RT info:eu-repo/semantics/article
T1 Structural Conformers of (1,3-Dithiol-2-ylidene)ethanethioamides: The Balance Between Thioamide Rotation and Preservation of Classical Sulfur-Sulfur Hypervalent Bonds
A1 Fuertes Lázaro, Pedro
A1 García Valverde, María
A1 Pascual, Ricardo
A1 Rodríguez Rodríguez, Mª Teresa
A1 Rojo Cámara, Mª Josefa
A1 García Calvo, José
A1 Calvo Gredilla, Patricia
A1 Cuevas Vicario, José Vicente
A1 García Herbosa, Gabriel
A1 Torroba Pérez, Tomás
K1 Chemistry, Organic
K1 Química orgánica
AB The reaction of N-(2-phthalimidoethyl)-N-alkylisopropylamines and S2Cl2 gave 4-N-(2-phthalimidoethyl)-N-alkylamino-5-chloro-1,2-dithiol-3-thiones that quantitatively cycloadded to dimethyl or diethyl acetylenedicarboxylate to give stable thioacid chlorides, which in turn reacted with one equivalent of aniline or a thiole to give thioanilides or a dithioester. Several compounds of this series showed atropisomers that were studied by a combination of dynamic NMR, simulation of the signals, conformational analysis by DFT methods, and single crystal X-ray diffraction, showing a good correlation between the theoretical calculations, the experimental values of energies, and the preferred conformations in the solid state. The steric hindering of the crowded substitution at the central amine group was found to be the reason for the presence of permanent atropisomers in this series of compounds and the cause of a unique disposition of the thioxo group at close-to-right angles with respect to the plane defined by the 1,3-dithiole ring in the dithiafulvene derivatives, thus breaking the sulfur–sulfur hypervalent bond that is always found in this kind of compounds.
PB American Chemical Society
YR 2015
FD 2015-01
LK http://hdl.handle.net/10259/4369
UL http://hdl.handle.net/10259/4369
LA eng
NO Ministeriode Economıá y Competitividad, Spain (Project CTQ2012-31611), Junta de Castilla y León, Consejeríade Educación yCultura y Fondo Social Europeo (Project BU246A12-1), andthe European Commission, Seventh Framework Programme(Project SNIFFER FP7-SEC-2012-312411)
DS Repositorio Institucional de la Universidad de Burgos
RD 19-abr-2024