New Fluorescent Sensors Based on 1<Emphasis Type="Italic">H</Emphasis>-pyrazolo[3,4-<Emphasis Type="Italic">b</Emphasis>]quinoline Skeleton

Novel fluorescing dyes 1,3,4-triphenyl-6-(1,4,7,10-tetraoxa-13-aza-cyclopentadec-13-ylmethyl)-1H-pyrazolo[3,4-b]quinoline (K1) and 2-[(2-hydroxyethyl)-(1,3,4-triphenyl-1H-pyrazolo[3,4-b]quinolin-6-ylmethyl)-amino]ethanol (L1) have been synthesized and investigated by the means of steady state and time-resolved fluorescence techniques. These compounds act as sensors for the fluorescence detection of small inorganic cations (lithium, sodium, barium, magnesium and calcium) in solvents of different polarities (THF and acetonitrile). The mechanism, which allows application of these compounds as sensors, is an electron transfer from the electro-donative part of molecule to the acceptor part (fluorophore), which is retarded upon complexation of the electro-donative part by inorganic cations. We found that crown ether-containing compound is very sensitive to the addition of any investigated ions but amino alcohol-containing one exhibits better selectivity to the addition of two-valued cations. Two kinds of the complexes (LM⁺ and L₂M⁺) were found in the investigated systems. In addition, the dyes may be used as fluorescence indicators in solvents of lower polarity like tetrahydrofuran.     

An efficient and facile synthesis of new tetracyclic fused pyrazolo[4,3-<Emphasis Type="Italic">c</Emphasis>][1,2,4]triazino[4,5-<Emphasis Type="Italic">a</Emphasis>]quinolin-4(5<Emphasis Type="Italic">H</Emphasis>)-ones

Reaction of amidrazones 1a–1i with (1,5-dihydro-3-methyl-5-oxo-1-phenyl-4H-pyrazol-4-ylidene)propanedinitrile (2) in ethyl acetate solution in one-step reaction led to the formation of unprecedented pyrazolo[4,3-c][1,2,4]triazino[4,5-a]quinolin-4(5H)-ones 3a–3g along with pyrazolo[4,3-c][1,2,4]triazino[4,5-a]quinolin-12b-oles 3h–3m in moderate to excellent yields. These novel heterocycles were formed via a Michael addition reaction followed by intramolecular cyclization via a dearomatization process.     

A new synthetic approach to functionalize pyrimido[4,5-<Emphasis Type="Italic">b</Emphasis>]quinoline-2,4(1<Emphasis Type="Italic">H</Emphasis>,3<Emphasis Type="Italic">H</Emphasis>)-diones via a three-component one-pot reaction

Functionalized pyrimido[4,5-b]quinoline-2,4 (1H,3H)-diones were synthesized by a three-component one-pot reaction involving barbituric acid, aldehydes, and anilines. The use of commercially available anilines allowed the facile syntheses of pyrimido[4,5-b]quinolinediones substituted in all the positions on the benzene ring with electron donor or electron withdrawing groups. This straightforward method circumvents the preparation of unstable substituted 2-aminobenzaldehydes that limits the scope of previously described syntheses. Furthermore, access to the 5-substituted derivatives is now also possible starting from aliphatic or aromatic aldehydes. Our strategy and methodology offer significant and practical improvements over other methodologies.     

Synthesis of highly substituted 2,3-dihydropyrimido[4,5-<Emphasis Type="Italic">d</Emphasis>]pyrimidin-4(1<Emphasis Type="Italic">H</Emphasis>)-ones from 4,6-dichloro-5-formylpyrimidine,amines and aldehydes

A practical strategy was developed for the preparation of highly substituted 2,3-dihydropyrimido[4,5-d]pyrimidin-4(1H)-ones from 4,6-dichloro-5-formylpyrimidine, primary amines, and aldehydes. The key step for this synthesis entails a cyclization reaction involving an intramolecular amide addition to an iminium intermediate formed in situ from 4-amino-pyrimidine-5-carboxamide 2 and aldehydes to form the pyrimido[4,5-d]pyrimidine core with a strategically placed 5-Cl group for further derivatization. The utility of this methodology was demonstrated through the preparation of a 27-membered library of representative 2,3-dihydropyrimido[4,5-d]pyrimidin-4(1H)-ones in moderate to good yields.     

