Mixed anhydride of acetic and formic acids in the synthesis of chromones

A study was carried out on the reaction of -substituted 2-hydroxyacetophenones with the mixed anhydride of acetic and formic acids in the presence of bases of different strength. Chromones containing a conjugated electron-withdrawing substituent at C₍₃₎ are formed in close to quantitative yield in the presence of triethylamine. The preparation of chromones containing an unconjugated substituent under these conditions is recommended only for 5-hydroxy chromones.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 595–600, May, 1992     

Simple and effective synthesis of isoflavones and 3-aryloxychromones

Conditions have been developed for an effective synthesis of 7-hydroxy- and 5,7-dihydroxyisoflavones and also of 3-aryloxy-7-hydroxychromones. The disadvantages and advantages of alternative pathways for the synthesis of these compounds are discussed. The proposed method of synthesis permits considerable simplification of the preparation of compounds of these series.T. G. Shevchenko Kiev State University. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 639–643, September–October, 1989.     

Spectral and Acid–Base Properties of Arylidene Derivatives of Dicyclopentano[b,e]pyridines Serving as Fluorescent pH-Indicators

The bathochromic shifts of absorption and emission bands upon the protonation of dicyclopentano[b,e]pyridines fall in the range of 3500-5500 cm^–1. Both the neutral and protonated forms show high fluorescence quantum yields. The spectral and acid–base properties of these compounds may be varied within a broad range by introducing electron-donor substituents into the aromatic side rings. The protonation constants in the ground and excited states of each of these compounds have similar values as a result of steric hindrance arising upon protonation of the pyridine nitrogen atom.     

Steric control of the excited-state intramolecular proton transfer in 3-hydroxyquinolones: steady-state and time-resolved fluorescence study

3-Hydroxyquinolones (3HQs), similarly to their 3-hydroxychromone analogs, undergo excited state intramolecular proton transfer (ESIPT) resulting in dual emission. In the ground state, 2-phenyl-3HQ derivatives are not flat due to a steric hindrance between the 2-phenyl group and the 3-OH group that participates in the ESIPT reaction. To study the effect of this steric hindrance on the ESIPT reaction, a number of 3HQ derivatives have been synthesized and characterized in different organic solvents by steady-state and time-resolved fluorescence techniques. According to our results, 2-phenyl-3HQ derivatives undergo much faster ESIPT (by nearly 1 order of magnitude) than their 2-methyl-3HQ analogs. Moreover, 1-methyl-2-phenyl-3HQ having a strongly twisted 2-phenyl group undergoes a two- to three-fold slower ESIPT compared to 2-phenyl-3HQ. These results suggest that the flatter conformation of 2-phenyl-3HQ, which allows a close proximity of the 2-phenyl and 3-OH groups, favors a fast ESIPT reaction. The absorption and fluorescence spectra of the 3HQ derivatives additionally confirm that the steric rather than the electronic effect of the 2-phenyl group is responsible for the faster ESIPT reaction. Based on the spectroscopic studies and quantum chemical calculations, we suggest that the 2-phenyl group decreases the rotational freedom of its proximal 3-OH group in the more planar conformation of 2-phenyl-3HQ. As a result, the conformations of 3HQ, where the 3-OH group orients to form an intramolecular H-bond with the 4-carbonyl group, are favored over those with a disrupted intramolecular H-bond. Therefore, the 2-phenyl group sterically favors the intramolecular H-bond and thus accelerates the ESIPT reaction. This conclusion provides a new understanding of the ESIPT process in 3-hydroxyquinolones and related systems and suggests new possibilities for the design of ESIPT based molecular sensors and switchers.     

Modulation of excited-state intramolecular proton transfer by viscosity in protic media

3-Hydroxyquinolones undergo excited-state intramolecular proton transfer (ESIPT), resulting in a dual emission highly sensitive to H-bonding perturbations. Here, we report on the strong effect of viscosity on the dual emission of 2-(2-thienyl)-3-hydroxyquinolone in protic solvents. An increase in viscosity significantly decreases the formation of the ESIPT product, thus changing dramatically the ratio of the two emission bands. Time-resolved studies suggest the presence of solvated species characterized by decay times close to the solvent relaxation times in viscous media. The intramolecular H bond in this species is probably disrupted by the solvent, and therefore, its ESIPT requires a reorganization of the solvation shell for restoring this intramolecular H bond. Thus, the ESIPT reaction of this dye and its dual emission depend on solvent relaxation rates and, therefore, on viscosity. The present results suggest a new physical principle for the fluorescence ratiometric measurement of local viscosity.     

