Reaction of N-methylformamide with dimethyl carbonate: a DFT study

IF 1.6 4区 化学 Q4 CHEMISTRY, PHYSICAL
Yakov D. Samuilov, Alexander Ya. Samuilov
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引用次数: 0

Abstract

The detailed analysis of the mechanism of metathesis of N-methylformamide with dimethyl carbonate leading to the formation of N, O-dimethylcarbamate was carried out using the B3LYP/6-311++G(df,p), B3LYP-D3(BJ)/6-311++G(df,p) and ωB97XD/6-311++G(df,p) density functional methods. The reactions proceed in three stages. The first step consists in the tautomeric conversion of N-methylformamide to iminol. The second stage, which is the rate-limiting step, involves the addition of dimethyl carbonate via the N=C π-bond of iminol. The third stage of the reaction is the cleavage of the methyl formate molecule from N-methyl-N-[(hydroxy)(methoxy)methyl]-O-methylcarbamate. This conversion results in the formation of N, O-dimethylcarbamate. All stages of the reactions are catalyzed by associates of alcohols, which lead to a strong decrease in activation enthalpies.

Abstract Image

N 甲基甲酰胺与碳酸二甲酯的反应:DFT 研究
采用 B3LYP/6-311++G(df,p)、B3LYP-D3(BJ)/6-311++G(df,p) 和 ωB97XD/6-311++G(df,p) 密度泛函方法,详细分析了 N-甲基甲酰胺与碳酸二甲酯发生偏析反应生成 N, O-二甲基氨基甲酸酯的机理。反应分三个阶段进行。第一步是将 N-甲基甲酰胺同分异构转化为亚氨基醇。第二步是限速步骤,包括通过亚氨基醇的 N=C π 键加入碳酸二甲酯。反应的第三阶段是从 N-甲基-N-[(羟基)(甲氧基)甲基]-O-甲基氨基甲酸酯中裂解出甲酸甲酯分子。这种转化的结果是形成 N,O-二甲基氨基甲酸酯。反应的所有阶段都是由醇类的同系物催化的,这导致活化焓的强烈下降。
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来源期刊
Theoretical Chemistry Accounts
Theoretical Chemistry Accounts 化学-物理化学
CiteScore
3.40
自引率
0.00%
发文量
74
审稿时长
3.8 months
期刊介绍: TCA publishes papers in all fields of theoretical chemistry, computational chemistry, and modeling. Fundamental studies as well as applications are included in the scope. In many cases, theorists and computational chemists have special concerns which reach either across the vertical borders of the special disciplines in chemistry or else across the horizontal borders of structure, spectra, synthesis, and dynamics. TCA is especially interested in papers that impact upon multiple chemical disciplines.
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