A convenient synthesis of quinazoline derivatives via cascade imino-Diels-Alder and oxidation reaction

Quinazoline derivatives were synthesized fromα-iminoesters via a cascade imino-Diels-Alder and then oxidation reaction catalyzed with CuBr_2.This method provided a new strategy for preparing quinazoline derivatives which may be useful in the synthesis of heterocyclic intermediates.

SYNTHESIS AND PROPERTIES OF NOVEL POLY(IMINO KETONE)S AS HIGH-PERFORMANCE POLYMERS

Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation reaction.The structures of PIKs are characterized by means of elemental analysis,FT-IR,~1H-NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structure.The general properties of PIKs are studied by DSC,TG and wide-angle X-ray diffraction,the solubility behavior is...

Synthesis and Crystal Structure of 2-(N-Cyclohexyl)-imino-1,4-succinic Acid Dihydrate

The title compound, 2-(N-cyclohexyl)-imino-1,4-succinic acid dihydrate 4, has been prepared and structurally determined by X-ray diffraction analysis. Crystal data: monoclinic, space group Cc, a = 7.5790(15), b = 24.860(5), c = 7.1394(14) ?, β = 104.23(3)°, V = 1303.9(4) ?3, C10H21NO6, Mr = 251.28, Z = 4, Dc = 1.280 g/cm3, μ = 0.105 mm-1, F(000) = 544, R = 0.0397 and wR = 0.0918 for 1212 observed reflections with I ≥ 2σ(I). X-ray structure analysis reveals that there exist two intramolecular and six intermolecular hydrogen-bonding interactions in the crystal lattice, which can stabilize the configuration of the α-imino acid dihydrate 4.

Epirubicin-[Anti-HER2/neu] Synthesized with an Epirubicin-(C13-imino)-EMCS Analog: Anti-Neoplastic Activity against Chemotherapeutic-Resistant SKBr-3 Mammary Carcinoma in Combination with Organic Selenium

Purpose: Discover the anti-neoplastic efficacy of epirubicin-(C13-imino)-[anti-HER2/neu] against chemotherapeutic- resistant SKBr-3 mammary carcinoma and delineate the capacity of selenium to enhance it’s cytotoxic anti-neoplastic potency. Methods: In molar excess, EMCH was combined with epirubicin to create a covalent epirubicin-(C13-imino)-EMCH-maleimide intermediate with sulfhydryl-reactive properties. Monoclonal immunoglobulin selective for HER2/neu was then thiolated with 2-iminothiolane at the terminal ε-amine group of lysine residues. The sulfhydryl-reactive epirubicin-(C13-imino)-EMCH intermediate was then combined with thiolated anti-HER2/neu monoclonal immunoglobulin. Western-blot analysis was utilized to characterize the molecular weight profiles while binding of epirubicin-(C13-imino)-[anti-HER2/neu] to membrane receptors was determined by cell-ELISA utilizing populations of SKBr-3 mammary carcinoma that highly over-expresses HER2/neu complexes. Anti-neoplastic potency of epirubicin-(C13-imino)-[anti-HER2/ neu] between the epirubicin-equivalent concentrations of 10–12 M and 10–7 M was determined by vitality staining analysis with and without the presence of selenium (5 μM). Results: Epiribucin-(C13-imino)-[anti-HER2/neu] between epirubicin-equivalent concentrations of 10–8 M to 10–7 M consistently evoked higher anti-neoplastic potency than “free” non- conjugated epirubicin which corresponded with previous investigations utilizing epirubicin-(C3-amide)-[anti-HER2/neu] and epirubicin-(C3-amide)-[anti-EGFR]. Selenium at 5 mM consistently enhanced the cytotoxic anti-neoplastic potency of epirubicin-(C13-imino)-[anti-HER2/neu] at epirubicin equivalent concentrations (10–12 to 10–7 M). Conclusions: Epirubicin-(C13-imino)-[anti-HER2/neu] is more potent than epirubicin against chemotherapeutic-resistant SKBr-3 mammary carcinoma and selenium enhances epirubicin-(C13-imino)-[anti-HER2/neu] potency. The methodology applied for synthesizing epirubicin-(C13-imino)-[anti-HER2/neu] is relatively time convenient and has low instrumentation requirements.

