尿素与甲胺反应的理论研究:亲核加成途径

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Accounts of Chemical Research Pub Date : 2023-11-25 DOI:10.1007/s00214-023-03074-w

Ekaterina P. Kozhanova, Yakov D. Samuilov, Alexander Y. Samuilov

{"title":"尿素与甲胺反应的理论研究:亲核加成途径","authors":"Ekaterina P. Kozhanova, Yakov D. Samuilov, Alexander Y. Samuilov","doi":"10.1007/s00214-023-03074-w","DOIUrl":null,"url":null,"abstract":"The B3LYP and wB97XD density functional methods were used to study the mechanisms and thermodynamic parameters of the activation and reactions of non-catalytic and catalyzed by phenol and p-toluenesulfonic acid reactions of urea with methylamine. The interaction proceeds stepwise with the intermediate formation of N-methylurea. The non-catalytic interaction has a large activation barrier. In the case of participation of methylamine dimer, the activation barrier decreases, but, nevertheless, remains high. During catalysis by phenol and p-toluenesulfonic acid, compounds exhibiting biphilic properties, the activation barrier decreases. The greatest decrease in the activation barrier is observed during catalysis with p-toluenesulfonic acid.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4000,"publicationDate":"2023-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Theoretical study of reaction of urea with methylamine: nucleophilic addition pathway\",\"authors\":\"Ekaterina P. Kozhanova, Yakov D. Samuilov, Alexander Y. Samuilov\",\"doi\":\"10.1007/s00214-023-03074-w\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The B3LYP and wB97XD density functional methods were used to study the mechanisms and thermodynamic parameters of the activation and reactions of non-catalytic and catalyzed by phenol and p-toluenesulfonic acid reactions of urea with methylamine. The interaction proceeds stepwise with the intermediate formation of N-methylurea. The non-catalytic interaction has a large activation barrier. In the case of participation of methylamine dimer, the activation barrier decreases, but, nevertheless, remains high. During catalysis by phenol and p-toluenesulfonic acid, compounds exhibiting biphilic properties, the activation barrier decreases. The greatest decrease in the activation barrier is observed during catalysis with p-toluenesulfonic acid.\",\"PeriodicalId\":1,\"journal\":{\"name\":\"Accounts of Chemical Research\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":16.4000,\"publicationDate\":\"2023-11-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Accounts of Chemical Research\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1007/s00214-023-03074-w\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Accounts of Chemical Research","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1007/s00214-023-03074-w","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

摘要

采用B3LYP和wB97XD密度泛函方法研究了非催化、苯酚催化和对甲苯磺酸催化尿素与甲胺反应的活化和反应机理及热力学参数。随着n -甲基脲的中间生成，相互作用逐步进行。非催化相互作用具有较大的激活势垒。在甲胺二聚体参与的情况下，激活势垒降低，但仍然很高。在苯酚和对甲苯磺酸的催化作用下，具有亲和性的化合物的活化势垒降低。在对甲苯磺酸催化过程中，活性势垒的降低幅度最大。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Theoretical study of reaction of urea with methylamine: nucleophilic addition pathway

查看原文本刊更多论文

Theoretical study of reaction of urea with methylamine: nucleophilic addition pathway

The B3LYP and wB97XD density functional methods were used to study the mechanisms and thermodynamic parameters of the activation and reactions of non-catalytic and catalyzed by phenol and p-toluenesulfonic acid reactions of urea with methylamine. The interaction proceeds stepwise with the intermediate formation of N-methylurea. The non-catalytic interaction has a large activation barrier. In the case of participation of methylamine dimer, the activation barrier decreases, but, nevertheless, remains high. During catalysis by phenol and p-toluenesulfonic acid, compounds exhibiting biphilic properties, the activation barrier decreases. The greatest decrease in the activation barrier is observed during catalysis with p-toluenesulfonic acid.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.