5-烷氧基-3,4-二卤-2(5H)-呋喃酮与脂肪胺类的反应研究有机化学.pdfVIP

DOI: 10.6023/cjoc1106302 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 5-烷氧基-3,4-二卤-2(5H)-呋喃酮与脂肪胺类的反应研究 傅建花 汪朝阳* 霍景沛 谭越河 曾荣华 (华南师范大学化学与环境学院 广州 510006) 摘要 在氟化钾作催化剂和四氢呋喃作溶剂的条件下, 研究了系列脂肪胺亲核试剂与 5-烷氧基-3,4-二卤-2(5H)-呋喃酮 发生的反应, 通过旋光度, UV-Vis, IR, 1H NMR, 13C NMR, MS, 元素分析和 X 射线单晶衍射等表征方法对产物进行结 构表征, 发现通常情况下发生预期的串联迈克尔加成-消除反应, 合成了 13 个新的β-胺基-2(5H)-呋喃酮. 但是, 空间位 阻较大的二环己基胺与 5-烷氧基-3,4-二卤-2(5H)-呋喃酮反应时, 却得到了 4 个异常的 2(5H)-呋喃酮开环产物, 其可能 是经开环重排反应的机理得到的. 关键词 5-烷氧基-3,4-二卤-2(5H)-呋喃酮; 脂肪族仲胺; 串联迈克尔加成-消除反应; β-胺基-2(5H)-呋喃酮; 开环重排 反应 Research on the Reaction of 5-Alkyloxy-3,4-dihalo-2(5H)- furanones with Aliphatic Amines Fu, Jianhua Wang, Zhaoyang* Huo, Jingpei Tan, Yuehe Zeng, Ronghua (School of Chemistry and Environment, South China Normal University, Guangzhou 510006) Abstract Using KF as catalyst and tetrahydrofuran as solvent, 5-alkyloxy-3,4-dihalo-2(5H)-furanones was reacted with sev- eral aliphatic amines. The chemical structures and absolute configurations of the products were confirmed via rotation, UV-Vis, IR, 1H NMR, 13C NMR, MS techniques, elemental analysis and X-ray single crystal diffraction. Thirteen new normal products β-amino-2(5H)-furanones were obtained via the tandem Michael addition-elimination reaction as anticipated in most cases. However, the reaction between the larger steric dicyclohexyl amine and 5-alkyloxy-3,4-dihalo-2(5H)-furanones yielded four new abnormal products, (E)-alkyl 2-halo-4-dicyclohexylamino-4-oxo