Parallel and automated library synthesis of 2-long alkyl chain benzoazoles and azole[4,5-<Emphasis Type="BoldItalic">b</Emphasis>]pyridines under microwave irradiation

Summary A versatile route to 40-membered library of 2-long alkyl chain substituted benzoazoles (1 and 2) and azole[4,5-b]pyridines (3 and 4) via microwave-assisted combinatorial synthesis was developed. The reactions were carried out in both monomode and multimode microwave oven. With the latter, all reactions were performed in high-throughput experimental settings consisting of an 8×5 combinatorial library designed to synthesize 40 compounds. Each step, from the addition of reagents to the recovery of final products, was automated. The microwave-assisted N-long chain alkylation reactions of 2-alkyl-1H-benzimidazole (1) and 2-alkyl-1H-benzimidazole[4,5-b] pyridines (3) were also studied.     

Solid-State NMR Studies on Ionic <Emphasis Type="Italic">closo</Emphasis>-Dodecaborates

Alkali metal dodecahydro-closo-dodecaborates M₂[B₁₂H₁₂] (M = K, Rb, Cs, NH₄, N(CH₃)₄) and the perhalogenated cesium salts Cs₂[B₁₂X₁₂] (X = Cl, Br, I) are studied by solid-state ¹¹B nuclear magnetic resonance (NMR) spectroscopy as well as X-ray diffraction (XRD) and differential scanning calorimetry. The present work addresses the molecular dynamics of the anionic [B₁₂X₁₂]²⁻ icosahedra which is examined by variable-temperature ¹¹B NMR line shape studies between 120 and 370 K. Characteristic line shape effects are observed which strongly depend on the actual substituent X and the counterion M⁺. All alkali metal dodecahydro-closo-dodecaborates M₂ [B₁₂H₁₂] exhibit at elevated temperatures ¹¹B NMR spectra with a single isotropic line which proves the presence of an efficient molecular process, resulting in dynamic (rotational) disorder along with vanishing dipolar and quadrupolar interactions. The positional order of the boron clusters, however, remains unaffected, as shown by the XRD data. At lower temperatures, the underlying motions are frozen on the NMR timescale resulting in characteristic ¹¹B NMR spectra with a dominant homonuclear ¹¹B–¹¹B dipolar splitting. The per-halogenated cesium salts Cs₂[B₁₂X₁₂] behave differently. Hence, from the experimental ¹¹B NMR spectra at room temperature a substantial mobility is only seen for the [B₁₂Cl₁₂]²⁻ anion. Obviously, the degree of anion mobility depends on the size of the substituent X in the [B₁₂X₁₂]²⁻ clusters (X = H, Cl, Br, I). A quantitative analysis of the experimental ¹¹B NMR spectra of the alkali metal dodecahydro-closo-dodecaborates M₂ [B₁₂H₁₂] is achieved by line shape simulations, considering [B₁₂H₁₂]²⁻ ions undergoing reorientational jumps between icosahedral sites. From the motional correlation times the activation energies are derived. It is found that a correlation exists between the activation energies, the motional correlation times and the lattice constant. Hence, the activation energies and correlation times strongly increase with decreasing size of the cation M⁺, which reflects an increasing sterical hindrance due to a decreasing crystallo-graphic lattice constant in the same direction. Authors' address: Klaus Müller, Institut für Physikalische Chemie, Universit?t Stuttgart, Pfaffen-waldring 55, Stuttgart 70569, Germany     

One-pot microwave-assisted protocol for the synthesis of substituted 2-amino-1<Emphasis Type="Italic">H</Emphasis>-imidazoles

Abstract  

An efficient microwave-assisted one-pot two-step protocol was developed for the construction of disubstituted 2-amino-1H-imidazoles. This process involves the sequential formation of 2,3-dihydro-2-hydroxyimidazo[1,2-a]pyrimidinium salts from readily available 2-aminopyrimidines and α-bromoketones, followed by cleavage of the pyrimidine ring with hydrazine.     

Weak annihilation and the effective parameters <Emphasis Type="Italic">a</Emphasis><Subscript>1</Subscript> and <Emphasis Type="Italic">a</Emphasis><Subscript>2</Subscript> in non-leptonic <Emphasis Type="Italic">D</Emphasis> decays

Based on SU(3) flavor symmetry, many of the quark-graph amplitudes in two-body non-leptonic decays of charmed mesons can be extracted from experiment, which enable us to see the relevance and importance of weak annihilation topologies and to determine the complex parameters a₁ and a₂ to test the factorization approach. It is found that a ₂ /a ₁ in and can be different by a factor of 2, indicating that non-factorizable corrections to the latter are far more important than the former. The relative phase between a₁ and a₂ is about 150°. Weak annihilation topologies induced by nearby resonances via final-state rescattering can be described in a model-independent manner. Although the W-exchange contribution in decays is dominated by resonant final-state interactions (FSIs), its amplitude in VP decays (V: vector meson, P: pseudoscalar meson) receives little contributions from FSIs in the quark-antiquark resonance formation. As a consequence, the sign flip of the W-exchange amplitude in and decays, which is needed to explain the relatively real decay amplitudes of , remains unexplained. SU(3) symmetry is badly broken in some Cabibbo-suppressed modes and this can be accounted for by the accumulation of some modest SU(3) violation in individual quark-graph amplitudes. Received: 19 July 2002 / Published online: 20 November 2002     

