丙烯酰胺的Oxa-Michael加成:β-烷氧基丙酰胺的合成
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摘要
本文利用醇与丙烯酰胺的oxa-Michael加成,合成了一系列β-烷氧基丙酰胺类化合物。通过NMR、HRMS表征了产物的结构。考察了催化剂、反应温度、原料配比对反应的影响。在40℃下,5(mol)%的活化碳酸钾能催化伯醇与丙烯酰胺发生oxa-Michael加成,仲醇的反应活性较低,叔醇及苯酚几乎不反应。温度升高及强碱会导致丙烯酰胺自身aza-Michael加成反应形成二聚体。醇与丙烯酰胺可以在等官能团比的无溶剂条件下反应。分子内的氢键有利于提高仲羟基的反应活性。
A series of β-alkoxypropionamides were synthesized by the oxa-Michael addition reaction of alcohol with acrylamide. The structure of product was characterized by NMR and HRMS. The effects of catalyst,reaction temperature,and ratio of reactants on the reaction were explored. At 40℃,the oxa-Michael addition reaction of primary alcohol with acrylamide went smoothly under promotion of 5( mol) % activated potassium carbonate. The activity of secondary alcohol is lower. As for tertiary alcohol and phenol,almost no reaction was observed. At higher temperature,the acrylamide underwent the aza-Michael addition to generate dimer of acrylamide. The reaction of alcohol with acrylamide can be run at equivalent ratio as the solvent-free mode. Intramolecular hydrogen bond can increase the reactivity of secondary hydroxyl group.
A series of β-alkoxypropionamides were synthesized by the oxa-Michael addition reaction of alcohol with acrylamide. The structure of product was characterized by NMR and HRMS. The effects of catalyst,reaction temperature,and ratio of reactants on the reaction were explored. At 40℃,the oxa-Michael addition reaction of primary alcohol with acrylamide went smoothly under promotion of 5( mol) % activated potassium carbonate. The activity of secondary alcohol is lower. As for tertiary alcohol and phenol,almost no reaction was observed. At higher temperature,the acrylamide underwent the aza-Michael addition to generate dimer of acrylamide. The reaction of alcohol with acrylamide can be run at equivalent ratio as the solvent-free mode. Intramolecular hydrogen bond can increase the reactivity of secondary hydroxyl group.
引文
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[3]J N Yuan,M H Li,N Ji et al.Curr.Org.Synth.,2017,21(13):1205~1226.
[4]C F Nising,S Brase.Chem.Soc.Rev.,2012,41(3):988~999.
[5]Y Fukata,R Miyaji,T Okamura et al.Synthesis,2013,45(12):1627~1634.
[6]F Wang,H J Yang,H Fu et al.Chem.Commun.,2013,49(5):517~519.
[7]H Y Sun,B Zhang,X Y Chen et al.Synthesis,2017,49(10):2205~2214.
[8]C Faltin,E M Fleming,S J Connon.J.Org.Chem.,2004,69(19):6496~6499.
[9]S Dabi,A Zilkha.Eur.Polym.J.,1977,13(7):545~552.
[10]F Nadeau,M Sindt,N Oget.New J.Chem.,2015,39(12):9155~9161.
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[12]W L F Armarego,B A Milloy,W Pendergast.J.Chem.Soc.,Perkin Transac.,1976,1(20):2229~2237.
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