超声辅助合成2-氨基-3,5-二氰基-4H-吡喃衍生物
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摘要
以苯甲酰乙腈、苯甲醛、丙二腈为原料,碳酸钠为催化剂,超声条件下三组分反应合成2-氨基-3,5-二氰基-4H-吡喃衍生物。单因素法筛选催化剂、溶剂,正交实验法考察反应时间及温度、原料物质的量比对产率的影响。获得的最优条件为:乙醇作溶剂,反应温度为70℃,反应时间25 min,n(苯甲醛)∶n(丙二腈)∶n(苯甲酰乙腈)=1.0∶0.9∶0.9,产率最高为98.1%。
2-Amino-3,5-dicyano-4H-pyran derivatives were synthesized using cyano acetophenone,benzaldehyde,malononitrile as raw material with sodium carbonate as catalysts.Catalysts,solvents were screened using single factor method and the effects of reaction time and temperature,molar ratio of raw materials on yield were investigated by orthogonal experiment.The optimal optimal conditions are:ethanol as solvent,reaction temperature 70 ℃,reaction finished in 25 min,molar ratio of n(benzaldehyde)∶n(malononitrile)∶n(benzoylacetonitrile)=1.0∶0.9∶0.9,the yield up to 98.1%.
2-Amino-3,5-dicyano-4H-pyran derivatives were synthesized using cyano acetophenone,benzaldehyde,malononitrile as raw material with sodium carbonate as catalysts.Catalysts,solvents were screened using single factor method and the effects of reaction time and temperature,molar ratio of raw materials on yield were investigated by orthogonal experiment.The optimal optimal conditions are:ethanol as solvent,reaction temperature 70 ℃,reaction finished in 25 min,molar ratio of n(benzaldehyde)∶n(malononitrile)∶n(benzoylacetonitrile)=1.0∶0.9∶0.9,the yield up to 98.1%.
引文
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[17]LI Z N,GAO Y,LIU P,et al.One-pot Synthesis of2-Amino-7-methyl-4-aryl-5-oxo-4 H,5 H-[4,3-b]-3-nitrile under Ultrasonic Irradiation[J].Chin Appl Chem,2008,25(6):744-746(in Chinese).(李卓宁,高原,刘波,等.超声辐射下2-氨基-7-甲基-4-芳基-5-氧代-4 H,5 H-吡喃并[4,3-b]吡喃-3-腈的“一锅法”合成[J].应用化学,2008,25(6):744-746.)
[18]WU X Y,YIN X G,GONG W.et al.Synthesis of2-Amino-3-cyano-4 H-pyran Derivatives Catalyzed by Zinc Acetate[J].Chin Chem Bull,2016,79(2):1 156-1 160(in Chinese).(吴小云,尹晓刚,龚维,等.醋酸锌催化串联反应合成2-氨基-3-氰基-4 H-吡衍生物[J].化学通报,2016,79(12):1 156-1 160.)
[2]WU J Y,FONG W F,ZHANG J X,et al.Reversal of Multidrug Resistance in Cancer Cells by Pyranocoumarins Isolated from Radix Peucedani[J].Eur J Pharmacol,2003,473(1):9-17.
[3]AMR A G,MOHAMED A M,MOHAMED S F,et al.Anticancer Activities of Some Newly Synthesized Pyridine,Pyrane,and Pyrimidine Derivatives[J].Bioorg Med Chem,2006,14(16):5 481-5 488.
[4]YALAGALA K,MADDILA S,RANA S,et al.Synthesis,Antimicrobial Activity and Molecular Docking Studies of Pyrano[2,3-d]pyrimidine Formimidate Derivatives[J].Res Chem Intermed,2015,42(4):1-12.
[5]WU J Y,FONG W F,ZHANG J X,et al.Reversal of Multidrug Resistance in Cancer Cells by Pyranocoumarins Isolated fromRadix peucedani[J].Eur J Pharmacol,2003,473(1):9-17.
[6]SUI X C,BAO N,JIA S,et al.Discovery of Substituted N-Phenyl Nicotinamides as Potent Inducers of Apoptosis Using a Cell-and Caspase-based High Throughput Screening Assay[J].J Med Chem,2003,46(12):2 474-2 481.
