超声辐射碳酸钾催化Knoevenagel反应及4H-色烯的合成
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摘要
在超声辐射下,无溶剂K_2CO_3催化芳醛与氰基乙酸酯发生Knoevenagel反应合成4种2-氰基肉桂酸酯和6种4H-色烯衍生物。实验结果表明:当苯甲醛与氰基乙酸甲酯用量各为10 mmol,无水碳酸钾用量为1 mmol,超声功率为150 W,室温下反应30 min以94.6%高产率得到2-氰基肉桂酸甲酯;推电子基的4-取代苯甲醛与氰基乙酸酯的缩合产率明显下降。当水杨醛用量为10 mmol,氰基乙酸乙酯用量为22.5 mmol,无水碳酸钾用量为0.1 mmol,超声功率为250 W,30℃下反应20 min以91%产率得到4H-色烯衍生物;推电子基的5-取代水杨醛则不能反应。产物结构通过熔点测定、IR和1H NMR进行表征。
Four 2-cyano-cinnamates and six 4H-chromene derivatives were synthesized from aromatic aldehydes with cyanoacetates via solvent-free Knoevenagel condensation using K_2CO_3 as catalyst under ultrasound irradiation.The experimental results indicate that the yield of methyl 2-cyano-cinnamate is up to 94.6%after reaction for 30 min at room temperature u nder ultrasonic power of 150 W when the dosages of benzaldehyde,methyl cyanoacetate and K_2CO_3 are 10,10 and 1 mmol,respectively.However,for the 4-substituted benzaldehyde with electron-donating groups,the yields of condensation with cyanoacetate significantly decrease in the same condition.In contrast,the yield of 4H-chromene derivative is up to 91%after reaction for 20 min at30℃under ultrasonic power of 250 W when the amounts of salicylaldehyde,ethyl cyanoacetate and K_2CO_3 are10,22.5 and 0.1 mmol,respectively.However,5-substituted salicylaldehyde with electron-donating groups can’t react with cyanoacetate.The products were characterized by mp,IR and ~1H NMR.
Four 2-cyano-cinnamates and six 4H-chromene derivatives were synthesized from aromatic aldehydes with cyanoacetates via solvent-free Knoevenagel condensation using K_2CO_3 as catalyst under ultrasound irradiation.The experimental results indicate that the yield of methyl 2-cyano-cinnamate is up to 94.6%after reaction for 30 min at room temperature u nder ultrasonic power of 150 W when the dosages of benzaldehyde,methyl cyanoacetate and K_2CO_3 are 10,10 and 1 mmol,respectively.However,for the 4-substituted benzaldehyde with electron-donating groups,the yields of condensation with cyanoacetate significantly decrease in the same condition.In contrast,the yield of 4H-chromene derivative is up to 91%after reaction for 20 min at30℃under ultrasonic power of 250 W when the amounts of salicylaldehyde,ethyl cyanoacetate and K_2CO_3 are10,22.5 and 0.1 mmol,respectively.However,5-substituted salicylaldehyde with electron-donating groups can’t react with cyanoacetate.The products were characterized by mp,IR and ~1H NMR.
引文
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[2]LiWenjun,LiuHui,JiangXuefeng,etal.Enantioselective organocatalytic conjugate addition of nitroalkanes to electrophilic2-iminochromenes[J]. ACS Catal, 2012(2):1535-1538.
[3]Kemn I W, Kasibhatla S, Jiang S. Discovery of 4-aryl-4H-chromenes as a new series of apoptosis inducers using a cell and caspase-based high-throughput screening assay. 2. Structure-activity relationships of the 7-and 5-, 6-, 8-positions[J]. Bioorganic&Medicinal Chemistry Letters, 2005, 15:4745-4751.
[4]Kemn I W, Drewe J, Jiang S. Discovery of 4-aryl-4H-chromenes as a new series of apoptosis inducers using a cell and caspase-based highthroughput screening assay. structure-activity relationships of the4-aryl group[J]. J Med Chem, 2004, 47:6299-6310.
[5]Ding Bangdong, Yang Ruihong, Du Bin, et al. Study on catalytic synthesis of propyl cinnamate with p-toluenesulphonic acid supported on polyaniline[J]. China Surfactant Detergent&Cosmetics, 2018,48(12):702-705.
[6]Shi Daqing, Wang Xiangshan, Tu Shujiang. Synthesis of 4H-chromene derivatives catalyzed by KF/Al2O3[J]. Chinese Journal of Organic Chemistry, 2002, 22(12):1053-1056.
[7]Wang Xiangshan, Zeng Zhaosen, Li Yuling, et al. Study on the reaction of substituted salicylaldehydes with cyanoacetate in water[J]. Chinese Journal of Organic Chemistry, 2006, 26(10):1379-1383.
[8]Zeng Yucai, Liu Xiaoling, Wen Yunming, et al. Synthesis of 2-amino-4H-chromene derivatives catalyzed by K2CO3[J]. Fine Chemicals,2014, 31(12):1522-1525.
[9]Bian Yanjiang, Qin Ying, Xiao Liwei, et al. New advances of Knoevenagel condensation reactions[J]. Chinese Journal of Organic Chemistry, 2006, 26(9):1165-1172.
[10]Wang Zheng, Li Zhifeng, Hou Hailiang, et al. DABCO based ionic liquid:efficient catalyst for Knoevenagel condensation[J].Chemical Research, 2014, 25(4):353-358.
[11]Dou Hui, Luo Lei, Fu Zhaolong, et al. Knoevenagel condensation and the synthesis of isoxazolones catalyzed by ionic liquid[2-aemim]im[J]. Chemical Research and Application, 2012, 24(3):474-479.
[12]Zhang Jiandong, Sun Hui, Jiang Wenqing, et al. Knoevenagel condensation reaction catalyzed by KF supported on molecular sieve at room temperature[J]. Experimental Technology and Management,2014, 7(31):38-42.
[13]ZanHuining,HouZhiai,ZhangLixuan,etal.Synthesis,characterization of strong bas es resin with guanidyl g roups and the application as catalyst in the Knoevenagel condensation[J]. Acta Polymerica Sinica, 2013(9):1204-1211.
[14]Zhang Wenfei, Liang Jinhua, Liu Yanqiu, et al. Knoevenagel condensation reaction over acid-base bifunctional MgO/HMCM-22catalysts[J]. Chinese Journal of Catalysis, 2013, 34(3):559-566.
[15]Mu Li, Zhang Long, Wu Xiuli. Synthesis and catalytic properties of ordered mesoporous amino-group functionalized mesopolymers as solid base catalysts[J]. Chemical Journal of Chinese Universities,2012, 33(12):2 746-2749.
[16]Yu Fuchao, Yan Shengjiao, Lin Jun. Application of solvent-free reaction in synthesis of heterocyclic compounds[J]. Chinese Journal of Organic Chemistry, 2010, 30(10):1421-1430.