A Proton Dance: Wheland Complexes and Ammonium Salts Obtained from Organic Acids and 1,3,5-Tris(N,N-dialkylamino)benzene Derivatives

Title:A Proton Dance: Wheland Complexes and Ammonium Salts Obtained from Organic Acids and 1,3,5-Tris(N,N-dialkylamino)benzene Derivatives

Volume: 18 Issue: 4

Author(s): Carla Boga, Luciano Forlani, Silvia Tozzi, Erminia Del Vecchio, Andrea Mazzanti, Magda Monari and Nicola Zanna

Affiliation:

Keywords: Aromatic substitution, nuclear magnetic resonance, proton, supernucleophiles, tautomerism, Wheland intermediate, X-ray diffraction.

Abstract: The reaction of a series of symmetric and unsymmetric triaminobenzene derivatives with proton as electrophile has been studied. The formation of both Wheland complex (C-H salt) and N-H salt in relative amount depending on the experimental conditions has been observed. In the case of the attack of the proton on the nitrogen atom, the ¹H and ¹³C NMR spectra showed the equivalence of three aromatic protons (and related carbon atoms) of the adduct thus indicating that salification occurs on a non-defined nitrogen atom. This behavior can be explained hypothesizing motion of the proton from a nitrogen atom to another in a motion that could not permit to define the protonation site. On the contrary, X-ray diffraction analysis on crystals of the NH salts reveals that in the solid state the proton is situated in a well-defined position.

Cite this article as:

Boga Carla, Forlani Luciano, Tozzi Silvia, Vecchio Del Erminia, Mazzanti Andrea, Monari Magda and Zanna Nicola, A Proton Dance: Wheland Complexes and Ammonium Salts Obtained from Organic Acids and 1,3,5-Tris(N,N-dialkylamino)benzene Derivatives, Current Organic Chemistry 2014; 18 (4) . https://dx.doi.org/10.2174/13852728113176660137