Derivational,Structural, and Biological Studies of Some New Pyrazolyl,Isoxazolyl, Pyrimidinyl,Pyridazinyl, and Pyridopyridazinyl from 4‐Substituted Antipyrine

(1,5‐Dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)carbono‐hydrazonoyl dicyanide was used as a key intermediate for the synthesis of novel pyrazole, isoxazole, pyrimidine, and pyridazine derivatives. The newly synthesized compounds were characterized by elemental analyses and spectral data (IR, ¹H‐NMR, ¹³C‐NMR, and mass spectra). The compounds were tested for their in vitro antibacterial activity against Gram‐positive bacteria as (Staphylococcus aureus and Bacillus subtilis ) and Gram‐negative bacteria (Pseudomonas aeruginosa and Escherichia coli ). The investigated compounds were tested against two strains of fungi Botrytis fabae and Fusarium oxysporum using diffusion agar technique. The biological results showed clearly that most of the synthesized compounds revealed mild to moderate activity against the used microorganisms.     

Design,synthesis, anticancer,antibacterial, and antifungal evaluation of 4-aminoquinoline-1,3,5-triazine derivatives

A series of 4-aminoquinoline 1,3,5-triazine derivatives were synthesized and evaluated for anticancer activity against cancer cell lines HeLa, MCF-7, HL-60, HepG2 where these derivatives exert significant anticancer activity. The molecules found nontoxic against MCF-12A. The molecules also showed potent inhibition of EGFR-TK as compared to eroltinib in enzyme-based assay. The newly synthesized derivatives were screened for their in vitro antibacterial and antifungal activity against Bacillus subtilis, Bacillus cereus, Staphylococcus aureus, Proteus vulgaris, Escherichia coli, Pseudomonas aeruginosa and Candida albicans, Aspergillus niger, Aspergillus fumigatus using cefixime and fluconazole as standard. Antibacterial screening results suggest that compound 7c showed potent activity against S. aureus, P. aeruginosa, and P. vulgaris. In antifungal screening, compound 7b showed significant activity against A. niger, A. fumigatus and moderate activity against C. albicans.     

A Theoretical Study of LiHe+ n , NaHe+ n , and MgHe+ n Complexes, with n=1, 2, 3, 4

The LiHe⁺ _n , the NaHe⁺ _n , and the MgHe⁺ _n complexes with n=1, 2, 3, 4 were studied using ab initio calculations with the MP2/6-311+G(3df, 3pd) method. The complexes are found to be stable. For the n=1 complexes, previous results were available and the calculations performed are in good agreement with those results. This lends credibility to the results obtained for the complexes with higher n.     

The Synthesis of Novel S-, S,S-, S,S,S-, and N,S-Substituted Nitrodienes from Polyhalonitrodienes and Thiols

Abstract

The novel S-, S,S-, and S,S,S-substituted nitrobutadienes were synthesized from the reactions of 2-nitrobutadiene compounds with some thiols. The new N,S-substituted nitrobutadienes were obtained from the reaction of the mono-thiosubstituted butadienes with morpholine, thiomorpholine, homopiperazine, and piperazine derivatives. The structures of new compounds were determined by spectroscopic techniques.

GRAPHICAL ABSTRACT      

Thermodynamics of Coordination Bonds in Metal closo-Heteroclusters of the Endofullerene Type M@N k B r C s n – (m = k + r + s = 12, 24, or 28; n = 0–4), Where M = Li,Mg, Al,Ti, Zr,Hf, V,Nb, Mo,Ru, Rh,Ir, Ta,Pt, Pd,and Au

The energy of coordination-induced stabilization and the enthalpy of formation of gaseous metal closo-heteroclusters of the M@N _k B _r C _s ^{n –} type (m = k + r + s = 12, 24, or 28; n = 0–4), where M = Li, Mg, Al, Ti, Zr, Hf, V, Nb, Mo, Ru, Rh, Ir, Ta, Pt, Pd, and Au, were estimated in terms of a structural-thermodynamic model. The stabilizing role of metals in clusters was demonstrated. The energies D ₀ of M–N, M–B, and M–C bonds were found to be underestimated by the MO LCAO method at the HF/6-31G* level.     

