Study On Hydroaminomethylation And Tandem Hydroformylation-Aldol Condensation With Rh/P Catalyst And Molecular Sieve Cocatalysis

At present,with the concept of green development deeply rooted among the people,the economic and environmentally friendly response of the plateau is increasingly attracting attention.The development of a class of zero pollution,low cost,high efficiency catalytic system has become an urgent need.Transition metal catalyzed-carbonylation has high atomic economy,which accords with the current concept of green development.As important chemical raw materials and intermediates,the products of carbonylation reaction cover all aspects of modern daily life.Hydroformylation can afford alcohols,acetals,amines and carboxylic acid derivatives in one step.These compounds are important raw materials in modern medicine,agriculture and polymer fields.Two types of tandem reactions are described in this paper:Hydroaminomethylation and hydroformylation/aldol condensation.In the hydroaminomethylation reaction and hydroformylation/aldol condensation reaction,the target products with high catalytic activities and selectivities were obtained by using the co-catalyst of rhodium/phosphine ligand and molecular sieve.1.In this work,for the first time,Rh（acac）（CO）₂ coordinated with the Sulfo-Xantphos ligand to form the Rh/P catalyst,which was mixed with ZSM-5 molecular sieve to give a Rh/phosphine ligand and molecular sieve co-catalytic system.The system was applied to the hydroaminomethylation of olefins using and amines as substrates with CO/H₂.First,the optimum reaction conditions were explored.Under these conditions,the system was used to catalyze the hydroaminomethylation of various linear olefin(C₅-C₁₀)with morpholine,to obtain saturated fatty amines with high regional selectivity（l/b>24）,and showed excellent catalytic activity.In addition,the catalytic system also showed good activity in the hydroaminomethylation of cyclic olefin.At the same time,the system also showed high regional selectivity（l/b>12）and catalytic activity in the hydroaminomethylation of primary amine,secondary amine with 1-hexene.2.In this work,Rh（acac）（CO）₂ coordinated with the BINAPa ligand to form the Rh/P catalyst,which was mixed with ZSM-5 molecular sieve The catalytic system was applied to hydroformylation-aldol condensation tandem reaction.The hydroformylation/aldol condensation reaction of 1-hexene was achieved through the porous structure and catalytic environment provided by molecular sieve.At 100℃,with toluene as the solvent and H₂/CO ratio of 5:15,a better yield of the target product（74%）was obtained.