Cycloaddition of benzoheteroazepine II Reactions and conformations of cycloadducts on1,5-benzothiazepines and 1,5-benzodiazepines with nitrile imine and nitrile oxides

Benzodiazepine and benzothiazepine derivatives have been well known as therapeutically important compounds. Four new tricyclic heterocyclic compounds, 3a,4,5,11-tetrahydro-3H-1,2,4-triazolo[4,3-d] [1, 5]benzothiazepines (3), 3a,4,5,11-tetrahydro-3H,6H-1,2,4-triazolo[4,3-d][1,5]benzodiazepine (4), 3a, 4,5,11-tetrahydro-1,2,4-oxadiazolo[4,5-d] [1,5]benzothiazepines (5, 6) and 3a,4,5,11-tetrahydro-6H-1, 2,4-oxadiazolo[4, 5-d] [ 1, 5 ] benzodiazepines (7,8), have been synthesized by 1,3-dipolar cycloaddition reactions of 2, 3-dihydro-1, 5-benzothiazepines and 2, 3-dihydro-1H-1, 5-benzodiazepine with benzonitrile N-phenylimine and benzonitrile oxides, respectively. The conformations of some cycloadducts and cycloaddition mechanism are described.     

Regio- and stereoselective reactions of a rhodanine derivative with optically active 2-methyl- and 2-phenyloxirane

The reaction of a rhodanine derivative (=(Z)-5-benzylidene-3-phenyl-2-thioxo-1,3-thiazolidin-4-one; 1) with (S)-2-methyloxirane (2) in the presence of SiO₂ in dry CH₂Cl₂ for 10 days led to two diastereoisomeric spirocyclic 1,3-oxathiolanes 3 and 4 with the Me group at C(2) (Scheme 2). The analogous reaction of 1 with (R)-2-phenyloxirane (5) afforded also two diastereoisomeric spirocyclic 1,3-oxathiolanes 6 and 7 bearing the Ph group at C(3) (Scheme 3). The structures of 3, 4, 6, and 7 were confirmed by X-ray crystallography (Figs. 1 and 2). These results show that oxiranes react selectively with the thiocarbonyl group (CS) in 1. Furthermore, the nucleophilic attack of the thiocarbonyl S-atom at the SiO₂-activated oxirane ring proceeds with high regio- and stereoselectivity via an S_N2-type mechanism.     

Synthesis of polyfluorophenyl substituted-4,5-dihydropyrazole derivatives via 1,3-dipolar cycloaddition of nitrile imine with ethyl acrylate

Oxidation of aldehyde 4-chloro-2,3,5,6-tetrafluorophenylhydrazones (1) with [bis(acetoxy)iodo]benzene leads to the formation of nitrile imines (2) which reacted in situ with ethyl acrylate to produce 3-substituted-1-(4-chloro-2,3,5,6-tetrafluorophenyl)-5-ethoxycarbonyl-4,5-dihydropyrazoles (3) in moderate to good yields. The structures of new compounds were fully confirmed by their spectral data, elemental analyses and X-ray diffraction (XRD) analysis. A plausible reaction mechanism for the synthesis of title compounds is presented.     

Molecular simulation of the interaction between novel type rhodanine derivative probe and bovine serum albumin

The interaction between 3-(4′-methylphenyl)-5-(4′-methyl-2′-sulfophenylazo) rhodanine (M4MRASP) and bovine serum albumin (BSA) was studied by using spectrofluorimetry. It was shown in fluorescence spectrums that the quenching mechanism of BSA by M4MRASP was a static quenching. Meanwhile, the binding constant and binding site numbers were calculated. The action distance (r = 8.03 nm) and energy transfer efficiency (E = 0.12) between donor (BSA) and acceptor (M4MRASP) were obtained according to the theory of Förster non-radiation energy transfer. The effect of M4MRASP on the conformation of BSA was further analyzed by using synchronous fluorescence spectrometry. A new model of the interaction between small organic molecule and biomacromolecule was established. The results offered a reference for the studies on the biological effects and action mechanism of small molecule with protein.     

