Carbon Ring Openging Reactions Of Aziridines And Simple Synthesis Of Spiro[4,4]Nonane-1,6-dione

The thesis contains two chapters. The first chapter studies the ring opening reactions of aziridines with carbon nucleophiles. The second chapter is about the simple synthesis of spiro[4,4]nonane-1,6-dione.The first subsection of the chapter1summarized the reactions of aziridines with various nucleophiles. In the second subsection of this chapter, we have synthesized various aziridines. In the third subsection of this chapter, we firstly studied the ring opening reactions of N-tosylcyclohexeneimine aziridine with various carbon nucleophiles, and found the reaction of N-tosylcyclohexeneimine aziridine with dimethyl malonate to produce derivatives of2-pyrrolidone in the presence of base. Then the reaction conditions were optimized. The reactions should be protected by argon, and the best base was NaH. The preferential molar ratio of N-tosylcyclohexeneimine aziridine/dimethyl malonate/NaH was1:2:3.36. When THF was used as a solvent in the reaction of N-tosylcyclohexeneimine aziridine, an derivative of2-pyrrolidone was obtained in the yield of75%under reflux; if DMF was used as a solvent instead of THF, the ring opening product was obtained in the yield of79%.Based the above investigation, we studied the reactions of various aziridines with dimethyl malonate in THF or DMF, and found the yields of30%-82%were obtained in4-4h. Then we compared the structure of the azidines each other and found it was easy for aziridines with smaller obstacles to form derivative of2-pyrrolidones, and it was difficult for the aziridines with huger obstacles.In the second chapter, the first subsection summarized the synthesis of the diones, and their applications in synthesis. In the second subsection of this chapter, firstly we synthesized the dione according to the procedure in the literature. Spiro[4,4]nonane-1,6-dione was synthesized using2-oxocyclopentanecarboxylate as the starting material by a series of the displacement reaction, hydrolysis and cyclization. In this reaction, we found the reaction of2-oxocyclopentanecarboxylate with ethyl4-bromobutanoate needing the expensive KH, and harsh reaction conditions, and the time of this reaction was long. So we tried to change the synthetic route of the dione. The reaction conditions were optimized. Then TBAI (15mol%) was used as a phase transfer catalyst, K2CO3as a base and THF as a solvent. The preferential molar ratio of2-oxocyclopentanecarboxylate and ethyl4-bromobutanoate was1:1.1.