Benzoylacetone Research Articles

Preparation of new half sandwich ruthenium arene complexes with aminophosphines as potential chemotherapeutics

Aminophosphines 2-(diphenylphosphino)-1-methylimidazole (dpim) and diphenyl-2-pyridylphosphine (PPh2py) have been used to prepare two series of Ru(II) arene complexes of formulae [(η6-p-cymene)Ru(κ2-O,O′-X)(κ1-P-dpim)]Y (series a: 1a·Y–3a·Y) and [(η6-p-cymene)Ru(κ2-O,O′-X)(κ1-P-PPh2py)]Y (series b: 1b·Y–3b·Y) (where X=acac, acetylacetonate; bzac, benzoyl acetonate; dbzm, dibenzoyl methanoate; Y=BF4, BPh4). The structures of 1a·BF4, 1a·BPh4, 3a·BF4, 1b·BPh4 and 3b·BPh4 were determined by X-ray diffraction. The tetrafluoroborate derivatives are more soluble in organic solvents than their tetraphenylborate counterparts. Five BF4− derivatives (all except the unstable 1b·BF4) were selected to evaluate the cytotoxic behavior in vitro against the human cancer cell lines MCF-7 (breast cancer) and CAPAN-1 (pancreatic cancer). 2b·BF4 and 3b·BF4 exhibited IC50 values similar to those of cisplatin. Electrophoresis and AFM studies showed good correspondence between the biological activity levels of 2b·BF4 and 3b·BF4 and their ability to modify the DNA structure. Hydrolytic studies indicate that aquation could be involved in the activation mechanism of these complexes and confirm that the hydrolysis rate of 3b·BF4 is higher than that of 3a·BF4. Thus, the cytotoxic activity trends are explained in terms of the higher reactivity of derivatives from series b, which in turn is rationalized as being the result of the electronic features of dpim and PPh2py established by cyclic voltammetry measurements.

Conformational analysis, tautomerization, IR, Raman, and NMR studies of ethyl benzoylacetate

Abstract A complete conformational analysis of the keto and enol forms of ethyl benzoylacetate (EBA), a β-ketoester, was carried out by ab initio calculations, at the density functional theory (DFT) level. The relative stabilities of cis-enol and keto forms were calculated in the gas phase and in solution. The intramolecular hydrogen bond characters of the most stable enol forms of EBA are discussed and compared with those of benzoylacetone (BA). Harmonic vibrational frequencies and 1 H and 13 C NMR chemical shifts of the most stable enol and keto forms were also calculated at the B3LYP/6-311++G ** level and compared with the experimental data.

Radiotracer study of synergic effect of trioctyl phosphine oxide on the solvent extraction of gold(III)-β-diketonates

Liquid–liquid extraction of gold(III) with two β-diketones e.g. Benzoyl acetone (BZAC) and theonyl trifluoro acetone (TTA) and enhancement effects of trioctyl phosphine oxide on such extractions in various organic media have been studied by radiotracer technique. Strong ternary adduct complex formation were reported in chloroform (BZAC chelate) and carbontetrachloride (TTA chelate) media. Effect of temperature variation established such processes as spontaneous, enthalpy favoured with net loss in entropy. Synergic effects were reported to be strongly diluent dependent and Hildebrand’s regular solution theory was found to be applicable in such systems.

Photoelectron spectra and electron structure of boron difluoride ethyl acetonate, boron difluoride benzoyl acetonate, and its derivatives

The electron structure of boron fluoride acetyl acetonate F2B(OCCH3)2CH, boron fluoride benzoylacetonate, and two its derivatives is investigated by ultraviolet electron spectroscopy and quantum chemistry in an approximation of the all-electron density functional theory. Sequences and preferential localization of the π levels of conjugated cycles are established, and the violation of coplanarity of the cycles in the presence of the methyl group in the ortho site of the substituent is shown. It is concluded that the values of the ionization energy and the calculated data indicate a sequential increase in the contribution of π orbitals of the benzoic cycle in the UOMO (upper occupied molecular orbital) upon substituting CH3 groups for hydrogen atoms.

