论文部分内容阅读
利用密度泛函理论(DFT)的B3LYP/6-31G(d,p)计算方法研究了次氯酸钠氧化环化5-氯-2-硝基苯胺合成5-氯-苯并氧化呋咱的反应,采用连续介质模型(PCM)评估了溶剂效应.提出两种可能的分步反应通道:(1)氧化、移氢、脱水和环化,(2)移氢、亚氨基氢扭转、氧化、脱水和环化;前者为优势通道.非极性的CCl4溶剂有较低的活化能垒,比极性的乙醇溶剂更有利于5-氯-2-硝基苯胺的合成.标题反应的机理类似于次氯酸钠氧化邻硝基苯胺合成苯并氧化呋咱,但其速控步的活化能垒更低,反应更易进行.
The reaction of 5-chloro-benzofuranoxan with 5-chloro-2-nitroaniline was oxidatively cyclized by sodium hypochlorite using the B3LYP / 6-31G (d, p) method of density functional theory (DFT) Solvent effects were evaluated by a continuous media model (PCM) Two possible step-reaction channels were proposed: (1) oxidation, hydrogen transfer, dehydration and cyclization, (2) hydrogen transfer, iminium hydrogen reversal, oxidation, dehydration and ring The former is the dominant channel.The non-polar CCl4 solvent has a lower activation energy barrier and is more favorable for the synthesis of 5-chloro-2-nitroaniline than the polar ethanolic solvent.The mechanism of the title reaction is similar to that of sodium hypochlorite Nitroaniline benzofuran furazan synthesis, but its speed control steps lower activation barrier, the reaction easier.