Studies On Formylation Of Amines And Carbonylation Of Halogenated Hydrocarbons

Amides are very important chemical raw materials and intermediates that are used in a wide range of applications and are in great demand in many fields such as petrochemicals,pharmaceuticals,pesticides and daily life.Amides are important raw materials for the synthesis of many biologically active molecules,fungicides and drugs.Based on the importance of amides,new methods for their synthesis have been investigated.The research is divided into two main parts:1.Study of the formylation reaction of amines with CO involving organic basesFormylation reactions of amines with CO involving bases have been investigated based on the use of organic bases as additives to promote ester exchange,cyclisation,N-amination and coupling reactions under mild conditions.Formylation reactions of amines were explored using sodium tert-butoxide（t-Bu ONa）as an additive in the presence of CO The reaction conditions were screened,which included the type of base,the ratio of base to reactant,the amount and type of solvent,the pressure of CO,the reaction temperature and the reaction time.We found that the optimum reaction conditions were:using 1.1 equivalents of sodium tert-butoxide（t-Bu ONa）with p-methylaniline as the substrate,at a CO of 2 atm and a temperature of 100 ^oC for 12 h,a reaction yield of 99%could be achieved.Subsequent expansion of the substrate revealed that the system had broad substrate suitability with product yields in the range of 50%-99%.Further gram-scale scale-up of the reaction was carried out and it was found that good yields（75%-93%）were still obtained after stoichiometric scale-up of the reaction,which is promising for application.2.POP-BINAP&PPh₃ catalyzed carbonyl acylation of bromobenzene and n-butylamine.Firstly we synthesized vinyl BINAP ligand,which was further polymerized with tris（4-vinyl）triphenylphosphine to give a porous organic polymer（POP-BINAP&PPh₃）;this was then loaded with metal Pd（OAc）₂ to produce the Pd/POP-BINAP&PPh₃catalyst.This type of catalyst was applied to the study of the carbonylation and amination of bromobenzene with n-butylamine.The catalysts were screened for reaction conditions temperature,additives,solvent and time and were able to give N-butylbenzamide in 99%yield.The catalyst was able to be simply separated and recycled five times.