Theoretical study of N-(o-aminophenyl amic) acid cyclodehydration to 1,2-benzoilenebenzimidazole as a model reaction of ladder polypyrrones synthesis: thermodynamic and thermochemical data

1999 ◽  
Vol 463 (3) ◽  
pp. 231-235 ◽  
Author(s):  
Roberto Salcedo ◽  
Leticia Valle ◽  
Larissa Alexandrova ◽  
Dmitri Likhatchev
Keyword(s):  
Theoretical Study ◽  
Amic Acid ◽  
Model Reaction ◽  
Thermochemical Data

scholarly journals Sterically Facilitated Intramolecular Nucleophilic NMe2 Group Substitution in the Synthesis of Fused Isoxazoles: Theoretical Study

Molecules ◽  
2020 ◽  
Vol 25 (24) ◽  
pp. 5977
Author(s):  
Alexander S. Antonov ◽  
Elena Yu Tupikina ◽  
Valerii V. Karpov ◽  
Valeriia V. Mulloyarova ◽  
Victor G. Bardakov
Keyword(s):  
Nucleophilic Substitution ◽  
Theoretical Study ◽  
Model Reaction ◽  
Steric Repulsion ◽  
Reaction Intermediates ◽  
Intramolecular Nucleophilic Substitution ◽  
Gibbs Energies ◽  
Naphthalene Series

The influence of steric repulsion between the NMe2 group and a second ortho-(peri-)substituent in the series of 1-dimethylaminonaphthalene and N,N-dimethylanilene ortho-oximes on the ease of the NMe2 group’s intramolecular nucleophilic substitution is studied. Possible reaction intermediates for three mechanisms are calculated (ωB97xd/def-2-TZVP), and their free Gibbs energies are compared to model reaction profiles. Supporting experiments have proved the absence of studied reactivity in the case of simple 2-dimethylaminobenzaldoxime, which allowed us to establish reactivity limits. The significant facilitation of NMe2 group displacement in the presence of bulky substituents is demonstrated. The possibility of fused isoxazoles synthesis via the intramolecular nucleophilic substitution of a protonated NMe2 group in the aniline and naphthalene series is predicted.

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