Biosynthesis of Cu/KF/Clinoptilolite@MWCNTs nanocomposite and its application as a recyclable nanocatalyst for the synthesis of new Schiff base of benzoxazine derivatives and reduction of organic pollutants.

In this work, we synthesized new Schiff base of benzoxazine derivatives in excellent yields using multicomponent reactions of phthalaldehyde or its derivatives, primary amines, isothiocyanate, 2,4-dihydroxyacetophenone, isopropenylacetylene and methyl or ethyl amine in the presence of catalytic amount of Cu/KF/CP@MWCNTs NCs in water at room temperature. Also, the catalytic activity of the green synthesized Cu/KF/CP@MWCNTs NCs was evaluated in the reduction in organic pollutants such as 4-nitrophenol (4-NP) in water at mild conditions. The results indicated that the biosynthesized NCs have very high and effective catalytic activity for organic pollutants within few seconds. As well the antioxidant activity of some synthesized benzoxazine was studied using trapping of radical by DPPH and ferric reduction activity potential (FRAP) experiment. The short time of reaction, high yields of product, easy separation of catalyst and products are some benefits of this procedure.

Ultrasound-promoted Green Synthesis of pyrido[2,1-a]isoquinoline Derivatives and Studies on their Antioxidant Activity.

Aims & Objective: An efficient procedure for the synthesis of pyrido[2,1-a]isoquinoline derivatives in excellent yields was investigated using catalyst-free multicomponent reaction of phthaladehyde, methylamine, activated acetylenic compounds, alkyl bromides and triphenylphosphine in water under ultrasonic irradiation at room temperature. In addition, Diels- Alder reactions of pyrido[2,1-a]isoquinoline derivatives with activated acetylenic compounds under ultrasonic irradiation are investigated in two procedures. The advantages of this procedure compared to report methods are short time of reaction, high yields of product, easy separation of product, clean mixture of reaction and green media for performing reaction. In addition, because of having isoquinoline core in synthesized compounds, in this research antioxidant activity of some synthesized compounds was studied. MATERIALS AND METHODS: To a stirred mixture of phthalaldehyde 1 (2 mmol) and methylamine 2 (2 mmol) in water (3 mL) under ultrasonic irradiation was added to activated acetylenic compounds 4 after 20 min. Alkyl bromide 3 and triphenylphosphine 5 react in another pot in water (3 mL) under ultrasonic irradiation for 15 min. After this time, this mixture was added to the first pot. After completion of the reaction, the solid residue was separated by filtration and washed with Et2O to afforded pure title compound 6. RESULTS: In this work, generation of pyrido[2,1-a]isoquinoline derivatives 6 are performed using phthalaldehyde 1, methylamine 2, α-halo substituted carbonyls 3, activated acetylenic compounds 4 and triphenylphosphine 5 in water under ultrasonic irradiation condition at room temperature in excellent yield at short time. CONCLUSION: In summary, multicomponent reaction of phthaladehyde, methylamine, activated acetylenic compounds, alkyl bromides and triphenylphosphine in water under ultrasonic irradiation at room temperature produced pyrido[2,1-a]isoquinoline derivatives in excellent yields. Also, Diels-Alder reaction of pyrido[2,1-a]isoquinoline derivatives with activated acetylenic compounds and triphenylphosphine under ultrasonic irradiation is investigated in two procedures. Also, the antioxidant activities of 6a, 6c, 6g and 6i were evaluated by DPPH radical scavenging and ferric reducing power analyzes. The compounds 6a exhibit excellent DPPH radical scavenging activity and FRAP compared to synthetic antioxidants BHT and TBHQ. The chief benefits of our method are high atom economy, green reaction conditions, higher yield, shorter reaction times, and easy work-up, which agree with some principles of green chemistry.

3,5-Bis(trifluoromethyl) Phenylammonium triflate(BFPAT) as a Novel Organocatalyst for the Efficient Synthesis of 2,3-dihydroquinazolin-4(1H)-one Derivatives.