Chromatographic Resolution,Circular Dichroism Spectra,Absolute Configurations,and Crystal Structures of Bridged Biphenyls,Containing Sulfide,Sulfoxide, and Sulfone Groups in the Bridge

Four chiral 1,1′‐biphenyls with one or two sulfur‐containing bridges in 2,2′‐ or 2,2′‐ and 6,6′‐positions, viz. 1,11‐dimethyl‐5,7‐dihydrodibenzo[c,e]thiepin ( 1 ), its S‐oxide ( 2 ) and S,S‐dioxide ( 3 ), and the doubly bridged 10,12‐dihydro‐4H,6H‐[2]benzothiepino[6,5,4‐def][2]benzothiepin ( 4 ) have been studied by chromatography, CD spectroscopy, X‐ray crystallography, and empirical force‐field and CNDO/S calculations. The structures obtained by force‐field calculations showed good agreement with the crystal structures determined for 2 and 3 . Compounds 2 , 3 , and 4 , but not 1 , could be resolved into enantiomers by chromatography on swollen microcrystalline triacetylcellulose. The barrier for biphenyl inversion in 2 was found to be higher than 167 kJ⋅mol⁻¹ by an attempted thermal racemization. The CD spectra of the enantiomers of 2 – 4 were recorded and resolved into individual bands, and the corresponding rotational strengths were calculated. The transitions showed considerable similarity to those of a 1,1′‐biphenyl with hydrocarbon bridge (cf. 5 ), albeit with bathochromic shifts, which permitted the assignment of the absolute configurations of the enantiomers of 2 – 4 . The assignments were supported by comparison of the experimental CD spectra with spectra calculated by the CNDO/S method. All first‐eluted enantiomers were found to have the (S)‐configuration.     

Synthesis and Antibacterial and Antifungal Properties of Novel S-, N-, N,S-, and S,O-Substituted 1,4-Naphthoquinone Derivatives

Abstract

A novel series of substituted 1,4-naphthoquinone derivatives were synthesized and evaluated for their antibacterial and antifungal activity. The structures of the novel products were characterized by spectroscopic methods. Among the tested compounds, 2,2′,3,3′-alkoxy substituted naphthoquinones, S,O-substituted naphthoquinone, and N,S-substituted naphthoquinone derivatives are the most potent antifungals against C. tenuis. 2,3-Thio-2′,3′-alkoxy substituted naphthoquinones are the most effective antifungal compounds against A. niger.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Phenylpropanoids from Medicinal Plants: Distribution, Classification, Structural Analysis, and Biological Activity

The literature and our own research results on phenylpropanoids from medicinal plants were reviewed and systematized. Data were presented for the distribution of phenylpropanoids. Their classification was proposed. The biological structure-activity relationships for compounds found in roseroot (Rhodiola rosea), thorny eleutherococcus (Eleutherococus senticosus), common lilac (Syringa vulgaris), purple echinacea (Echinacea purpurea), medicinal melissa (Melissa officinalis), variegated milk-thistle (Silybum marianum), and others were discussed.     

Synthesis,Crystal Structure,Antifungal Activity,and Docking Study of Difluoromethyl Pyrazole Derivatives

Nine novel difluoromethylpyrazole acyl urea derivatives were synthesized via seven steps conveniently. All the structures were determined by ¹H‐NMR, ¹³C‐NMR, HRMS, and X‐ray diffraction. The in vivo fungicidal activities were determined against Corynespora mazei, Botrytis cinerea, Fusarium oxysporum, and Pseudomonas syringae, respectively. The bioassay results indicated that some of them displayed good control effective (around 50 and 80%) against P. syringae and B. cinerea at 50 mg/L, respectively, which is better than control. It is possible that difluoromethylpyrazole acyl urea derivatives can be a leading compound for the development of new fungicides against the two fungi with further structure optimization. Furthermore, docking model was studied to establish structure–activity relationship of difluoromethylpyrazole acyl urea derivatives.     