A highly fluorescent adenine derivative and its interaction with iron ions

In this paper, an adenine-derived fluorescent chromophore (HCC-APA) was synthesized to detect its interaction with iron ions. The results showed that a large stokes shift (υ = 10981.5 cm^?1) fluorescence of the HCC-APA was appeared. The fluorescence quantum yields of HCC-APA in DMF and THF were 3.49% and 17.54%, respectively, demonstrating its higher fluorescence performance than unmodified adenine. Besides, the fluorescence quenching of HCC-APA with iron ions was further detected. Fluorescence titration experiments confirmed that the detection limit of HCC-APA for Fe³⁺ was 3.69 μM. The interaction between iron ions and HCC-APA was investigated by continuous variable method, indicating that the binding ratio is 1:1. And the interaction site was deeply explored by ¹H NMR and molecular simulation.     

Study on the interaction among molecules and the determination of DNA by light scattering with a new type rhodanine derivative

In this paper the resonance Rayleigh scattering (RRS) and second-order scattering (SOS) spectrums of interaction between deoxyribonucleic acid (DNA) and 3-(4′-methylphenyl)-5-(2′-sulfophenylazo) rhodanine (4MRASP) in the environment of surface active substance sodium dodecyl sulfate (SDS) were reported. The light scattering intensity of 4MRASP was enhanced obviously and directly proportional to the concentrations of DNA when DNA was present. Based on this, two new determination methods of DNA were established with high sensitivity and selectivity, and the limits of detection were 8.00 and 1.07 ng mL⁻¹. They were applied to the determination of trace amounts of nucleic acid in synthetic and practical samples with satisfactory results. At last, the active mechanism among molecules was studied by ultraviolet spectrum, scattering spectrum and thermodynamics, which showed that the active force was changed from hydrophobic force to electrostatic force before and after SDS was added, and the mechanism of sensitization effect of SDS was proposed.     

High open-circuit voltage solution-processed organic solar cells based on a star-shaped small molecule end-capped with a new rhodanine derivative

A new star-shaped small molecule named TCNR3TTPA,with a triphenylamine(TPA)unit as the central building block and2-(1,1-dicyanomethylene)-3-octyl rhodanine(CNR)as the end-capped group,has been designed and synthesized.TCNR3TTPA showed a deep highest occupied molecular orbital(HOMO)energy level( 5.60 e V)and broad absorption.The solution-processed bulk heterojunction(BHJ)solar cells based on TCNR3TTPA:PC61BM(1:1,w/w)exhibited a high open-circuit voltage(Voc)of 0.99 V,a short-circuit current density(Jsc)of 5.76 m A/cm2,and a power conversion efficiency(PCE)of 2.50%under the illumination of AM 1.5 G,100 m W/cm2.The high Voc is ascribed to the strong electron-with-drawing ability of the end-capped 2-(1,1-dicyanomethylene)-3-octyl rhodanine group.These results demonstrated that the Voc of small-molecule organic solar cells could be increased by introducing a strong electron-withdrawing end-capped block,and that this is an effective strategy to design high-performance small molecules for organic solar cells.     

Structure of the crystalline C60 photopolymer and the isolation of its cycloadduct components

We produced C60 photopolymer in gram quantity by a new monomer recycling method and extracted its soluble components. The most abundant components, the (2 + 2) cycloadduct dimer, C120, and several oligomers were isolated by high-performance liquid chromatography (HPLC). Three different C180 isomers were identified on the basis of their formation and decomposition reactions. The crystal structure of the insoluble photopolymer is face-centered cubic (fcc) with a contracted lattice parameter relative to the pristine C60. The lattice parameter and the amounts of soluble oligomers depend on the preparation temperature. We explain this variation with a topochemical model of photopolymerization: The geometrical conditions allow the formation of only linear or planar oligomers in the triangular or square sublattices. Competing reactions in the intersecting planes prevent the formation of large oligomers. The lattice contraction is proportional to the number of cycloadduct bonds.     

