杂环多苯基β-氨基酮类化合物的合成
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摘要
常温下,乙醇作溶剂,无配体参与,以1-苯基-3-甲基-吡唑啉酮-5、芳香醛和芳香胺为原料,在CuMCM-41作催化剂下,三组分"一锅法"实现了C-C键和C-N键的同时合成,共合成了15种新的杂环多苯基β-氨基酮类化合物.探讨了溶剂和催化剂对反应的影响,产物结构通过IR、~1 H NMR和元素分析确定.实验结果表明,当原料摩尔比为2.1∶2.0∶2.0,乙醇用量为4~5mL,0.2mmol的Cu-MCM-41分子筛作催化剂时,产率可达76%~89%.该方法具有操作简单、无需碱性介质和配体参与、溶剂选择要求低、条件温和、产率高、选择性高等特点.
In the presence of catalytical amount of Cu-MCM-41,a new way was designed to synthesized fifteen novel heterocyclic multi phenylβ-aminoketone compounds through 1-phenyl-3-methyl pyrazole-5,aromatic aldehydes and aromatic amines by three components "one pot" without ligand in ethanol at 25 ℃.At the same time,the synthesis of C-C bond and C-N bond was realized.The products are determined by IR,~1 H NMR and elemental analysis.The results showed that the yields reached 76% -89% in the molar ratio(2.1∶2.0∶2.0)of raw material,4-5 mL ethanol and 0.2 mmol catalyst.The experiment has the following characteristics:simple operation,no basic medium and ligand,low solvent requirement,mild condition,high yield and selectivity.
In the presence of catalytical amount of Cu-MCM-41,a new way was designed to synthesized fifteen novel heterocyclic multi phenylβ-aminoketone compounds through 1-phenyl-3-methyl pyrazole-5,aromatic aldehydes and aromatic amines by three components "one pot" without ligand in ethanol at 25 ℃.At the same time,the synthesis of C-C bond and C-N bond was realized.The products are determined by IR,~1 H NMR and elemental analysis.The results showed that the yields reached 76% -89% in the molar ratio(2.1∶2.0∶2.0)of raw material,4-5 mL ethanol and 0.2 mmol catalyst.The experiment has the following characteristics:simple operation,no basic medium and ligand,low solvent requirement,mild condition,high yield and selectivity.
引文
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[3]马学林,张骁勇,李璇,等.硅胶负载稀土氯化铽一步催化合成多取代的β-氨基酮类化合物[J].有机化学,2013,33(3):602-606.
[4]Ting A,Schaus S E.Organocatalytic Asymmetric Mannich Reactions:New Methodology,Catalyst Design,and Synthetic Applications[J].Eur J Org Chem,2007,35:5797-5815.
[5]Li Z,Ma X L,Liu J,et al.Silica-supported aluminum chloride:A recyclable and reusable catalyst for one-pot three-component Mannichtype reactions[J].J Mol Cata A:Chem,2007,272(1-2):132-135.
[6]马学林,张骁勇,雍胜利,等.硅胶支载稀土氯化钐一步催化合成多取代Mannich碱[J].高等学校化学学报,2013,34(12):2759-2764.
[7]Tao R H,Yin Y,Duan Y H,Yuxing Sun,et al.Fe(OTf)3-catalyzed tandem Meyer-Schuster rearrangement/intermolecular hydroamination of 3-aryl propargyl alcohols for the synthesis of acyclicβ-Aminoketones[J].Tetrahedron,2017,73(13):1762-1768.
[8]姚元勇,舒华,邢明明,等.SO2-4/TiO2固体酸协同金鸡纳碱奎尼丁催化不对称Mannich反应[J].有机化学,2016,36(1):196-201.
[9]刘玉婷,吴倩倩,尹大伟,等.Mannich反应的最新研究进展及其应用[J].有机化学,2016,36(5):927-938.
[10]Zhang Y,Yang Y X,Yao Q Z,et al.CuI/DMPAO-Catalyzed N-Arylation of Acyclic Secondary Amines[J].Org Lett,2012,14(12):3056-3059.
[11]Serrano C M,Looper R E.Synthesis of Cytimidine through a One-Pot Copper-Mediated Amidation Cascade[J].Org Lett,2011,13(19):5000-5003.
[12]Yang D,Fu H,Hu L,et al.Copper-Catalyzed Synthesis of Benzimidazoles via Cascade Reactions of o-Haloacetanilide Derivatives with Amidine Hydrochlorides[J].J Org Chem,2008,73(19):7841-7844.
[13]徐向亚,张明森.运用C-N偶联反应高效合成N-杂环卡宾前体[J].石油化工,2014,43(10):1133-1136.
[14]Ghorbani-Vaghei R,Hemmati S,Veisi H.An in Situ Generated CuI/Metformin Complex as a Novel and Efficient Catalyst for C-N and C-O Cross-Coupling Reactions[J].Tetrahedron Lett,2013,54(52):7095-7099.
[15]Wang Y L,Luo J,Liu Z L.8-Hydroxyquinoline Functionalized PEG-1000Bridged Dicationic Ionic Liquid as a Novel Ligand for CopperCatalyzed N-Arylation of Imidazoles[J].J Chin Chem Soc,2013,60(8):1007-1013.
[16]Zhu Z Q,Xiang S J,Chen Q Y,et al.Novel Low-Melting Salts with Donor-Acceptor Substituents as Tar-gets for Second-Order Nonlinear Optical Applications[J].Chem Commun,2008,40(0):5016-5018.
[17]陈静,韩梅,孙蕊.苄基磺酸接枝MCM-41介孔分子筛的合成与表征[J].无机化学学报,2006,22(9):1568-1572.
[18]陈静,唐俊杰,胡晨晖,等.一种无机-有机高分子杂化催化剂Pd(0)-CS/MCM-41的制备及其性能研究[J].无机化学学报,2009,25(1):147-153.