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.     

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.     

Sulfamic acid catalyzed solvent-free synthesis of 10-aryl-7,7-dimethyl-6,7,8,10-tetrahydro-9H-[1,3]-dioxolo [4,5- <Emphasis Type="Italic">b</Emphasis>]xanthen-9-ones and 12-aryl-9,9-dimethyl-8,9,10,12-tetrahydro-11H-benzo[<Emphasis Type="Italic">a</Emphasis>]xanthen-11-ones

Three-component one-pot synthesis of some novel 10-aryl-7,7-dimethyl-6,7,8,10-tetrahydro-9H-[1,3]-dioxolo[4,5-b]xanthen-9-ones, which have not been published before, and 12-aryl-9,9-dimethyl-8,9,10,12-tetrahydro-11H-benzo[a]xanthen-11-ones from condensation of 3,4-methylenedioxyphenol or β-naphthol, aldehydes and dimedone under solvent-free conditions at 120 °C is reported.     

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.     

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.     

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.     

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.     

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.     

Diversity oriented heterocyclizations of pyruvic acids,aldehydes and 5-amino-<Emphasis Type="Italic">N</Emphasis>-aryl-1<Emphasis Type="Italic">H</Emphasis>-pyrazole-4-carboxamides: catalytic and temperature control of chemoselectivity

Heterocyclization reactions of pyruvic acids, aromatic aldehydes and 5-amino-N-aryl-1H-pyrazole-4-carboxamides yielding four different types of final compounds are described. The reactions involving arylidenpyruvic acids lead with high degree of selectivity to either 4,7-dihydropyrazolo[1,5-a]pyrimidine-5-carboxylic acids or 5-[(2-oxo-2,5-dihydrofuran-3-yl)amino]-1H-pyrazoles, depending on the catalyst type or temperature regime. The interactions based on arylpyruvic acids can take place under kinetic or thermodynamic control producing 7-hydroxy-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidine-7-carboxylic acids or 3-hydroxy-1-(1H-pyrazol-5-yl)-1,5-dihydro-2H-pyrrol-2-ones, respectively.     

Substituted <Emphasis Type="Italic">N</Emphasis>-aminothioglycolurils containing thiosemicarbazone moiety and their cytotoxic activity in vitro

A library of hybrid molecules bearing thioglycoluril and (hetero)aromatic aldehyde thiosemicarbazone moieties was synthesized via a tandem hydrazone formation—ring contraction reaction of 5,7-dialkyl-3-thioxoperhydroimidazo[4,5-e]-1,2,4-triazin-6-ones with (hetero)aromatic aldehydes. All synthesized compounds were tested for their cytotoxic activity against rhabdomyosarcoma, A549, and MS human cancer cell lines by MTT-assay. Among the derivatives, (E)-4-benzylideneamino-1,3-dimethyl-5-thioxohexahydroimidazo[4,5-d]imidazol-2(1H)-one 1f was found to have the most marked antiproliferative activity toward the tested cell lines (1f: IC\(_{50}= 20.6,\) 23.7, and 6.4 \(\upmu \)M, respectively). The IC\(_{50}\) value of thioglycoluril 1f against normal human embryonic kidney cells HEK293 was 72.5 \(\upmu \)M, which appeared to be 3–11-fold higher than IC\(_{50}\) values of 1f against human cancer cells.     

Microwave-assisted green synthesis of 4,5-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrazole-1-carbothioamides in water

Rapid, efficient, simple and green procedure for the synthesis of 4,5-dihydro-1H-pyrazole-1-carbothioamides via the multicomponent reaction of aryl aldehydes, acetophenones and thiosemicarbazide in water in the presence of tetrabutylammonium hydroxide under microwave irradiation is reported.     

Multiple two-variable <Emphasis Type="Italic">p</Emphasis>-adic <Emphasis Type="Italic">q-L</Emphasis>-function and its behavior at <Emphasis Type="Italic">s</Emphasis> = 0

The objective of this paper is to construct a multiple p-adic q-L-function of two variables which interpolates multiple generalized q-Bernoulli polynomials. By using this function, we solve a question of Kim and Cho. We also define a multiple partial q-zeta function which is related to the multiple q-L-function of two variables. Finally, we give a finite-sum representation of the multiple p-adic q-L-function of two variables and prove a multiple q-extension of the generalized formula of Diamond and Ferrero-Greenberg.     

