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Synthesis and structural analysis of 1,4‐bis[ n ‐( N,N ‐dimethylamino)phenyl]buta‐1,3‐diynes and charge‐transfer complexes with TCNE
Author(s) -
Gonzalo Rodríguez J.,
Lafuente Antonio,
MartínVillamil Rosa,
MartínezAlcazar M. Paz
Publication year - 2001
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.422
Subject(s) - chemistry , benzaldehyde , dimer , phosphine , substituent , wittig reaction , medicinal chemistry , conjugate , ylide , base (topology) , crystallography , stereochemistry , catalysis , organic chemistry , mathematical analysis , mathematics
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.