Aerobic oxidation of 2-hydrazinyl-1-methyl-1H-benzo[d]imidazole in situ: A quantum chemical insight into the reaction background

IF 2.218 Q2 Chemistry

Chemical Data Collections Pub Date : 2024-08-26 DOI:10.1016/j.cdc.2024.101161

Andrei V. Erkin, Viktor I. Krutikov

{"title":"Aerobic oxidation of 2-hydrazinyl-1-methyl-1H-benzo[d]imidazole in situ: A quantum chemical insight into the reaction background","authors":"Andrei V. Erkin, Viktor I. Krutikov","doi":"10.1016/j.cdc.2024.101161","DOIUrl":null,"url":null,"abstract":"<div>Herein, attempts at hydrazinolysis of 1-methyl-1H-benzo[d]imidazole-2-sulfonic acid 6 and its potassium salt 9 have been reported. None of them resulted in the isolation of 2-hydrazinyl-1-methyl-1H-benzo[d]imidazole 3. Instead, 1-methyl-1H-benzo[d]imidazol-2(3H)-one 10 was obtained in some cases. The hydrazinolysis failure may be due to the aerobic oxidation of hydrazine 3 in situ. To get into the background for the reaction, the highest occupied molecular orbitals (HOMOs) of compound 3 and relatively oxidation-resistible 2-hydrazinyl-1H-benzo[d]imidazole 11 were comparatively considered. Based on the analysis of the regions of highest density of HOMOs in both hydrazines, the aminoguanidine moiety in compound 3 appeared to be more susceptible to oxidation as compared to the moiety in compound 11.</div>","PeriodicalId":269,"journal":{"name":"Chemical Data Collections","volume":"53 ","pages":"Article 101161"},"PeriodicalIF":2.2180,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Data Collections","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2405830024000491","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"Chemistry","Score":null,"Total":0}

引用次数: 0

Abstract

Herein, attempts at hydrazinolysis of 1-methyl-1H-benzo[d]imidazole-2-sulfonic acid 6 and its potassium salt 9 have been reported. None of them resulted in the isolation of 2-hydrazinyl-1-methyl-1H-benzo[d]imidazole 3. Instead, 1-methyl-1H-benzo[d]imidazol-2(3H)-one 10 was obtained in some cases. The hydrazinolysis failure may be due to the aerobic oxidation of hydrazine 3 in situ. To get into the background for the reaction, the highest occupied molecular orbitals (HOMOs) of compound 3 and relatively oxidation-resistible 2-hydrazinyl-1H-benzo[d]imidazole 11 were comparatively considered. Based on the analysis of the regions of highest density of HOMOs in both hydrazines, the aminoguanidine moiety in compound 3 appeared to be more susceptible to oxidation as compared to the moiety in compound 11.

Abstract Image

查看原文本刊更多论文

2-肼基-1-甲基-1H-苯并[d]咪唑的原位有氧氧化：从量子化学角度洞察反应背景

在此，报告了 1-甲基-1H-苯并[d]咪唑-2-磺酸 6 及其钾盐 9 的肼解尝试。这些尝试都没有分离出 2-肼基-1-甲基-1H-苯并[d]咪唑 3。相反，在某些情况下会得到 1-甲基-1H-苯并[d]咪唑-2(3H)-酮 10。肼解失败的原因可能是肼 3 在原位发生了有氧氧化。为了了解反应的背景，我们对化合物 3 和相对抗氧化的 2-肼基-1H-苯并[d]咪唑 11 的最高占位分子轨道（HOMOs）进行了比较研究。根据对两种肼中 HOMOs 最高密度区域的分析，化合物 3 中的氨基胍分子似乎比化合物 11 中的氨基胍分子更容易被氧化。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Chemical Data Collections Chemistry-Chemistry (all)

CiteScore

6.10

自引率

0.00%

发文量

169

审稿时长

24 days

期刊介绍： Chemical Data Collections (CDC) provides a publication outlet for the increasing need to make research material and data easy to share and re-use. Publication of research data with CDC will allow scientists to: -Make their data easy to find and access -Benefit from the fast publication process -Contribute to proper data citation and attribution -Publish their intermediate and null/negative results -Receive recognition for the work that does not fit traditional article format. The research data will be published as ''data articles'' that support fast and easy submission and quick peer-review processes. Data articles introduced by CDC are short self-contained publications about research materials and data. They must provide the scientific context of the described work and contain the following elements: a title, list of authors (plus affiliations), abstract, keywords, graphical abstract, metadata table, main text and at least three references. The journal welcomes submissions focusing on (but not limited to) the following categories of research output: spectral data, syntheses, crystallographic data, computational simulations, molecular dynamics and models, physicochemical data, etc.