Oleksii Pidvyshennyi , Kostiantyn P. Melnykov , Oleksandr Liashuk , Dmytro Lesyk , Yuliia Holota , Petro Borysko , Oleksandr O. Grygorenko
{"title":"Acidity of saturated (hetero)cyclic α-fluoro carboxylic acids and lipophilicity of their amide derivatives","authors":"Oleksii Pidvyshennyi , Kostiantyn P. Melnykov , Oleksandr Liashuk , Dmytro Lesyk , Yuliia Holota , Petro Borysko , Oleksandr O. Grygorenko","doi":"10.1016/j.jfluchem.2024.110316","DOIUrl":null,"url":null,"abstract":"<div><p>Analysis of the physicochemical parameters of saturated (hetero)cyclic carboxylic acids and their α-fluorinated analogues is described. Measured p<em>K</em><sub>a</sub> values revealed a significant influence of the single fluorine substituent on the compound's acidity (p<em>K</em><sub>a</sub> decreased by 1.3–2.4 units). This effect did not demonstrate additivity with electronic effects of other heteroatom (i.e., cyclic ether moiety). On the contrary, lipophilicity (Log<em>P</em>) of the corresponding anilides was almost unaffected upon α-substitution with a fluorine atom and mainly governed by the nature of the (hetera)cycloalkyl substituent. The obtained results suggest that polarization of the C–F bonds themselves does not define the fluorine effect on the compound's lipophilicity.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":"278 ","pages":"Article 110316"},"PeriodicalIF":1.7000,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Fluorine Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022113924000769","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Analysis of the physicochemical parameters of saturated (hetero)cyclic carboxylic acids and their α-fluorinated analogues is described. Measured pKa values revealed a significant influence of the single fluorine substituent on the compound's acidity (pKa decreased by 1.3–2.4 units). This effect did not demonstrate additivity with electronic effects of other heteroatom (i.e., cyclic ether moiety). On the contrary, lipophilicity (LogP) of the corresponding anilides was almost unaffected upon α-substitution with a fluorine atom and mainly governed by the nature of the (hetera)cycloalkyl substituent. The obtained results suggest that polarization of the C–F bonds themselves does not define the fluorine effect on the compound's lipophilicity.
期刊介绍：
The Journal of Fluorine Chemistry contains reviews, original papers and short communications. The journal covers all aspects of pure and applied research on the chemistry as well as on the applications of fluorine, and of compounds or materials where fluorine exercises significant effects. This can include all chemistry research areas (inorganic, organic, organometallic, macromolecular and physical chemistry) but also includes papers on biological/biochemical related aspects of Fluorine chemistry as well as medicinal, agrochemical and pharmacological research. The Journal of Fluorine Chemistry also publishes environmental and industrial papers dealing with aspects of Fluorine chemistry on energy and material sciences. Preparative and physico-chemical investigations as well as theoretical, structural and mechanistic aspects are covered. The Journal, however, does not accept work of purely routine nature.
For reviews and special issues on particular topics of fluorine chemistry or from selected symposia, please contact the Regional Editors for further details.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
