Arianna M H Wheeler, Sei-Chang Ahn, Niklas Kraemer, Thomas R Hoye
{"title":"Relative Rates of Transesterification vis-à-vis Newman's Rule of Six.","authors":"Arianna M H Wheeler, Sei-Chang Ahn, Niklas Kraemer, Thomas R Hoye","doi":"10.1021/acs.joc.4c01673","DOIUrl":null,"url":null,"abstract":"<p><p>The relative reactivity of a systematic series of simple aliphatic acetate esters has been measured. Exposure of pairs of esters of increasing remote steric hindrance (by altering the degree of branching of the ester alkyl group) to a methanolic solution of Cs<sub>2</sub>CO<sub>3</sub> proved to be a reliable (and general) method for quantitating the rate differences in these base-catalyzed transesterification reactions. The trends in relative rates are in accordance with the qualitative \"Rule of Six\" put forward by Melvin S. Newman in 1950, as deduced then from interpretation of earlier reports of ease of Fischer esterification reactions.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3000,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Organic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.joc.4c01673","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/9/6 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
引用次数: 0
Abstract
The relative reactivity of a systematic series of simple aliphatic acetate esters has been measured. Exposure of pairs of esters of increasing remote steric hindrance (by altering the degree of branching of the ester alkyl group) to a methanolic solution of Cs2CO3 proved to be a reliable (and general) method for quantitating the rate differences in these base-catalyzed transesterification reactions. The trends in relative rates are in accordance with the qualitative "Rule of Six" put forward by Melvin S. Newman in 1950, as deduced then from interpretation of earlier reports of ease of Fischer esterification reactions.
期刊介绍:
The Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.