ISSN:
0020-7608
Schlagwort(e):
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
The alkylation of arylamines is an important reaction in many large scale industrial processes. Three possible mechanisms are evaluated at the semiempirical level using the alkylation of aniline with ethylene as a model system. A molecular orbital analysis is performed for each mechanism to determine the appropriate type of wavefunction required to describe the transition state. Successive levels of refinement in search algorithms are used to locate the transition state on a potential surface with up to 60 degrees of freedom. A reasonable mechanism for the AlCl3-catalyzed Friedel-Crafts alkylation is shown to be analogous to a Diels-Alder [4 + 2] concerted cycloaddition after initial β-elimination of HCl. The Brönsted acid-catalyzed reaction shown is likely to occur via a mechanism similar to the Ene reaction, rather than initial protonation of the olefin followed by electrophilic addition to a nearby aromatic ring. © 1995 John Wiley & Sons, Inc.
Zusätzliches Material:
12 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/qua.560530605
