Differentiating Between Dipolarity and Polarizability Effects of Solvents Using the Solvatochromism of Barbiturate Dyes

Bauer, Mirko; Rollberg, Anja; Barth, Anina; Spange, Stefan

doi:10.1002/ejoc.200800355

Cited by 31 publications

(21 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This might be ascribed to steric interactions which the Kamlet-Taft equation does not take into account. The similar situations were reported in the literature [24,25]. However, this was afterwards overcome by inclusion of the Taft steric parameter in the analysis of structural effects on ADMETox properties of the molecules investigated in this work.…”

Section: Resultssupporting

confidence: 74%

Solvent effects on the structure-property relationship of anticonvulsant hydantoin derivatives: A solvatochromic analysis

Trišović

Valentić

Ušćumlić

2011

Chemistry Central Journal

View full text Add to dashboard Cite

Considering the pharmaceutical importance of hydantoins, a set of 25 derivatives of phenytoin, nirvanol and 5-methyl-5-phenylhydantoin, the lipophilicities of which were gradually increased by the introduction of different alkyl, cycloalkyl and alkenyl groups in position N3, was synthesized. Their properties under consideration were either estimated empirically, by UV/Vis spectroscopy, or calculated using established medicinal chemistry software. The UV absorption spectra of the investigated compounds were recorded in the region from 200 to 400 nm, in selected solvents of different polarities. The effects of solvent dipolarity/polarizability and solvent-solute hydrogen bonding interactions were analyzed by means of the linear solvation energy relationship (LSER) concept proposed by Kamlet and Taft. Furthermore, the relationships between solvent-solute interactions and selected structural features of the solutes, which are believed to markedly affect the processes of absorption, distribution, metabolism, excretion and toxicity (ADMETox), were discussed. Satisfactory correlations were found between hydrogen bonding properties and solute size and the in silico calculated bioactivity descriptors, in particular %Abs. (human intestinal absorption), log BB (blood-brain barrier permeation) and log kA (protein binding affinities) parameters. In view of the results of this study, the investigated hydantoin derivatives met the pharmacokinetic criteria for pre-selection as drug candidates and qualified them for the pharmacodynamic phase of antiepileptic drug development.

show abstract

Section: Resultssupporting

confidence: 74%

Solvent effects on the structure-property relationship of anticonvulsant hydantoin derivatives: A solvatochromic analysis

Trišović

Valentić

Ušćumlić

2011

Chemistry Central Journal

View full text Add to dashboard Cite

show abstract

“…The barbiturate BA1 was obtained by a simple one‐step synthesis starting from triflic anhydride activated Michler's ketone (Scheme ) which provides an easier access to this type of compounds compared to the previously published two‐step procedure for the synthesis of BA2 13…”

Section: Resultsmentioning

confidence: 99%

“…A first impression of the interactions of these dyes with their surrounding can be derived from solvatochromic studies whereby specific and nonspecific interactions can be separated 13,14. Hereto, the UV/Vis absorption maxima of BA1 and BA2 were measured in a set of 22–24 solvents and evaluated by multiple regression analysis using the solvent parameter set of Catalán15 (see Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Enhancing the Reactivity of an Electrophilic Barbiturate Dye by Cooperative Hydrogen Bonding

Bauer

Spange

2009

Eur J Org Chem

Self Cite

View full text Add to dashboard Cite

The supramolecular complex formation by cooperativehydrogen bonding of a highly dipolar barbiturate dye and 2,6‐diacetamidopyridine is shown to have a marked effect on the reactivity of the barbiturate. The increase of both Lewis acidity and electrophilicity by hydrogen bonding is demonstrated by thermodynamic and kinetic studies using the electrophile–nucleophile recombination reaction with cyanide.

show abstract

“…The facts of Table clearly indicate a positive solvatochromism for BA dyes of the merocyanine type, because a , s , d and e coefficients from Equations (4) and (5) altogether show a negative algebraic sign. Likewise, pyridinium‐betaine dyes of the Reichardt‐type, which contain the BA moiety anion as negative part, unambiguously show a negative solvatochromic property because a , s , d and e coefficients from Equations (4) and (5) altogether show a positive algebraic sign …”

Section: Resultsmentioning

confidence: 90%

Interactions of Enolizable Barbiturate Dyes

Schade

Schreiter

Rüffer

et al. 2016

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The specific barbituric acid dyes 1-n-butyl-5-(2,4-dinitro-phenyl) barbituric acid and 1-n-butyl-5-{4-[(1,3-dioxo-1H-inden-(3 H)-ylidene)methyl]phenyl}barbituric acid were used to study complex formation with nucleobase derivatives and related model compounds. The enol form of both compounds shows a strong bathochromic shift of the UV/Vis absorption band compared to the rarely coloured keto form. The keto-enol equilibria of the five studied dyes are strongly dependent on the properties of the environment as shown by solvatochromic studies in ionic liquids and a set of organic solvents. Enol form development of the barbituric acid dyes is also associated with alteration of the hydrogen bonding pattern from the ADA to the DDA type (A=hydrogen bond acceptor site, D=donor site). Receptor-induced altering of ADA towards DDA hydrogen bonding patterns of the chromophores are utilised to study supramolecular complex formation. As complementary receptors 9-ethyladenine, 1-n-butylcytosine, 1-n-butylthymine, 9-ethylguanidine and 2,6-diacetamidopiridine were used. The UV/Vis spectroscopic response of acid-base reaction compared to supramolecular complex formation is evaluated by (1)H NMR titration experiments and X-ray crystal structure analyses. An increased acidity of the barbituric acid derivative promotes genuine salt formation. In contrast, supramolecular complex formation is preferred for the weaker acidic barbituric acid.

show abstract

Differentiating Between Dipolarity and Polarizability Effects of Solvents Using the Solvatochromism of Barbiturate Dyes

Cited by 31 publications

References 52 publications

Solvent effects on the structure-property relationship of anticonvulsant hydantoin derivatives: A solvatochromic analysis

Solvent effects on the structure-property relationship of anticonvulsant hydantoin derivatives: A solvatochromic analysis

Enhancing the Reactivity of an Electrophilic Barbiturate Dye by Cooperative Hydrogen Bonding

Interactions of Enolizable Barbiturate Dyes

Contact Info

Product

Resources

About