AIMS AND OBJECTIVES: A one-pot synthesis of 2,3-dihydroquinazolin-4(1H)-one derivatives by threecomponent cyclo-condensation of isatoic anhydride, aldehydes and amine or ammonium acetate has been developed using 3,5-Bis(trifluoromethyl) phenylammonium triflate (BFPAT) as a new organocatalyst. MATERIALS AND METHODS: All of the obtained products are known compounds and identified by IR, 1HNMR, 13CNMR and melting points. RESULTS: A wide variety of structurally different aldehydes reacted easily and rapidly to result in the relating 2,3-dihydroquinazolin-4(1H)-ones in good to excellent yield. CONCLUSION: We have demonstrated an extremely effective and new process for synthesizing 2,3- dihydroquinazolin-4(1H)-ones employing BFPAT as a novel organocatalyst in one-pot fashion.

Ionic Liquid-assisted Preparation of Two-dimensional ZnO/Fe3O4 Nano-composites and their Application in Polysubstituted Pyrroles Synthesis.

AIMS AND OBJECTIVE: Ionic liquids are a suitable medium for stabilization and preparation of catalytic systems. MATERIALS AND METHODS: The two-dimensional (2D) ZnO/Fe3O4 nanocomposites were synthesized using ionic liquid [OMIM]Br as a stabilizer and soft template. The nanocomposites were characterized via FTIR, XRD, VSM and SEM analysis. RESULT: The catalytic activity of these composites was evaluated using a multicomponent reaction of primary amines, acetylacetone, and 2-bromoacetophenone. CONCLUSION: 2D ZnO/Fe3O4 as a recyclable and green catalyst showed excellent catalytic performance for the preparation of poly-substituted pyrroles.

ZnO-nanoparticles as an Efficient Catalyst for the Synthesis of Functionalized Benzenes: Multicomponent Reactions of Sulfonoketenimides.

OBJECTIVE: Functionalized benzenes are prepared from the reaction of sulfonoketenimides that is produced from the Copper catalyzed reaction of terminal alkynes and sulfonyl azides with zwitterionic intermediate that is generated from the reaction of dialkyl acetylenedicarboxylates, alkyl bromides and triphenylphosphine in the presence of ZnO-nanoparticles in good yields. MATERIAL AND METHODS: All chemicals employed in this work were prepared from Fluka (Buchs, Switzerland) and were used without further purification. Nanoparticles of ZnO were synthesized according to literature report. Melting points were measured on an Electrothermal 9100 apparatus. Elemental analyses for C, H, and N were performed using a Heraeus CHN­O-Rapid analyzer. Mass spectra were recorded on a FINNIGAN-MAT 8430 spectrometer operating at an ionization potential of 70 eV. IR spectra were measured on a Shimadzu IR-460 spectrometer. 1H, and 13C NMR spectra were measured with a BRUKER DRX-500 AVANCE spectrometer at 500.1 and 125.8 MHz, respectively. RESULTS: In these reactions, the first step is optimization of reaction conditions for achieving best conditions. For this reason, solvent, catalyst, and reaction time is changed so that the best result is obtained. For optimization, several catalysts such as CuI, CuBr, CuCl, ZnO-nanoparticles, CM-ZnO, pyridine, piperidine, CuO-NPs, TiO2-NPs and copper powder were checked. Among them CuI and ZnO-NPs give the best results. Also, several solvents such as CH3CN, H2O, solvent-free conditions, toluene and diethyl ether are employed and CH3CN is the best solvent. CONCLUSION: In summary, sulfonoketenimides react with intermediate that is generated from the reaction of dialkyl acetylenedicarboxylate, alkyl bromides and triphenylphosphine in the presence of ZnO-NPs (10 mol%) to produce benzene derivatives in good yields.

ZnO-Nanorods as an Efficient Heterogeneous Catalyst for the Synthesis of Thiazole Derivatives in Water.

