A Novel Green Preparation ofα,α′-Bis(substituted benzylidene)-cycloalkanones Promoted by FeCl3·6H2O in Ionic Liquid

a, a'-Bis(substituted benzylidene)cycloalkanones were efficiently prepared from cycloalkanones and benzaldehydes in [bmim][BF4] by using iron(III) chloride hexahydrate as a catalyst. It is shown that [bmim][BF4] and iron(III) chloride hexahydrate can be quantitatively recovered and be reused effectively for many times. Compared with the known methods, this novel process has the advantage of being an envkonmentally benign process together with good yields and mild reaction conditions.

Synthesis of Poly[(3-octanoylpyrrole-2,5-diyl)-p-(N,N-dimethylamino)benzylidene] and Its Properties by Nitrogen Ion Implantation

A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-(N,N-dimethylamino)benzylidene](POPDMABE), was synthesized firstly by the condensation of 3-octanoylpyrrole with para-dimethylaminobenzaldehyde. The chemical structure of the polymer was characterized by FTIR and 1H NMR spectrometries. The polymer is a potential nonlinear optical(NLO) material. According to the function of optical forbidden band gap(E_g) and photon energy(hν), the optical forbidden band gaps of the polymer before and after ion implantation were calculated. The resonant third-order nonlinear optical properties of POPDMABE before and after ion implantation were also studied by using the degenerate four-wave mixing(DFWM) technique at 532 nm. When the energy is 25 keV and the dose is 2.2×10 17 ions/cm 2, the {polymer′s} optical forbidden band gap is about 1.63 eV which is smaller than that of the non-implanted sample(1.98 eV) and the resonant third-order NLO susceptibility of POPDMABE is about 4.3×10 -7 esu, 1 order of magnitude higher than that of the non-implanted sample(4.1×10 -8 esu). The results show that nitrogen ion implantation is an effective method to improve the resonant third-order NLO property of the polymer.

Preparation and Properties of 1-octadecanol/1,3:2,4-di-(3,4-dimethyl) Benzylidene Sorbitol/Expanded Graphite Form-stable Composite Phase Change Material

A 1 -octadecanol (OD)/1,3:2,4-di-(3,4-dimethyl) benzylidene sorbitol (DMDBS)/expander graphite (EG) composite was prepared as a form-stable phase change material (PCM) by vacuum melting method. The results of field emission-scanning electron microscopy (FE-SEM) showed that 1 -octadecanol was restricted in the three-dimensional network formed by DMDBS and the honeycomb network formed by EG. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) results showed that no chemical reaction occurred among the components of composite PCM in the preparation process. The gel-to-sol transition temperature of the composite PCMs containing DMDBS was much higher than the melting point of pure 1-octadecanol. The improvements in preventing leakage and thermal stability limits were mainly attributed to the synergistic effect of the three-dimensional network formed by DMDBS and the honeycomb network formed by EG. Differential scanning calorimeter (DSC) was used to determine the latent heat and phase change temperature of the composite PCMs. During melting and freezing process the latent heat values of the PCM with the composition of 91% OD/3% DMDBS/6% EG were 214.9 and 185.9 kJ kg'1, respectively. Its degree of supercooling was only 0.1 °C. Thermal constant analyzer results showed that its thermal conductivity (k) changed up to roughly 10 times over that of OD/DMDBS matrix.

Anticancer efficacy of 3-(4-isopropyl)benzylidene-8-ethoxy,6-methyl,chroman-4-one(SBL-060),a novel,dual,estrogen receptor-Akt kinase inhibitor in acute myeloid leukemia cells

Estrogen receptor(ER)αis expressed in a subset of patient-derived acute myeloid leukemia(AML)cells,whereas Akt is predominantly expressed in most types of AML.Targeting AML with dual inhibitors is a novel approach to combat the disease.Herein,we examined a novel small molecule,3-(4-isopropyl)benzylidene-8-ethoxy,6-methyl,chroman-4-one(SBL-060),capable of targeting AML cells by inhibiting ERαand Akt kinase.The chemical properties of SBL-060 were identified by proton nuclear magnetic resonance(^(1)H-NMR),^(13)C-NMR,and mass spectroscopy.In silico docking was performed using an automated protocol with AutoDock-VINA.THP-1 and HL-60 cell lines were differentiated using phorbol 12-myristate 13-acetate.ERαinhibition was assessed using ELISA.The MTT assay assessed cell viability.Flow cytometry was performed for cell cycle,apoptosis,and p-Akt analyses.Chemical analysis identified the compound as 3-(4-isopropyl)benzylidene-8-ethoxy,6-methyl,chroman-4-one,which showed high binding efficacy toward ER,with aΔG_(binding) score of−7.4 kcal/mol.SBL-060 inhibited ERα,exhibiting IC50 values of 448 and 374.3 nM in THP-1 and HL-60 cells,respectively.Regarding inhibited cell proliferation,GI50 values of SBL-060 were 244.1 and 189.9 nM for THP-1 and HL-60 cells,respectively.In addition,a dose-dependent increase in sub G_(0)/G_(1) phase cell cycle arrest and total apoptosis was observed after treatment with SBL-060 in both cell types.SBL-060 also dose-dependently increased the p-Akt-positive populations in both THP-1 and HL-60 cells.Our results indicate that SBL-060 has excellent efficacy against differentiated AML cell types by inhibiting ER and Akt kinase,warranting further preclinical evaluations.

