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Theoretical Investigation of Regiodivergent Addition of Anilines and Phenolates to

Theoretical Investigation of Regiodivergent Addition of Anilines and Phenolates to

Authors :
Haroldo C, Da Silva
Talita O C, Leite
Searitha C, Rodrigues
Beatriz L C, De Carvalho
Maria Tereza, Martins
Rodolfo G, Fiorot
Flaviana R F, Dias
Vinícius R, Campos
Vitor F, Ferreira
Anna C, Cunha
Wagner B, De Almeida
Source :
ACS omega. 7(44)
Publication Year :
2022

Abstract

Two different products were obtained by the regiodivergent reaction of benzoquinone derivatives with phenolates and anilines: 3-aryloxybenzoquinone and 2-phenylamino-3-bromobenzoquinone. Calculated density functional theory free energies of reaction values corroborate the experimental observation of the formation of the substitution product in the reaction with phenolates in acetonitrile and the product of addition/oxidation for the reaction with aniline in water. Calculated charges and Fukui functions are similar for C2 and C3 atoms, indicating an equal possibility to suffer a nucleophilic attack. The calculated energy barriers for nucleophilic attack steps indicated that the first steps of the substitution with phenolates and addition/oxidation with anilines are faster, which justifies the formation of the respective products. The natural bond order analysis for the transition states revealed that there is a strong interaction between lone pairs of N and O atoms and the π

Details

ISSN :
24701343
Volume :
7
Issue :
44
Database :
OpenAIRE
Journal :
ACS omega
Accession number :
edsair.pmid..........c828818848bd81c3119238bda8e8c29d