Preparation and Characterization of Low Density Poly(Imino Imino Ketone)Foam

Poly（Imino Ketone） （PIK） is a group of novel high performance polymer material with excellent thermal properties and dissolubility. Aiming at the requirements of inertial confined fusion （ICF） studies on low density polymer foams, we firstly synthesized poly（imino imino ketone） （PIIK） by palladium catalyzed C-N cross-coupling reaction, and successfully prepared the PIIK foam material with a density of 80-300 mg/cm3 by using PIIK as the raw material with thermal-induced phase separation and lyophilization technique. Mercury injection method was used to determine the structure of PIIK foams, and the results indicated that the mean pore diameter was lower than 5 ~tm and it had relatively high voidage and specific surface area.

SYNTHESIS AND PHOTOPHYSICAL PROPERTIES OF POLY(ARYL IMINO)CONTAINING ACRIDINE UNITS(PAIA)

1,4-Bis-(4-bromobenzoyl)benzene and proflavine,3,6-diaminoacridine free base were synthesized first.Using 1,4- bis-(4-bromobenzoyl)benzene and proflavine,3,6-diaminoacridine free base as the monomers,poly(aryl imino) containing acridine units(PAIA) was synthesized via palladium-catalyzed amination.The structure of PAIA was characterized by means of FTIR,~1H-NMR spectroscopy and elemental analysis,the results show an agreement with the proposed structure.The UV absorption and photoluminescence spectra were t...

Synthesis, Crystal Structure and Magnetic Properties of Cobalt(II) Complex Involving Imino Nitroxide Radicals

A novel compound [Co(IM2-Py)2(NO3)]?(NO3) (IM2-Py = 2-(2?-pyridyl)-4,4,5,5- tetramethylimidazoline-1-oxyl) has been prepared and structurally characterized by X-ray diffrac- tion method. It crystallizes in orthorhombic, space group P212121 with a = 11.031(2), b = 13.492(3), c = 20.467(4) ?, V = 3046.0(11) ?3, C24H32CoN8O8, Mr = 619.51, Z = 4, Dc = 1.351 g/cm3, μ(MoKα) = 0.620 mm?1, F(000) = 1292, R = 0.0506 and wR = 0.0845 for 3752 observed reflections with I > 2σ(I). X-ray analysis reveals that the crystal structure consists of [Co(IM2- Py)2(NO3)]+ moiety and a NO3 anion. The cobalt(II) ion is six-coordinated with a distorted octahedral geometry. Tempera- ? ture dependence of susceptibility measurements show that there exist an antiferromagnetic inter- action in the compound.

Crystal Structure and Conformation of an Imino Sugar

The title compound 3 was synthesized and characterized by IR, NMR and HRMS, and its crystal structure was determined by X-ray diffraction analysis. The crystal is of monoclinic system （CI6H23NOTS, Mr = 373.41）, space group P21, with a = 12.000（2）, b = 5.5970（11）, c = 13.689（3） A. β= 93.25（3）°, V= 917.9（3） A^3, Z= 2, Dc = 1.351 g/cm^3, F（000） = 396, μ = 0.213 mm^-1, the final R = 0.0489 and ωR = 0.0777 for observed reflections （I 〉 2σ（I））. Three intramolecular and three intermolecular hydrogen bonds were found. The absolute configuration of this molecule was confirmed by comparing with the original material.

POLYMERIZATION OF ETHYLENE WITH UNSYMMETRIC 2,6-BIS(IMINO)PYRIDINE IRON(Ⅱ)COMPLEX

An unsymmetric 2,6-bis(imino)pyridine iron(II) complex 1' was synthesized. The relationship between catalyststructure and its activity in ethylene polymerization is discussed. The kinetic behavior of ethylene polymerization and theeffects of polymerization conditions such as temperature, aluminum/iron molar ratio on the activity of catalyst and thecharacteristics of polyethylene were reported. The unsymmetric catalyst 1' has a good catalytic performance of 3.47×10~6 gPE·mol^(-1)·Fe·h^(-1) at 40℃ with aluminum/iron molar ratio = 2500. A dependence of catalyst activity on themethylaluminoxane (MAO) concentration and reaction temperature was found. The molecular weight (MW) of polyethylenewith broad dispersity is about 10~4-10~5 g/mol. The melting temperature and branching of polyethylenes vary with changingreaction temperature and aluminum/iron molar ratio.

