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A molecular electron density theory study of the Lewis acid–catalyzed decomposition reaction of nitroethyl benzoate using aluminum derivatives
Author(s) -
KąckaZych Agnieszka,
RíosGutiérrez Mar,
Domingo Luis R.
Publication year - 2019
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3938
Subject(s) - chemistry , lewis acids and bases , catalysis , benzoic acid , decomposition , dimethylacetamide , reaction mechanism , density functional theory , lewis acid catalysis , computational chemistry , medicinal chemistry , solvent , organic chemistry
The molecular mechanism of the decomposition reaction of nitroethyl benzoate (NEB‐1) catalyzed by Lewis acids (LAs) based on aluminum metal, AlMe 3 , and AlCl 3 , in N , N ‐dimethylacetamide, has been analyzed within the molecular electron density theory (MEDT) using calculations at the B3LYP(PCM)/6‐31+G(d) computational level. These LA‐catalyzed decomposition reactions take place via a two‐step mechanism involving a zwitterionic intermediate. The use of a more acidic AlCl 3 LA favors the decomposition reaction, both kinetically and thermodynamically. The bonding evolution theory (BET) analyses indicate that these LA‐catalyzed decomposition reactions begin with the proton transfer process, followed by the extrusion of benzoic acid at the second step of the reaction.