Solvent Extraction Studies of Two Isomeric 5, 7, 7, 12, 12, 14-Hexamethy-1, 4, 8, 11-Tetraazacyclotetradecanes

The distribution ratios of two isomeric 5, 7, 7, 12, 12, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradecane, tet c and tet d, in several solvent systems at 25.0°C as functions of hydrogen ion concentration were determined. The protonation constants and the distribution constants of these macrocyclic ligands and their protonated species were obtained from the variations of the distribution ratios in the range of 6<–log [H⁺]<14.     

Synthesis of new chiral mono-, di-, tri-, and tetraalkylglycolurils

Two general procedures were developed for the synthesis of chiral N-mono-, N, N′-di-, N, N′ N″-tri-, and N, N′, N″, N′″-tetraalkylglycolurils based on the reactions of 4,5-dihydroxy-imidazolidin-2-ones or glyoxal with one or two moles of alkylureas, respectively, by acid catalysis. The reactions of N-monoalkyl- and N, N′-dialkylureas with glyoxal proceed regioselectively. The mechanism of these reactions was suggested and partly confirmed by quantum-chemical calculations and experimental data. The enantiomeric separation of some chiral glycolurils by chiral-phase HPLC was carried out for the first time.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 680–692, March, 2005.     

Novel dibenzosuberene substituted aroyl selenoureas: Synthesis,crystal structure,DFT, molecular docking and biological studies

Abstract

A series of aroyl selenourea dibenzosuberene (1–3) derivatives were synthesized and characterized by different analytical methods and single crystal X-ray crystallography. Quantum chemical computations were made using DFT to determine the structural and molecular properties of the compounds. The in vitro antibacterial action of the compounds was evaluated against chosen gram-negative (Pseudomonas aeruginosa, Klebsiella pneumoniae, and Escherichia coli), and gram-positive (Bacillus subtilis, Staphylococcus aureus, and Staphylococcus epidermidis) bacteria for their antifungal activity against Curvularia lunata, Penicillium notatum, and Aspergillus niger. Using molecular docking studies, the binding modes were understood along with the mechanism in opposing the target protein MurB.     

Thermodynamics ofN,N,N-octylpentyldimethyl-ammonium chloride in water-urea mixtures

Specific conductivities, densities, heat capacities, and enthalpies of dilution at 25‡C were measured forN,N,N-octylpentyldimethylammonium chloride (OPAC) in water-urea mixtures at various urea concentrations m_u as functions of the surfactant concentration m_s. From conductivity data, the cmc and the degree of the counterion dissociation Β of the OPAC micelles were calculated. The cmc increases linearly with increasingm _u while Βvs. m_u is a smooth concave curve. From the experimental thermodynamic data, the apparentY _Φ and partialY ₂ molar properties (volumes, heat capacities, and relative enthalpies) are derived as functions of m_u andm _s . The effect of urea on the dependences of the different properties on m_s are discussed. From data in the premicellar region the standard partial molar volumesV ₂ ⁰ and heat capacitiesC _p2 ⁰ were evaluated. It was observed thatV ₂ ⁰ increases linearly withm _u whileC _p2 ⁰ decreases. The properties of OPAC in the dispersed and micellized forms at the cmc were obtained and, therefore, the thermodynamic functions of micellization were calculated on the basis of the pseudo-phase transition model.     

Syntheses and Crystal Structures of LaRhMg,CeRhMg, PrRhMg,and NdRhMg

New intermetallic rare earth compounds LaRhMg, CeRhMg, PrRhMg, and NdRhMg were prepared by reaction of the elements in sealed tantalum tubes in a high‐frequency furnace. The compounds were investigated by X‐ray diffraction both on powders and single crystals. LaRhMg crystallizes with the LaNiAl type structure, space group Pnma, Z = 8, a = 760.1(2), b = 419.92(8), c = 1702.6(2) pm, wR2 = 0.0482, 740 F² values and 38 variable parameters. The cerium compound adopts the ZrNiAl structure: P6¯2m, Z = 3, a = 752.3(1), c = 417.6(1) pm, wR2 = 0.0497, 250 F²2 values and 17 variable parameters. PrRhMg and NdRhMg crystallize with the TiNiSi type: Pnma, Z = 4, a = 721.62(7), b = 415.98(4), c = 869.47(8) pm, wR2 = 0.1864, 440 F² values, 20 variables for PrRhMg and a = 720.6(1), b = 417.6(1), c = 868.8(1) pm, wR2 = 0.0779, 425 F² values, 22 variables for NdRhMg. Refinements of the occupancy parameters revealed mixed Mg/Rh occupancy for the magnesium sites of the cerium and the neodymium compound leading to the compositions CeRh_1.262(8)Mg_0.738(8) and NdRh_1.114(9)Mg_0.886(9) for the investigated single crystals. From a geometrical point of view, the four crystal structures are built up from different rhodium centered trigonal prisms. The rhodium and magnesium atoms form three‐dimensional [RhMg] networks in which the rare earth metal atoms are located in different types of channels. The networks show Rh—Mg and Mg—Mg bonding.     

