Evidence of Proton Transfer from the Hydroxy O Atom to the Imine N Atom, Crystal structure of N-Salicylideneamine-1-Tris(Hydroxymethyl)Methane

O composto 4-(fenildiazenil)-2-{[tris(hidroximetil)metil]aminometileno}ciclohexa-3,5-dien-1(2H)-ona foi sintetizado e caracterizado por análise elementar, espectroscopia infravermelho, ressonância magnética nuclear, espectro eletrônico e voltametria cíclica. O equilíbrio tautomérico do 4-(fenildiazenil)-2-{[tris(hidroximetil)metil]aminometileno} ciclohexa-3,5-dien-1(2H)-ona em dimeteilsulfóxido deuterado é comprovado por dados de 1 H RMN. A natureza do processo eletroquímico do 4-(fenildiazenil)-2-{[tris(hidroximetil)metil]aminometileno} ciclohexa-3,5-dien-1(2H)-ona em solução tampão de Britton-Robinson (pH 2-9) foi estudada com o eletrodo gotejante de mercúrio utilizando voltametria de onda quadrada, onda quadrada adsortiva e voltametria cíclica. Os parâmetros eletroquímicos do composto (I p /E p , I p /v, I p /pH, I p /t acc ) foram determinados. methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one in Britton-Robinson buffer (pH 2-9) was studied on the HMDE by square-wave (SWV), adsorptive stripping square-wave (AdSWV) and cyclic voltammetry (CV). The electrochemical parameters (I p /E p , I p /v, I p /pH, I p /t acc ) of the compound were determined.

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“…A mixture of aniline (0.93 g, 10 mmol), water (50 mL) and concentrated hydrochloride acid (2.5 mL, 30 mmol) was 15 …”

Section: Synthesismentioning

confidence: 99%

Electrochemical and spectroscopic study of 4-(Phenyldiazenyl)-2-{[tris-(hydroxymethyl)methyl] aminomethylene}cyclohexa-3,5-dien-1(2H)-one: mechanism of the azo and imine electroreduction

Çakır¹,

Bíçer²,

Odabaşoğlu³

et al. 2005

J. Braz. Chem. Soc.

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“…For instance, Chumakov et al [33] found that at 292 K the unit cell of compound 14 contains two tautomeric molecules with imine and enamine forms, respectively. However, Cungen et al [34] could only locate the enamine form at 298 K, a result further corroborated by Büyükgüngör and co-workers [35] at 208 K. The structures of a series of Schiff bases generated from TRIS and salicylaldehydes bearing different substituents -5-nitro- (15) [36] and 3-hydroxy-(16) at 223 K, [35] 3-methoxy-(17) at 213 K, [35] and 5-phenylazo-(18) [37] -were all determined to be enamine tautomers in the solid state. In the cases of the halogenated derivatives 19 [33] and 20, [36] the unit cell contains two molecules at 293 K, although both exhibit an enamine structure.…”

Section: Introductionmentioning

confidence: 99%

Schiff Bases from TRIS and ortho‐Hydroxyarenecarbaldehydes: Structures and Tautomeric Equilibria in the Solid State and in Solution

Martínez¹,

Авалос²,

Babiano³

et al. 2011

Eur J Org Chem

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Three Schiff bases generated by conventional condensation of a simple aminopolyol (TRIS) and 5‐bromo‐ and 5‐iodosalicylaldehyde, and 2‐hydroxy‐1‐naphthaldehyde, have been fully characterized, both in solution and in the solid state. This study provides a complete analysis of imine–enamine equilibria, and sheds light onto the mechanism of hydrogen transfer, which has been controversial in the literature. Low‐temperature X‐ray diffraction accompanied by electron‐density maps have further been complemented by theoretical studies at the B3LYP/6‐31G* and M06‐2X/6‐311++G** levels. To ascertain the influence of crystal packing on tautomeric stability, the lattice has also been simulated by computation. This protocol involves the assessment of a supramolecular cluster around a core tautomer possessing either imine or enamine structures. Such an analysis, in full agreement with solid‐state data, reveals the greater stability of zwitterionic structures for the salicyl derivatives. In contrast, these substances show preferential imine forms in solution, whereas the naphthyl‐based compound exhibits a prevalent keto‐enamine structure in all cases.