Extraction Behavior of Rare Earths in Ion Liquid Extraction System Using 1-Butyl-3-Methyl-Imidazolium Hexafluorophosphate and Benzoyl Acetone

The extraction behavior of five rare earth ions (RE3+) was investigated in ionic liquid (IL) extraction system using 1-butyl-3-methyl-imidazolium hexafluorophosphate ionic liquid ([Bmim]PF6) as extraction solvent and benzoyl acetone (HA) as extractant. The extraction percentage of RE3+ using [Bmim]PF6 was less than 8% without HA. When sufficient HA was included in IL phase, the extraction percentage of RE3+ could be higher than 98%. The extracted species in the RE3+-[Bmim]PF6-HA system was neutral REA3 and the recovery of RE3+ extracted into [Bmim]PF6 can be achieved using the mixture of hydrazine hydrate and ethylenediamine tetraacetic acid (EDTA) as stripping agent. [Bmim]PF6 can be recycled in the experiment.

Competitive extraction of Cu(II), Zn(II), Ni(II), and Mn(II) cations using acetyl acetone and benzoyl acetone as carriers

The competitive metal ion extraction of Cu(II), Ni(II), Zn(II) and Mn(II) with acetyl acetone and benzoyl acetone were examined and compared with each other. The experiments were buffered (acetic acid/sodium acetate and formic acid/sodium formate) at pH 3–7. The extraction behaviors for Cu(II), using both acetyl acetone and benzoyl acetone are similar. In fact the extraction behavior for Cu(II) is much better than the other cations. The extraction results are closely parallel for the other cations using the present ligands. The concentration in extraction experiments for the cations and ligands used was 10mM and 1.0mM, respectively.

Volatile Oil Composition of Pogostemon heyneanus and Comparison of its Composition with Patchouli Oil

The volatile oil of the leaves of Pogostemon heyneanus Benth. (Lamiaceae) was analyzed by GC and GC-MS. Twenty-six components representing 96.0% of the oil were identified. The major components of the oil were acetophenone (51.0%), beta-pinene (5.3%), (E)-nerolidol (5.4%), and patchouli alcohol (14.0%). Comparison of the compositions of the oils of P. heyneanus and P. cablin (Blanco) Benth. (Patchouli oil) showed wide variation between them. Though 13 sesquiterpenes and oxygenated sesquiterpenes were detected in both oils, their concentrations in the oils differed widely. Acetophenone, benzoyl acetone and (E)-nerolidol present in the oil of P. heyneanus were not detected in patchouli oil.

The relative effect of structural forms on the ionizing constituents of acids derived from benzoyl acetone and dimedome at different temperatures

The project deals with the determination of ionization constants Ka for ten acidic compounds whose nomenclatures and structures are seen in the text, derived from benzoyl acetone and dimedone by using conductivity method. These compounds are in forms of monoxime, dioxime and phenolic Schiff bases having phenolic groups in ortho, meta and para positions on the aromatic rings. The relative values of ionization constants Kr are calculated in water for the three systems mentioned at five different temperatures and showed a different relationships. The thermodynamic parameters of ionization for acids are also estimated. This shows that the process of ionization of acidic compounds under study in water solvent is non spontaneous (+ΔG), endothermic (+ΔH) and is accompanied by an increase of order (-ΔS) for the ionization systems. Finally a suitable interpretations for any one of these thermodynamic parameters are given and discussed.

Effect of ethanol and water solvents on the ionizing constituents of acids derived from benzoyl acetone and dimedone acids .

Effect of ethanol and water solvents on the ionizing constituents of acids derived from benzoyl acetone and dimedone acids .

