4-羟基-3-甲氧基苯乙酮肟环钯配合物催化Suzuki偶联反应的研究
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摘要
以4-羟基-3甲氧基苯乙酮为原料,通过肟化反应合成了4-羟基-3甲氧基苯乙酮肟,并以氯钯酸锂为钯源,合成了4-羟基-3-甲氧基苯乙酮肟环钯配合物。通过傅立叶红外(FT-IR)和紫外-可见漫反射光谱(UV-vis-DRS)对合成的配合物进行了表征。考察了溶剂与溶剂含水量、碱、催化剂用量等反应条件对4-羟基-3甲氧基苯乙酮肟环钯配合物催化Suzuki偶联反应的影响。当以碳酸钾为碱,乙醇水溶液(50vol%)为溶剂,催化剂量为0.01%(1×10-4mmol),60℃下催化对溴苯乙酮与苯硼酸Suzuki偶联反应,反应15min时,产品收率可达98.76%,表明4-羟基-3-甲氧基苯乙酮肟环钯配合物催化剂具有很高的催化效率。
The 4-hydroxy-3-methoxyacetophonene oxime is synthesized from 4-hydroxy-3-methoxyacetophonene by the oximation reaction and the 4-hydroxy-3-methoxyacetophenone oxime palladiumcycle complex is prepared with the lithium palladium chloride as palladium source.The asprepared complex is characterized by Fourier transform infrared spectroscopy(FT-IR)and UV-visible diffuse reflection spectrum(UV-vis-DRS).The effects of reaction conditions,such as solvent,water content,alkali,catalyst adding amount on the Suzuki coupling reaction catalyzed with 4-hydroxyl-3-methoxyacetophenone oxime palladiumcycle complex are investigated.When the Suzuki coupling reaction between p-bromine acetophenone with phenylboronic acid is carried out at 60℃ with K_2 CO_3 as alkali,ethanol aqueous solution(50 vol%)as solvent,catalyst adding amount of 0.01%(1×10-4 mmol),the yield can reach 98.76% in 15 min.The results show that 4-hydroxy-3-methoxyacetophenone oxime palladiumcycle complex catalyst has high catalytic efficiency.
The 4-hydroxy-3-methoxyacetophonene oxime is synthesized from 4-hydroxy-3-methoxyacetophonene by the oximation reaction and the 4-hydroxy-3-methoxyacetophenone oxime palladiumcycle complex is prepared with the lithium palladium chloride as palladium source.The asprepared complex is characterized by Fourier transform infrared spectroscopy(FT-IR)and UV-visible diffuse reflection spectrum(UV-vis-DRS).The effects of reaction conditions,such as solvent,water content,alkali,catalyst adding amount on the Suzuki coupling reaction catalyzed with 4-hydroxyl-3-methoxyacetophenone oxime palladiumcycle complex are investigated.When the Suzuki coupling reaction between p-bromine acetophenone with phenylboronic acid is carried out at 60℃ with K_2 CO_3 as alkali,ethanol aqueous solution(50 vol%)as solvent,catalyst adding amount of 0.01%(1×10-4 mmol),the yield can reach 98.76% in 15 min.The results show that 4-hydroxy-3-methoxyacetophenone oxime palladiumcycle complex catalyst has high catalytic efficiency.
引文
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[8]徐光宪.配位化学-原理与应用[M].北京:化学工业出版社,2008.
[2]MIYAURA N,YAMADA K,SUZUKI A.A new stereospecific crosscoupling by the palladium-catalyzed reaction of 1-alkenylboranes with 1-alkenyl or 1-alkynyl halides[J].Tetrahedron Letters,1979,20(36):3437~3440.
[3]ALTENDORFER M,MENCHE D.Efficient synthesis of diverse hetero-bis-metallated alkenes as modular reagents towards highly conjugated and isolated olefinic systems[J].Chem.Commun.,2012,48(66):8267~8269.
[4]LI Y,TANG J,GU J,et al.Chiral 1,2-Cyclohexane-Bridged Bis-NHC Palladium Catalysts for Asymmetric Suzuki-Miyaura Coupling:Synthesis,Characterization,and Steric Effects on Enantiocontrol[J].Organometallics,2014,33(4):876~884.
[5]CHEN Q,HIRD M.Synthesis,mesomorphic behaviour and optical anisotropy of some novel liquid crystals with lateral and terminal fluoro substituents and a 2,6-disubstituted naphthalene core[J].Liq.Cryst.,2015,42(5~6):877~886.
[6]ALONSO D A,NAJERA C.Oxime-derived palladacycles as source of palladium nanoparticles[J].Chemical Society Reviews.2010.39(8):2891~2902.
[7]HIROSHI O K M,KUNIO N.Aromatic Metalation Reactions by Palladium(II)and Platinum(II)on aromatic Aldoximes and Ketoximes[J].Bulletin of the Chemical Society of Japan.1970,43:3480~3485.
[8]徐光宪.配位化学-原理与应用[M].北京:化学工业出版社,2008.