Application Of Condensation Amination Of Alcohols In Synthesis Of ?-branched Primary Amines

The ?-branched primary amines are important organic synthesis intermediates andessential chemical raw materials for production,and widely used in the medicine,pesticides and life sciences field.Alcohol catalytic amination method,which includes condensation amination method and reductive amination method,is to use the alcohols as reaction substrates to synthesize amines.Because of the cheap price of reaction materials and simple synthetic route,alcohol catalytic amination method has become the simplest,most effective and most promising synthesis method for preparation of amines.In this paper,tert-butanol and 2-phenyl-2-propanol were used as substrates to prepare tert-butylamine and 2-phenyl-2-propanamine with condensation amination,and synthetic route of 2-phenyl-2-propanol which is the raw material of the amination reaction was explored.A process flow for tert-butylamine synthesis in the dynamic equilibrium was explored by screening the catalyst and optimizing the reaction process.In this process,tert-butanol reacts with ammonia catalyzed by ZAS-1 zeolite at 275 ?.Isobutylene is taken as a circulating substance in amination reaction.On the one hand addition of isobutylene can reduce the formation of water,which facilitates product separation.On the other hand addition of isobutylene can inhibit elimination reaction,which can improve the reaction selectivity.When the molar ratio of tert-butanol to isobutylene in the raw material is 1:1.7,the yield of tert-butylamine can reach 32.07%,which is the optimum reaction yield.In the separation of liquid products,packed distillation column is used in the laboratory and Aspen plus process simulation software is used in industrial simulation.Process simulation tools such as design specifications and sensitivity analysis were carried out to optimize the process parameters of the water separation column and the tert-butylamine separation column.Tert-butylamine product with molar purity of 99% and molar recovery of 99% can be obtained by simulation.2-phenyl-2-propanamine was prepared by the reaction of 2-phenyl-2-propanol with ammonia gas under the action of acidic catalysts and solvents.At 220 ?,the highest yield is when using water as the solvent and(NH4)2SO4 as the catalyst.Compared with tert-butanol,the yield of amination reaction is higher when 2-phenyl-2-propanol is used as the reaction substrate.The synthetic route of 2-phenyl-2-propanol was explored through the processes such as raw material screening,reducing agent assisting and condition optimization.The reaction is carried out by using cumene as the substrate,metal porphyrin as the catalyst,and oxygen as the oxidizing agent.The reaction takes place at 35-120 ?,and the best yield 29.96% is obtained at 80 ?.DBT which is added as a reducing agent can reduce the degree of destruction of the catalyst in the oxidation process,which can increase reaction conversion by6%-11%.The oxidation product DBTO is autocatalyticly deoxidized to DBT by photocatalysis without any catalyst,achieving the purpose of the recycling process.Calender irradiation can increase the reaction yield of oxidation reaction by 11.59% at room temperature.