A DFT study of the Al₂Cl₆-catalyzed Friedel-Crafts acylation of phenyl aromatic compounds.
Identifieur interne : 000011 ( Hal/Corpus ); précédent : 000010; suivant : 000012A DFT study of the Al₂Cl₆-catalyzed Friedel-Crafts acylation of phenyl aromatic compounds.
Auteurs : Sigismund T A G. Melissen ; Vincent Tognetti ; Georges Dupas ; Julien Jouanneau ; Guillaume Lê ; Laurent JoubertSource :
Abstract
The reaction pathways of several Friedel-Crafts acylations involving phenyl aromatic compounds were studied using density functional theory. The reactions were related to the Friedel-Crafts polycondensation of polyaryletherketones. In particular, the acylation of benzene with benzoyl chloride to form benzophenone and variations on this reaction were investigated. The acylation of benzene by one molecule of terephthaloyl chloride or isophthaloyl chloride as well as acylations at the m-, o-, and p-positions of diphenyl ether with one molecule of benzoyl chloride were studied. Adding an additional acyl chloride group to the electrophile appeared to have little influence on the reaction pathway, although the activation energy for the C-C bond-forming steps that occurred when isophthaloyl choride was used was different to the activation energy observed when terephthaloyl chloride was used. Upon changing the nucleophile to diphenyl ether, the reactivity changed according to the trend predicted on based on the o-, p-directing effects of the ether group. The deprotonation step that restored aromaticity varied widely according to the reaction. The rate-determining step in all of the studied reactions was the formation of the acylium ion, followed in importance by either the formation of the Wheland intermediate or the abstraction of hydrogen, depending on the reactivity of the nucleophile.
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DOI: 10.1007/s00894-013-1984-8
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The reactions were related to the Friedel-Crafts polycondensation of polyaryletherketones. In particular, the acylation of benzene with benzoyl chloride to form benzophenone and variations on this reaction were investigated. The acylation of benzene by one molecule of terephthaloyl chloride or isophthaloyl chloride as well as acylations at the m-, o-, and p-positions of diphenyl ether with one molecule of benzoyl chloride were studied. Adding an additional acyl chloride group to the electrophile appeared to have little influence on the reaction pathway, although the activation energy for the C-C bond-forming steps that occurred when isophthaloyl choride was used was different to the activation energy observed when terephthaloyl chloride was used. Upon changing the nucleophile to diphenyl ether, the reactivity changed according to the trend predicted on based on the o-, p-directing effects of the ether group. The deprotonation step that restored aromaticity varied widely according to the reaction. The rate-determining step in all of the studied reactions was the formation of the acylium ion, followed in importance by either the formation of the Wheland intermediate or the abstraction of hydrogen, depending on the reactivity of the nucleophile.</div></front></TEI><hal api="V3"><titleStmt><title xml:lang="en">A DFT study of the Al₂Cl₆-catalyzed Friedel-Crafts acylation of phenyl aromatic compounds.</title><author role="aut"><persName><forename type="first">Sigismund T A G</forename><surname>Melissen</surname></persName><email></email><idno type="halauthor">1026844</idno></author><author role="aut"><persName><forename type="first">Vincent</forename><surname>Tognetti</surname></persName><email></email><idno type="halauthor">204351</idno><affiliation ref="#struct-141329"></affiliation></author><author role="aut"><persName><forename type="first">Georges</forename><surname>Dupas</surname></persName><email></email><idno type="halauthor">475814</idno><affiliation ref="#struct-797"></affiliation><affiliation ref="#struct-23832"></affiliation></author><author role="aut"><persName><forename type="first">Julien</forename><surname>Jouanneau</surname></persName><email></email><idno type="halauthor">1026845</idno><affiliation ref="#struct-558"></affiliation></author><author role="aut"><persName><forename type="first">Guillaume</forename><surname>Lê</surname></persName><email></email><idno type="halauthor">1026846</idno></author><author role="aut"><persName><forename type="first">Laurent</forename><surname>Joubert</surname></persName><email></email><idno type="halauthor">885675</idno><affiliation ref="#struct-141329"></affiliation></author><editor role="depositor"><persName><forename>Umr 6014</forename><surname>Cobra</surname></persName><email>dir-cobra@insa-rouen.fr</email></editor></titleStmt><editionStmt><edition n="v1" type="current"><date type="whenSubmitted">2014-05-26 15:14:11</date><date type="whenModified">2016-05-14 01:04:07</date><date type="whenReleased">2014-05-26 15:14:11</date><date type="whenProduced">2013-11</date></edition><respStmt><resp>contributor</resp><name key="195158"><persName><forename>Umr 