{"title":"Reaction of N-methylformamide with dimethyl carbonate: a DFT study","authors":"Yakov D. Samuilov, Alexander Ya. Samuilov","doi":"10.1007/s00214-024-03144-7","DOIUrl":null,"url":null,"abstract":"<p>The detailed analysis of the mechanism of metathesis of <i>N</i>-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 <i>N</i>-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 <i>N</i>-methyl-<i>N</i>-[(hydroxy)(methoxy)methyl]-O-methylcarbamate. This conversion results in the formation of <i>N</i>, O-dimethylcarbamate. All stages of the reactions are catalyzed by associates of alcohols, which lead to a strong decrease in activation enthalpies.</p>","PeriodicalId":23045,"journal":{"name":"Theoretical Chemistry Accounts","volume":null,"pages":null},"PeriodicalIF":1.6000,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Theoretical Chemistry Accounts","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1007/s00214-024-03144-7","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
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.
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.