Structure, intramolecular hydrogen bonding, and vibrational spectra of 2,2,6,6-tetramethyl-3,5-heptanedione

Molecular structure, intramolecular hydrogen bonding (IHB) and vibrational frequencies of 2,2,6,6-tetramethyl-3,5-heptanedione (TMHD, also known as dipivaloylmethane), have been investigated by means of the density functional theory (DFT) calculations and IR and Raman spectroscopies. In addition, the geometry of the cis - and trans -enol conformers were also optimized at the MP2/6-31G ∗∗ level of theory. The results are compared with those of acetylacetone (AA), benzoylacetone (BA), and dibenzoylmethane (DBM). The energy differences between two stable E1 and E2 chelated enol forms, calculated at different levels of theory, are negligible. Comparing the calculated and experimental band frequencies and intensities suggests coexisting of two stable cis -enol conformers in comparable proportions in the sample. Also the IR and Raman spectra of TMHD and its deuterated analogue were clearly assigned. According to the theoretical calculations, TMHD has a hydrogen bond strength of about 17.8–18.0 kcal/mol, calculated at the B3LYP/6-311++G ∗∗ level of theory, which is about 3.0 kcal/mol stronger than that of AA. This enhancement in the IHB strength is also consistent with the experimental results of the band frequency shifts for the modes of OH/OD and O ⋯ O stretching and OH/OD out-of-plane bending frequencies. The theoretical calculations and spectroscopic results indicate that the IHB strength of TMHD is between those of AA and DBM.

Selective Extraction and Bulk Liquid Membrane Transport of Cu(II) from Aqueous Nitrate Solution in the Presence of Zn(II), Ni(II) and Mn(II) Cations Using Benzoyl Acetone

The competitive metal ion extraction and transport of Cu(II), Ni(II), Zn(II) and Mn(II) with benzoyl acetone and EDTA was studied. In the experiments the ligand was dissolved in chloroform and the pH and time of extraction or transport were varied. Also the rate of shaking and ligand concentration on the efficiency of extraction and transport was studied. The results revealed that the ligands exclusively extract Cu(II) from the mixture of the above cations.

Synthesis of New 1,4-Dihydropyridine Derivatives Containing Thiazolyl Substituents

A series of 4-[2-methyl (or aryl) thiazole-4-yl]-2,6-dimethyl-3,5-diacetyl (or dibenzoyl) 1,4-dihydropyridines were synthesized using a modified Hantzsch reaction involving the condensation of the corresponding aldehyde with acetyl acetone or benzoyl acetone. The preparation of the corresponding aldehydes (2-methylthiazole-4-carboxaldehyde and some 2-arylthiazole-4-carboxaldehydes) was achieved by a simplified protocol of the published synthesis.

Four new dinuclear Cu(ii) hydrazone complexes using various organic spacers: syntheses, crystal structures, DNA binding and cleavage studies and selective cell inhibitory effect towards leukemic and normal lymphocytes

Syntheses and crystal structures of four new hydrazone-based Cu(ii) complexes, [{Cu(L(1))(H(2)O)}(2)(mu-pyraz)](ClO(4))(2) (), [{Cu(L(1))(OClO(3))}(2)(mu-4,4'-bipy)] (), [{Cu(L(2)H)}(mu-pyraz){Cu(L(2)H)(OClO(3))}].(ClO(4)) () and [{Cu(L(2))}(2)(mu-bpe)] () [L(1)H = condensation product of benzhydrazide and pyridine-2-carbaldehyde and L(2)H(2) = condensation product of benzoyl acetone and benzhydrazide], bridged by various organic spacers [pyrazine (pyraz), 4,4'-bipyridine (4,4'-bipy) and 1,2-di(4-pyridyl)ethane (bpe)] are reported in this paper. The single-crystal X-ray crystallographic studies reveal that all are dinuclear units where and form strong intermolecular H-bonding to form sheets of interconnected ions, whereas forms sheets of dinuclear chains through pi-pi interactions; in , molecules are linked only through van der Waals interactions. The variable-temperature magnetic moment studies reveal that and show antiferromagnetic coupling between the Cu(ii) centers at lower temperatures. The binding ability of with calf thymus DNA [CT-DNA] is reported using various spectroscopic studies (UV-Vis titration, circular dichroism and fluorescence). The binding constants of with CT-DNA, as calculated by different methodologies, are of the order of 10(5) M(-1). The mode of interaction between and CT-DNA has been predicted using circular dichroic (CD) spectroscopy, where it has been shown that most probably interacts with DNA via intercalation between the base pairs leading to a change in B-DNA conformation. is also able to cleave supercoiled (SC) plasmid DNA pUC19 in a time and dose dependent manner as demonstrated by agarose gel electrophoresis, and also demonstrates its potential to cleave the SC plasmid DNA via both oxidative and hydrolytic mechanisms. Approximately 50% of leukemic cells are found to be dead when two representative leukemic cell lines are exposed to ( approximately 80 muM) even for 24 h as determined by different cell cytotoxicity assays. Preliminary results also showed that, at 20 muM, could selectively induce apoptosis in leukemic cells without affecting normal lymphocytes.