Electron paramagnetic resonance of spin-variable metallomesogens [Fe<Emphasis Type="Italic">L</Emphasis><Subscript>2</Subscript>]<Emphasis Type="Italic">X</Emphasis> (<Emphasis Type="Italic">X</Emphasis> = PF<Subscript>6</Subscript>, SCN)

Significant differences in the manifestation of spin-crossover properties of the mesogen compounds [FeL ₂]X with oxysalicylidene-N′-ethyl-N-ethylenediamine ligands L and anions X = PF₆⁻ and SCH⁻ have been found by means of electron paramagnetic resonance. The electron paramagnetic resonance data and the quantum-chemical calculation within the density functional theory enables us to establish that the observed specific features are associated with the incorporation of the SCH⁻ ion into the first coordination sphere of the Fe(III) ion. The role of the transition of the material to the liquid-state phase in the formation of a low-dimensional (two-dimensional) structure with stronger intermolecular interactions has been revealed.     

Effect of surface free energy on critical field <Emphasis Type="Italic">H</Emphasis><Subscript><Emphasis Type="Italic">c</Emphasis>3</Subscript>

The emergence of surface superconductivity in a type I superconductor is considered taking into account the surface free energy of the superconducting phase. It is shown that the disregard of the surface energy leads to a substantial error in determining the Ginzburg-Landau parameter from the measurements of the H _c3 field.     

Constraints on unified models for dark matter and dark energy using <Emphasis Type="Italic">H</Emphasis>(<Emphasis Type="Italic">z</Emphasis>)

The differential age data of astrophysical objects that have evolved passively during the history of the universe (e.g. red galaxies) allows us to test theoretical cosmological models through the predicted Hubble function expressed in terms of the redshift z, H(z). We use the observational data for H(z) to test unified scenarios for dark matter and dark energy. Specifically, we focus our analysis on the Generalized Chaplygin Gas (GCG) and the viscous fluid (VF) models. For the GCG model, it is shown that the unified scenario for dark energy and dark matter requires some priors. For the VF model we obtain estimations for the free parameters, which may be compared with further analysis mainly at perturbative level.     

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.     

Effect of dehydration on the ferrimagnetic resonance in [Cr(CN)<Subscript>6</Subscript>][Mn(<Emphasis Type="Italic">S</Emphasis>)-<Emphasis Type="Italic">pn</Emphasis>H(H<Subscript>2</Subscript>O)](H<Subscript>2</Subscript>O) single crystals

The effect of dehydration-induced structural transitions on the ferrimagnetic resonance spectra of the [Cr(CN)₆][Mn(S)-pnH(H₂O)](H₂O) chiral molecular magnet has been studied for three crystalline modifications. The differences in the anisotropy field and exchange interaction constants due to the change in the dimensionality of the magnetic ordering upon the phase transitions have been established. In the dehydrated amorphous phase, apart from the ferrimagnetic resonance, additional isotropic magnetic resonance lines corresponding to the spin-glass state have been revealed.     

An efficient one-pot synthesis of functionalized chromeno[4,3-<Emphasis Type="Italic">b</Emphasis>]pyridine derivatives under catalyst-free conditions

A concise, efficient one-pot synthesis of functionalized chromeno[4,3-b]pyridine derivatives via a three-component reaction of 4-oxo-4H-chromene-3-carbaldehydes, malononitrile or cyanoacetates, and aromatic amines under catalyst-free conditions in an environmentally friendly medium (ethanol–water, 3:1 v/v) is described. This synthesis involves a group-assisted purification process, which avoids traditional recrystallization and chromatographic purification methods.     

A simple and facile synthesis of tricyclic-fused pyrimido[4,5-<Emphasis Type="Italic">b</Emphasis>]indol-2-amines

In the present investigation, a simple and facile synthetic strategy for the construction of a series of structurally interesting tricyclic-fused N-alkyl-9H-pyrimido[4,5-b]indol-2-amines has been successfully achieved. Our synthesis, based on the annulation reaction between readily available 2-chloroindole-3-carbaldehydes or 3-acetyl-2-chloroindoles and guanidine nitrate using KOH as the base in refluxing EtOH medium, has the attractive features such as mild and economical reaction conditions and easy handing with lesser impact on the environment.     

T-Duality: Topology Change from <Emphasis Type="Italic">H</Emphasis>-Flux

T-duality acts on circle bundles by exchanging the first Chern class with the fiberwise integral of the H-flux, as we motivate using E₈ and also using S-duality. We present known and new examples including NS5-branes, nilmanifolds, lens spaces, both circle bundles over Pⁿ, and the AdS⁵×S⁵ to AdS⁵×P²×S¹ with background H-flux of Duff, Lü and Pope. When T-duality leads to M-theory on a non-spin manifold the gravitino partition function continues to exist due to the background flux, however the known quantization condition for G₄ receives a correction. In a more general context, we use correspondence spaces to implement isomorphisms on the twisted K-theories and twisted cohomology theories and to study the corresponding Grothendieck-Riemann-Roch theorem. Interestingly, in the case of decomposable twists, both twisted theories admit fusion products and so are naturally rings.