引用本文:
唐瑞仁, 刘长辉, 罗一鸣, 郭灿城. 组氨酸水杨醛Schiff碱铜(Ⅱ)配合物催化氧化β-紫罗兰酮的反应[J]. 应用化学,
2006, 23(7): 718-723.
Citation: TANG Rui-Ren, LIU Chang-Hui, LUO Yi-Ming, GUO Can-Cheng. Studies on the Catalytic Oxidation of β-Ionone to 4-Oxo-β-Ionone[J]. Chinese Journal of Applied Chemistry, 2006, 23(7): 718-723.
Citation: TANG Rui-Ren, LIU Chang-Hui, LUO Yi-Ming, GUO Can-Cheng. Studies on the Catalytic Oxidation of β-Ionone to 4-Oxo-β-Ionone[J]. Chinese Journal of Applied Chemistry, 2006, 23(7): 718-723.
组氨酸水杨醛Schiff碱铜(Ⅱ)配合物催化氧化β-紫罗兰酮的反应
摘要:
合成了芳环上含不同取代基的Schiff碱配体(水杨醛缩组氨酸(H2L1)、5-溴水杨醛缩组氨酸(H2L2)、5-硝基水杨醛缩组氨酸(H2L3))及其铜(Ⅱ)配合物,研究了其作为催化剂应用于催化分子氧氧化β-紫罗兰酮制备4-氧代-β-紫罗兰酮中的行为。提出了可能的催化反应机理。结果表明,取代基影响铜(Ⅱ)配合物的催化性能,其催化效果为CuL2> CuL1> CuL3,吡啶可增强其催化活性。以CuL2作催化剂,当反应时间为10 h、反应温度为75℃、催化剂用量为1.6%(摩尔分数)、O2气压力为1 MPa、添加摩尔分数为30%吡啶时,4-氧代-β-紫罗兰酮的收率为50.2%,纯度超过98.5%。氧化产物、Schiff碱配体及其铜(Ⅱ)配合物的结构经EA、IR、1H NMR和MS等测试方法表征。未反应的原料经减压蒸馏回收利用,催化剂经过滤分离、活化,其重复使用性良好。
English
Studies on the Catalytic Oxidation of β-Ionone to 4-Oxo-β-Ionone
Abstract:
A series of L-histidine Schiff bases that include Sal-His (H2L1),Br-Sal-His (H2L2),NO2-Sal-His (H2L3) and their Cu(Ⅱ) complexes were synthesized,and the catalytic behavior of Schiff-base-Cu for the oxidation of β-ionone to 4-oxo-β-ionone as well as the effects of substitutents on these properties were examined.The effects of reaction temperature,reaction time,molar ratio of catalyst to β-ionone, the amount of pyridine additive and O2 pressure on the catalytic activity of the various catalysts were optimized and a probable catalytic mechanism was proposed.The results showed that the catalytic performances of Schiff-base-Cu(Ⅱ) complexes were affected by substituted groups and enhanced by additive pyridine.The main product was 4-oxo-β-(ionone) with a yield of 50.2% and a purity over 98.5% under O2 pressure(1 MPa) at 75℃ with additive pyridine over catalyst CuL2 in 10 h.The structures of L-histidine Schiff bases,their Cu(Ⅱ) complexes and oxidation product were characterized by IR,MS,1H NMR and EA.The excessive β-ionone and the catalysts can be reused via vacuum distillation and filtration.
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Key words:
- β-ionone
- / oxo-β-ionone
- / Schiff base
- / Cu(Ⅱ) complex
- / catalytic oxidation
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