Reaction Of Acetylacetonate Research Articles

Fabrication and characterization of inorganic-organic hybrid copper ferrite anchored on chitosan Schiff base as a reusable green catalyst for the synthesis of indeno[1,2-b]indolone derivatives.

This study presents a description of the catalytic synthesis of indeno[1,2-b]indolone derivatives. In this method, initially, a Schiff base compound was synthesized from the reaction of acetylacetone with 2-hydroxyaniline. Then, the prepared Schiff base was immobilized on chelated magnetic copper ferrite nanoparticles with a chitosan surface to design and prepare the CuFe2O4@CS-SB nanocomposite. Further, the one-pot multi-component cyclization reaction of aniline, dimedone and ninhydrin was conducted using the synthesized nanocomposite as a heterogeneous acid catalyst in water solvent under thermal conditions. In this reaction, the products were obtained in excellent yields and short reaction times, and the catalyst could be recycled and reused six times without any loss in product yields. By conducting FT-IR spectroscopy, 1H NMR spectroscopy, XRD, FE-SEM, TGA, elemental mapping scanning, EDX and BET analyses, the structure of the nanocatalyst was characterized. In addition, for the identification of organic compounds, FT-IR, 1H NMR, and 13C NMR spectroscopies and melting point analysis were used, which confirmed the synthesis of this class of derivatives.

Application of the Knorr reaction for the directional synthesis of pyrazole derivative as a biologically active co-ligandes of gold glyco-nanoparticles

Based on the reaction of acetylacetone with 6-mercaptohexanoic and 11-mercaptoundecanoic acid hydrazides, a method was developed for the synthesis of previously unknown 1-(ω-mercaptoacyl)-3,5-dimethylpyrazole as promising сo-ligand for the preparation of gold glyco-nanoparticles for biomedical purposes.

Bifunctional Interface Passivation via Copper Acetylacetonate for Efficient and Stable Perovskite Solar Cells.

Manipulating interface defects can minimize interfacial nonradiative recombination, thus increasing the stability and performance of perovskite solar cells (PSCs). Here, copper acetylacetonate [Cu(acac)2] as a passivator is used to treat the interface between Spiro-OMeTAD and perovskite. Owing to the strong chelation, the uncoordinated Pb2+ could react with -C═O/-COH functional groups, firmly anchoring acetylacetonate at this interface or the grain boundaries (GBs) of perovskite films to construct multiple ligand bridges, accompanied by the p-type copper iodide formation with copper substituting lead. Simultaneously, Cu+-Cu2+ pairs transfer electrons from Pb0 to I0, suppressing deep level defects of Pb0 and I0 near the perovskite interface. These can be beneficial to hole-transferring. Moreover, the Schiff base complexes with hydrophobicity, from the reaction of acetylacetonate with perovskite, can lead to tightly packed adjacent perovskite surfaces and self-seal the GBs of the perovskite, inhibiting moisture diffusion for long-term stability. Consequently, the Cu(acac)2-based PSC has achieved more than 24% champion efficiency while retaining ca. 92% of the initial power conversion efficiency after 1680 h of storage.

New Reaction Products of Acetylacetone with Semicarbazide Derivatives.

A new approach is suggested herein for the synthesis of pyrazole derivatives by reacting 4-nitrosemicarbazide with acetylacetone. Additional studies were done on the reaction of acetylacetone with semicarbazide and its derivatives (4-aminosemicarbazide, methylsemicarbazide, and dimethylsemicarbazide). The study on the reaction with acetylacetone resulted in monocyclic 3,5-dimethyl-N-nitropyrazole-1-carboxamide, monocyclic 5-hydroxy-3,5-dimethyl-2-pyrazoline, and bicyclic bis(3,5-dimethylpyrazole-1-carbonyl)hydrazine, and conditions for the formation of acetone semicarbazone were identified. The structures of the resultant compounds were validated by physicochemical analytical methods, including X-ray diffraction. The computer-aided screening in the PASS prediction software discovered a high biological activity of the newly obtained compounds.

Synthesis and Characterization of β-Diketimine Schiff Base Complexes with Ni(II) and Zn(II) Ions: Experimental and Theoretical Study

Schiff base diethyl 4,4-(pentane-2,4-diylidenebis(azanylylidene))benzoate (1) as a new ligand (L) was prepared by the reaction of acetylacetone with benzocaine in the ratio of 1 : 1. Two transition-metal complexes, [Ni(II)(LCl(HOEt))] (2) and [Zn(II)(LCl(HOEt))] (3), have been synthesized from metal salts with didentate Schiff base ligand (L) and characterized by elemental analyses, FT-IR, 1H NMR, 13C NMR UV-Vis spectroscopy, and magnetic susceptibility. The biological activity of the complexes was studied. In addition, the M06-2x density function theory method and the 6-31G(d) basic set were applied to determine the optimized structures of 1–3 and to determine their IR and 1H NMR, 13C NMR spectra theoretically. The data are in good agreement with the experimental results. The geometries of complexes 2 and 3 were determined to be square-planar for 2 and tetrahedral for 3.