Quantification of local hydration at the surface of biomolecules using dual-fluorescence labels

By using four labels of the 3-hydroxyflavone family displaying selective sensitivity to hydrogen bond (HB) donors and poor response to other polar molecules, we developed an approach for measuring local water concentration [H(2)O](L) (or partial volume of water: W(A) = [H(2)O](L)/55.6) in the label surrounding both in solvent mixtures and in biomolecules by the intensity ratio of two emissive forms of the label, N*/T*. Using a series of binary water/solvent mixtures with limited preferential solvation effects, a linear dependence of log(N*/T*) on the local concentration of HB donor was obtained and then used as a calibration curve for estimating the W(A) values in the surroundings of the probes conjugated to biomolecules. By this approach, we estimated the hydration of the labels in different peptides and their complexes with DNAs. We found that W(A) values for the label at the peptide N-terminus are lower (0.63-0.91) than for free labels and depend strongly on the nature of the N-terminal amino acid. When complexed with different DNAs, the estimated hydration of the labels conjugated to the labeled peptides was much lower (W(A) = 0-0.47) and depended on the DNA nature and linker-label structure. Thus, the elaborated method allows a site-specific evaluation of hydration at the surface of a biomolecule through the determination of the partial volume of water. We believe the developed procedure can be successfully applied for monitoring hydration at the surface of any biomolecule or nanostructure.     

Shape resonances in slow electron scattering by aromatic molecules. I. Anthraquinone derivatives

A series of anthraquinone (C(14)O(2)H(8)) derivatives has been studied by means of electron capture negative ion mass spectrometry (ECNI-MS), photoelectron spectroscopy (PES), and AM1 quantum chemical calculations. Mean lifetimes of molecular negative ions M(-.) (MNI) have been measured. The mechanism of long-lived MNI formation in the epithermal energy region of incident electrons has been investigated. A simple model of a molecule (a spherical potential well with the repulsive centrifugal term) has been applied for the analysis of the energy dependence of cross sections at the first stage of the electron capture process. It has been shown that a temporary resonance of MNI at the energy approximately 0.5 eV corresponds to a shape resonance with lifetime 1-2.10(-13) s in the f-partial wave (l = 3) of the incident electron. The next resonant state of MNI at the energy approximately 1.7 eV has been associated with the electron excited Feshbach resonance (whose parent state is a triplet npi* transition). In all cases the initial electron state of the MNI relaxes into the ground state by means of a radiationless transition, and the final state of the MNI is a nuclear excited resonance with a lifetime measurable on the mass spectrometry timescale. Copyright 1999 John Wiley & Sons, Ltd.     

Synthesis of 7-O-β-D-glucopyranosides of isoflavones and their heterocyclic analogues

The products of the interaction of -acetobromoglucose with 2,4,5-trihydroxyphenyl benzyl ketone and 2,4-dihydroxyphenyl 4-hydroxybenzyl ketone and also with their heterocyclic analogues, which are present completely or partially in the enolic form, have been investigated. It has been shown that in this reaction a tetra-O-acetylglucosyl residue is added at the 4-OH hydroxy group of the phenyl residue of the ketone. The compounds obtained have been converted into isoflavone 7-O-glucosides by the action of the vilsmeier reagent or acetoformic anhydride.Taras Shevchenko Kiev University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 220–227, March–April, 1993.     

Synthesis and fluorescence properties of 2-aryl-3-hydroxyquinolones, a new class of dyes displaying dual fluorescence

A series of 2-aryl-3-hydroxyquinolones (3HQs) with different electron donating aryl substituents at the position 2 were synthesized. Their absorption and fluorescence properties were studied in solvents of medium and high polarity. Almost all the synthesized 3HQs display dual fluorescence in the tested solvents, in line with an excited state intramolecular proton transfer reaction. For N-methyl substituted compounds, the intensity ratio of the two emission bands was found to be exquisitely sensitive to solvent polarity, with a two orders of magnitude change from toluene to dimethylsulfoxide. Consequently, these compounds appear as prospective polarity fluorescent labels for proteins and nucleic acids.