[60]fullerene-pyrrolidine-N-oxides.
Eight members of a new family of fullerene derivatives, [60]fulleropyrrolidine-N-oxides, have been synthesized and characterized. Facile oxidation, by a peracid, of the parent [60]fulleropyrrolidine gave clean conversions into the product molecules, in which the tertiary amine is transformed into a quaternary amine bearing an oxygen atom. The reaction is very selective, favoring the nitrogen atom of the pyrrolidine ring in preference to epoxidation of the fullerene cage. The 1H NMR shows an AB quartet splitting pattern, characteristic of nonequivalent hydrogens in the pyrrolidine ring and at a chemical shift displacement of 0.8 ppm downfield. Other methods of characterization are described, including MS, differential scanning calorimetry, thermogravimetric analysis, HPLC, UV/vis, and IR. Conclusive evidence for the formation of an N-oxide moiety is provided by the synthesis, oxidation, and NMR characterization of a novel [60]fulleropyrrolidine containing a 15N isotope, showing an 85 ppm downfield heteroatom chemical shift. Preliminary details of the effects of substitution on the reactivity of the pyrrolidine ring are also reported.
Dipartimento di Scienze Farmaceutiche, Università degli Studi di Trieste, 34127 Trieste, Italy.
Peter
P
Brough
Cedric
C
Klumpp
Alberto
A
Bianco
Stephane
S
Campidelli
Maurizio
M
Prato
D002851:Chromatography, High Pressure Liquid; D037741:Fullerenes / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry; D010084:Oxidation-Reduction; D010087:Oxides / Q000138:chemical synthesis / Q000737:chemistry*; D011759:Pyrrolidines / Q000737:chemistry*; D013057:Spectrum Analysis
D037741:Fullerenes; D010087:Oxides; D011759:Pyrrolidines; C032519:pyrrolidine; D009584:Nitrogen; C069837:fullerene C60