Premium
Tautomerism of amidoximes and other oxime species
Author(s) -
Novikov Alexander S.,
Bolotin Dmitrii S.
Publication year - 2018
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.3772
Subject(s) - tautomer , chemistry , oxime , moiety , density functional theory , solvent , medicinal chemistry , computational chemistry , organic chemistry
The tautomerism of the aliphatic MeC(NH 2 )═NOH and the aromatic PhC(NH 2 )═NOH amidoximes in protic (H 2 O, MeOH) and aprotic (Me 2 CO, Me 2 SO, and CHCl 3 ) solvents was studied by density functional theory calculations at the M06‐2X/6‐311+G(d,p) level of theory. In both types of solutions, these species exist in 3 tautomeric forms, viz, ( Z )‐ or ( E )‐amidoximes, and ( Z )‐aminonitrone. The ( Z )‐form is the dominant, and energy gap between the ( Z )‐ and ( E )‐tautomers of the amidoximes slightly depends on the nature of a solvent and significantly higher than that for other oxime species. For the amidoximes, the zwitterionic ( Z )‐aminonitrone form is stabilized by protic solvents. The oxime‐nitrone energy gap is reduced by electron‐donor substituents at the oxime moiety at different types of oxime species.