[7]JIANG H,TU S J,FANG F,et al.An Efficient One-pot Synthesis of 2-Amino-3-cyano-4-ary1-4 H,5 H-pyrano[3,2-c]benzo[b]pyran-5-one under Microwave Irradiation[J].Chin J Org Chem,2004,24(11):1 458-1 460(in Chinese).(蒋虹,屠树江,房芳等.微波辐射下“一锅煮”法合成2-氨基-3-氰基-4-芳基-4 H,5 H-吡喃-[3,2-c]苯并吡喃-5-酮[J].有机化学,2004,24(11):1 458-1 460.)
[8]FENG J,ABLAJAN K,MA X B,et al.Multi-Component One-pot Reactions for the Synthesis of Spirooxindole-pyrano[2,3-c]pyrazole Derivatives[J].Chin J Org Chem,2016,36(1):222-228(in Chinese).(冯俊,阿布拉江·克依木,马夏冰,等.多组分反应合成螺吲哚-吡喃并[2,3-c]吡唑类化合物的研究[J].有机化学,2016,36(1):222-228.)
[9]SHI Y N,SONG F Y,DNG K N,et al.One Pot Synthesis of Pyrano[3,2-c]pyran Derivatives in Inonic Liquid[J].J Jingsu Normal Univ,2015,33(4):53-56(in Chinese).(史亚南,宋飞跃,丁凯娜,等.离子液体中吡喃并[3,2-c]吡喃衍生物的一步合成[J].江苏师范大学学报(自然科学版),2015,33(4):53-56.)
[10]NARAYANA M S,SURESH M,VAN ZYL W E,et al.Ceria-vanadia/Silica Catalyzed Cascade for C—C and C—O Bond Activation:Green One-pot Synthesis of 2-Amino-3-cyano-4 H-pyrans[J].J Cell Sci,2015,5(1):38-42.
[11]KANCHITHALAIVAN S,SUMESH R V,KUMAR R R.Ultrasound-assisted Sequential Multicomponent Strategy for the Combinatorial Synthesis of Novel Coumarin Hybrids[J].ACS Comb Sci,2014,16(10):566-572.
[12]RADZIUK D,GRIGORIEV D,ZHANG W,et al.Ultrasound-assisted Fusion of Preformed Gold Nanoparticles[J].J Phys Chem C,2010,114(4):1 835-1 843.
[13]ZOU Y,HU Y,LIU H,et al.Rapid and Efficient Ultrasound-Assisted Method for the Combinatorial Synthesis of Spiro[indoline-3,4′-pyrano[2,3-c]-Pyrazole]Derivatives[J].ACS Comb Sci,2011,14(1):38-43.
[14]XU Y,ZHANG X,HSING Y,et al.Ultrasonic-assisted Synthesis of Fe Nanoparticles in the Presence of Poly(N-vinyl-2-pyrrolidone)[J].Chin J Chem,2011,29(9):1 829-1 836.
[15]MAREK I.Multicomponent Reactions[J].Tetrahedron,2005,61(48):1 1309-1 1310.
[16]TU S J,JIANG H,ZHUANG Q Y,et al.One-Pot Synthesis of 2-Amimo-3-cyano-4-aryl-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4 H-benzo[b]pyran Under Ultrasonic Irradiation without Catalyst[J].Chin J Org Chem,2003,23(5):488-490(in Chinese).(屠树江,蒋虹,庄启亚,等.超声辐射下一步法合成2-氨基-3-氰基-4-芳基-7,7-二甲基-5-氧代-5,6,7,8-四氢-4 H-苯并[b]吡喃[J].有机化学,2003,23(5):488-490.)
[17]LI Z N,GAO Y,LIU P,et al.One-pot Synthesis of2-Amino-7-methyl-4-aryl-5-oxo-4 H,5 H-[4,3-b]-3-nitrile under Ultrasonic Irradiation[J].Chin Appl Chem,2008,25(6):744-746(in Chinese).(李卓宁,高原,刘波,等.超声辐射下2-氨基-7-甲基-4-芳基-5-氧代-4 H,5 H-吡喃并[4,3-b]吡喃-3-腈的“一锅法”合成[J].应用化学,2008,25(6):744-746.)
[18]WU X Y,YIN X G,GONG W.et al.Synthesis of2-Amino-3-cyano-4 H-pyran Derivatives Catalyzed by Zinc Acetate[J].Chin Chem Bull,2016,79(2):1 156-1 160(in Chinese).(吴小云,尹晓刚,龚维,等.醋酸锌催化串联反应合成2-氨基-3-氰基-4 H-吡衍生物[J].化学通报,2016,79(12):1 156-1 160.)