Hantzsch reaction approach for determination of teicoplanin and vancomycin in real human plasma: Application to pharmaceutical preparations and to synthetic mixture with rifampicin for drug-resistant strain of Staphylococcus aureus

Teicoplanin (TEIC) and vancomycin hydrochloride (VAN) are glycopeptide antimicrobial drugs against methicillin-resistant Staphylococcus aureus and Gram-positive organisms. So, simple, quick, cost-effective and ultra-sensitive spectrofluorimetric method was developed and bio-analytically validated for assay of TEIC and VAN. The proposed method is based on the reaction of acetylacetone with primary amine moiety in the presence of formaldehyde producing highly fluorogenic product measured at 485 nm (λex at 420 nm). The calibration range was constructed from (50–400 ng mL−1) and (70–800 ng mL−1) for TEIC and VAN, respectively. The presented method exhibited low LOD (7.04 and 3.55 ng mL−1) and LOQ (21.33 and 10.77 ng mL−1) values for TEIC and VAN, respectively. The presented method was effectively applied to determine TEIC and VAN in real human plasma with percentage of recovery ranged from 95.57 ± 2.06% to 97.43 ± 1.66% for the studied drugs. Also, the developed method was applied for the first time to study synthetic mixtures of the studied drugs with rifampicin (RIF), as a combination therapy to treat drug-resistant strains of Staphylococcus aureus without interferences from RIF. The synthetic mixtures of TEIC or VAN with RIF were prepared in three different ratios in order to measure the stability of the studied drugs TEIC or VAN in presence of RIF in pure forms and human plasma.

Preparation and Diagnosis of Pyrimidines Derivatives by Conventional And Microwave Ways.

This work includes synthesis and characterization of new derivatives of pyrimidine (R. or Ar. -1, 2, 3, 4-tetrahydropyrimidin-5-yl) ethan-1-one), via the reaction of acetyl acetone with different aldehydes and guanidine hydrochloride. Using absolute ethanol as a solvent .This mixture was refluxed for (6– 20) hrs.at pH 6 we prepared .The same derivatives of pyrimidine were prepared in microwave way. This compounds were prepared characterized by melting point, FT-IR , UV-Vis and some of the with 1H-NMR and 13C-NMR spectroscopy .

Synthesis, Structure and Electrochemistry of Tetranuclear Oxygen-Centered Copper(II) Clusters with Acetylacetone and Benz-pyrazole Hydrolyzed Derivatives as Ligand

Two copper(II) clusters Cu(4)OCl(6)(pyrazole)4, 1, and Cu(4)OBr(6)(Br-pyrazole)4, 2, have been synthesized by reacting acetylacetone and benzohydrazide (1:1 ratio) with CuX(2) (X = Cl for 1 and X= Br for 2) in methanol solutions. The structures of both clusters have been established by X-ray crystallography. The clusters contain four Cu, one O, six μ(2)-X atoms, and four pyrazole ligands. The pyrazoles was prepared in situ by the reaction of acetylacetone with benzohydrazide in methanol under reflux. In 2, the methine hydrogens of the pyrazole ligands have been replaced by bromine atoms. The four copper atoms encapsulate the central O atom in a tetrahedral arrangement. All copper atoms are five-coordinate and have similar coordination environments with slightly distorted trigonal bipyramidal geometry. The cyclic voltammogram of the clusters 1 and 2 show a one-electron quasi-reversible reduction wave in the region 0.485 to 0.731 V, and a one-electron quasi-reversible oxidation wave in the region 0.767 to 0.898 V. In 1, one irreversible oxidative response is observed on the positive of side of the voltammogram at 1.512 V and this can be assigned to Cu(II) to Cu(III) oxidation.

Design and synthesis of new thiophene derivatives together with their antitumor evaluations

A series of new thiophene derivatives (3a,b) have been prepared by the reaction of acetylacetone with either cyanoacetanilide or 2-cyano- N -( p -tolyl)acetamide and elemental sulfur in the presence of triethylamine as basic catalyst. The two synthesized compounds were used to further synthesize new thiophene derivatives. The structures of all the newly synthesized products have been established on the basis of analytical and spectral data. The antitumor activity of the newly thiophene derivatives was evaluated against six human cancer cell lines, namely gastric cancer (NUGC), colon cancer (DLD1), liver cancer (HA22T and HEPG2), nasopharyngeal carcinoma (HONE1), breast cancer (MCF) and normal fibroblast cells (WI38).