Aims & Scope: Thiazole derivatives are produced using one-pot multicomponent reactions of acid chlorides, potassium thiocyanate, amino acids, alkyl bromides and ZnO nanorods (NR-ZnO) as the catalyst in water at ambient temperature. These reactions were no't performed without using NR-ZnO as the catalyst. Nanorods of ZnO have been prepared by reflux procedure using sodium dodecylsulfate (SDS). Nanorods of ZnO showed a considerable improvement in the yield of the product and displayed significant reusable activity. MATERIALS AND METHODS: In these reactions, all chemicals were prepared from Fluka (Buchs, Switzerland). Nanorods of ZnO were synthesized in the laboratory according to literature report. By using an electrothermal 9100 apparatus, melting points of synthesized compounds were determined. Heraeus CHN-O-Rapid analyzer was employed for elemental analyses for C, H, and N. FINNIGANMAT 8430 spectrometer operating at an ionization potential of 70 eV was used for mass spectra. Shimadzu IR-460 spectrometer was employed for IR spectra. BRUKER DRX-500 AVANCE spectrometer at 500.1 and 125.8 MHz was used for 1H, and 13C NMR spectra for solutions in CDCl3 with TMS as internal standard or 85% H3PO4 as external standard, respectively. RESULTS: We describe a facile and green synthetic method for the synthesis of thiazole derivatives 5 from acid chlorides, potassium thiocyanate, alkyl bromides and amino acids using NR-ZnO- as the catalyst in water at room temperature. CONCLUSION: In conclusion, we describe an efficient, green procedure and high yielding synthesis of thiazole derivatives using acid chlorides, potassium thiocyanate, alkyl bromides and amino acids in the presence of NR-ZnO as the catalyst in water at room temperature.

Synthesis of 9H-furo [2,3-f]Chromene Derivatives by Promoting ZnO Nanoparticles.

Three- component reactions of 1-(6-hydroxy-2-isopropenyl-1-benzofuran-yl)-1-ethanone, aldehydes and malononitrile or ethyl cyanoacetate in the presence of nanoparticles of ZnO as catalyst are explained as effective and green synthetic method for generating 9H- furo[2,3-f]chromenes in good yield.

High Cytotoxicity and Apoptotic Effects of Natural Bioactive Benzofuran Derivative on the MCF-7 Breast Cancer Cell Line.

This study was focused on evaluation of the cytotoxicity and apoptotic affects of benzofuran derivative on MCF-7 breast cancer cell line. This effective compound was isolated from the root of Petasites hybridus plant. For experiments, the MCF-7 cells were treated with several concentrations (0-500µM) of 1-(6-hydroxy-2- isopropenyl-1-benzofuran-5-yl)-1-ethanone 1 at different times. In this study, test of neutral red was also employed for cytotoxicity assay and quantity of P53, P21. Bax genes expression was analyzed using Real-Time PCR and ELISA techniques. Results show that compound 1 has cytotoxicity and apoptotic effects on Human breast cancer (Michigan Cancer Foundation-7) MCF-7 cells.

Green synthesis of phosphoryl-2-oxo-2H-pyran via three component reaction of trialkyl phosphites.

An effective one-pot synthesis of dialkoxyphosphoryl-2-oxo-2H-pyran derivatives by three-component reaction of alky bromides and dialkyl acetylenedicarboxylates in the presence of trialkyl phosphite is described. The reactions were performed under solvent-free conditions at 50°C and neutral conditions and provided good yields of products.

Molecular dynamic simulation and spectroscopic investigation of some cytotoxic palladium(II) complexes interaction with human serum albumin.

Studies on the interactions between metallodrugs and human serum albumin (HSA), as carrier for drugs and biological molecules, are extremely important to design and discover new drugs. The interaction of three novel synthesized complexes of [Pd(phen)(R-gly)]NO3, where R-gly is methyl-, propyl-, and amyl-glycine and phen is 1,10- phenanthroline, with HSA were investigated using spectroscopic studies in combination with a molecular dynamic simulation. These water soluble complexes can denature HSA at ~50 µM. According to the results obtained for the isothermal titration at 27 and 37°C, it was found that there are 10, 8, and 6 binding sites (g) for methyl-, propyl-, and amyl-glycine complexes on the HSA with positive cooperativity in binding, respectively. Also, the binding and thermodynamic parameters were analyzed. We found a good consistency between secondary structure and simulation data with spectroscopic studies, and the experimental data are confirmed by molecular simulation results. In addition, the results related to helix, beta sheets, and coil percentages revealed that all complexes decrease the helix structure and increase the beta structure; and that the amyl derivative is more effective in denaturing the HSA structure.

A facile one-pot synthesis of functionalized 1,3-oxathiolan-2-yliden derivatives: multicomponent reaction of oxiranes in water.

An efficient synthesis of 1,3-oxathiolan-2-yliden derivatives is described via a simple reactions between CHacids, CS2 and oxiranes in the presence of triethylamine at 70° C in water as the solvent. The mild reaction conditions and high yields of the products exhibit the good synthetic advantage of this method.

