Arylation of [60]fullerene via electrophilic aromaticsubstitution involving the electrophile C60Cl6:frontside nucleophilic substitution of fullerenes

摘要: Reaction of C60Cl6 and ferric chloride with aromatic compounds gives the corresponding Cs-symmetric aryl derivatives C60Ar5Cl, where Ar = phenyl, tolyl, anisyl, tert-butylphenyl, fluorophenyl, trimethylsilylphenyl and thienyl. The derivatives arising from exclusive para substitution in anisole fluorobenzene, together with C60(4-FC6H4)5H have been isolated fully characterised. Toluene undergoes substitution the ortho as well para position. Traces octaaryl derivatives are obtained reaction with toluene anisole. The steric bulk chlorofullerene (the largest electrophile known) accounts for failure to achieve mesitylene the abnormal deprotonation rather than desilylation with trimethylsilylbenzene. Protiodesilylation trimethylsilylphenyl derivative was achieved by acid. With triphenylphosphine, C60Ar5Cl react give C60Ar5H toluene/FeCl3, C60Ph5Cl C60Ph5tolyl. C60(4-FC6H4)5H showed a marked tendency acquire oxygen, suggesting that this oxygenation is facilitated electron withdrawal. FAB mass spectrometry of C60(4-FC6H4)5H, C60Ph5Cl, C60Ph5H also of C70Ph10 shows addition up 9C2 fragments each case; parallels two previous reports of C2 during spectrometry. replacement of chlorine groups at same site indicates frontside nucleophilic on cage must occur, involving a cationic fullerene intermediate.