Design and Synthesis of Coordination Compounds with Tetradentate Ligands Derived from Alkylated Thiosemicarbazide

This work is devoted to the investigation of the template reactions of organic compounds derived from S-alkylisothiosemicarbazide and β-dicarbonylic compounds (acetyl(benzoyl)acetone, 2,6-diformylpyridine, 2,6-diformyl-4-methylphenol, 1-hydroxy-2-naphthaldehyde, sodium nitromalonic dialdehyde, 1,1,3,3-tetraetoxypropane, 3-ethoxyacroleine) in the presence of 3d-metal ions, determination of the structure and properties of the prepared complexes. There were elaborated original methods for synthesis of open-chain or macrocyclic coordination compounds of nickel(II), copper(II), oxovanadium(IV) and cobalt(II) with N4, N3O and N2O2 tetradentate ligands. Two types of hexaazamacrocyclic systems with trans- and cis- arrangement of thiosemicarbazide fragments have been obtained using template condensation of different precursors. The biostimulative properties (biomass accumulation and increasing of enzymatic activity) of complexes have been established. Some complexes of nickel(II) have been studied as coloring agents for plastics.

Synthesis and molluscicidal activity of some new thiophene, thiadiazole and pyrazole derivatives

The base-catalyzed reaction of benzoyl acetone 1 with phenyl isothiocyanate yields the non-isolable intermediate 2. Treatment of 2 with dilute HCl afforded the corresponding thiocarbamoyl derivative 3. Reaction of the intermediate 2 with phenacyl bromide, ethyl bromoacetate, chloroacetonitrile, chloroacetyl chloride, bromodiethyl malonate and chloroacetone afforded the corresponding thiophene derivatives 5, 8, 15 and 17. The thiocarbamoyl derivative 3 reacts with arylazophenacyl bromide and/or hydrazine hydrate to afford the corresponding thiadiazole and pyrazole derivatives 20a– c and 22, respectively. These new synthesized compounds show generally a moderate molluscicidal activity to Biomphalaria alexandrina snails.

P2O5-Promoted Efficient and Diastereoselective Synthesis of Substituted 5-Methylene-dihydropyran-2,6-diones and 3-Methylene-3,4-dihydropyran-2-ones

A simple, efficient, and diastereoselective synthesis of 5-methylene-dihydropyran-2,6-diones and 3-methylene-3,4-dihydropyran-2-ones from substrates afforded by the SN2 reaction between the acetyl derivatives of the Baylis–Hillman adducts and methylacetoacetate or acetylacetone or benzoyl acetone via saponification followed by P2O5-mediated cyclization is described.

Highly Selective Potentiometric Membrane Sensor for Hg(II) Based on Bis(Benzoyl Acetone) Diethylene Triamine

