Study On Synthetic Process Of 1,3-Propyldiamine And Its Derivatives

1,3-propanediamine is an important fine organic chemical intermediate, which can be widely used in medicine, pesticides, dyes, petrochemical, semiconductor manufacturing, macromolecule and so on. But the study on synthetic process of 1,3-propanediamine is few in the world. Especially there aren't any related synthetic reportes in china. Thus, the study and optimization on synthetic process of 1,3-propanediamine can fill the internal gap, break blockade of foreign technology and patent protection. So it has important practical value and theoretical significance.Based on the careful analysis and summarization of the related literatures, synthetic process of 1,3-propanediamine and its derivatives are studied. The following are main work and conclusion in the dissertation.1,1,3-Propanediamine and N-(3-aminopropyl)-1,3-propanediamine were prepared from liquid ammonia and acrylonitrile by two-step reactions of addition and catalytic hydro-genation continuously, and the different process conditions were studied and optimized.(1) Preparation of 1,3-propanediamine:tested seven catalysts used on the addition of liquid ammonia and acrylonitrile in the fixed-bed reactor, and eventually selected the DUT-0 as catalyst to prepare 3-aminopropionitrile at the condition of 110℃,9.0MPa, liquid ammonia and acrylonitrile molar ratio of 20:1 and LHSV of 0.8h-1.The conversion of acrylonitrile reached 100% and the content of 3-aminopropionitrile was 87.9%. The hydrogenation of 3-aminopropionitrile fixed-bed reaction mixture without purification catalyzed by Raney-Ni was carried out directly in the autoclave at the optimal condition of 70℃, hydrogen pressure of 2.5MPa,10-15%(by weight) Rainey-Ni,1%(by weight) sodium hydroxide. The content of 1,3-propanediamine in the final solution was about 82% and the two-step reaction total yield of distillation was 74-78%.(2) Preparation of N-(3-aminopropyl)-1,3-propanediamine:tested five catalysts used on the addition of liquid ammonia and acrylonitrile in the fixed-bed reactor, and eventually selected the 3A molecular sieve as catalyst to prepare N-(2-cyanoethyl)-3-aminopropionitrile at the condition of 50℃,5.0 MPa, liquid ammonia and acrylonitrile molar ratio of 1.5:1 and LHSV of 0.5h-1. The conversion of acrylonitrile reached 99% and the content of N-(2-cyanoethyl)-3-aminopropionitrile was 86.8%. The hydrogenation of N-(2-cyanoethyl)-3-aminopropionitrile fixed-bed reaction mixture without purification catalyzed by Raney-Ni was carried out directly in the autoclave at the optimal condition of THF solvent,70℃, hydrogen pressure of 2.5MPa,20-25%(by weight) Rainey-Ni,1%(by weight) sodium hydroxide. The content of N-(3-aminopropyl)-1,3-propanediamine in the final solution was about 81% and the two-step reaction total yield of distillation was 73-78%.2,N-(2-hydroxyethyl)-1,3-propanediamine as broad-spectrum cytoprotective agent amifostine intermediate was prepared from ethanolamine and acrylonitrile by two-step reactions of Michael addition and catalytic hydrogenation continuously. We chose the total mole ratio of ethanolamine and acrylonitrile 1:1, the reaction solution was stirred at 50℃, the conversion of acrylonitrile was more than 99% and the content of N-(2-hydroxy-ethyl)-3-aminopropionitrile was more than 98%. The hydrogenation of N-(2-hydroxy-ethyl)-3-aminopropionitrile reaction mixture without purification catalyzed by Raney-Ni was carried out directly in the autoclave at the optimal condition of ethanol solvent, liquid ammonia as co-catalyst,70℃, hydrogen pressure of 2.5MPa,10-15%(by weight) Rainey-Ni. The content of N-(2-hydroxyethyl)-1,3-propanediamine in the final solution was more than 97% and the two-step reaction total yield of distillation was 89-92%. Utilizing this process route to prepare N-(2-hydroxyethyl)-1,3-propanediamine has not been reported.