J. Gonzalo Rodríguez, A. Lafuente, Rosa Martín-Villamil
Dec 1, 2001
Citations
0
Influential Citations
25
Citations
Journal
Journal of Physical Organic Chemistry
Abstract
n-(N,N-Dimethylamino)phenylethynes were satisfactorily prepared by a Wittig reaction between chloromethylene(triphenyl)phosphine ylide and the appropriate n-(N,N-dimethylamino)benzaldehyde, followed by dehydrochlorination with a strong base. The conjugate dimers 1,4-bis[n-(N,N-dimethylamino)phenyl]buta-1,3-diyne were obtained by oxidative dimerization with copper(I) chloride. X-ray molecular structure analysis of the dimer 1,4-bis[2-(N,N-dimethylamino)phenyl]buta-1,3-diyne corroborated the resonance contribution of the o-dimethylamino substituent, which was confirmed in the solid state by the molecular crystalline packing. Both o- and p-(N,N-dimethylamino) conjugate dimers develop 1:1 charge-transfer complexes with TCNE and their structure was identified by NMR, IR and UV–visible spectroscopic data. Differential scanning calorimetric analyses of the 1,3-diynes showed an irreversible transformation to a thermopolymer as a unimolecular reaction. Copyright © 2001 John Wiley & Sons, Ltd.