6014</forename><surname>Cobra</surname></persName><email>dir-cobra@insa-rouen.fr</email></name></respStmt></editionStmt><publicationStmt><distributor>CCSD</distributor><idno type="halId">hal-00996442</idno><idno type="halUri">https://hal.archives-ouvertes.fr/hal-00996442</idno><idno type="halBibtex">melissen:hal-00996442</idno><idno type="halRefHtml">J Mol Model, 2013, 19 (11), pp.4947-58. <10.1007/s00894-013-1984-8></idno><idno type="halRef">J Mol Model, 2013, 19 (11), pp.4947-58. <10.1007/s00894-013-1984-8></idno></publicationStmt><seriesStmt><idno type="stamp" n="CNRS">CNRS - Centre national de la recherche scientifique</idno><idno type="stamp" n="UNIV-SAVOIE">Université Savoie Mont Blanc</idno><idno type="stamp" n="UGA">HAL Grenoble Alpes</idno><idno type="stamp" n="UNIV-LEHAVRE">Université du Havre</idno><idno type="stamp" n="UNIV-ROUEN">Université de Rouen</idno><idno type="stamp" n="LITIS">Laboratoire d'Informatique, de Traitement de l'Information et des Systèmes</idno><idno type="stamp" n="COMUE-NORMANDIE">Normandie Université</idno><idno type="stamp" n="INC-CNRS">Institut de Chimie du CNRS</idno><idno type="stamp" n="INPG" p="UGA">Institut polytechnique de Grenoble</idno><idno type="stamp" n="UNIV-GRENOBLE1" p="UGA">Université Joseph Fourier - Grenoble I</idno><idno type="stamp" n="LEPMI" p="UNIV-GRENOBLE1">Laboratoire d'Electrochimie et de Physicochimie des Matériaux et des Interfaces</idno></seriesStmt><notesStmt><note type="audience" n="2">International</note><note type="popular" n="0">No</note><note type="peer" n="1">Yes</note></notesStmt><sourceDesc><biblStruct><analytic><title xml:lang="en">A DFT study of the Al₂Cl₆-catalyzed Friedel-Crafts acylation of phenyl aromatic compounds.</title><author role="aut"><persName><forename type="first">Sigismund T A G</forename><surname>Melissen</surname></persName><idno type="halAuthorId">1026844</idno></author><author role="aut"><persName><forename type="first">Vincent</forename><surname>Tognetti</surname></persName><idno type="halAuthorId">204351</idno><affiliation ref="#struct-141329"></affiliation></author><author role="aut"><persName><forename type="first">Georges</forename><surname>Dupas</surname></persName><idno type="halAuthorId">475814</idno><affiliation ref="#struct-797"></affiliation><affiliation ref="#struct-23832"></affiliation></author><author role="aut"><persName><forename type="first">Julien</forename><surname>Jouanneau</surname></persName><idno type="halAuthorId">1026845</idno><affiliation ref="#struct-558"></affiliation></author><author role="aut"><persName><forename type="first">Guillaume</forename><surname>Lê</surname></persName><idno type="halAuthorId">1026846</idno></author><author role="aut"><persName><forename type="first">Laurent</forename><surname>Joubert</surname></persName><idno type="halAuthorId">885675</idno><affiliation ref="#struct-141329"></affiliation></author></analytic><monogr><idno type="halJournalId" status="INCOMING">63720</idno><title level="j">J Mol Model</title><imprint><biblScope unit="volume">19</biblScope><biblScope unit="issue">11</biblScope><biblScope unit="pp">4947-58</biblScope><date type="datePub">2013-11</date></imprint></monogr><idno type="doi">10.1007/s00894-013-1984-8</idno><idno type="pubmed">24052340</idno></biblStruct></sourceDesc><profileDesc><langUsage><language ident="en">English</language></langUsage><textClass><classCode scheme="halDomain" n="chim.orga">Chemical Sciences/Organic chemistry</classCode><classCode scheme="halTypology" n="ART">Journal articles</classCode></textClass><abstract xml:lang="en">The reaction pathways of several Friedel-Crafts acylations involving phenyl aromatic compounds were studied using density functional theory. The reactions were related to the Friedel-Crafts polycondensation of polyaryletherketones. In particular, the acylation of benzene with benzoyl chloride to form benzophenone and variations on this reaction were investigated. The acylation of benzene by one molecule of terephthaloyl chloride or isophthaloyl chloride as well as acylations at the m-, o-, and p-positions of diphenyl ether with one molecule of benzoyl chloride were studied. Adding an additional acyl chloride group to the electrophile appeared to have little influence on the reaction pathway, although the activation energy for the C-C bond-forming steps that occurred when isophthaloyl choride was used was different to the activation energy observed when terephthaloyl chloride was used. Upon changing the nucleophile to diphenyl ether, the reactivity changed according to the trend predicted on based on the o-, p-directing effects of the ether group. The deprotonation step that restored aromaticity varied widely according to the reaction. The rate-determining step in all of the studied reactions was the formation of the acylium ion, followed in importance by either the formation of the Wheland intermediate or the abstraction of hydrogen, depending on the reactivity of the nucleophile.</abstract></profileDesc></hal></record>Pour manipuler ce document sous Unix (Dilib)
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