A new ion selective PVC membrane sensor is described based on bis(benzoyl acetone) diethylene triamine as a potentiometric sensor for Hg <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2+</sup> ions. The membrane having bis(benzoyl acetone) diethylene triamine as an electroactive material, sodium tetraphenyl phthalate (NaTPB), and dibutyl phthalate (DBP) as an anion excluder in PVC matrix in the percentage ratio 4.21:2.11:60.25:33.43 (Ionophore:NaTPB:DBP:PVC) (w/w) of exhibits a linear response to Hg <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2+</sup> of 1.0 times 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-6</sup> to 1.0 times 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-1</sup> M with a limit of detection of 3.7 times 10 <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-7</sup> M and with a slope of 29.8 plusmn 1.0 mV/decade over the pH range of 2.0-11.5. Selectivity coefficients for Hg(II) relative to a numbers of potential interfering ions were investigated. The sensor is highly selective for Hg <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2+</sup> ions over a large number of mono-, bi-, and trivalent cations. Normal interferents like Ag <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> and Cd <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2+</sup> do not interfere in the working of the sensor. The sensor has been found to be chemically inert to other ions and showing a fast response time of 1 s and was used over a period of three months with a good reproducibility. The sensor was successfully applied to determine mercury(II) in water samples with satisfactory results.

Synthesis and structural characterization of a novel dinuclear complex compound formed by the aerial oxidation of cobalt(ii) having an interligand C–C σ-bond

The aerial oxidation of cobalt(II) salt, in a methanolic solution, containing a hydrazone ligand, (E)-N'-(4-oxo-4-phenylbutan-2-ylidene)benzohydrazide (condensation product of benzoyl acetone and benzhydrazide, LH2) leads to the coupling of two such ligand units through the formation of a rather long C-C bond [1.601(6) A] giving rise to a dinuclear Co (III) hydrazone complex, [Co2(L)2(L')(].0.25H2O (L' = C-C coupled hydrazone ligand). The structure of the complex has been determined by X-ray crystallography and IR, UV-Vis spectroscopy and elemental analysis have characterized the complex.

Mechanochemical synthesis of mixed-ligand europium β-diketonates with nitrogen-containing neutral ligands

The solid-phase reaction between europium salts of β-diketones and nitrogen-containing neutral ligands in a planetary mill produces luminescent mixed-ligand compounds Eu(β-dic)3 · D, where β-dic stands for dibenzoylmethane (DBM), benzoylacetone (BA), thenoyltrifluoroacetone (TTA), or benzoyltrifluoroacetone (BTFA); and D stands for 1,10-phenanethroline (Phen), 2,2-dipyridyl (Dipy), or diphenylguanidine (DPG). The mechanosynthesis and yield of lanthanide β-diketonates are studied as affected by the treatment parameters and the nature of the reagents. Powder X-ray diffraction demonstrates a staged course of the mechanochemical synthesis. Examination of formation-rate curves shows that grinding/stirring is the rate-controlling stage of the process. Thermogravimetric analysis (TGA) shows that the mechanosynthesis can proceed in the self-propagation mode. The relative luminescence intensity is determined as a function of treatment time. Particles of the mechanically activated mixture have sizes of 10–100 μm.

Tautomerization Equilibria in Aqueous Micellar Solutions: A Spectrophotometric and Factor-Analytical Study

The keto-enol equilibria of benzoylacetone (BZA) as a model for 1,3-dicarbonyl compounds are studied in aqueous acid and cationic micellar solution. Evolving factor analysis (EFA), multivariate curve resolution-alternating least-squares (MCR-ALS), and rank annihilation factor analysis (RAFA) are used for complete resolving of measured spectrophotometric data. The acidity constants of the enolic, KaE, and ketonic, KaK, forms of BZA and also the tautomerization constant, Kt, and its related thermodynamic parameters have been determined by using EFA and MCR-ALS methods and spectral variation of BZA solutions in various pHs and temperatures. The concentration and spectral profiles of all species were calculated without any assumption about chemical models. The spectral variation of BZA solutions as a function of cationic micelle concentration sufficiently beyond its critical micelle concentration is analyzed according to the partition model for distribution between water and micellar pseudo-phase and RAFA. The outputs of using RAFA on measured rank deficient data are the spectrum of enolic form in the micellar pseudo-phase, free from contribution of the enolic form in the aqueous phase, the partition coefficient of enolic form, KdE, between the micelle and water phases, and the tautomerization constant in the micellar pseudo-phase, Ktm.