusively obtained. Other attempts to tether-control bisadditions have given alternate fortunes. − …”

Synthesis and electrochemical properties of individual isomers of isocyanurate-substituted bis-organodiazadihomofullerenes

“…10, [16][17][18][19] In these studies, the data on these structures were compared with related or ganic compounds, and it was concluded that only struc ture III contains no carbon atoms, whose signals would appear in the 13 C NMR spectra outside the region δ 133-146. Based on this conclusion, we have assigned 11 the structure of regioisomer III to compound 2.…”