Synthesis, Crystal Structure, and Catalytic Performance of 2,6-Bis[1-(2,4,6-trimethylphenylimino)ethyl]pyridine Nickel(Ⅱ) Complex

A novel nickel（II）-complex Ni[L]Cl2-CH3CN（1） containing the tridentate ligand 2,6-bis[1-（2,4,6- trimethylphenylimino）ethyl]pyridine（L） has been synthesized. The crystal structure of complex 1 was determined by single crystal X-ray diffraction analysis. The catalytic activity of complex 1 for the polymerization of ethylene was studied under activation with methylaluminoxane（MAO）.

Synthesis and Crystal Structure of an Imino Nitroxide Complex [Cd(IM2py)_2Cl_2]

The title compound [Cd(IM2py)2Cl2], where IM2py = 2-(2?-pyridinyl)-4,4,5,5-tetra- methylimidazoline-1-oxyl, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in monoclinic, space group C2/c with a = 18.436(6), b = 9.255(3), c = 15.831(5) ? b = 100.274(5)? C24H32CdCl2N6O2, Mr = 619.86, V = 2658.0(14) ?, Z = 4, Dc = 1.549 g/cm3, m(MoKa) = 1.056 mm-1, F(000) = 1264, the final R = 0.0324 and wR = 0.0659 for 2725 independent reflections with Rint = 0.0378. The title complex exists as discrete mononuclear molecules, adopting a distorted octahedral [cis(Cl)-trans(py)] configuration with the cadmium(II) ion being bonded to two bidentate radicals and two chlorine atoms. There exist p???p stacking interactions between the adjacent parallel pyridyl rings of the complex in the ac plane.

Synthesis and Uncommon Structural Characterization of Novel Zinc and Cadmium Complexes with Imino Nitroxide Radical

Two novel complexes {[Zn（IM4py）2（tp）（H2O）]2H2O}. 1 and {[Cd（IM4py）2（tp）- （H2O）]1.25H2O},, 2 （IM4py = 2-（4＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-l-oxyl and tp = terephthalate dianion） have been synthesized and characterized by elemental analyses, IR spectrum and single-crystal X-ray diffraction. Crystal data for complex I： monoclinic, space group C2/c, a = 20.648（7）, b = 12.130（4）, c = 14.036（4） A, β = 106.351（5）°, C32H42N6O9Zn, Mr = 720.09, V = 3373.3（2） A3, Z= 4, Dc = 1.418 g/cm^3μt（MoKα） = 0.790 mm^-1, F（000） = 1512, the final R = 0.0407 and wR = 0.0894 for 3480 independent reflections with Rint = 0.0432. Crystal data for complex 2： monoclinic, space group C2/c, a = 21.332（6）, b = 12.063（3）, c = 14.246（4） A, β = 106.704（4）°, C32H40.50N6O8.25Cd, Mr = 753.60, V= 3511.2（2） A^3, Z = 4, Dc = 1.426 g/cm^3,μ（MoKα） = 0.679 mm^--1, F（000） = 1554, the final R = 0.0419 and wR = 0.0961 for 3627 independent reflections with Rint = 0.0440. The framework structures of complexes 1 and 2 are 3-D networks via the hydrogen bonds among 1-D chains. The notable characteristics of the two complexes are that the coordination polyhedron of Zn（Ⅱ） adopts a rare distorted five-coordinate square pyramidal geometry in 1, and the Cd（Ⅱ） complex exhibits an unusual distorted seven-coordinate pentagonal bipyramid in 2.

1-Imino Nitroxide Pyrene, a Burst-type H^(+) Fluorescent Switch

1-Imino nitroxide pyrene 1 has been characterized as a H^＋ fluorescent switch. The effects of various interfering species, solvents and the irradiation of ultraviolet light on the fluorescence intensity of 1 are also investigated. 1 fluoresces weakly in the 85% ethanol media containing no more than 4.5x10-5 mol/L of H^＋ （HCI）, but can produce a burst increase of about 4 times in the fluorescence intensity when the concentration of H＋ is increased to or over 4.9×10^-5mol/L. The extremely sharp response of 1 to H＋ occurs only within such a narrow concentration range. Moreover, the decrease of H^＋ concentration through adding sodium hydroxide causes the fluorescence quenching, suggesting that 1 may serve as a fluorescent switch for monitoring the concentration change of H＋ around the point of 4.5×10^-5 mol/L.

