Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid

Bucher, G. (2010) Ester pyrolysis of carbonates: bis(benzene hydrate) carbonate as potential precursor for monomeric carbonic acid. European Journal of Organic Chemistry, 2010(6), pp. 1070-1075. (doi:10.1002/ejoc.200901212)

Full text not currently available from Enlighten.

Abstract

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.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Bucher, Dr Goetz
Authors: Bucher, G.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:European Journal of Organic Chemistry
ISSN:1434-193X
Published Online:13 January 2010

University Staff: Request a correction | Enlighten Editors: Update this record