用微反应器连续合成吡啶-N-氧化物工艺
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摘要
以吡啶为原料,在微反应器[1]中,研究连续合成吡啶-N-氧化物工艺。考查了氧化剂浓度、反应温度、反应物料摩尔比、原料进料停留时间对反应的影响,并优化了工艺。结果表明:最佳工艺条件为30%双氧水作氧化剂,吡啶∶双氧水∶乙酸的摩尔比为1∶5∶8,反应温度70℃,反应物料停留时间为41 s,产物吡啶-N-氧化物粗品收率为96.6%。产物经质谱和1HNMR表征。
Using pyridine as raw materials to synthesis of pyridine-N-oxide in the micro-reactor for continuous process.Oxidant concentration, reaction temperature, reaction material mole ratio, residence time of raw material in reactor is investigated and optimize the process conditions further. Results show that in the optimum technological conditions of 30%hydrogen peroxide as oxidant, pyridine : hydrogen peroxide : acetic acid = 1 : 5 : 8, reaction temperature 70℃, raw material feeding residence time of 41 s, the coarse product yield of pyridine-N-oxide is 96.6%. Products is characterized by mass spectrometry and1 HNMR.
Using pyridine as raw materials to synthesis of pyridine-N-oxide in the micro-reactor for continuous process.Oxidant concentration, reaction temperature, reaction material mole ratio, residence time of raw material in reactor is investigated and optimize the process conditions further. Results show that in the optimum technological conditions of 30%hydrogen peroxide as oxidant, pyridine : hydrogen peroxide : acetic acid = 1 : 5 : 8, reaction temperature 70℃, raw material feeding residence time of 41 s, the coarse product yield of pyridine-N-oxide is 96.6%. Products is characterized by mass spectrometry and1 HNMR.
引文
[1]刘兆利,张鹏飞.微反应器在化学化工领域中的应用[J].化工进展,2016,35(1):10-17.
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[4]Ismael Colon,Donald R.Kelsey.Coupling of aryl chlorides by nickel and reducing metals[J].Org.Chem.,1986,51(14):2627-2637.
[5]Masahiko Iyoda.Homocoupling of aryl halides using nickel(II)complex and zinc in the presence of Et4Ni.An efficient method for the synthesis of biaryls and bipyridines[J].Bull.Chem.Soc.Jpn.,1990,63(1):80-87.
[6]Cyril Gardner.Improved process for the manufacture of 2,2'-dipyridyl[P].GB:829838,1960.
[7]Lian-Yan Liao.Reductive couplings of 2-halopyridines without external ligand:phosphine-free nickel-catalyzed synthesis of symmetrical and unsymmetrical 2,2'-bipyridines[J].Org.Chem.,2014,79:777-782.
[8]Koichi Sato.Method for producing biaryl compound[P].US:20100087680A1,2010.
[9]Hida Noriyuki.Method for producing biaryl compound[P].JP:2460789A1,2010.
[10]Raghu Nath Dhital.Bimetallic gold-palladium alloy nanoclusters:an effective catalyst for Ullmann coupling of chloropyridines under ambient conditions[J].Catal.Sci.Technol.,2013,3:3030-3035.
[11]Sakurai.Method for producing biaryl compound[P].JP:2013184947A,2013.
[2]孙炜.基于氧化吡啶碳氢键活化的有机官能化反应[D].硕士论文,2015.
[3]Richard J.Fielden,Ronald F.Homer.New quaternary salts[P].GB:2823987,1958.
[4]Ismael Colon,Donald R.Kelsey.Coupling of aryl chlorides by nickel and reducing metals[J].Org.Chem.,1986,51(14):2627-2637.
[5]Masahiko Iyoda.Homocoupling of aryl halides using nickel(II)complex and zinc in the presence of Et4Ni.An efficient method for the synthesis of biaryls and bipyridines[J].Bull.Chem.Soc.Jpn.,1990,63(1):80-87.
[6]Cyril Gardner.Improved process for the manufacture of 2,2'-dipyridyl[P].GB:829838,1960.
[7]Lian-Yan Liao.Reductive couplings of 2-halopyridines without external ligand:phosphine-free nickel-catalyzed synthesis of symmetrical and unsymmetrical 2,2'-bipyridines[J].Org.Chem.,2014,79:777-782.
[8]Koichi Sato.Method for producing biaryl compound[P].US:20100087680A1,2010.
[9]Hida Noriyuki.Method for producing biaryl compound[P].JP:2460789A1,2010.
[10]Raghu Nath Dhital.Bimetallic gold-palladium alloy nanoclusters:an effective catalyst for Ullmann coupling of chloropyridines under ambient conditions[J].Catal.Sci.Technol.,2013,3:3030-3035.
[11]Sakurai.Method for producing biaryl compound[P].JP:2013184947A,2013.