Combined Kinetic, and Theoretical Approaches for the Study of the SEAr Reactions of 2-(2’,4’,6’-trinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide with 5-R-substituted Indoles in Acetonitrile

Combined Kinetic, and Theoretical Approaches for the Study of the SEAr Reactions of 2-(2’,4’,6’-trinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide with 5-R-substituted Indoles in Acetonitrile | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Combined Kinetic, and Theoretical Approaches for the Study of the SEAr Reactions of 2-(2’,4’,6’-trinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide with 5-R-substituted Indoles in Acetonitrile Ons Amamou, Amel Hedhli, Takwa Slama, Sahbi Ayachi, Taoufik Boubaker This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3882437/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 13 Apr, 2024 Read the published version in Chemical Papers → Version 1 posted 4 You are reading this latest preprint version Abstract We present a kinetic and theoretical study of nucleophilic addition reactions involving 2-(2’,4’,6’-trinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide 1 with a series of 5-R-substituted indoles 2a-e (R = CN, Cl, H, Me and NH 2 ) in acetonitrile at 20°C. Single electron transfer (SET) mechanism was proposed and confirmed by the agreement between the rate constants (k) and the oxidation potentials (E p ox ) of these series of indoles. Using Mayr's equation, the electrophilicity parameter ( E) of 1 at C-7 position is derived and compared with the same parameter estimate using empirical equation E vs . pK a . Density Functional Theory (DFT) calculations were performed to confirm the suggested reaction mechanisms and elucidate the origin of the electrophilic reactivity of 1 . Notably, a linear correlation (R 2 = 0.9957) between the experimental nucleophilicity ( N ) and the theoretical model of nucleophilicity (ω −1 ) determined in this work of various 5-R-substituted indoles has been obtained and discussed. Kinetics Benzotriazoles Equation of Mayr Electrophilicity Nucleophilicity Single Electron Transfer Mecanism DFT Analysis Full Text Supplementary Files SupportingInformation.doc Cite Share Download PDF Status: Published Journal Publication published 13 Apr, 2024 Read the published version in Chemical Papers → Version 1 posted Reviewers agreed at journal 02 Feb, 2024 Reviewers invited by journal 02 Feb, 2024 Editor assigned by journal 22 Jan, 2024 First submitted to journal 19 Jan, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3882437","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":270815853,"identity":"78d6185e-00c5-4021-8d74-387c2c07de34","order_by":0,"name":"Ons Amamou","email":"","orcid":"","institution":"Université de Monastir Faculté des Sciences de Monastir: Universite de Monastir Faculte des Sciences de Monastir","correspondingAuthor":false,"prefix":"","firstName":"Ons","middleName":"","lastName":"Amamou","suffix":""},{"id":270815854,"identity":"f3ff48f2-916e-412d-8265-6856709a334c","order_by":1,"name":"Amel 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Acetonitrile","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"chemical-papers","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"chpa","sideBox":"Learn more about [Chemical Papers](http://link.springer.com/journal/11696)","snPcode":"11696","submissionUrl":"https://www.editorialmanager.com/CHPA/default.aspx","title":"Chemical Papers","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Kinetics, Benzotriazoles, Equation of Mayr, Electrophilicity, Nucleophilicity, Single Electron Transfer Mecanism, DFT Analysis","lastPublishedDoi":"10.21203/rs.3.rs-3882437/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3882437/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eWe present a kinetic and theoretical study of nucleophilic addition reactions involving 2-(2\u0026rsquo;,4\u0026rsquo;,6\u0026rsquo;-trinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide \u003cb\u003e1\u003c/b\u003e with a series of 5-R-substituted indoles \u003cb\u003e2a-e\u003c/b\u003e (R\u0026thinsp;=\u0026thinsp;CN, Cl, H, Me and NH\u003csub\u003e2\u003c/sub\u003e) in acetonitrile at 20\u0026deg;C. Single electron transfer (SET) mechanism was proposed and confirmed by the agreement between the rate constants (k) and the oxidation potentials (E\u003csub\u003ep\u003c/sub\u003e\u003csup\u003eox\u003c/sup\u003e) of these series of indoles. Using Mayr's equation, the electrophilicity parameter (\u003cem\u003eE)\u003c/em\u003e of \u003cb\u003e1\u003c/b\u003e at C-7 position is derived and compared with the same parameter estimate using empirical equation \u003cem\u003eE vs\u003c/em\u003e. pK\u003csub\u003ea\u003c/sub\u003e. Density Functional Theory (DFT) calculations were performed to confirm the suggested reaction mechanisms and elucidate the origin of the electrophilic reactivity of \u003cb\u003e1\u003c/b\u003e. Notably, a linear correlation (R\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;=\u0026thinsp;0.9957) between the experimental nucleophilicity (\u003cem\u003eN\u003c/em\u003e) and the theoretical model of nucleophilicity (ω\u003csup\u003e\u0026minus;1\u003c/sup\u003e) determined in this work of various 5-R-substituted indoles has been obtained and discussed.\u003c/p\u003e","manuscriptTitle":"Combined Kinetic, and Theoretical Approaches for the Study of the SEAr Reactions of 2-(2’,4’,6’-trinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide with 5-R-substituted Indoles in Acetonitrile","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-02-06 17:24:44","doi":"10.21203/rs.3.rs-3882437/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2024-02-02T11:54:12+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-02-02T11:51:35+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-01-22T10:17:45+00:00","index":"","fulltext":""},{"type":"submitted","content":"Chemical Papers","date":"2024-01-19T11:00:20+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"chemical-papers","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"chpa","sideBox":"Learn more about [Chemical Papers](http://link.springer.com/journal/11696)","snPcode":"11696","submissionUrl":"https://www.editorialmanager.com/CHPA/default.aspx","title":"Chemical Papers","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"1fdb10b3-ca7a-4e7a-8e06-3c2815659465","owner":[],"postedDate":"February 6th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-04-15T15:10:54+00:00","versionOfRecord":{"articleIdentity":"rs-3882437","link":"https://doi.org/10.1007/s11696-024-03440-3","journal":{"identity":"chemical-papers","isVorOnly":false,"title":"Chemical Papers"},"publishedOn":"2024-04-13 15:02:06","publishedOnDateReadable":"April 13th, 2024"},"versionCreatedAt":"2024-02-06 17:24:44","video":"","vorDoi":"10.1007/s11696-024-03440-3","vorDoiUrl":"https://doi.org/10.1007/s11696-024-03440-3","workflowStages":[]},"version":"v1","identity":"rs-3882437","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3882437","identity":"rs-3882437","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}