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Static and Dynamic Properties of Fluorinated 4‐Aryl‐1,5‐Benzodiazepinones
Author(s) -
Martín Olga,
PérezTorralba Marta,
García M. Ángeles,
Claramunt Rosa M.,
Torralba M. Carmen,
Torres M. Rosario,
Alkorta Ibon,
Elguero José
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201600167
Subject(s) - tautomer , chemistry , aryl , imine , solid state , chemical shift , computational chemistry , ring (chemistry) , enamine , carbon 13 nmr , crystallography , stereochemistry , organic chemistry , catalysis , alkyl
Six 4‐aryl‐6,7,8,9‐tetrafluoro‐1,5‐benzodiazepine‐2‐ones have been synthesized and fully characterized by 1 H, 13 C, 15 N and 19 F NMR in solution and in the solid state. In addition, the structures of three of them have been determined by X‐ray crystallography. The imine/enamine tautomerism has been experimentally studied by NMR in solution (in the solid state, only the imino tautomer is present). Three barriers corresponding to the inversion of the seven‐membered ring have been determined (N1‐unsubstituted derivatives). Both for the tautomerism and for the conformational aspects, theoretical calculations at the B3LYP/6‐311++G(d,p) level including GIAO calculations of the NMR chemical shifts have been carried out with satisfying results. Different energy profiles have been considered and several transition states located.