Dual properties of orthogonal polynomials of discrete variables associated with the quantum algebra <Emphasis Type="Italic">U</Emphasis><Subscript><Emphasis Type="Italic">q</Emphasis></Subscript>(<Emphasis Type="Italic">su</Emphasis>(2))

We show that for every set of discrete polynomials y _n (x(s)) on the lattice x(s), defined on a finite interval (a, b), it is possible to construct two sets of dual polynomials z _k (ξ(t)) of degrees k = s-a and k = b-s-1. Here we do this for the classical and alternative Hahn and Racah polynomials as well as for their q-analogs. Also we establish the connection between classical and alternative families. This allows us to obtain new expressions for the Clerbsch-Gordan and Racah coefficients of the quantum algebra U _q (su(2)) in terms of various Hahn and Racah q-polynomials. Dedicated to the memory of our teacher and friend Arnold F. Nikiforov (18.11.1930–27.12.2005).     

A new one-pot three-component synthesis of 2,4-diamino-5<Emphasis Type="Italic">H</Emphasis>-chromeno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridine-3-carbonitrile derivatives

In this study, a three-component one-pot synthesis of new 2,4-diamino-5H-chromeno[2,3-b]pyridine-3-carbonitriles derived from 2-amino-1,1,3-tricyanopropene, salicylic aldehydes and secondary cyclic amines is reported. The reaction is conducted in ethanol at ambient temperature in good-to-excellent yields.     

High regioselective ultrasonic-assisted synthesis of 2,7-diaryl-4,7-dihydropyrazolo[1,5-a]pyrimidine-5-carboxylic acids

New and high regioselective method of the synthesis of 2,7-diaryl-4,7-dihydropyrazolo[1,5-a]pyrimidine-5-carboxylic acids by reaction of 3-aryl-5-aminopyrazoles with arylidenpyruvic acid at room temperature under ultrasonication was developed and discussed.     

Ionic liquid-promoted multi-component reaction: novel and efficient preparation of pyrazolo[3,4-<Emphasis Type="Italic">b</Emphasis>]pyridinone,pyrazolo[3,4-<Emphasis Type="Italic">b</Emphasis>]-quinolinone and their hybrids with pyrimidine nucleoside

The utilization of an ionic liquid, [bmim][BF₄] as both reaction medium and promoter for a multi-component reaction of aldehyde (1) and 5-amino-3-methyl-1-phenylpyrazole (2) with Meldrum acid (3) or dimedone (5) is studied. From this reaction, pyrazolo[3,4-b]pyridinone (4) and pyrazolo[3,4-b]quinolinone (6) derivatives were prepared in high yields. This novel procedure showed such advantages as environmentally benign nature, enhanced efficiency, simple operation process, and mild reaction conditions. As an application, the procedure was successfully used in the preparation of a set of pyrimidine nucleoside–pyrazolo[3,4-b]pyridine and pyrazolo[3,4-b]quinolinone hybrids with potential biological activities.     

Synthesis of cyano-2,3-dihydropyrrolo[1,2-<Emphasis Type="Italic">f</Emphasis>]phenanthridine derivatives via a domino-Knoevenagel-cyclization

Abstract  

In a new multicomponent reaction phenanthridine reacts with isocyanides and malonitrile in the presence of benzaldehyde derivatives to produce 2-aryl-3-(alkyl- or arylimino)-2,3-dihydropyrrolo[1,2-f]phenanthridine-1,1(12b H)-dicarbonitrile in a simple, mild, and efficient protocol in excellent yields.     

Investigations of low <Emphasis Type="Italic">q</Emphasis><Subscript><Emphasis Type="Italic">a</Emphasis></Subscript> discharges in the SINP tokamak

Low edge safety factor discharges including very low q _a (1<q _a <2) and ultra low q _a (0<q _a <1) have been obtained in the SINP tokamak. It has been observed that accessibility of these discharges depends crucially on the fast rate of plasma current rise. Several interesting results in terms of different time scales like T _{q a} · τ _R etc have been obtained using a set of softwares developed at SINP. From fluctuation analysis of the external magnetic probe data it has been found that MHD instabilities m=1, n=1 and m=2, n=1 etc. play major role in the evolution of these discharges. To investigate the internal details of these discharges, an internal magnetic probe system has been developed using which current density j _φ and other related parameters have been estimated. By carrying out a resistive stability analysis, evidence of the above-mentioned MHD instabilities have again been found. The physical processes lying behind the accessibility and evolution of the low q _a discharges have been thoroughly investigated.     

