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Article: Unusual Acetonitrile Adduct Formed via Photolysis of 4′-Chloro-2-Hydroxybiphenyl in Aqueous Solution

TitleUnusual Acetonitrile Adduct Formed via Photolysis of 4′-Chloro-2-Hydroxybiphenyl in Aqueous Solution
Authors
Issue Date2020
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
The Journal of Organic Chemistry, 2020, v. 85 n. 18, p. 11635-11640 How to Cite?
AbstractIn this work, 2,4′-dichlorobiphenyl (1) yielded 4′-chloro-2-hydroxybiphenyl (2) after photolysis in neutral acetonitrile aqueous (ACN–H2O) solutions. Ultrafast spectroscopic measurements and density functional theory (DFT) computations were performed for 2 in ACN and ACN–H2O (v/v, 1:1). These results were compared with previously published results for 2-hydroxybiphenyl (3). The counterparts 2 and 3 went through a singlet excited state intramolecular proton transfer (ESIPT) in ACN but behaved differently in ACN–H2O with a dehydrochlorination process occurring for 2 and an ESIPT taking place for 3. Computational results indicate that the phenol O–H bond elongates after photoexcitation to induce a concerted asynchronous process with the C–Cl bond increasing first followed by HCl elimination. A biradical intermediate (IM1) is then formed with some spin located at the phenyl 4′-C radical that appears to favor a hydrogen atom transfer (HAT) process and some spin located on phenoxyl that appears to prefer a subsequent •CH2CN radical rebound. The hydrogen bond promotes HCl elimination, while this is disfavored for ESIPT, making 4′-Cl extrusion the predominant process in ACN–H2O solutions. The mechanistic investigations have fundamental and significant implications for the understanding of polychlorinated biphenyl photolysis in an aqueous environment and hence the photodegradation of these kinds of pollutants in the natural environment.
Persistent Identifierhttp://hdl.handle.net/10722/300917
ISSN
2023 Impact Factor: 3.3
2023 SCImago Journal Rankings: 0.724
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorZhang, X-
dc.contributor.authorGuo, Y-
dc.contributor.authorDallin, E-
dc.contributor.authorMa, J-
dc.contributor.authorDai, M-
dc.contributor.authorPhillips, DL-
dc.date.accessioned2021-07-06T03:12:01Z-
dc.date.available2021-07-06T03:12:01Z-
dc.date.issued2020-
dc.identifier.citationThe Journal of Organic Chemistry, 2020, v. 85 n. 18, p. 11635-11640-
dc.identifier.issn0022-3263-
dc.identifier.urihttp://hdl.handle.net/10722/300917-
dc.description.abstractIn this work, 2,4′-dichlorobiphenyl (1) yielded 4′-chloro-2-hydroxybiphenyl (2) after photolysis in neutral acetonitrile aqueous (ACN–H2O) solutions. Ultrafast spectroscopic measurements and density functional theory (DFT) computations were performed for 2 in ACN and ACN–H2O (v/v, 1:1). These results were compared with previously published results for 2-hydroxybiphenyl (3). The counterparts 2 and 3 went through a singlet excited state intramolecular proton transfer (ESIPT) in ACN but behaved differently in ACN–H2O with a dehydrochlorination process occurring for 2 and an ESIPT taking place for 3. Computational results indicate that the phenol O–H bond elongates after photoexcitation to induce a concerted asynchronous process with the C–Cl bond increasing first followed by HCl elimination. A biradical intermediate (IM1) is then formed with some spin located at the phenyl 4′-C radical that appears to favor a hydrogen atom transfer (HAT) process and some spin located on phenoxyl that appears to prefer a subsequent •CH2CN radical rebound. The hydrogen bond promotes HCl elimination, while this is disfavored for ESIPT, making 4′-Cl extrusion the predominant process in ACN–H2O solutions. The mechanistic investigations have fundamental and significant implications for the understanding of polychlorinated biphenyl photolysis in an aqueous environment and hence the photodegradation of these kinds of pollutants in the natural environment.-
dc.languageeng-
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc-
dc.relation.ispartofThe Journal of Organic Chemistry-
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in [JournalTitle], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, see http://pubs.acs.org/page/policy/articlesonrequest/index.html].-
dc.titleUnusual Acetonitrile Adduct Formed via Photolysis of 4′-Chloro-2-Hydroxybiphenyl in Aqueous Solution-
dc.typeArticle-
dc.identifier.emailZhang, X: heeteen@hku.hk-
dc.identifier.emailPhillips, DL: phillips@hku.hk-
dc.identifier.authorityPhillips, DL=rp00770-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/acs.joc.0c01115-
dc.identifier.pmid32842735-
dc.identifier.scopuseid_2-s2.0-85092921063-
dc.identifier.hkuros323195-
dc.identifier.volume85-
dc.identifier.issue18-
dc.identifier.spage11635-
dc.identifier.epage11640-
dc.identifier.isiWOS:000574920600006-
dc.publisher.placeUnited States-

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