Université de Fribourg

Tautomerism in azo dyes: Border cases of azo and hydrazo tautomers as possible NMR reference compounds

Deneva, Vera ; Lyčka, Antonin ; Hristova, S. ; Crochet, Aurélien ; Fromm, Katharina M. ; Antonov, Liudmil M.

In: Dyes and Pigments, 2019, vol. 165, p. 157–163

In order to meet the need for NMR reference compounds in the study of tautomeric azo dyes, two series of azo dyes, derived from 3-methyl-1-phenyl-4- (phenyldiazenyl)-1H-pyrazol-5-amine and 5-methyl-2-phenyl-4-(2- phenylhydrazono)-2,4-dihydro-3H-pyrazol-3-one, have been studied by using molecular spectroscopy (UV–Vis and NMR) and quantum-chemical calculations (M06- 2X/TZVP) in solution. The...

Université de Fribourg

A concept for stimulated proton transfer in 1-(phenyldiazenyl)naphthalen-2-ols

Hristova, S. ; Deneva, Vera V. ; Pittelkow, M. ; Crochet, Aurélien ; Kamounah, Fadhil S. . ; Fromm, Katharina M. ; Hansen, P. E. ; Antonov, Liudmil M.

In: Dyes and Pigments, 2018, vol. 156, p. 91–99

A series of aryl azo derivatives of naphthols (1–3) were studied by means of UV–Vis and NMR spectroscopy in different solvents as well as by quantum chemical calculations and X-ray analysis. Previous studies have shown that Sudan I (1) exists as a tautomeric mixture. The effect of the solvents is minimized by the existing intramolecular hydrogen bond. Therefore, the influence on the...

Université de Fribourg

4-Hydroxy-1-naphthaldehydes: proton transfer or deprotonation

Manolova, Y. ; Kurteva, Vanya B. ; Antonov, Liudmil M. ; Marciniak, H. ; Lochbrunner, S. ; Crochet, Aurélien ; Fromm, Katharina M. ; Kamounah, Fadhil S. ; Hansen, P. E.

In: Physical Chemistry Chemical Physics, 2015, vol. 17, no. 15, p. 10238–10249

A series of naphthaldehydes, including a Mannich base, have been investigated by UV-Vis spectroscopy, NMR and theoretical methods to explore their potential tautomerism. In the case of 4-hydroxy-1-naphthaldehyde concentration dependent deprotonation has been detected in methanol and acetonitrile. For 4-hydroxy-3-(piperidin-1-ylmethyl)-1-naphthaldehyde (a Mannich base) an intramolecular proton...

Université de Fribourg

Switching azonaphthols containing a side chain with limited flexibility. Part 1. Synthesis and tautomeric properties

Kurteva, Vanya B. ; Antonov, Liudmil M. ; Nedeltcheva, Daniela V. ; Crochet, Aurélien ; Fromm, Katharina M. ; Nikolova, Rositsa P. ; Shivachev, Boris L. ; Nikiforova, Maya S.

In: Dyes and Pigments, 2012, vol. 92, no. 3, p. 1266–1277

A series of azo dyes, possessing amide fragments with restricted flexibility tethered to 4-(phenyldiazenyl)naphthalen-1-ol, was obtained from 1-hydroxy-2-naphthoic acid by subsequent conversion to amides and diazo coupling. It was shown that the position of the tautomeric equilibrium in solution strongly depends on the solvent in both UV and NMR concentration scale. The compounds exist as pure...

Université de Fribourg


Crochet, Aurélien ; Fromm, Katharina M. ; Kurteva, Vanya B. ; Antonov, Liudmil M.

In: Acta Crystallographica Section E, 2011, vol. 67, no. 4, p. o993

The title compound, C₂₁H₁₆N₂O, has an E-conformation about the diazene N=N bond. It is reasonably planar with the phenyl ring being inclined to the mean plane of the anthracene moiety [planar to within 0.077 (3) Å] by 6.43 (10)°. The crystal structure is stabilized by C-H..π and weak π-π interactions [centroid-centroid distances of 3.7192 (16) and 3.8382 (15) Å],...

Université de Fribourg

Tautocrowns: a concept for a sensing molecule with an active side-arm

Antonov, Liudmil M. ; Kurteva, Vanya B. ; Simeonov, Svilen P. ; Deneva, Vera V. ; Crochet, Aurelien ; Fromm, Katharina M.

In: Tetrahedron, 2010, vol. 66, no. 24, p. 4292-4297

A new sensing molecule containing aza-15-crown-5 as a receptor and 4-(phenyldiazenyl)naphthalen-1-ol as a signal converter has been synthesized. In the free ligand, the hydrogen bonding between the tautomeric OH group and the nitrogen atom from the macrocycle fully shifts the tautomeric equilibrium towards the enol form. The complexation reverses the equilibrium as a result of the strong...