Open AccessThe addition of ethylhydrazine to α,β- and β,γ-unsaturated ketones: a quantum-chemical modeling
Author(s) -
G. R. Gnatovsky,
Vladimir B. Orel,
N. M. Vitkovskaya
Publication year - 2021
Publication title -
journal of physics. conference series
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.21
H-Index - 85
eISSN - 1742-6596
pISSN - 1742-6588
DOI - 10.1088/1742-6596/1847/1/012052
Subject(s) - ketone , chemistry , double bond , molecule , nucleophile , nitrogen atom , reactivity (psychology) , nitrogen , nucleophilic addition , carbonyl group , quantum chemical , addition reaction , medicinal chemistry , photochemistry , organic chemistry , group (periodic table) , catalysis , medicine , alternative medicine , pathology
The reactivity of α,β- and β,γ-unsaturated ketones with respect to the nucleophilic attack by ethylhydrazine in one of the key stages of the formation of 4,5-dihydropyrazole has been studied. It is shown that the addition of the terminal nitrogen atom of ethylhydrazine to the carbonyl group of β,γ- and α,γ-unsaturated ketones with the formation of β,γ- and α,β-unsaturated hydrazones is energetically preferable with the participation of two water molecules. At the same time, the addition of the internal nitrogen of ethylhydrazine to the double C=C bond of the α,β-unsaturated ketone (which is preferable in the presence of one water molecule) to give β-ethylhydrazinyl ketone occurs with a lower activation barrier and is thermodynamically more favorable than the addition to the C=O bond.