THE MECHANISM OF ACID-CATALYZED DECARBOXYLATION OF PYRROLE-2-CARBOXYLIC ACID: INSIGHTS FROM CLUSTER-CONTINUUM MODEL CALCULATIONS
Ministry of Science and Technology [2011CB808504, 2012CB214900]; National Science Foundation of China [21133007] The decarboxylation of pyrrole-2-carboxylic acid comprises the addition of water to the carboxyl group and the C-C bond cleavage leading to the protonated carbonic acid. Herein possible c...
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ftxiamenuniv:oai:dspace.xmu.edu.cn:2288/88990 2023-05-15T15:52:30+02:00 THE MECHANISM OF ACID-CATALYZED DECARBOXYLATION OF PYRROLE-2-CARBOXYLIC ACID: INSIGHTS FROM CLUSTER-CONTINUUM MODEL CALCULATIONS Liang, Jinxia Wang, Binju Cao, Zexing 曹泽星 2013 http://dspace.xmu.edu.cn/handle/2288/88990 en_US eng WORLD SCIENTIFIC PUBL CO PTE LTD JOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY, 2013,12(4) WOS:000321055400002 http://dspace.xmu.edu.cn/handle/2288/88990 http://dx.doi.org/10.1142/S021963361350017X PHYSICAL ORGANIC-CHEMISTRY HYDRATION FREE-ENERGY AQUEOUS-SOLUTION CARBONIC-ACID RATE ACCELERATION HYDROLYSIS MECHANISM TWISTED AMIDES WATER SOLVATION FORMAMIDE Article 2013 ftxiamenuniv 2020-07-21T11:43:19Z Ministry of Science and Technology [2011CB808504, 2012CB214900]; National Science Foundation of China [21133007] The decarboxylation of pyrrole-2-carboxylic acid comprises the addition of water to the carboxyl group and the C-C bond cleavage leading to the protonated carbonic acid. Herein possible concerted and stepwise mechanisms for the C-protonated and O-protonated pathways were extensively investigated by using the cluster-continuum model. The calculated results indicate that the initial hydration or the nucleophilic attack of water at the carbonyl group of both C-and O-protonated derivatives is the rate-determining step for the overall reaction, and the O-protonated pathway will dominate the whole reaction. The predicted activation Gibbs energies for the overall reaction initialized by the O-protonated species fall in the range of 83.3 similar to 123.0 kJ/mol, showing good agreement with experimental values of 91.6 similar to 101.3 kJ/mol. On the basis of extensive calculations, the remarkable dependence of the predicted mechanisms and thermodynamic values on the number of explicit water molecules in the cluster-continuum model was discussed. Article in Journal/Newspaper Carbonic acid Xiamen University Institutional Repository |
institution |
Open Polar |
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Xiamen University Institutional Repository |
op_collection_id |
ftxiamenuniv |
language |
English |
topic |
PHYSICAL ORGANIC-CHEMISTRY HYDRATION FREE-ENERGY AQUEOUS-SOLUTION CARBONIC-ACID RATE ACCELERATION HYDROLYSIS MECHANISM TWISTED AMIDES WATER SOLVATION FORMAMIDE |
spellingShingle |
PHYSICAL ORGANIC-CHEMISTRY HYDRATION FREE-ENERGY AQUEOUS-SOLUTION CARBONIC-ACID RATE ACCELERATION HYDROLYSIS MECHANISM TWISTED AMIDES WATER SOLVATION FORMAMIDE Liang, Jinxia Wang, Binju Cao, Zexing 曹泽星 THE MECHANISM OF ACID-CATALYZED DECARBOXYLATION OF PYRROLE-2-CARBOXYLIC ACID: INSIGHTS FROM CLUSTER-CONTINUUM MODEL CALCULATIONS |
topic_facet |
PHYSICAL ORGANIC-CHEMISTRY HYDRATION FREE-ENERGY AQUEOUS-SOLUTION CARBONIC-ACID RATE ACCELERATION HYDROLYSIS MECHANISM TWISTED AMIDES WATER SOLVATION FORMAMIDE |
description |
Ministry of Science and Technology [2011CB808504, 2012CB214900]; National Science Foundation of China [21133007] The decarboxylation of pyrrole-2-carboxylic acid comprises the addition of water to the carboxyl group and the C-C bond cleavage leading to the protonated carbonic acid. Herein possible concerted and stepwise mechanisms for the C-protonated and O-protonated pathways were extensively investigated by using the cluster-continuum model. The calculated results indicate that the initial hydration or the nucleophilic attack of water at the carbonyl group of both C-and O-protonated derivatives is the rate-determining step for the overall reaction, and the O-protonated pathway will dominate the whole reaction. The predicted activation Gibbs energies for the overall reaction initialized by the O-protonated species fall in the range of 83.3 similar to 123.0 kJ/mol, showing good agreement with experimental values of 91.6 similar to 101.3 kJ/mol. On the basis of extensive calculations, the remarkable dependence of the predicted mechanisms and thermodynamic values on the number of explicit water molecules in the cluster-continuum model was discussed. |
format |
Article in Journal/Newspaper |
author |
Liang, Jinxia Wang, Binju Cao, Zexing 曹泽星 |
author_facet |
Liang, Jinxia Wang, Binju Cao, Zexing 曹泽星 |
author_sort |
Liang, Jinxia |
title |
THE MECHANISM OF ACID-CATALYZED DECARBOXYLATION OF PYRROLE-2-CARBOXYLIC ACID: INSIGHTS FROM CLUSTER-CONTINUUM MODEL CALCULATIONS |
title_short |
THE MECHANISM OF ACID-CATALYZED DECARBOXYLATION OF PYRROLE-2-CARBOXYLIC ACID: INSIGHTS FROM CLUSTER-CONTINUUM MODEL CALCULATIONS |
title_full |
THE MECHANISM OF ACID-CATALYZED DECARBOXYLATION OF PYRROLE-2-CARBOXYLIC ACID: INSIGHTS FROM CLUSTER-CONTINUUM MODEL CALCULATIONS |
title_fullStr |
THE MECHANISM OF ACID-CATALYZED DECARBOXYLATION OF PYRROLE-2-CARBOXYLIC ACID: INSIGHTS FROM CLUSTER-CONTINUUM MODEL CALCULATIONS |
title_full_unstemmed |
THE MECHANISM OF ACID-CATALYZED DECARBOXYLATION OF PYRROLE-2-CARBOXYLIC ACID: INSIGHTS FROM CLUSTER-CONTINUUM MODEL CALCULATIONS |
title_sort |
mechanism of acid-catalyzed decarboxylation of pyrrole-2-carboxylic acid: insights from cluster-continuum model calculations |
publisher |
WORLD SCIENTIFIC PUBL CO PTE LTD |
publishDate |
2013 |
url |
http://dspace.xmu.edu.cn/handle/2288/88990 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
http://dx.doi.org/10.1142/S021963361350017X |
op_relation |
JOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY, 2013,12(4) WOS:000321055400002 http://dspace.xmu.edu.cn/handle/2288/88990 |
_version_ |
1766387668929740800 |