The Study Of Carbonylation Reactions Based On Alternative CO Sources

Green chemistry is committed to developing environmentally friendly and effective synthetic methods.Catalysis and organometallic chemistry are the key technologies which are helpful to develop green chemistry.In different catalytic reactions,it is particularly important to refine available raw materials into more functional products.The main example of such conversion is the carbonylation reaction,which mostly uses CO(currently the most important Cl structural unit).CO is a gas that we often use in scientific research.This gas is cheap and has high atomic utilization,especially in industrial applications.However,CO gas itself has great shortcomings:(1)It is colorless,odorless,but highly toxic,so the leakage is not easy to find;(2)Industrial applications generally require the use of high-voltage equipment,which poses a greater safety risk.To this end,people have developed many alternative carbonyl sources,such as:Mo(CO)6,formamide and so on.Our research group has been mainly engaged in the research,development and application of alternative carbonyl sources in recent years.TFBen is an ideal carbonyl source and a green solid carbonyl source.It has many advantages such as simple preparation,convenient storage and stable properties.This thesis is mainly about using TFBen as the carbonyl source to synthesize heterocyclic compounds through selenium catalysis,and using transition-metal rhodium to accomplish the synthesis of important esters and amides.The work described is as follows:(1)The one-pot method was used for the first time to synthesize benzimidazolones using a new solid carbonyl source 1,3,5-trisphenol(TFben).This type of reaction is based on the raw material 2-nitroaniline,non-metallic selenium is used as the catalyst,and triethylamine is used as a base.The reaction is simple,the reaction conditions are mild,and the separation is simple.It is one of the simple methods for synthesizing benzimidazolone compounds.(2)For the first time,quinazolinone heterocyclic compounds were synthesized using a novel solid carbonyl source 1,3,5-phenol trimesate(TFben).The reaction uses simple and easily prepared amino compound as a substrate,with selenium as a catalyst,DIPEA as a base,has a very wide range of functional group compatibility and substrate applicability,can get a good to excellent yield of quinazolinone structure product.(3)For the first time,we synthesized furfuryl esters and tertiary amide compounds by using biomass-derived intermediate HMF/furfural as a CO alternative carbonyl source.A green and cheap CO alternative has been developed.Here we use the transition metal rhodium as the catalyst.Through the free radical mechanism,we have achieved the integration of the removal of carbonyl groups and the insertion of carbonyl groups,which is equivalent to the migration of CO.And using halogenated materials as raw materials,so the reaction has a wide range substrate and excellent compatibility.