Thermodynamic Properties of Tetraphenyltetrahydroxycyclotetrasiloxane,Octaphenyltetrahydroxytricyclooctasiloxane, Octaphenylpentacyclosilsesquioxane,and Polyphenylsilsesquioxane in the Range 0-300 K

The temperature dependences of the heat capacities of crystalline tetraphenyltetrahydroxycyclotetrasiloxane, octaphenyltetrahydroxytricyclooctasiloxane, and octaphenylpentacyclosilsesquioxane and of glassy polyphenylsilsesquioxane were measured in the range 6-300 K with an adiabatic vacuum calorimeter, with an accuracy of 0.3%. From these data, the thermodynamic functions C ⁰ _p (T), H ⁰(T) - H ⁰(0), S ⁰(T) - S ⁰(0), and G ⁰(T) - H ⁰(0) of these substances were calculated for the range 0-300 K. The standard entropies of their formation from elements at 298.15 K, _f S ⁰, and the entropies of mutual transformations of these substances in the range 0-298.15 K were calculated.     

Synthesis,characterization, and polymerization of N-vinylarylamines

Several N-vinylarylamines have been prepared by direct N-vinylation of arylamine salts with acetylene at atmospheric pressure. Nuclear magnetic resonance (NMR) spectra of the various N-vinylarylamines were recorded and chemical shift assignments were made for the first time. The vinyl protons of the enamines generally exhibit an ABX pattern. The electron-rich monomers are sensitive to acid-catalyzed hydrolysis in a wet solvent. Polymerizations of the monomers were carried out at low temperatures with phosphorous pentafluoride as an initiator. It was found that PF₅ generated directly from thermal decomposition of p-chlorobenzenediazonium hexafluorophosphate is useful in the preparation of an extremely high-molecular-weight poly(N-vinylcarbazole) (M _w = 3 × 10⁶) with a narrow molecular weight distribution (MWD = 2.1). The polymerizability of N-vinylarylamines appears to vary with the amine functional groups of the monomers. N-vinylarylamine containing a planar amine moiety such as carbazole forms a higher-molecular-weight polymer than the monomers with the nonplanar bulky amine groups.     

Synthesis and properties of fringelite D (1,3,4,6,8,10,11,13-octahydroxy-phenanthro[1,10,9,8,o,p,q,r,a]perylene-7,14-dione)

Summary Fringelite D was synthesized from 1,3,6,8-tetramethoxyanthracen-9-olvia two different efficient routes. The first one involved demethylation and subsequent dimerization. The other one started with dimerization to yield octamethylfringelite D and subsequent demethylation. The starting material was prepared in four steps from commercially available educts, the key step being a benzamideortho-lithiation. The spectroscopic properties of fringelite D were measured and are discussed. The dissociation, deprotonation, and protonation equilibria of fringelite D were characterized by their respectivepK values in ground and excited states and compared with those of hypericin. Homo- and heteroassociation properties of fringelite D were found to be similar to those of hypericin.