A novel derivative of geldanamycin and its antitumor activity

A new derivative of geldanamycin was synthesized by introducing the 6-cinnamamido-hexyl-amino group into the 17-site of geldanamycin,a heat shock protein 90(Hsp90)inhibitor,to obtain 17-(6-cinnamamido-hexylamino)-17-demethoxygel-danamycin (CNDG).Its in vitro and in vivo anfitumor effects were evaluated by MTT assay and xenografl in nude mice.     

A new water‐soluble branched poly(ethylene imine) derivative having hydrolyzable imidazolidine moieties and its application to long‐lasting release of aldehyde

A new water‐soluble poly(ethylene imine)‐derivative having imidazolidine moieties was developed. With using branched poly(ethylene imine) (BPEI) as a precursor, it was modified by Michael addition reaction of its primary amino group to an acrylate having poly(ethylene glycol) (PEG) chain. The modified BPEI was reacted with octanal to give the corresponding BPEI derivative having octanal‐derived imidazolidine moieties. The obtained polymer inherited the high hydrophilicity of the attached PEG chains to allow hydrolysis of the imidazolidine moieties under homogeneous conditions in aqueous media, leading to long‐lasting release of octanal. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

A new economical method with eliminated phase-lag and its derivative for problems in chemistry

Journal of Mathematical Chemistry - A new EcoFinDif (Economical Finite Difference) method with eliminated phase-lag and its first derivative, for periodical and/or oscillating initial or boundary...     

A family of explicit linear six-step methods with vanished phase-lag and its first derivative

A family of explicit linear sixth algebraic order six-step methods with vanished phase-lag and its first derivative is obtained in this paper. The investigation of the above family of methods contains:

theoretical study of the new family of methods and

computational study of the new family of methods.

The theoretical study of the above mentioned family of methods contains:

1. the development of the method,
2. the computation of the local truncation error,
3. the comparative local truncation error analysis. The comparison is taken place between the new family of methods with the corresponding method with constant coefficients and
4. the stability analysis of the new family of methods. The stability analysis is taken place using test equation with different frequency than the frequency of the test equation used for the phase-lag analysis of the methods.

The application of the new family of linear six-step sixth algebraic order methods to the resonance problem of the one-dimensional time independent Schrödinger equation is used for the computational study of the new family of methods. The result of the above mentioned theoretical and computational investigation is that the new proposed family of linear explicit schemes are computationally and theoretically more effective than other well known methods for the approximate solution of the radial Schrödinger equation and related initial or boundary value problems with periodic and/or oscillating solutions.     

A new alkaloid and its artificial derivative with an indazole ring from Nigella glandulifera

A new compound, nigeglanine (1), and its new artificial derivative (1a), were isolated from the seeds of Nigella glandulifera, together with a known aporphine alkaloid, fuzitine (2). Their structures were established by spectral analysis, including two-dimensional (2D)-NMR spectroscopy. Nigeglanine (1) is the third natural product determined to contain an indazole nucleus.     

The reaction of diphenyl carbonate with amines and its application to polymer synthesis

Selective formation of biscarbamates from diphenyl carbonate (DPC) and diamines and the preparation of polyurethanes from the carbamates and diols under mild conditions were studied. The reaction of DPC and diamines was significantly affected by catalysts, biscarbamates being exclusively prepared in high yields in the presence of 2-hydroxypyridine. The polycondensation reaction of the biscarbamates with diols was facilitated by catalysts such as metal salts; among the catalysts examined magnesium chloride in pyridine gave the best results. Metal chlorides in pyridine also promoted the reaction of DPC with aromatic amines to give the corresponding ureas, and the direct synthesis of polyureas was achieved by the polycondensation of DPC with diamines in the presence of the chloride.     

Chitosan-supported imine palladacycle complex and its catalytic performance for heck reaction

Summary A chitosan-supported imine palladacycle complex has been synthesized by salicyladehyde via grafting on chitosan to form chitosan-Schiff base, followed by reacting with Li₂PdCl₄ in methanol. The catalyst has high activity and stereoselectivity for arylation of conjugate alkenes with aryl halides. This chitosan-supported imine palladium catalyst can be recovered and reused.