Photodeamination Reaction Mechanism in Aminomethyl p-Cresol Derivatives: Different Reactivity of Amines and Ammonium Salts

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dc.contributor.authorSkalamera, Dani
dc.contributor.authorBohne, Cornelia
dc.contributor.authorLandgraf, Stephan
dc.contributor.authorBasaric, Nikola
dc.date.accessioned2020-08-21T23:56:23Z
dc.date.available2020-08-21T23:56:23Z
dc.date.copyright2015en_US
dc.date.issued2015
dc.description.abstractDerivatives of p-cresol 1–4 were synthesized, and their photochemical reactivity, acid–base, and photophysical properties were investigated. The photoreactivity of amines 1 and 3 is different from that for the corresponding ammonium salts 2 and 4. All compounds have low fluorescence quantum yields because the excited states undergo deamination reactions, and for all cresols the formation of quinone methides (QMs) was observed by laser flash photolysis. The reactivity observed is a consequence of the higher acidity of the S1 states of these p-cresols and the ability for excited-state intramolecular proton transfer (ESIPT) to occur in the case of 1 and 3, but not for salts 2 and 4. In aqueous solvent, deamination depends largely on the prototropic form of the molecule. The most efficient deamination takes place when monoamine is in the zwitterionic form (pH 9–11) or diamine is in the monocationic form (pH 7–9). QM1, QM3, and QM4 react with nucleophiles, and QM1 exhibits a shorter lifetime when formed from 1 (τ in CH3CN = 5 ms) than from 2 (τ in CH3CN = 200 ms) due to the reaction with eliminated dimethylamine, which acts as a nucleophile in the case of QM1. Bifunctional QM4 undergoes two types of reactions with nucleophiles, giving adducts or new QM species. The mechanistic diversity uncovered is of significance to biological systems, such as for the use of bifunctional QMs to achieve DNA cross-linking.en_US
dc.description.reviewstatusRevieweden_US
dc.description.scholarlevelFacultyen_US
dc.description.sponsorshipThese materials are based on work financed by the Croatian Foundation for Science (HRZZ, IP-2014-09-6312), the Natural Sciences and Engineering Research Council (NSERC) for CB (RGPIN-121389-2012), the University of Victoria (UVIC), and EPA-Austria. N.B. and Đ.Š. thank Dr. K. Mlinarić-Majerski for the useful discussions. N.B. thanks UVIC for support and Professor P. Wan for support and useful discussions.en_US
dc.identifier.citationSkalamera, D., Bohne, C., Landgraf, S., & Basaric, N. (2015). Photodeamination Reaction Mechanism in Aminomethyl p-Cresol Derivatives: Different Reactivity of Amines and Ammonium Salts. Journal of Organic Chemistry, 80(21), 10817-10828. https://doi.org/10.1021/acs.joc.5b01991.en_US
dc.identifier.urihttps://doi.org/10.1021/acs.joc.5b01991
dc.identifier.urihttp://hdl.handle.net/1828/12013
dc.language.isoenen_US
dc.publisherJournal of Organic Chemistryen_US
dc.subjectSaltsen_US
dc.subjectAminesen_US
dc.subjectFluorescenceen_US
dc.subjectSolventsen_US
dc.subjectIrradiationen_US
dc.titlePhotodeamination Reaction Mechanism in Aminomethyl p-Cresol Derivatives: Different Reactivity of Amines and Ammonium Saltsen_US
dc.typePostprinten_US

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