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Catalytic Systems Containing p-Toluenesulfonic Acid for the Coupling Reaction of Formaldehyde and Methyl Formate

机译:含对甲苯磺酸的甲醛与甲基甲酸酯偶联反应的催化体系

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The coupling reaction of formaldehyde (FA) and methyl formate (MF) to form methyl glycolate (MG) and methyl methoxy acetate(MMAc),catalyzed by p-toluenesulfonic acid(p-TsOH) as well as assisted by different kinds of solvents or Ni-containing compounds.had been investigated.The results showed that when the reaction was carried out at 140℃ with a molar ratio of FA to MF of 0.65:1,molar fraction of p-TsOH to total feedstock of 11.0%,and reaction time of 3 h,the yield of MG and MMAc Was 31.1% and 17.1%.respectively.p-TsOH catalyzed the coupling reaction by means of the synergistic catalysis of protonic acidity and soft basicity.Adding extra solvents to the reaction system Was unfavorable for the reaction.The composite catalytic system consisting of p-TsOH and NiX2(X=Cl,Br,I)exhibited a high catalytic performance for the coupling reaction,and NiX2 acted as a promoter in the reaction,whose promotion for the catalysis increased in the following order:NiCl2<NiBr2<NiI2.The present system is less corrosive when compared with the previous system,in which strong inorganic liquid acids were used as catalysts.
机译:在对甲苯磺酸(p-TsOH)的催化下,在不同种类的溶剂或辅助下,甲醛(FA)与甲酸甲酯(MF)的偶联反应形成乙醇酸甲酯(MG)和乙酸甲氧基乙酸甲酯(MMAc)。结果表明,当反应在140℃,FA与MF的摩尔比为0.65:1,对-TsOH与总原料的摩尔分数为11.0%的条件下进行时,反应发生。 3 h的MG和MMAc收率分别为31.1%和17.1%。p-TsOH通过质子酸和软碱的协同催化催化偶合反应。由p-TsOH和NiX2(X = Cl,Br,I)组成的复合催化体系对偶联反应表现出较高的催化性能,NiX2在反应中起促进剂的作用,其催化促进作用增加NiCl 2 <NiBr 2 <NiI 2。与以前的系统(其中使用强无机液体酸作为催化剂)相比具有腐蚀性。

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