One‐Pot Synthesis of an Oxalato‐Bridged CuII Coordination Polymer Containing an In Situ Produced Pyrazole Moiety: A Precursor for the Preparation of CuO Nano­structures

AbstractThe synthesis, characterization, and thermal decomposition behaviour of the oxalato‐bridged copper(II) coordination polymer [Cu2(C2O4)(L)2Cl2(MeOH)2]n (1) (L = 3,5‐dimethyl‐1H‐pyrazole) is reported. Complex 1 is prepared in a straightforward fashion by a one‐pot reaction of acetylacetone, thiosemicarbazide, oxalic acid and copper(II) chloride in a molar ratio of 2:2:1:2. Complex 1 was characterized by means of FT‐IR spectroscopy, mass spectrometry and elemental analysis as well as single‐crystal X‐ray diffraction. Furthermore, the electrochemical behavior of 1 was investigated in DMSO by cyclic voltammetry. The thermal stability of complex 1 was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). Solventless thermolysis of complex 1 at 550 °C and 1000 °C under air afforded copper oxide nanoparticles and nanosheets, respectively. The CuO nanostructures were characterized by using a series of techniques including FT‐IR, UV/Vis, XRD, XPS, EDAX, and SEM.

Reaction of CH-acids with Michael acceptors in the presence of potassium carbonate. Syntheses of 6-acetyl- and 3,5-dialkylcyclohex-2-enones

The reaction of acetylacetone with α,β-enones in the presence of potassium carbonate affords 6-acetylcyclohex-2-enones. The assembly of two acetoacetate and one alkanal molecules gives 3,5-dialkylcyclohex-2-enones. Facile one-pot procedures for these reactions were developed.

The Coordination of Novel, Hard Ligand Systems to Tantalum(V) and Niobium(V) Metal Centres

The formation reaction of acetylacetone to solvated tantalum pentachloride ([TaCl5]2) in methanol, is defined by limiting kinetic behaviour and is indicative of a two-step process. This involves the rapid formation of an intermediate, possiblytrans-[TaCl2(OMe)3(η1-acacH)]) with the stability constant,K1, equal to 2.4 ± 0.3 x 103M-1at 25 °C. The second order rate constant,k1, at 25 °C was determined as 3.1 ± 0.1 x 102M-1s-1. A fit of the data obtained from the UV-Vis study, and describing the total reaction, yielded a value of 1.7 ± 0.2 x 103M-1s-1forK1, which is in agreement with the value obtained earlier. Comparison ofk1andk2indicates that the first reaction is roughly six orders of magnitude (106) faster than the second rate determining step.

An efficient one-pot three-component synthesis and antimicrobial evaluation of tetra substituted thiophene derivatives

Abstract A convenient one-pot three-component method for the preparation of tetra-substituted thiophene derivatives has been developed. Reaction of acetyl acetone 1 , phenyl isothiocynate 2 and 2-chloromethyl derivatives 3a – 3c in the presence of potassium carbonate afforded the target compounds, namely ethyl 2-(4-acetyl-3-methyl-5-(phenylamino)thiophen-2-yl)-2-oxoacetate derivatives 4a – 4e , ethyl 3-(4-acetyl-3-methyl-5-(phenylamino)thiophen-2-yl)-3-oxopropanoate derivatives 4f – 4i , di((4-acetyl-3-methyl-5-phenylamino)thiophen-2-yl)ketone derivatives 4j – 4n in reasonable overall yields. The synthesized compounds were screened for antimicrobial activity. The detailed synthesis, spectroscopic data and antimicrobial activities of synthesized compounds were reported.

Superparamagnetic Copper Ferrite Nanoparticles as an Efficient Heterogeneous Catalyst for the α‐Arylation of 1,3‐Diketones with CC Cleavage

AbstractSuperparamagnetic CuFe2O4 nanoparticles were synthesized from CuCl2 and FeCl3 by a co‐precipitation method in ethylene glycol and characterized by several techniques, which included vibrating sample magnetometry, XRD, SEM, TEM, atomic absorption spectrometry, and nitrogen physisorption measurements. The CuFe2O4 nanoparticles could be used as a solid catalyst for the α‐arylation reaction of acetylacetone with iodobenzene to form phenylacetone as the principal product and 3‐phenyl‐2,4‐pentanedione as the byproduct. The reaction that used the CuFe2O4 nanoparticles as catalyst could proceed to completion with 95 % selectivity to phenylacetone. The CuFe2O4 nanoparticles could be separated easily from the reaction mixture by magnetic decantation and could be reused several times for the α‐arylation reaction without a significant degradation in catalytic activity.

