The Application Of C₆₀ Dianion On The Reductive Coupling Of α, β-unsaturated Ketone

Fulleride is a kind of important fullerene compounds,which can be used as organic reaction intermediates and reducing agents and have potential applications in superconductors,optical,electrical and magnetic aspects.This paper is to study C₆₀^2-on the reduction of chalcone,explore the reduction selectivity and the influences on the reductive coupling of Chalcone.1.A series of diphenyl pentadione derivatives(4-phenyl-2,6-diphenyl pentandione etc.)and cyclohexanol derivatives(1,3,5-triphenyl-2, 4-benzoyl-cyclohexanol etc.)were synthesized by reaction of Al-Ni alloy with chalcone(1,3-phenyl-2-propen ketone etc.)at room temperature in alkaline media,which were characterized by ¹H-NMR,¹³C-NMR,EI-MS and IR spectroscopy.And two diphenyl pentanedione derivatives and three cyclohexanol derivatives' single crystals were obtained.When CH₃, OCH₃ and N(Me)₂ were attached to phenyl inα,β-unsaturated ketone,the reaction taken place smoothly,the reaction didn't conduct properly while NO₂ as the substituent.The mechanism of the reaction was suggested.2.Cyclopentene derivatives(2,3,5-triphenyl-1-benzeneacyl-1-cyclopentene etc.)and diphenyl pentanedione derivatives and cyclohexanol derivatives were synthesized by reacting C₆₀^2-with Chalcone(1,3-diphenyl-2-propen ketene,etc),which were characterized by ¹H-NMR,¹³C-NMR and IR spectroscopy.And the crystal structure of 2,3,5-triphenyl-1-benzeneacyl-1-cyclopentene was obtained. Cyclopentene derivatives were synthesized when the substituent was H, CH₃ rather than OCH₃,N(Me)₂ and NO₂.The results indicated that C₆₀^2- could induce the reductive coupling of Chalcone,that the selectivity in the reductive coupling may be caused by the structure and electron density of C₆₀^2-.The mechanism of the reaction was suggested. 3.In order to explore the mechanism of the reductive coupling of Chalcone,the reaction was carried out with different conditions such as refluxing in caustic solution,using Raney-Ni,using Al in caustic solution, using Al-Ni in caustic solution etc.,which indicated the hydrogen formed in situ and the temperature were important to the four substituted cyclohexanol formation.