Condensation Of Aromatic Alcohols With Methyl Ketones To Synthesize Chalcone Derivatives Catalyzed By Cu(Ⅰ)

The synthesis of chalcone derivatives has always been a hotspot in organic reactions research.Its unique enol structure can be combined with various receptors,which provides possibilities for the occurrence of many chemical reactions.Compared with the traditional method of synthesizing chalcone derivatives,this paper uses the two alcohol and ketone raw materials for condensation reaction directly.And it also uses one-pot cooking synthesis method to reduce the reaction steps and the reaction cost,which provides a more green and economical resolve resolution for synthesizing chalcone derivatives.The specific study as follows:First,the reaction conditions for the synthesis of chalcone from benzyl alcohol and acetophenone are optimized.In the substrate benzyl alcohol 1.2 mmol,acetophenone 1 mmol,CuI（5 mol%）,bipy（5 mol%）,TEMPO（10 mol%）,NaOH（110 mol%）),H₂O（2ml）,T=35°C,t=48h,chalcone synthesis yield up to 88%.Second,a series of chalcone substrates are developmented under the optimal conditions.Aromatic alcohol derivatives and methyl ketone derivatives as raw materials,The synthesis of chalcone substrates under（bipy）Cu-TEMPO catalyzed system.The conclusion is that the catalytic system is suitable for the reaction of mono-substituted,double-substituted and some special substituted raw materials such as halogen,methyl and methoxy for the corresponding chalcone compounds,the yield can reach 30%to 88%.Third,the theoretical calculation study is conducted on the synthesis of chalcone from benzyl alcohol and acetophenone.After consulting the literature,the intermediate process of the alcohol ketone condensation reaction is explored,and the feasible reaction path is inferred.In this article,the two transition states TS1 and TS2 during the oxidation of alcohols are described.Comparing the energy data,that is△E2<△E1,the alcohol oxidation process is more likely to TS2 process.The transition state during the aldehyde condensation reaction is studied,and the structural configuration of TS3 is calculated and the transition energy value△G=8.1 Kcal/mol is obtained.The theoretical study of the condensation reaction of alcohol ketone is described from the aspect of Gaussian calculation.