2-苯基-3-氨基氮杂环丁烷开环形成噻唑或噁唑的机理研究  

Ring-opening Mechanism of 2-Phenyl-3-amineazetidine to Form Thiazole or Oxazole

作　　者：顼兴宇 解晓明 邱萍 XU Xingyu;XIE Xiaoming;QIU Ping(Department of Chemistry,Xinzhou Normal University,Xinzhou 034000,China)

机构地区：[1]忻州师范学院化学系,忻州034000

出　　处：《高等学校化学学报》2025年第5期63-74,共12页Chemical Journal of Chinese Universities

基　　金：山西省高等学校科技创新项目(批准号:2021L456)资助.

摘　　要：为深入研究(2S,3S)-2-苯基-1-[(S)-1-苯乙基]氮杂环丁烷-3-胺的开环反应机理,根据密度泛函理论(DFT),采用明尼苏达泛函M06-2X方法计算了其分别与苯基异硫氰酸酯和苯基异氰酸酯在室温下的反应历程,并对比了不同溶剂对反应过程中能量变化的影响.基于计算结果提出了如下反应机理:(2S,3S)-2-苯基-1-[(S)-1-苯乙基]氮杂环丁烷-3-胺与苯基异硫氰酸酯反应生成中间体,中间体发生质子转移;然后硫原子对四元环C2位进行亲核进攻得到五元环中间体;最后异构化得到二氢噻唑.该化合物与苯基异氰酸酯反应更倾向于生成脲类化合物.脲发生开环反应时,需借助质子酸或三氟甲基磺酸铜进行催化.Based on the density functional theory(DFT),the Minnesota functional M06-2X method was employed to study the ring-opening reaction mechanism of(2S,3S)-2-phenyl-1-[(S)-1-phenylethyl]azetidin-3-amine reacting with phenylisothiocyanate or phenylisocyanate.The amine reacting with phenylisothiocyanate generates an intermediate,which then undergoes proton transfer.Subsequently,the sulfur atom conducts a nucleophilic attack on the C2 position of the four-membered ring to give dihydrothiazole after isomerization from a five-membered ring.The amine reacting with phenylisocyanate forms urea.Protic acid or copper trifluoromethanesulfonate is required when the four-membered ring of the urea undergoes a ring-opening reaction.

关 键 词：3-氨基氮杂环丁烷 开环反应 密度泛函理论 反应机理 

分 类 号：O626[理学—有机化学]