dc.contributor.author |
Llinás, Antonio
|
|
dc.contributor.author |
Donoso Pardo, Josefa Laurentina
|
|
dc.contributor.author |
Vilanova Canet, Bartolomé
|
|
dc.contributor.author |
Frau Munar, Juan
|
|
dc.contributor.author |
Muñoz Izquierdo, Francisco
|
|
dc.contributor.author |
Page, Michael I.
|
|
dc.date.accessioned |
2018-11-20T08:26:47Z |
|
dc.identifier.uri |
http://hdl.handle.net/11201/148546 |
|
dc.description.abstract |
[eng] Thiolysis of benzylpenicillin has been investigated by HPLC and 1H-NMR techniques. Thiols catalyse the hydrolysis of benzylpenicillin through the formation of a thioester intermediate. The catalytically reactive form of the thiol has been demonstrated to be the thiolate anion. Variation of reactivity with changing basicity of the thiolate anion generates a Brønsted βnuc value of 0.96, indicating that the breakdown of the tetrahedral intermediate is the rate-limiting step, as occurs in aminolysis and alcoholysis. Solvent kinetic isotope effects of 2.2<br>2.4 indicate that the solvent, water, probably acts as a general acid catalyst in the breakdown of the tetrahedral intermediate. PM3 theoretical calculations support the proposal that breakdown of the tetrahedral intermediate is rate-limiting. The experimental activation energies for the thiolysis of benzylpenicillin vary from 6.9 to 10.4 kcal/mol. |
|
dc.format |
application/pdf |
|
dc.relation.isformatof |
Versió postprint del document publicat a: https://doi.org/10.1039/B001091J |
|
dc.relation.ispartof |
Journal of the Chemical Society-Perkin Transactions 2, 2000, p. 1521-1525 |
|
dc.rights |
(c) Llinás, Antonio et al., 2000 |
|
dc.subject.classification |
54 - Química |
|
dc.subject.other |
54 - Chemistry. Crystallography. Mineralogy |
|
dc.title |
Thiol-catalysed hydrolysis of benzylpenicillin |
|
dc.type |
info:eu-repo/semantics/article |
|
dc.type |
info:eu-repo/semantics/acceptedVersion |
|
dc.date.updated |
2018-11-20T08:26:47Z |
|
dc.date.embargoEndDate |
info:eu-repo/date/embargoEnd/2075-01-01 |
|
dc.embargo |
2075-01-01 |
|
dc.rights.accessRights |
info:eu-repo/semantics/embargoedAccess |
|
dc.identifier.doi |
https://doi.org/10.1039/B001091J |
|