Cargando…

Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters

The specific rates of solvolysis of isobutyl chloroformate (1) are reported at 40.0 °C and those for isobutyl chlorothioformate (2) are reported at 25.0 °C, in a variety of pure and binary aqueous organic mixtures with wide ranging nucleophilicity and ionizing power. For 1, we also report the first-...

Descripción completa

Detalles Bibliográficos
Autores principales: D’Souza, Malcolm J, McAneny, Matthew J, Kevill, Dennis N, Kyong, Jin Burm, Choi, Song Hee
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2011
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3107482/
https://www.ncbi.nlm.nih.gov/pubmed/21647255
http://dx.doi.org/10.3762/bjoc.7.62
_version_ 1782205229860651008
author D’Souza, Malcolm J
McAneny, Matthew J
Kevill, Dennis N
Kyong, Jin Burm
Choi, Song Hee
author_facet D’Souza, Malcolm J
McAneny, Matthew J
Kevill, Dennis N
Kyong, Jin Burm
Choi, Song Hee
author_sort D’Souza, Malcolm J
collection PubMed
description The specific rates of solvolysis of isobutyl chloroformate (1) are reported at 40.0 °C and those for isobutyl chlorothioformate (2) are reported at 25.0 °C, in a variety of pure and binary aqueous organic mixtures with wide ranging nucleophilicity and ionizing power. For 1, we also report the first-order rate constants determined at different temperatures in pure ethanol (EtOH), methanol (MeOH), 80% EtOH, and in both 97% and 70% 2,2,2-trifluoroethanol (TFE). The enthalpy (ΔH(≠)) and entropy (ΔS(≠)) of activation values obtained from Arrhenius plots for 1 in these five solvents are reported. The specific rates of solvolysis were analyzed using the extended Grunwald–Winstein equation. Results obtained from correlation analysis using this linear free energy relationship (LFER) reinforce our previous suggestion that side-by-side addition–elimination and ionization mechanisms operate, and the relative importance is dependent on the type of chloro- or chlorothioformate substrate and the solvent.
format Online
Article
Text
id pubmed-3107482
institution National Center for Biotechnology Information
language English
publishDate 2011
publisher Beilstein-Institut
record_format MEDLINE/PubMed
spelling pubmed-31074822011-06-06 Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters D’Souza, Malcolm J McAneny, Matthew J Kevill, Dennis N Kyong, Jin Burm Choi, Song Hee Beilstein J Org Chem Full Research Paper The specific rates of solvolysis of isobutyl chloroformate (1) are reported at 40.0 °C and those for isobutyl chlorothioformate (2) are reported at 25.0 °C, in a variety of pure and binary aqueous organic mixtures with wide ranging nucleophilicity and ionizing power. For 1, we also report the first-order rate constants determined at different temperatures in pure ethanol (EtOH), methanol (MeOH), 80% EtOH, and in both 97% and 70% 2,2,2-trifluoroethanol (TFE). The enthalpy (ΔH(≠)) and entropy (ΔS(≠)) of activation values obtained from Arrhenius plots for 1 in these five solvents are reported. The specific rates of solvolysis were analyzed using the extended Grunwald–Winstein equation. Results obtained from correlation analysis using this linear free energy relationship (LFER) reinforce our previous suggestion that side-by-side addition–elimination and ionization mechanisms operate, and the relative importance is dependent on the type of chloro- or chlorothioformate substrate and the solvent. Beilstein-Institut 2011-04-29 /pmc/articles/PMC3107482/ /pubmed/21647255 http://dx.doi.org/10.3762/bjoc.7.62 Text en Copyright © 2011, D’Souza et al. https://creativecommons.org/licenses/by/2.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms)
spellingShingle Full Research Paper
D’Souza, Malcolm J
McAneny, Matthew J
Kevill, Dennis N
Kyong, Jin Burm
Choi, Song Hee
Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters
title Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters
title_full Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters
title_fullStr Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters
title_full_unstemmed Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters
title_short Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters
title_sort kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3107482/
https://www.ncbi.nlm.nih.gov/pubmed/21647255
http://dx.doi.org/10.3762/bjoc.7.62
work_keys_str_mv AT dsouzamalcolmj kineticevaluationofthesolvolysisofisobutylchloroandchlorothioformateesters
AT mcanenymatthewj kineticevaluationofthesolvolysisofisobutylchloroandchlorothioformateesters
AT kevilldennisn kineticevaluationofthesolvolysisofisobutylchloroandchlorothioformateesters
AT kyongjinburm kineticevaluationofthesolvolysisofisobutylchloroandchlorothioformateesters
AT choisonghee kineticevaluationofthesolvolysisofisobutylchloroandchlorothioformateesters