Synthesis of Imino[60]fullerenes Using Nitriles and Trimethylsilylmethyl Triflate

Abstract

The synthesis of a new class of fullerene derivatives, 1-imino-4-silylmethyl[60]fullerene derivatives, is described. The anion (C(60)R(1-)) of an alkyl- or aryl-adduct of [60]fullerene, C(60)R(1)H (R(1) = CH(2)SiMe(3), CH(2)SiMe(2)Ph, C(6)H(4)-OMe-4, C(6)H(4)-NMe(2)-4, C(6)H(4)-CF(3)-4 and C(6)H(4)-OMe-2), was allowed to react with a nitrilium salt [R(2)CNCH(2)SiMe(3)][OTf] (Tf = SO(2)CF(3)) that was generated in situ by the reaction of Me(3)SiCH(2)OTf and a nitrile solvent R(1)CN (R(2) = Ph and Me). The desired imino[60]fullerene derivative C(60)(R(1)) [C(=NCH(2)SiMe(3))R(2)] was produced in a yield up to 80%. The structure of the product with R(1) = C(6)H(4)-OMe-4 and R(2) = Ph was determined by single-crystal X-ray analysis.

Fullerenes

“…95 An efficient method to introduce an imine group to a monoadduct of C 60 fullerene to produce a 1-imino-4-organo-C 60 fullerene has been achieved using nitriles and trimethylsilylmethyl triflate. 96 2.1.7 Fullerene derivatives containing oxygen. 1,4-fullerenols C 60 ArOH were synthesised via the reaction of C 60 with 4-substituted phenylhydrazine hydrochlorides and sodium nitrite under mild conditions.…”

One-Pot Synthesis of 1,3,5-Triazine Derivatives via Controlled Cross-Cyclotrimerization of Nitriles: A Mechanism Approach

“…Nitriles have been shown to react with methyl triflate to initially form nitrilium salts, which are then converted into synthetically useful molecules by reaction with a variety of nucleophiles . This led us to postulate that the first step of the mechanism pathway involves the initial formation of triflate nitrilium salt 4 from nitrile R 1 CN ( 1 ) and Tf 2 O (Scheme ).…”

Oxazoline and Imidazoline Functionalization of a C60 Dimer via the Reaction of C60HBn and Aromatic Nitriles with a Bifunctional Hydroxide

“…The reactions are also applicable to fullerene derivatives such as 1,4-R 2 C 60 , where the C 60 cage is oxazolinated with a distinctive regioselectivity with respect to the existing addends . It would be of interest to extend the work to the acidic organo(hydro)[60]fullerenes (C 60 HR), since C 60 HR would not only be deprotonated by strong bases − to form the singly bonded C 60 dimers via subsequent oxidation, but should also be capable of undergoing the OH – -initiated heterocyclic additions engaging aromatic nitriles, − which may constitute a novel approach for the derivatization of fullerene dimers.…”