Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid
The twofold ester pyrolysis of carbonates, yielding monomeric carbonic acid, was investigated by computational methods. By comparison with CCSD(T)/cc-pVTZ//B3LYP/ccpVTZ benchmark calculations, the M05-2X method was found to give the most accurate reaction enthalpies among the DFT methods employed. W...
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ftuglasgow:oai:eprints.gla.ac.uk:36936 2023-05-15T15:52:07+02:00 Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid Bucher, G. 2010-02 http://eprints.gla.ac.uk/36936/ unknown Bucher, G. <http://eprints.gla.ac.uk/view/author/5673.html> (2010) Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid. European Journal of Organic Chemistry <http://eprints.gla.ac.uk/view/journal_volume/European_Journal_of_Organic_Chemistry.html>, 2010(6), pp. 1070-1075. (doi:10.1002/ejoc.200901212 <http://dx.doi.org/10.1002/ejoc.200901212>) Articles PeerReviewed 2010 ftuglasgow https://doi.org/10.1002/ejoc.200901212 2021-09-23T22:20:01Z The twofold ester pyrolysis of carbonates, yielding monomeric carbonic acid, was investigated by computational methods. By comparison with CCSD(T)/cc-pVTZ//B3LYP/ccpVTZ benchmark calculations, the M05-2X method was found to give the most accurate reaction enthalpies among the DFT methods employed. While the first ester pyrolysis of diethyl carbonate, (E)-bis(acetdldoxime) carbonate or diN,N-dimethylhydroxylaniine carbonate will yield the corresponding monocarbonates, these highly labile compounds are predicted to decay via alternative reaction channels that result in the formation of carbon dioxide. Due to competing O-O bond homolyis reactions, dialkyl diperoxycarbonates are predicted to afford at best moderate yields of monomeric carbonic acid upon flash vacuum pyrolysis. The carbonate derived frorn "benzene hydrate" (cyclohexa-2,4-dien-l-ol), however, is predicted to be an ideal precursor for monomeric carbonic acid, undergoing ester pyrolysis in a very facile reaction, with no competing bond homolysis processes. Article in Journal/Newspaper Carbonic acid University of Glasgow: Enlighten - Publications European Journal of Organic Chemistry 2010 6 1070 1075 |
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Open Polar |
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University of Glasgow: Enlighten - Publications |
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ftuglasgow |
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unknown |
description |
The twofold ester pyrolysis of carbonates, yielding monomeric carbonic acid, was investigated by computational methods. By comparison with CCSD(T)/cc-pVTZ//B3LYP/ccpVTZ benchmark calculations, the M05-2X method was found to give the most accurate reaction enthalpies among the DFT methods employed. While the first ester pyrolysis of diethyl carbonate, (E)-bis(acetdldoxime) carbonate or diN,N-dimethylhydroxylaniine carbonate will yield the corresponding monocarbonates, these highly labile compounds are predicted to decay via alternative reaction channels that result in the formation of carbon dioxide. Due to competing O-O bond homolyis reactions, dialkyl diperoxycarbonates are predicted to afford at best moderate yields of monomeric carbonic acid upon flash vacuum pyrolysis. The carbonate derived frorn "benzene hydrate" (cyclohexa-2,4-dien-l-ol), however, is predicted to be an ideal precursor for monomeric carbonic acid, undergoing ester pyrolysis in a very facile reaction, with no competing bond homolysis processes. |
format |
Article in Journal/Newspaper |
author |
Bucher, G. |
spellingShingle |
Bucher, G. Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid |
author_facet |
Bucher, G. |
author_sort |
Bucher, G. |
title |
Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid |
title_short |
Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid |
title_full |
Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid |
title_fullStr |
Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid |
title_full_unstemmed |
Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid |
title_sort |
ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid |
publishDate |
2010 |
url |
http://eprints.gla.ac.uk/36936/ |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_relation |
Bucher, G. <http://eprints.gla.ac.uk/view/author/5673.html> (2010) Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid. European Journal of Organic Chemistry <http://eprints.gla.ac.uk/view/journal_volume/European_Journal_of_Organic_Chemistry.html>, 2010(6), pp. 1070-1075. (doi:10.1002/ejoc.200901212 <http://dx.doi.org/10.1002/ejoc.200901212>) |
op_doi |
https://doi.org/10.1002/ejoc.200901212 |
container_title |
European Journal of Organic Chemistry |
container_volume |
2010 |
container_issue |
6 |
container_start_page |
1070 |
op_container_end_page |
1075 |
_version_ |
1766387417648988160 |