Preparation Of A Novel Cu/C Heterogeneous Catalyst:Application In Goldberg And The Oxidation Of Diazoesters Reaction

In this dissertation,a simple method for preparing Cu/C catalyst had been developed by using charcoal as a support.The copper source of the catalyst was screened by using the Goldberg reaction as a template reaction during the preparation of the catalyst.According to the catalytic effect of Goldberg reaction,the Cu/C catalyst prepared by using CuCl2·2H2O as the copper source showed the best reaction effect.The Cu/C heterogeneous catalyst had been characterized by a series of tests,such as ICP,XPS,XRD and TEM.The results showed that the metal copper in the catalyst is zero-valent copper nanoparticles and had good dispersion performance in charcoal.The application of prepared Cu/C heterogeneous catalyst had been expanded in organic synthesis reactions.The second part explores the effect of Cu/C heterogeneous catalyst in the Goldberg(C-N)coupling reaction.First,a systematic summary of the literature review reported on the Goldberg reaction was carried out.It can be found that this type of reaction mostly uses homogeneous catalysts and relies on the use of ligands.The disadvantage of this reaction is that the post-reaction processing is complicated and heavy metal residues caused to the product.On this basis,this subject attempted to use the prepared Cu/C heterogeneous catalyst in the amidation reaction of aryl halide without ligands.By screening of reaction conditions,we realized the arylation of primary amides and lactam under mild conditions,and showed good catalytic effect.Furthermore,the scope of reaction was wide.In the third part,we realized the aerobic and water oxidation of a-diazo esters by using the Cu/C catalyst and discuss its oxidation mechanism.In this subject,it was the first time to report that heterogeneous Cu/C as a catalyst,and oxygen as an oxidant,which can efficiently and highly selectively catalyze oxidize α-diazo ester to α-keto ester under mild conditions.At the same time,the scope of substrate was wide,and the good amplification experiment effect further showed that the catalytic system has certain application value.In further experiments,it was found that water as a reactant can also react with α-diazo esters.The deuteroxide and H218O labeling experiment further proved that water as a reactant reacted with α-diazo ester.The research on the mechanism shows that the oxidation of α-diazo ester by oxygen was free radical mechanisms.