{"title":"First Report of Hydrolysis of Dihydrazides into Carboxylates in Mild Aqueous Conditions","authors":"Kilian Caillaud, Kilian Pouchelon, Fernande Da Cruz-Boisson, Élodie Fromentin, Agnès Crépet, Catherine Ladavière","doi":"10.1002/hlca.202400086","DOIUrl":null,"url":null,"abstract":"<p>The hydrolysis of dihydrazides was studied at different pH values in water at 25 °C. The resulting species were analyzed by HPLC, <sup>1</sup>H-NMR, and MALDI-TOF mass spectrometry. Among these species, unexpected molecules bearing carboxylate moieties were detected. Based on this analysis, a 2-step hydrolysis mechanism was proposed involving the formation of cyclic and linear intermediates before the addition of a water molecule to lead to carboxylate moieties. The first step was shown to be rate-determining and catalyzed in acidic conditions. To the best of our knowledge, this study shows for the first time that the hydrolysis of some dihydrazides can spontaneously occur in mild aqueous conditions, contrary to monohydrazides which do not reveal such a hydrolysis in same conditions. This draws attention to an overlooked degradation which might need more consideration, and possibly highlights new ways of soft hydrolysis conditions.</p>","PeriodicalId":12842,"journal":{"name":"Helvetica Chimica Acta","volume":"108 5","pages":""},"PeriodicalIF":1.5000,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Helvetica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/hlca.202400086","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The hydrolysis of dihydrazides was studied at different pH values in water at 25 °C. The resulting species were analyzed by HPLC, 1H-NMR, and MALDI-TOF mass spectrometry. Among these species, unexpected molecules bearing carboxylate moieties were detected. Based on this analysis, a 2-step hydrolysis mechanism was proposed involving the formation of cyclic and linear intermediates before the addition of a water molecule to lead to carboxylate moieties. The first step was shown to be rate-determining and catalyzed in acidic conditions. To the best of our knowledge, this study shows for the first time that the hydrolysis of some dihydrazides can spontaneously occur in mild aqueous conditions, contrary to monohydrazides which do not reveal such a hydrolysis in same conditions. This draws attention to an overlooked degradation which might need more consideration, and possibly highlights new ways of soft hydrolysis conditions.
期刊介绍：
Helvetica Chimica Acta, founded by the Swiss Chemical Society in 1917, is a monthly multidisciplinary journal dedicated to the dissemination of knowledge in all disciplines of chemistry (organic, inorganic, physical, technical, theoretical and analytical chemistry) as well as research at the interface with other sciences, where molecular aspects are key to the findings. Helvetica Chimica Acta is committed to the publication of original, high quality papers at the frontier of scientific research. All contributions will be peer reviewed with the highest possible standards and published within 3 months of receipt, with no restriction on the length of the papers and in full color.
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