A New Method for the Cleavage of Carbohydrate Benzylidene Acetal by Ceric (IV) Ammonium Nitrate in CH_3CN-H_2O (10: 1)

A new method for the cleavage of carbohydrate benzylidene acetal has been developed using Ceric (YV) ammonium nitrate (CAN) [(NH4)2Ce(NO3)6] in CH3CN-H2O (10/1, v/v).

Synthesis,Crystal Structure and Fluorescent Properties of 1-(4-(Dimethylamino)benzylidene)-4-(naphthalen-1-yl) Thiosemicarbazide

The title compound, 1-4-（dimethylamino）benzylidene）-4-（naphthalene-1-yl） thiosemicarbazide （DMABNTS, C20H20N4S, Mr = 348.47）, was synthesized and characterized by elemental analysis, 1R, ^1H NMR and MS. The crystal structure of DMABNTS with 1,4-dioxane （Diox, C4H8O2） solvent molecules （DMABNTS·2Diox, C28H36N4O4S, Mr = 524.67） was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic system, space group P21/c with a = 14.418（4）, b = 7.1702（19）, c = 28.350（7）°A,β= 101.154（6）°, V= 2875.4（13） °A^3, Z= 4, Dc= 1.212 g/cm^3, F（000） = 1120 and μ= 0.151 mm^-1. A total of 6458 reflections were collected, of which 4671 were unique. The structure was solved by direct methods and refined to the final R = 0.0732 and wR = 0.2127 for 3921 observed reflections （I〉 2σ（I））. There exist intermolecular hydrogen bonds （N（2）-H（2B）…S（1A）and N（1）-H（1A）…O（4B）） in the structure. The study of fluorescent properties ＇shows that DMABNTS emits bright solid-state fluorescence in the visible region and exhibits blue photoluminescence.

Synthesis and Crystal Structure of [2-Hydroxy-5-(4-hydroxy-3-phenyliminomethyl-benzyl)-benzylidene]-phenyl-amine

The title compound [2-hydroxy-5-（4-hydroxy-3-phenyliminomethyl-benzyl）-benzylidene]-phenyl-amine （C27H22N2O2, Mr = 406.47） was synthesized by 5,5′-methylene-bissalicylal- dehyde with aminobenezene, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 4.4026（6）, b = 1.501（13）, c = 0.95818（12） nm, β = 90.868（2）°, V= 4.2813（9） nm^3, Z= 8, Dc= 1.292 g/cm^3,μ = 0.010, F（000） = 1744, R = 0.0576 and wR = 0.1450 for 3766 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the molecule has a pair of intramolecular OH…N hydrogen bonds.

Formation of α,α'-Bis(substituted benzylidene)cycloalkanones from Masked Aldehydes Promoted by Samarium(III) Triiodide

Diacetates 1 and N-[(1-benzotriazol-l-yl)alkyl]amides 2, both masked forms of aldehydes, could undergo deprotection and condensation with cycloalkanones in a one-pot procedure promoted by samarium(III) iodide (SmI3) to afford α,α'-bis(substituted benzylidene) cycloalkanones in good yields.

