高等学校化学学报
高等學校化學學報
고등학교화학학보
CHEMICAL JOURNAL OF CHINESE UNIVERSITIES
2014年
3期
538-549
,共12页
刘倩%李文红%邱召来%李媛
劉倩%李文紅%邱召來%李媛
류천%리문홍%구소래%리원
七水合三氯化铈-碘化钠%催化%迈克尔加成%氨基苯硫酚%催化机理
七水閤三氯化鈰-碘化鈉%催化%邁剋爾加成%氨基苯硫酚%催化機理
칠수합삼록화시-전화납%최화%매극이가성%안기분류분%최화궤리
CeCl3·7H2O-NaI%Catalysis%Michael addition%Aminothiophenol%Catalytic mechanism
对七水合三氯化铈-碘化钠(CeCl3·7H2O-NaI)化邻氨基苯硫酚、对氯邻氨基苯硫酚、间氨基苯硫酚、对氨基苯硫酚和对甲基苯硫酚与α,β-不饱和酮(1a~1o)的迈克尔加成反应进行了系统研究.结果表明, CeCl3·7H2O-NaI-SiO2复合催化剂能有效催化邻氨基苯硫酚及对氯邻氨基苯硫酚与α,β-不饱和酮(1a~1o)的迈克尔加成反应.在优化的反应条件下,即 n(CeCl3·7H2O): n(NaI): n(α,β-不饱和酮)=1:2:2, m(CeCl3·7H2O):m(SiO2)=1:1.6,三氯甲烷作溶剂,反应温度为回流温度,反应时间为2 h,反应可达到中等产率(43.1%~58.8%).催化剂重复使用4次基本稳定.此外,提出了可能的催化机理.
對七水閤三氯化鈰-碘化鈉(CeCl3·7H2O-NaI)化鄰氨基苯硫酚、對氯鄰氨基苯硫酚、間氨基苯硫酚、對氨基苯硫酚和對甲基苯硫酚與α,β-不飽和酮(1a~1o)的邁剋爾加成反應進行瞭繫統研究.結果錶明, CeCl3·7H2O-NaI-SiO2複閤催化劑能有效催化鄰氨基苯硫酚及對氯鄰氨基苯硫酚與α,β-不飽和酮(1a~1o)的邁剋爾加成反應.在優化的反應條件下,即 n(CeCl3·7H2O): n(NaI): n(α,β-不飽和酮)=1:2:2, m(CeCl3·7H2O):m(SiO2)=1:1.6,三氯甲烷作溶劑,反應溫度為迴流溫度,反應時間為2 h,反應可達到中等產率(43.1%~58.8%).催化劑重複使用4次基本穩定.此外,提齣瞭可能的催化機理.
대칠수합삼록화시-전화납(CeCl3·7H2O-NaI)화린안기분류분、대록린안기분류분、간안기분류분、대안기분류분화대갑기분류분여α,β-불포화동(1a~1o)적매극이가성반응진행료계통연구.결과표명, CeCl3·7H2O-NaI-SiO2복합최화제능유효최화린안기분류분급대록린안기분류분여α,β-불포화동(1a~1o)적매극이가성반응.재우화적반응조건하,즉 n(CeCl3·7H2O): n(NaI): n(α,β-불포화동)=1:2:2, m(CeCl3·7H2O):m(SiO2)=1:1.6,삼록갑완작용제,반응온도위회류온도,반응시간위2 h,반응가체도중등산솔(43.1%~58.8%).최화제중복사용4차기본은정.차외,제출료가능적최화궤리.
In this paper, the Michael additions of o-aminothiophenol, p-chloro-o-aminothiophenol, m-amino-thiophenol, p-aminothiophenol and p-methylthiophenol to α,β-unsaturated ketones ( 1a-1o ) catalyzed by CeCl3·7H2 O-NaI were systematically studied. The results show that the CeCl3·7H2 O-NaI-SiO2 system works well for the reaction of the o-aminothiophenol and p-chloro-o-aminothiophenol to the α,β-unsaturated ketones (1a-1o). Under the optimal reaction conditions, i. e. , n(CeCl3·7H2O):n(NaI):n(α,β-unsaturated ke-tones)=1:2:2, m(CeCl3 ·7H2O):m(SiO2)=1:1.6, the reaction time of 2 h, at reflux temperature and CHCl3 as solvent, the reactions proceed with moderate yields ( 43.1%-58.8%) . The catalyst is basically stable after recycling the conjugate addition reaction four times. In addition, the possible catalytic mechanism was proposed.