[2 + 3]-Cycloadditions to C60 fullerene. Synthesis of pyrrolidinofullerenes

Abstract

Pyrrolidinofullerenes were synthesized by reaction of C 60 fullerene with N-methylglycine and substituted aromatic aldehydes.A promising line in the chemistry of carbon clusters includes functionalization of fullerenes in various ways. Functionalization of C 60 fullerene is often achieved via cycloaddition reactions [1], in particular, [2 + 3] cycloaddition [235]. Especially interesting is the synthesis by [2 + 3]-cycloaddition reactions of new functional C 60 fullerene derivatives which contain pharmacophoric groups and exhibit high biological activity [1,6]. The use of fullerenes in pharmacology seems to be most reasonable from the economic view-ÄÄÄÄÄÄÄÄÄÄÄÄ point, for only a small amount of the substance is required.The present communication reports on the synthesis and chemical properties of new pyrrolidinofullerenes. We found that C 60 fullerene reacts with N-methylglycine and aromatic aldehydes in boiling toluene under argon to give pyrrolidinofullerenes I3IV (Scheme 1). The products were isolated by column chromatography on silica gel. Scheme 1. I, R 1 = H, R 2 = CH 3 O; II, R 1 = R 2 = CH 3 O; III, R 1 = H, R 2 = NO 2 ; IV, R 1 = H, R 2 = N(CH 3 ) 2 . ÄÄÄÄÄÄÄÄÄÄÄÄPresumably, the first stage of the process is condensation of aromatic aldehyde with N-methylglycine. The primary adduct successively undergoes dehydration and decarboxylation to give ylide A. Nucleophilic ÄÄÄÄÄÄÄÄÄÄÄÄ attack by the latter on fullerene at the (636) bond, followed by intramolecular ring closure, leads to a fused pyrrolidinofullerene system (Scheme 2). 76?? B R 2 CH3N3CH 2 COO ! + C CH 3 C OH C H R 1 M M ---------M M ---------

Thioacetate-Functionalized Fullerene: Redox Properties and Self-Assembly on the Au(111) Surface

“…Almost identical positions in the spectra of both pairs of bands are complying with the fact that the normal vibrations of the pristine fullerene are practically the same as for [C 60 ]fullerene-pyrrolidine adducts 31 but, as expected, the absorption intensity changed. 32 Furthermore, following absorption modes ascertain the structure of the fullerenethioacetate 3 substituent attached to C 60 molecule: 2800-3000 cm −1 (CC-H, pyrrolidine); 31 2775 cm −1 (NC-H, pyrrolidine) 33 1690 cm −1 (thioacetyl C = O group stretch); 34,35 1060-1150 cm −1 (C-H in plane bending of the 1,4-disubstituted benzene ring); 820 cm −1 (CH-out-of-plane C-H bending). The contribution of pyrrolidine CH 2 groups is visible at 1462 cm −1 , overlapping probably with the benzene C=C stretching motion.…”