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Synthese und Eigenschaften von Fringelit D (1,3,4,6,8,10,11,13-Octahydroxy-phenanthro[1,10,9,8,o,p,q,r,a]perylen-7,14-dion)

Zusammenfassung Fringelit D wurde auf zwei effizienten Routen aus 1,3,6,8-Tetramethoxyanthracen-9-ol synthetisiert. Die erste umfaßt Demethylierung und anschließende Dimerisierung. Die andere beginnt mit der Dimerisierung zu Octamethylfringelit D und endet mit einer Demethylierung. Das Ausgangsmaterial wurde in vier Stufen aus kommerziell zugänglichen Edukten dargestellt; der Schlüsselschritt ist eineortho-Lithiierung eines Benzamids. Die spektroskopischen Eigenschaften von Fringelit D wurden gemessen und werden diskutiert. Die Dissoziations-, Deprotonierungs- und Protonierungsgleichgewichte wurden durch ihrepK-Werte in Grundzustand und angeregtem Zustand charakterisiert und mit jenen des Hypericins verglichen. Die Homo- und Hetero-assoziationseigenschaften von Fringelit D sind jenen des Hypericins ähnlich.

     

Prearranged Glycosides,Part 10. Intramolecular Glycosylation with Cellobiosyl,Lactosyl, and Maltosyl Donors

ABSTRACT

Acetyl protected 1,2-O-(1-methoxyethylidene)-disaccharides 1 of maltose, cellobiose, and lactose, respectively were converted via the corresponding benzyl protected couterparts 2, the benzyl protected phenyl 2-O-acetyl- 3 and 2-O-unprotected 1-thio-glycoside disaccharides 4 into 2-O-succinoylated disaccharides 5. The latter were esterified with benzyl 2-O-benzoyl-4,6-di-O-benzylidene-α-D-glucopyranoside (6) to afford succinyl linked derivatives 7 the benzylidene groups of which were regioselectively opened to give prearranged glycoside trisaccharides 8. Intramolecular glycosylation of the latter with N-iodosuccinimide resulted in exclusive formation of the corresponding α-(1→4)-linked trisaccharides 9. No influence of the donor moiety on the diastereoselectivity of the intramolecular glycosylation was observed.     

All-trans- and t,T,t,C,t,T,t-deca-1,3,5,7,9-Pentaenes: Ab Initio Structures,Vibrational Analyses,and Some Regularities in the Series of Related Molecules

Total geometry optimization and calculation of the force constants for all-transand t,T,t,C,t,T,tdeca-1,3,5,7,9-pentaene were carried out at the ab initio, HF/6-31G level. The HF/6-31G//HF/ 6-31G force fields were modified using empirical scale factors transferred from trans-buta-1,3-diene augmented by an additional scale factor for the central formal carbon-carbon double bond coordinates (determined previously for all-trans-hexa-1,3,5-triene). The total number of scale factors was seven. The vibrational problems for both decapentaenes were solved using the respective scaled HF/6-31G//HF/6-31G force field. Infrared intensities and Raman activities were calculated from the unscaled HF/6-31G//HF/6-31G force fields. Complete assignment of all the fundamental vibrational frequencies is given. Geometrical parameters, vibrational frequencies and force constants are compared with the corresponding values of buta-1,3-diene, hexa-1,3,5-triene and octa-1,3,5,7-tetraene. Regularities in the properties of this molecular series are discussed. Special attention is given to the possibility of using the vibrational spectra for detection of distortions from the regular trans structure of these oligoenes.     

Synthesis,Structure, and Transformations of New Endic Anhydride Derivatives

4-Azatricyclo[5.2.1.02,6]dec-8-ene and its N-phenyl derivative were synthesized by reaction of endic anhydride with amines, transformation of the amido acids thus obtained to imides, and subsequent reduction of the latter with lithium aluminum hydride. The unsubstituted tricyclic amine was brought into reactions with electrophilic reagents: p-toluenesulfonyl chloride, p-toluoyl chloride, m-tolyl isocyanate, phenyl isothiocyanate, and endic anhydride to obtain a number of new derivatives; also, the corresponding salt with 1-adamantanecarboxylic acid was isolated. N-(p-Tolylsulfonyl)- and N-(m-tolylcarbamoyl)-4-azatricyclo-[5.2.1.02,6]dec-8-enes were oxidized to the corresponding 8,9-epoxy derivatives with monoperoxyphthalic acid. The structure of the products was confirmed by the data of IR, ¹H and ¹³C NMR, and mass spectra. The molecular structures of N-(p-iodophenyl)bicyclo[2.2.1]hept-2-ene-endo-5,endo-6-dicarboximide and N-phenyl-4-azatricyclo[5.2.1.02,6]dec-8-ene were established by X-ray analysis.