Bis(1-(4-(dimethylamino)benzylidene)-4-phenylthiose micarbaznato)palladium(Ⅱ):Synthesis,Crystal Structure and Its Dual Fluorescence Property

The title compound bis（1-（4-（dimethylamino）benzylidene）-4-phenylthiosemicar-bazato）-palladium（Ⅱ）（PdL2） was obtained by reacting 1-（4-（dimethylamino）benzylidene）-4-phenyl-thiosemicarbazide with dichlorobis（benzonitrile）palladium（Ⅱ） in methanol,and its structure was characterized by single-crystal X-ray diffraction.The crystal of PdL2 was obtained in dimethyl-formamide（DMF） solvent with solvent molecules involved in the cell and crystallizes in the monoclinic system,space group C2 with a = 18.485（15）,b = 7.090（5）,c = 17.595（11） ,β = 121.21（3）o,V = 1972（2） 3,Z = 2,Mr = 847.40,Dc = 1.427 g/cm3,μ = 0.624 mm-1,F（000） = 880,R = 0.0607 and wR = 0.1358.The Pd atom adopts a distorted square planar coordination geometry with two Pd-N and two Pd-S bonds.The ligand loses a proton from its tautomeric thiol form and coordinates to the Pd atom via mercapto sulfur and the imine nitrogen atom,which binds to palladium as bidentate N,S-donors forming five-membered chelate rings.The complex formed hydrogen bonding interaction with solvent DMF molecules from the hydrogen of phenylamine to the oxygen of DMF and several intramolecular hydrogen bonds.Pd（Ⅱ） perturbed ligand π-π＊ transition and metal-to-ligand charge transfer（MLCT） transition are observed in its electronic absorption spectra.The complex exhibits intraligand 1π-π＊（IL） state and MLCT state dual fluorescent emissions in organic solvent at room temperature.

Sodium-Modified Fluorapatite: A Mild and Efficient Reusable Catalyst for the Synthesis of <i>α,α</i>’-Bis(Substituted Benzylidene) Cycloalkanones under Conventional Heating and Microwave Irradiation

A versatile and environmentally friendly method for α,α’-bis(substituted ben-zylidene) cycloalkanones has been developed using a heterogeneous catalysis technology. We have synthesized a series of the α,α’-bis(substituted benzylidene) cycloalkanones, a biologically important class of compounds, via the cross aldol condensation between arylaldehydes and cycloketones using sodium-modified fluorapatite (Na/FAP) as a highly efficient solid catalyst under conventional heating in aqueous media and solventless conditions under microwave. Catalyst reuse, ease of separation of the pure product, and high yields are some of the unique features of this process. Shorter reaction times (4 - 7 min) and higher yields (80% - 94%) were achieved under microwave irradiation conditions.

Synthesis,antimicrobial evaluation and QSAR studies of 3-ethoxy-4-hydroxybenzylidene/4-nitrobenzylidene hydrazides

A series of 3-ethoxy-4-hydroxybenzylidene/4-nitrobenzylidene hydrazides（1-20） was synthesized and tested for in vitro antimicrobial activity.The results of antimicrobial studies indicated that the compounds having dinitro,methoxy,hydroxy and nitro substituents on phenyl ring of the aromatic acids were most active ones.The QSAR investigation indicated the importance of the topological parameter,third order molecular connectivity index（~3x） in describing the antimicrobial activity of synthesized hydrazides.

Visible-light-induced novel cyclization of 2-(2-(arylethynyl)benzylidene)-malononitrile derivatives with 2,6-di(tert-butyl)-4-methylphenol to bridged spirocyclic compounds

A green and highly efficient strategy for the preparation of bridged spirocyclic compounds via visible-light-induced cyclization of 2-(2-(arylethynyl)benzylidene)malononitrile derivatives with 2,6-di(tert-butyl)-4-methylphenol(BHT)at room temperature was developed.The photoinduced radical reactions generated the corresponding products in good yields under simple and mild reaction conditions.

Potential anti-tubercular agents:Hexahydro-3-phenyl indazol-2-yl(pyridin-4-yl)methanones from anti-tubercular drug isoniazid and bis(substituted-benzylidene)cycloalkanones

A series of indazol-2-yl（pyridin-4-yl）methanones, 4 were acquired from 2,6-bisbenzylidene cyclohex- anones, 3 and anti-tubercular drug （isoniazid）, and their anti-tubercular impacts were screened. Among the test compounds used against Mycobacterium tuberculosis H37 Ra cell line in the microplate alamar blue assay, the compounds 4g-j revealed moderate anti-tubercular activity with MIC 12.5 μg/mL, comparable to standard drugs （streptomycin, MIC, 6.25 μg/mL, pyrazinamide, isoniazid and ciprofloxacin with MICs of 3.125 μg/mL）.

An unexpected synthesis of an α,β,γ,δ-unsaturated ketone due to an abnormal opening of benzylidene acetal by bromide anion

An unexpected synthesis of an α, β, γ, δ-unsaturated ketone, which embodies a new type of oxy-carbon cyclic structure, was achieved, while we tried to construct the taxane CB-ring system. Also, a series of abnormal reaction phenomens was found to be related to the formation and reaction of seven membered cyclic benzylidene acetal.

