A DFT study of the Al₂Cl₆-catalyzed Friedel-Crafts acylation of phenyl aromatic compounds.
Identifieur interne : 000370 ( France/Analysis ); précédent : 000369; suivant : 000371A DFT study of the Al₂Cl₆-catalyzed Friedel-Crafts acylation of phenyl aromatic compounds.
Auteurs : Sigismund T A G. Melissen ; Vincent Tognetti [France] ; Georges Dupas [France] ; Julien Jouanneau [France] ; Guillaume Lê ; Laurent Joubert [France]Source :
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.
Url:
DOI: 10.1007/s00894-013-1984-8
Affiliations:
- France
- Auvergne-Rhône-Alpes, Haute-Normandie, Rhône-Alpes, Région Normandie
- Grenoble, Rouen
- Université Joseph Fourier, Université de Grenoble, Université de Rouen
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Hal:hal-00996442Le document en format XML
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76821 - Mont Saint Aignan</addrLine><country key="FR"></country></address></desc><listRelation><relation active="#struct-301288" type="direct"></relation><relation active="#struct-301232" type="indirect"></relation><relation name="UMR6014" active="#struct-441569" type="direct"></relation></listRelation><tutelles><tutelle active="#struct-301288" type="direct"><org type="department" xml:id="struct-301288" status="VALID"><orgName>Institut National des Sciences Appliquées - Rouen</orgName><orgName type="acronym">INSA Rouen</orgName><desc><address><country key="FR"></country></address></desc><listRelation><relation active="#struct-301232" type="direct"></relation></listRelation></org></tutelle><tutelle active="#struct-301232" type="indirect"><org type="institution" xml:id="struct-301232" status="VALID"><orgName>Institut National des Sciences Appliquées</orgName><orgName type="acronym">INSA</orgName><desc><address><country key="FR"></country></address></desc></org></tutelle><tutelle name="UMR6014" active="#struct-441569" type="direct"><org type="institution" xml:id="struct-441569" status="VALID"><idno type="ISNI">0000000122597504</idno><idno type="IdRef">02636817X</idno><orgName>Centre National de la Recherche Scientifique</orgName><orgName type="acronym">CNRS</orgName><date type="start">1939-10-19</date><desc><address><country key="FR"></country></address><ref type="url">http://www.cnrs.fr/</ref></desc></org></tutelle></tutelles></hal:affiliation><country>France</country></affiliation></author></analytic><idno type="DOI">10.1007/s00894-013-1984-8</idno></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="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.</div></front></TEI><affiliations><list><country><li>France</li></country><region><li>Auvergne-Rhône-Alpes</li><li>Haute-Normandie</li><li>Rhône-Alpes</li><li>Région Normandie</li></region><settlement><li>Grenoble</li><li>Rouen</li></settlement><orgName><li>Université Joseph Fourier</li><li>Université de Grenoble</li><li>Université de Rouen</li></orgName></list><tree><noCountry><name sortKey="Le, Guillaume" sort="Le, Guillaume" uniqKey="Le G" first="Guillaume" last="Lê">Guillaume Lê</name><name sortKey="Melissen, Sigismund T A G" sort="Melissen, Sigismund T A G" uniqKey="Melissen S" first="Sigismund T A G" last="Melissen">Sigismund T A G. Melissen</name></noCountry><country name="France"><noRegion><name sortKey="Tognetti, Vincent" sort="Tognetti, Vincent" uniqKey="Tognetti V" first="Vincent" last="Tognetti">Vincent Tognetti</name></noRegion><name sortKey="Dupas, Georges" sort="Dupas, Georges" uniqKey="Dupas G" first="Georges" last="Dupas">Georges Dupas</name><name sortKey="Jouanneau, Julien" sort="Jouanneau, Julien" uniqKey="Jouanneau J" first="Julien" last="Jouanneau">Julien Jouanneau</name><name sortKey="Joubert, Laurent" sort="Joubert, Laurent" uniqKey="Joubert L" first="Laurent" last="Joubert">Laurent Joubert</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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|texte= A DFT study of the Al₂Cl₆-catalyzed Friedel-Crafts acylation of phenyl aromatic compounds.
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