Tert‐butyl hydroperoxide‐promoted guanylation of amines with benzoylthioureas: mechanistic insights by HRMS and 1H NMR
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Universidade Federal de Minas Gerais
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Artigo de periódico
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Herein, we present a mechanistic study on tert‐butyl hydroperoxide‐promotedguanylation of thioureas by monitoring short lifetime intermediates using electrosprayionisation/time‐of‐flight high resolution mass spectrometry (ESI‐Q‐TOF HRMS).Moreover, 1H nuclear magnetic resonance data allowed us to access kinetic parametersfor the main species involved which, allied to the HRMS results, furnished valuableinsights over previously reported observations. The results suggested an addition/elimina-tion mechanism involving the aminoiminomethanesulphinic acid, RNC(SO2H)NHR′,and the nucleophilic amine as the main pathway to yield the guanidine. Noteworthy,benzoylthiourea consumption rate presented a nonlinear kinetic behaviour, while tBuOOHand the nucleophilic amine consumptions were found to follow second‐order kinetics.
Abstract
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Química, Espectrometria de massa, Ressonância magnética nuclear, Guanidina, Aminas, Reação nucleofilica, Tiouréia - Oxidação, Cinética química
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Guanylation, Terc-Butyl hydroxyperoxide, Thiourea oxidation, Mass spectrometry
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https://www.sciencedirect.com/org/science/article/abs/pii/S0894323022010967