The effect of the electrophilic group on the hierarchy of nucleofuges in the aminolysis reactions of thiol- and dithiocarbonates with secondary alicyclic amines: A kinetic and theoretical study

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dc.contributor.authorMontecinos, Rodrigo
dc.contributor.authorGazitua, Marcela
dc.contributor.authorSantos, Jose G.
dc.date.accessioned2025-01-23T21:15:58Z
dc.date.available2025-01-23T21:15:58Z
dc.date.issued2019
dc.description.abstractThe aminolysis reactions of O-(4-nitrophenyl) S-aryl dithiocarbonates with different secondary alicyclic amines (SAA) lead to the formation of different 4-nitrophenyl:S-aryl ratios (56:44 and 47:53 for benzenethiol and 4-chlorobenzenethiol, respectively). For the corresponding thiolcarbonates, 4-nitrophenol was the lone product, evidencing the effect of the electrophile moiety on the nucleofugacity hierarchy. The kinetic results show that in the mechanism there are two tetrahedral intermediates: one zwitterionic (T-+/-) and one anionic (T-). As model reactions, the reactions of O-(4-nitrophenyl) S-phenyl thiol- and dithiocarbonates with morpholine were theoretically examined using DFT methods. Theoretical calculations were performed using a continuous solvation model in the absence and presence of one and two explicit water molecules. The microsolvation of T- by one explicit water molecule was predicted as having O-(4-nitrophenyl):S-phenyl distributions of 52:48 and 98:2 for dithiocarbonates and thiolcarbonates, respectively. These results have allowed us to establish that processes such as microsolvation, electronic distribution and the structure of the reactive centers participate in the departure of the leaving groups in the thiolcarbonate and dithiocarbonate aminolysis, although the preferential solvation of these centers seems to have a predominant role in the nucleofuge hierarchy.
dc.fuente.origenWOS
dc.identifier.doi10.1039/c9nj00385a
dc.identifier.eissn1369-9261
dc.identifier.issn1144-0546
dc.identifier.urihttps://doi.org/10.1039/c9nj00385a
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/101105
dc.identifier.wosidWOS:000465091000032
dc.issue.numero16
dc.language.isoen
dc.pagina.final6379
dc.pagina.inicio6372
dc.revistaNew journal of chemistry
dc.rightsacceso restringido
dc.subject.ods03 Good Health and Well-being
dc.subject.odspa03 Salud y bienestar
dc.titleThe effect of the electrophilic group on the hierarchy of nucleofuges in the aminolysis reactions of thiol- and dithiocarbonates with secondary alicyclic amines: A kinetic and theoretical study
dc.typeartículo
dc.volumen43
sipa.indexWOS
sipa.trazabilidadWOS;2025-01-12
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