Studies On Amidation Reaction Of Methyl (Meth)Acrylate And Amines

The synthesis of N,N-diethylacrylamide(DEAA) was studied using methyl acrylate(MA) and diethylamine as starting materials, including Michael addition reaction, amidation reaction and pyrolysis reaction. The effects of reaction temperature, time, n(MA):n(diethylamine), types and amounts of catalyst and inhibitor on reaction result were examined. It was shown that the optimal Michael addition reaction conditions and result were:n(MA):n(diethylamine)=1:1.1, reaction temperature75℃, reaction time4h, the yield of methyl3-(diethylamino)propanoate98.7%and purity over99.5%after purification; the optimal amidation reaction conditions and result:sodium methoxide as catalyst, n(methyl3-(diethylamino)propanoate):n(diethylamine)=1:3, m(sodium methoxide):m(methyl3-(diethylamino)propanoate))=1:50, reaction temperature170℃, reaction time24h, the yield of3-(diethylamino)-N,N-diethyl-propanamide81.1%; the optimal pyrolysis reaction conditions and result:ZJ705as inhibitor, m(ZJ705):m(MA)=1:100, pyrolysis time3h, pyrolysis temperature170℃, the yield of DEAA74.4%and the purity over98.5%after purification.The synthesis of N-[3-(dimethylamino)propyl]acrylamide(DMAPAA) was studied using MA and N,N-dimethyl-1,3-propanediamine as starting materials, including Michael addition reaction, amidation reaction and pyrolysis reaction. The effects of reaction temperature, time, n(MA):n(N,N-dimethyl-1,3-propanediamine), types and amounts of catalyst and inhibitor on reaction result were examined. It was shown that the optimal "one-pot" reaction conditions and result:n(MA):n(N,N-dimethyl-1,3-propanediamine)=1:2.5, in first stage, reaction temperature100℃, reaction time2h, conversion of MA above98.9%; in second stage, reaction temperature175℃, reaction time4h, the yield of amidation product up to94.5%; the optimal pyrolysis reaction conditions and result:36.5%(m) hydrochloric acid as catalyst, phenothiazine as inhibitor, m(HCl):(MA)=1.5:100, m(phenothiazine):m(MA)=1:100, pyrolysis temperature240±10℃, pyrolysis time3h, pyrolysis rate90.1%, the yield of DMAPAA62.4%and the purity over98.4%after purification.The synthesis of N-[3-(dimethylamino)propyl]methacrylamide(DMAPMAA) was primarily studied using methyl methacrylate(MMA) and N,N-dimethyl-1,3-propanediamine as starting materials, dibutyltin oxide as catalyst, ZJ705as inhibitor.The effects of types of catalyst and inhibitor and reaction time on reaction result were examined. The obtained primary reaction conditions of DMAPMAA were: n(MMA):n(N,N-dimethyl-1,3-propanediamine)=3:1, m(dibutyltin oxide):m(total materials)=2:100, m(ZJ705):m(total materials)=0.2:100, reflux temperature110℃reaction time3h. The yield of DMAPMAA over87.5%and the purity over97.5%after purification.The structures of DEAA and DMAPAA were characterized by FT-IR and1HNMR. The structure of DMAPMAA was characterized by FT-IR.