Design and Synthesis of New Compounds Derived from Phenyl Hydrazine and Different Aldehydes as Anticancer Agents

In this work we synthesized new derivatives from Phenyl Hydrazine and series of different Aldehydes (derivatives of benzylidenes). The synthesized compounds contain different aromatic Aldehydes which attached by Benzene ring via Hydrazine moiety in glacial acetic acid. These derivatives were characterized by TLC, melting points, Infrared Red, Proton Nuclear Magnetic Resonance, Carbon Thirteen Nuclear Magnetic Resonance and Mass Spectroscopy. Finally, these synthesized derivatives were tested for antiproliferative activity against multiple normal and cancerous cell lines, HepG2 (Liver cancer) and MCF-7 (Breast cancer) cell lines were used for cytotoxic assay.

Design and Synthesis of Some New Oxadiazole Derivatives as Anticancer Agents

In this work, some new oxadiazole derivatives have been prepared, by reacting phenyl hydrazine and acetic anhydride together, which furnished 2,4-dimethyl-4-phenyloxadiazole. This product was reacted with a series of aromatic aldehydes, to obtain a series of oxadiazole derivatives. These derivatives were characterized by TLC, melting points, infrared red, proton nuclear magnetic resonance, carbon thirteen nuclear magnetic resonance and mass spectroscopy. Finally, these synthetized derivatives were tested for antiproliferative activity by two different cell lines. MCF-7 (Breast cancer cell line) and HepG2 (Liver cancer cell line) were used to assess the antiproliferative activity of the prepared compounds.

Synthesis of Substituted Benzothiazepine Compounds with Medicinal Potential

A versatile synthetic approach toward a series of benzothiazepines with medicinal potential (for example, compound 1) that allows incorporation of structural variation at the three aromatic regions of the structure, and at the sulfur atom, was developed. Knoevenagel condensation of indan-1,3-diones with benzaldehydes, yielded 2-benzylidineindan-1,3-diones, which undewent thio-Michael addition and intramolecular imine formation upon reaction with 2-aminothiophenols, to produce the target benzothiazepines. Use of indan-1,3-diones, benzaldehydes or 2-aminothiophenols bearing further substitution enabled production of novel 5,11-dihydro-12H-benzo[b]indeno [1,2-e][1,4]thiazepin-12-one analogs 1 - 14, including compounds bearing substitution at novel positions within the scaffold.

A Novel Tetraphenylethylene-Based“Turn On”Fluorescent Sensor with Highly Sensitive Response to Mercury Ions

A novel 4-tert-butyl-N’-(4-(1,2,2-triphenylvinyl)benzylidene)benzohydrazide(TBB)was successfully synthesized in simple one-step process.It was characterized by FT-IR,1H NMR,13C NMR and HRMS.Its fluorescence sensing ability to 15 metal ions was investigated.Weak emission from TBB could be efficiently increased by trace Hg^2+,through coordination reaction between TBB and Hg^2+ with"turn on"character.The fluorescence intensity of TBB/Hg^2+([TBB]=3.0×10^–6 mol/L,[Hg2+]=1.3×10^–4 mol/L)was 7.5 times higher than that of TBB.This TBB sensor exhibited high selectivity for Hg^2+ and other metal ions did not interfere in this determination.The limit of detection was 0.566μmol/L(S/N=3).The experimental results showed that this TBB sensor could sensitively respond to Hg^2+ within concentration range(from 5×10–6 mol/L to 1.3×10^–4 mol/L).

Synthesis of propyl O-(α-L-rhamnopyranosyl)-(1→3)-[2,4-di-O-(2s-methylbutyryl)-α-L-rhamno-pyranosyl]-(1→2)-(3-O-acetyl-β-D-glucopyranosyl)-(1→2)-β-D-fucopyranoside,the tetrasaccharide moiety of Tricolorin A

Propyl O-(α-L-rhamncpyranosyl)-(1→3)-[2,4-di-O-(2s-methylbutyryl)-α-L-rham-nopyranosyl]-(1→2)-(3-O-acetyl-β-D-glucopyranosyl)-(1→2)-β-D-fucopyranoside (1), the tetrasac-charide moiety of Tricolorin A, was synthesized in total 23 steps with a longest linear sequence of 10 steps, and overall yield of 3.7% from D-Glucose. The isomerization of the dioxolane-type berzyli-dene in the presence of NIS/AgOTf was observed. Tetrasaccharide 1 exhibited no activity against the cultured P388 cell as Tricolorin A did.