Lipase-Catalyzed Condensation Reaction of 4-Nitrobenzaldehyde with Acetyl Acetone in Aqueous–Organic Cosolvent Mixtures and in Nearly Anhydrous Media

The nature of the product(s) in lipase-catalyzed reaction of acetyl acetone with 4-nitrobenzaldehyde was found to depend upon the source of lipase and the reaction medium. Mucor javanicus lipase was found to give 70% aldol with 80% enantiomeric excess in anhydrous t-amyl alcohol. A 2:2 adduct was formed by the dimerization of the aldol along with an unsaturated cyclic ether as the side products in varying proportions depending upon the reaction medium and the lipase used. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]

Preparation of Polyfunctionally Substituted Pyridine-2(1<i>H</i>)-Thione Derivatives as Precursors to Bicycles and Polycycles

Reaction of acetylacetone with 1 mole of dimethylformamide dimethyl acetal (DMFDMA) affords enamine 2a which reacts with cyanothioacetamide to give pyridinethione 3a. Pyridinethione 3a reacts with methyl iodide, halogenated compounds, aromatic aldehyde and malononitrile/elemental sulfur to yiled compounds 7-10 respectively. Reactions of thioether 7 in ethanolic K2CO3, 1 mole DMFDMA and 4-(dimethylamino)benzaldehyde give compounds 11, 13, 14 respectively. Enaminone 12 can be prepared by reaction of compound 11 with DMFDMA. We have demonstrated some reactions in order to show the potential usefulness of the prepared compounds for the preparation of new bipyridyl compounds 15, 16, 18, bicyclic compounds 17 and uncommon tricyclic compounds 20, 21, 22 and 23 respectively using DMFDMA.

Reactions of hydrogen peroxide with acetylacetone and 2-acetylcyclopentanone

A reaction of acetylacetone with equimolar amount of concentrated aqueous H2O2 in both organic solvents (ButOH, AcOH) and water at various temperatures gave the corresponding 3,5-dihydroxy-1,2-dioxolanes with different configuration of stereogenic centers. In the presence of an excess of H2O2, 3,5-dihydroxy-1,2-dioxolanes were converted to a mixture of 5-hydroperoxy-3-hydroxy-1,2-dioxolanes and further to a mixture of dimeric 1,2-dioxolan-3-ylperoxides. All the peroxides formed exist in solutions as equilibrium mixtures with the starting reagents. A prolonged reflux of solutions of 3,5-dihydroxy-1,2-dioxolanes in ButOH in the presence of a large excess of H2O2 led to the skeletal rearrangements of the substrates to a mixture of propionic acid and hydroxyacetone, which underwent further oxidative transformations. Unlike acetylacetone, 2-acetylcyclopentanone reacted with H2O2 in aqueous phase or in solutions in ButOH under thermodynamic or kinetic control with the formation of the corresponding 5-hydroperoxy-3-hydroxy-1,2-dioxolanes, rather than 3,5-dihydroxy-1,2-dioxolanes. Thermodynamically controlled process in solution in AcOH gave a mixture of all four possible hydroperoxyhydroxy-1,2-dioxolanes. These cyclic peroxides in solutions in ButOH or AcOH readily converted to a mixture of AcOH, glutaric, α-methyladipic, and α-hydroxy-α-methyladipic acids. An active α-hydroxylation of the substrate was observed upon reflux of a solution of 2-acetylcyclopentanone and H2O2 in AcOH.

Synthesis and Antitumor Evaluation of Some New Fused and Binary Pyridines

Syntheses of some new heterocyclic compounds containing pyridone, thioxopyridine, halogenated‐pyridine‐carbonitriles, pyrazolopyridine, and pyridine derivatives were achieved. Besides, a modified synthetic method for the synthesis of 2‐chloro‐4,6‐dimethyl‐nicotinonitrile (3) through the reaction of acetylacetone and malononitrile as starting materials was implemented. The reaction of 2‐chloronicotinonitrile 3 with substituted amines to 2‐aminonicotinonitrile were also investigated. Fused or binary pyridines were tested for cytotoxicity against well‐known established model Ehrlich ascites cells in vitro. Compound 13 exhibited a high antitumor activity compared with 5‐fluorouracil.

Reaction of 4-iminothiazolidin-2-one with acetylacetone

By the reaction of acetylacetone and arylazoacetylacetones with 4-iminothiazolidin-2-one thiazolo[4,5-b]pyridines were obtained in good yields. Optimum reaction conditions were chosen and some properties of compounds obtained were studied.

ChemInform Abstract: Synthesis and Reactions of 3‐Cyano‐4,6‐dimethyl‐2‐pyridone.

AbstractThe base‐mediated reaction of acetylacetone with malononitrile leads to cyanopyridone (III), which is used as a convenient starting compound in the synthesis of a variety of pyridone derivatives including isoquinolinecarbonitriles (XIV) and pyridylpyridazines (X).