Microwave Synthesis and Crystal Structure of Bis{2-[(2,4-dichloro-phenylimino)methyl]-4,6-diiodo-phenol}-copper(Ⅱ)

Bis{2-[（2,4-dichloro-phenytimino）-methyl]-4,6-diiodo-phenol}-copper（II） （1） has been synthesized and its structure determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 14.7558（17）, b = 20.770（2）, c = 20.3260（19） A, β = 90.6110（10）°, V= 6229.2（11） A3 and Z = 8. The Cu atom is surrounded by two O atoms and two N atoms from two 2-[（2,4-diehloro-phenylimino）-methyl]-4,6-diiodo-phenol molecules to form a tetrahedral coordination environment. The complex is linked into a column by weak intermolecular interactions.

Synthesis and Antibacterial Activities of 1,4-Disubstituted Phenyl-5-(halo-2-hydroxyphenyl)imino-1,2,3-triazole

According to the superposition principle of reinforcement of biological activities, 24 novel 1,4- disubstituted phenyl-5-（halo-2-hydroxyphenyl）imino-l,2,3-triazoles was synthesized and characterized by 1H NMR, ^13C NMR, elemental analysis and IR. All the target compounds were screened for their antibacterial potential in vitro against Monilia albican, Escherichia coli and Staphylococcus aureus. It was shown that all the compounds possessed efficient antibacterial activities at a concentration of 0.1 mg/mL, even at a concentration of 0.01 mg/mL, some of the compounds still exhibited antibacterial activities against Escherichia coli and Monilia albican. At last, the struc- ture-activity relationship was discussed based on the antibacterial results.

Kinetics on Thermal Decomposition of Iron(III) Complexes of 1,2-Bis(Imino-4’-Antipyrinyl)Ethane with Varying Counter Anions

A comparative thermal decomposition kinetic investigation on Fe(III) complexes of a antipyrine Schiff base ligand, 1,2-Bis(imino-4’-antipyrinyl)ethane (GA)), with varying counter anions viz. CIO4-, NO3-, SCN-, Cl-, and Br-, has been done by thermogravimetric analysis by using Coats-Redfern equation. The kinetic parameters like activation energy (E), pre-exponential factor (A) and entropy of activation (ΔS) were quantified. On comparing the various kinetic parameters, lower activation energy was observed in second stage as compared to first thermal decomposition stage. The same trend has been observed for pre-exponential factor (A) and entropy of activation (ΔS). The present results show that the starting materials having higher activation energy (E), are more stable than the intermediate products, however;the intermediate products possess well-ordered chemical structure due to their highly negative entropy of activation (ΔS) values. The present investigation proves that the counter anions play an important role on the thermal decomposition kinetics of the complexes.

A Simple and Convenient Synthesis of Isolated-Fused Heterocycles Based on: 2-Imino-<i>N</i>-phenyl-2<i>H</i>-chromene-3-carboxamide

Starting from 2-imino-N-phenyl-2H-chromene-3-carbox-amide, (1) a series of functionalized chromenes were achieved;such as, 2-ethoxy-2,3-dihydro-3-phenylchromeno[2,3-d]pyrimidin-4-one (2), and 2-hydrazinyl-2,3-dihydro-3-phenylchromeno-[2,3-d]pyrimidin-4-one (3). Furthermore, reactions of (3) with some of laboratory available compounds gave pyrazoles (4-9, 12, 13a, 13b), tetrazoles (11), 2-(2-benzylidenehydrazinyl)-3-phenyl-3H-chromeno[2,3-d]pyrimidin4(10H)-oneisoxazoles (14), 5-chloro-1-(4-oxo-3-phenyl-4,10-dihydro-3H-chromeno[2,3-d]pyrimidin-2-yl)-3-phenyl-2, 3-dihydro-1H-pyrazole-4-carbonitrile (17), pyrimidines (28a, b), pyridines (29a-29e, 30, 33a, 33b), benzo[b][1, 4]oxazepin-2- amines (32a, b), 3-chloro-4-(2-imino-2H-chromen-3-yl)-1-phenyl-4-(phenylamino) azetidin-2-one (34a-34e) and 2-(2- imino-2H-chromen-3-yl)-3-phenyl-2-(phenyl amino)thiazolidin-4-onee (35a-35e). The structures of these compounds were established by elemental analysis, IR, MS and NMR spectral analysis.