Facile and efficient synthesis of new class of imidazole derivatives via one-pot multicomponent reactions in water.

A water-accelerated multicomponent synthesis of organic target molecules has been used as a key method for the preparation of novel imidazole derivatives. The three-component condensation reactions of primary amines with trichloroacetonitrile in the presence of ninhydrine in water are developed as efficient and clean green synthetic procedures for the high-yielding preparation of imidazoles.

A novel three-component reaction for the synthesis of 1,3-benzoxazines in water.

A simple and proficient method for the synthesis of 1,3-benzoxazine derivatives via three-component reaction of isocyanide and isoquinoline with 1-(6-hydroxy-2-isopropenyl-1-benzofuran-yl)-1-ethanone or 4-hydroxycumarine in water in the presence of piperidine at 70°C is reported.

Solvent-free synthesis of functionalized thiazoles using multicomponent reaction of isothiocyanates.

An efficient synthesis of thiazoles is described via an one-pot reaction between acid chlorides, ammonium thiocyanate tetramethylguanidine and α-bromocarbonyl compounds under solvent-free conditions without using any catalyst. The method offers several advantages including high yields of products and an easy work-up procedure at room temperature in excellent yield.

Multicomponent reactions for the synthesis of functionalized imidazoles.

An efficient synthesis of functionalized tetrahydroimidazoles via a one-pot tandem reaction between ninhydrin, primary alkylamines, arylisocyanates or arylisothiocyanates, acetylenic esters and triphenylphosphine is described.

Perlite filtration of phenolic compounds from cigarette smoke.

Adsorption of phenolic compounds and chemical analysis of them from a local production cigarette (named by Farvardin cigarette) smoke have been investigated by using perlite filtration. In this research, the mainstream smoke was tested by three filtration methods: Perlite filter, Cambridge filter and general cigarette filter. Then the used filter was extracted by pure methanol as solvent. After that, the extracted solution was analysed by GC-MS. By this consideration, the phenolic derivatives such as phenol, hydroquinone, resorcinol, pyrocatechol, m-cresol, p-cresol and o-cresol were detected. The structure of the perlite filtration after absorption was studied by SEM. In addition, its chemical structure was investigated by XRD and XRF.

Microwave-assisted multicomponent reactions of alkyl bromides: synthesis of thiophene derivatives.

A series of thiophene derivatives were synthesized via one-pot multicomponent reactions of alkyl bromides, aroyl or alkanoyl isothiocyanates, 1,3-dicarbonyl compounds and secondary amines under microwave irradiation at 80°C. Particularly valuable features of this method include high yields of products, broad substrate scope, short reaction time and straightforward procedure.

Expeditious solvent-free synthesis of chromene derivatives via three-component reactions of N-nucleophiles.

Multicomponent reactions involving 4-hydroxycumarine, activated acetylenic compounds and N-nucleophiles under solvent-free conditions were investigated. The reactions could also be extended to quinoline or CH-acides. Substituted chromen could be obtained from this routine, which may have potential applications in drugs fields.

Expeditious microwave-assisted synthesis of functionalized oxaphosphaphenanthrenes and chromenes via multicomponent reactions of trivalent phosphorus nucleophiles.

Stable derivatives of oxaphosphaphenanthrenes were prepared by using the reactions of dialkyl acetylenedicarboxylate with 3-bromo-2-naphthol in the presence of trimethyl or triphenyl phosphite under microwave conditions at 70°C in good yields. Under similar conditions, chromene derivatives were produced by using triethyl phosphite and dialkyl acetylenedicarboxylate in the presence of OH-acids in excellent yields.

Microwave-assisted synthesis of cyclopentanones using the relevant phosphorus ylides.

A one-pot synthesis of cyclopentanone derivatives from phosphorus ylide under lab-type microwave assisted methodology was described. The phosphorus ylides were obtained via the reaction of activated acetylenic compounds, ethyl 4-chloroacetoacetate and triphenylphosphine. The structure of phosphorus ylides was assigned by ¹H, ¹³C and ³¹PNMR. The phosphorus ylides as precursor were crystallized as two enantiomers (R,R) and (S,S) and one of the phosphorus ylide structures was confirmed by single X-ray crystallography.