Synthesis Of 3-Aminopyrrodine

3-Aminopyrrodine is an important intermediate for organic chemical industry. A large number of drugs, herbicides, pesticides, medicines, and other chemicals are originated from reactions with such intermediates.On the basis of consulting a large amount of literatures and comparing the different routes synthesizing 3-aminopyrrodine, we studied two methodologies in the works, the first with ethyl acrylate as raw material and the second with 2-butylene-l,4-dialcohol. As for the first craft, the better reaction conditions were studied and optimized, which offered the fundamental data to make the synthesis process industrialization. At the same time, the works studied the feasibility of preparing 3-aminopyrrodine with 2-butylene-l,4-dialcohol as the raw material, which offered a simple way to prepare 3-aminopyrrodine. The new synthesis route was the shortest route to synthesis 3-aminopyrroiidine at present, and has a broad foreground. Moreover, the synthesis route has applied the patent.The first craft: the raw material ethyl acrylate react an additive reaction with benzylamine, a substitution reaction with ethyl chloroacetate, Dieckmann cyclization and hydrolytic decarboxylzation to generate N-benzyl-pyrrolidine-3-dione. Then N-benzyl- pyrrolidine-3-dione react with hydroxylamine hydrochloride and the produce was deoxidize by sodium borohydride, hydrogenolytic cleavage with the presence of pd-c catalyst. In this paper, the reaction conditions were studied and optimized, which offered a satisfactory result for the synthesis process. The contribution the works doing to the route of synthesis 3-aminopyrrolidine with ethyl acrylate as raw material were as follows.Ethyl acrylate react with excess benzylamine, which avoid side reaction effectively. Introduced a high efficiency catalyst, which is the sodium in the form of granule.Adding a little acetic acid to the dissolvent using in the hydrogenolytic cleavage reaction, will improved the fractional conversion greatly.The second craft: the reagent 2-butylene-l,4-dialcohol was chloridized at the presence of pyridine to generate 2-butylene-l,4-dichloride ,which was added by hydrogen chloride with zinc chloride as catalyst and was further aminolysised by liquid ammonia with pd-c as catalyst to prepare 3-aminopyrrolidine in the yield of 54% and the pure is 98%. Although the technological parameter was not completely optimized, which lead to the relatively slashing reaction conditions. As a new craft, the route was subject to consummation for the low reaction selectivity and the dissatisfactory yield. But the course of reaction is short and fast, it was a potential route to prepare 3-aminopyrrolidine.We think the new craft with 2-butylene-l,4-dialcohol as raw material is superior through comparing the difference between the two craft in the costing, the reaction conditions and so on.