The K<Emphasis Type="Italic">π</Emphasis> and <Emphasis Type="Italic">ππ</Emphasis> S-wave amplitude from D-meson decays

The issue of Kπ and ππ S-wave amplitude is addressed using decays of D-mesons. Model-independent measurements of the phases of the π ⁺ π ⁺ and K ^- π ⁺ S-wave amplitude from D ⁺→π ^- π ⁺ π ⁺ and D ⁺→K ^- π ⁺ π ⁺ decays are discussed. The result indicates a deviation from the phase of the K ^- π ⁺ S-wave amplitude obtained by scattering experiments. This could be interpreted as an indication of the presence of 3-body final-state interaction, or in other words, that the phases from production and scattering process cannot be directly compared.     

Efficient Construction of Pyrazolo[1,5-a]pyrimidine Scaffold and its Exploration as a New Heterocyclic Fluorescent Platform

An efficient, fast and facile pyrazolo[1,5-a]pyrimidine synthetic protocol has been established by the condensation of aminopyrazoles with 1,3-dicarbonyl components in AcOH/H₂SO₄ system. The pyrazolo[1,5-a]pyrimidine sulfides were selectively oxidized to the sulfones via a temperature-controlled stepwise oxidative fashion. The correlation between the substitution patterns of these pyrazolo[1,5-a]pyrimidines and their fluorescent spectroscopic properties were further examined, which provided the fundamentals for their potential applications in the development of new fluorescent probes. Red-shifts were easily achieved by the incorporation of unsaturated groups at the 5- and 7-positions, which suggested an approach for synthesizing long wavelength pyrazolo[1,5-a]pyrimidine dyes. The fluorescent spectroscopic properties were found to be sensitive to the hydroxy-containing and carbonyl-containing media such as alcohol and acetone, which helps to confirm the promising perspectives of further investigations in this area.     

<Emphasis Type="Italic">Q</Emphasis> kink of the nonlinear <Emphasis Type="Italic">O</Emphasis>(3) <Emphasis Type="Italic">σ</Emphasis> model involving an explicitly broken symmetry

The (1 + 1)-dimensional nonlinear O(3) σ model involving an explicitly broken symmetry is considered. Sphalerons are known to exist in this model. These sphalerons are of a topological origin and are embedded kinks of the sine-Gordon model. In the case of a compact spatial manifold S ¹, sine-Gordon multikinks exist in the model. It is shown that the model admits a nonstatic generalization of the sine-Gordon kink/multikink, Q kink/multikink. Explicit expressions are obtained for the dependence of the Q kink energy and charge on the phase frequency of rotation. The Q kink is studied for stability, and expressions are obtained for the eigenfunctions and eigenfrequencies of the operator of quadratic fluctuations. It is shown that the Q kink is unstable over the entire admissible frequency range ω ∈ [−1, 1]. The one-loop quantum correction to the static-kink mass is calculated, and the Q-kink zero mode is quantized. It is shown that, in a general static case, the field equations of the model are integrable in quadratures.     

New tetracyclic tetrahydro-<Emphasis Type="Italic">β</Emphasis>-carbolines as tryptophan-derived peptidomimetics

The Pictet–Spengler reaction is known as a useful tool for the synthesis of constrained analogs of tryptophan. Herein, we present the further cyclization of 1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid methyl esters with 1-(1′-aminoalkyl) side chain. These transformations lead to heterocyclic structures which can find useful applications in medicinal chemistry as peptide mimetics.     

<Emphasis Type="Italic">X</Emphasis>(3): An exactly separable <Emphasis Type="Italic">γ</Emphasis>-rigid version of the <Emphasis Type="Italic">X</Emphasis>(5) critical point symmetry

A γ-rigid version (with γ = 0) of the X(5) critical point symmetry is constructed. The model, to be called X(3) since it is proved to contain three degrees of freedom, utilizes an infinite well potential, is based on exact separation of variables, and leads to parameter-free (up to overall scale factors) predictions for spectra and B(E2) transition rates which are in good agreement with existing experimental data for ¹⁷²Os and ¹⁸⁶Pt. An unexpected similarity of the β ₁ bands of the X(5) nuclei ¹⁵⁰Nd, ¹⁵²Sm, ¹⁵⁴Gd, and ¹⁵⁶Dy to the X(3) predictions is observed. The text was submitted by the authors in English.     

Idempotents as <Emphasis Type="Italic">J</Emphasis>-Projections

Let B(H) ^Id be the set of all bounded idempotents on a Hilbert space H. Fix p∈B(H) ^Id . The aim of the paper is to show a set of symmetries J on H for which p is a J-projection.