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“…The synthesis of compounds 1-3 was based on previous articles; nevertheless, variations in the reaction conditions were necessary. [21][22][23][24] The ei/ka tautomeric equilibrium of aromatic Schiff bases can be observed via UV-Vis, IR and NMR spectroscopy. UV-Vis spectra of 1-3 showed the tautomers' transitions that were assigned with the help of TDDFT simulations.…”

Section: Synthesis Of 1-3mentioning

confidence: 99%

Tautomeric Study of Schiff Bases Derived from o‐Dihydroxybenzaldehyde by UV‐Vis, IR, ¹H NMR, ¹³C NMR Spectroscopy and Computational Modeling.

et al. 2020

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Tautomeric equilibria at room temperature were studied for three aromatic imine polyol compounds, previously reported 2-((2-hydroxybenzylidene)amino)-2-(hydroxymethyl)propane-1,3diol 1 and two new compounds 2-(((1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl)imino)methyl)benzene-1,4-diol 2 and 3-(((1,3-dihydroxy-2-(hydroxymethyl)propan-2 yl)imino) methyl)benzene-1,2-diol 3. The dynamic behavior of these equilibria is described by a combination of IR, UV-Vis and NMR spectroscopic measurements with DFT and TDDFT calculations in condensed phase. Among the different approaches, the combination of UV-Vis experimental spectra with the oscillator strengths values estimated from TDDFT calculations allowed for the assessment of the tautomeric populations in DMSO and methanol. These results were consistent with different functionals employed GGA, Hybrid and MetaGGA.

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Evidence of Proton Transfer from the Hydroxy O Atom to the Imine N Atom, Crystal structure of N-Salicylideneamine-1-Tris(Hydroxymethyl)Methane

Cited by 10 publications

References 9 publications

Electrochemical and spectroscopic study of 4-(Phenyldiazenyl)-2-{[tris-(hydroxymethyl)methyl] aminomethylene}cyclohexa-3,5-dien-1(2H)-one: mechanism of the azo and imine electroreduction

Electrochemical and spectroscopic study of 4-(Phenyldiazenyl)-2-{[tris-(hydroxymethyl)methyl] aminomethylene}cyclohexa-3,5-dien-1(2H)-one: mechanism of the azo and imine electroreduction

Schiff Bases from TRIS and ortho‐Hydroxyarenecarbaldehydes: Structures and Tautomeric Equilibria in the Solid State and in Solution

Tautomeric Study of Schiff Bases Derived from o‐Dihydroxybenzaldehyde by UV‐Vis, IR, ¹H NMR, ¹³C NMR Spectroscopy and Computational Modeling.

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Evidence of Proton Transfer from the Hydroxy O Atom to the Imine N Atom, Crystal structure of N-Salicylideneamine-1-Tris(Hydroxymethyl)Methane

Cited by 10 publications

References 9 publications

Electrochemical and spectroscopic study of 4-(Phenyldiazenyl)-2-{[tris-(hydroxymethyl)methyl] aminomethylene}cyclohexa-3,5-dien-1(2H)-one: mechanism of the azo and imine electroreduction

Electrochemical and spectroscopic study of 4-(Phenyldiazenyl)-2-{[tris-(hydroxymethyl)methyl] aminomethylene}cyclohexa-3,5-dien-1(2H)-one: mechanism of the azo and imine electroreduction

Schiff Bases from TRIS and ortho‐Hydroxyarenecarbaldehydes: Structures and Tautomeric Equilibria in the Solid State and in Solution

Tautomeric Study of Schiff Bases Derived from o‐Dihydroxybenzaldehyde by UV‐Vis, IR, 1H NMR, 13C NMR Spectroscopy and Computational Modeling.

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Tautomeric Study of Schiff Bases Derived from o‐Dihydroxybenzaldehyde by UV‐Vis, IR, ¹H NMR, ¹³C NMR Spectroscopy and Computational Modeling.