1-Phenylbutane-1,3-dione

Synthesis, Photoluminescence Behavior of Green Light Emitting Tb(III) Complexes and Mechanistic Investigation of Energy Transfer Process.[Pubmed:29869051]

J Fluoresc. 2018 May;28(3):775-784.

A series of five new terbium(III) ion complexes with 4,4-difluoro-1-Phenylbutane-1,3-dione (HDPBD) and anciliary ligands was synthesized. The composition and properties of complexes were analyzed by elemental analysis, IR, NMR, powder X-ray diffaraction, TG-DTG and photoluminescence spectroscopy. These complexes exhibited ligand sensitized green emission at 546 nm associated with (5)D4 --> (7)F5 transitions of terbium ion in the emission spectra. The photoluminescence study manifested that the organic ligands act as antenna and facilitate the absorbed energy to emitting levels of Tb(III) ion efficiently. The enhanced luminescence intensity and decay time of ternary C2-C5 complexes observed due to synergistic effect of anciliary ligands. The CIE color coordinates of complexes came under the green region of chromaticity diagram. The mechanistic investigation of intramolecular energy transfer in the complexes was discussed in detail. These terbium(III) complexes can be thrivingly used as one of the green component in light emitting material and in display devices. Graphical Abstract Illustrate the sensitization process of the Tb ion and intramolecular energy transfer process in the Tb(3+) complex.

Synthesis, Characterization and Biological Studies of Metal(II) Complexes of (3E)-3-[(2-{(E)-[1-(2,4-Dihydroxyphenyl) ethylidene]amino}ethyl)imino]-1-phenylbutan-1-one Schiff Base.[Pubmed:26023939]

Molecules. 2015 May 27;20(6):9788-802.

Co(II), Ni(II), Zn(II) and Cu(II) complexes of (3E)-3-[(2-{(E)-[1-(2,4-dihydroxyphenyl)ethylidene]amino}ethyl)imino]-1-phenylbut an-1-one (DEPH2) derived from ethylenediamine, 2',4'-dihydroxyacetophenone and 1-Phenylbutane-1,3-dione have been synthesized and characterized by elemental analysis, FTIR, UV-Visible spectroscopy, and screened to establish their potential as antibacterial agents, antioxidants and DPPH radical scavengers. The FTIR spectra showed that the ligand behaves as a dibasic tetradentate ligand with the dioxygen-dinitrogen donor atom system oriented towards the central metal ion. The analytical and spectroscopic data suggest a square planar geometry for Cu(II) and Ni(II) complexes and an octahedral geometry for the Co(II) complex. The ligand and their metal complexes were screened for antibacterial activity against Gram (+) and Gram (-) bacteria by the agar well diffusion method. In addition, the antioxidant activities of the complexes were also investigated through their scavenging effect on DPPH and ABTS radicals. The obtained IC50 value of the DPPH activity for the copper complex (2.08 +/- 0.47 microM) and that of the ABTS activity for the copper complex (IC50 = 2.11 + 1.69 microM) were higher than the values obtained for the other compounds.

Solvent-free and catalyst-free Biginelli reaction to synthesize ferrocenoyl dihydropyrimidine and kinetic method to express radical-scavenging ability.[Pubmed:22489679]

J Org Chem. 2012 Apr 20;77(8):3952-8.

Benzoyl and ferrocenoyl 3,4-dihydropyrimidin-2(1H)-ones (-thiones) (DHPMs) were synthesized in modest yields via catalyst-free and solvent-free Biginelli condensation of 1-Phenylbutane-1,3-dione or 1-ferrocenylbutane-1,3-dione, hydroxyl benzaldehyde, and urea or thiourea. This synthetic protocol revealed that catalysts may not be necessary for the self-assembling Biginelli reaction. The radical-scavenging abilities of the obtained 11 DHPMs were carried out by reacting with 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radical (ABTS(+*)), galvinoxyl radical, and 2,2'-diphenyl-1-picrylhydrazyl radical (DPPH), respectively. The variation of the concentration of these radicals with the reaction time (t) followed exponential function, [radical] = Ae(-t/a) + Be(-t/b) + C. Then, the differential style of this equation led to the relationship between the reaction rate (r) and the reaction time (t), -d[radical]/dt = (A/a)e(-t/a) + (B/b)e(-t/b), which can be used to calculate the reaction rate at any time point. On the basis of the concept of the reaction rate, r = k[radical][antioxidant], the rate constant (k) can be calculated with the time point being t = 0. By the comparison of k of DHPMs, it can be concluded that phenolic ortho-dihydroxyl groups markedly enhanced the abilities of DHPMs to quench ABTS(+*), but the introduction of ferrocenoyl group made DHPMs efficient ABTS(+*) scavengers even in the absence of phenolic hydroxyl group. This phenomenon was also found in DHPM-scavenging galvinoxyl radical. In contrast, the ferrocenoyl group cannot enhance the abilities of DHPMs to scavenge DPPH, and phenolic ortho-dihydroxyl groups still played the key role in this case.

Modulating spin dynamics of cyclic LnIII-radical complexes (LnIII = Tb, Dy) by using phenyltrifluoroacetylacetonate coligand.[Pubmed:22266722]

Dalton Trans. 2012 Mar 14;41(10):2904-9.

Three novel ring-like compounds formulated as [Ln(Phtfac)(3)(NITpPy)](2) (Ln(III) = Gd 1, Tb 2, Dy 3; HPhtfac = 4,4,4-trifluoro-1-Phenylbutane-1,3-dione; NITpPy = 2-(4-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxide) were synthesized and structurally and magnetically characterized. Three compounds possess cyclic dimer structure in which each pyridine substituted radical links two different metal ions through the oxygen of nitroxide group and the pyridine nitrogen. DC magnetic studies show the Ln(III) ion interacts ferromagnetically with the directly bonding nitronyl nitroxide. Both Tb(III) and Dy(III) clusters show frequency-dependent ac magnetic susceptibilities, indicating single-molecule magnet behavior. It is demonstrated that the beta-diketonate coligand may play an important role in determining the magnetic relaxation for the lanthanide-radical system.

Systematic study of the formation of the lanthanoid cubane cluster motif mediated by steric modification of diketonate ligands.[Pubmed:21837343]

Dalton Trans. 2011 Dec 7;40(45):12169-79.

The treatment of ortho ring-functionalised 1-Phenylbutane-1,3-dione ligands bearing nitro (Hnpd, Hnmc), methoxy (Hmmc) or fluoro (Hfpp) groups with hydrated lanthanoid salts has provided [Er(4)(mu(3)-OH)(4)(H(2)O)(2)(npd)(8)] (3), [Ln(4)(mu(3)-OH)(4)(nmc)(8)] (Ln = Gd (4), Tb (5), Dy (6) and Er (7)), [Er(4)(mu(3)-OH)(4)(mmc)(8)] (8) and [Er(4)(mu(3)-OH)(4)(H(2)O)(2)(fpp)(8)] (9), respectively. The products were all obtained as cubane clusters in the solid state, as distinct from previous diketonato clusters, with control over motif formation attributed to the steric influence of the ortho-positioned functional groups at the cluster periphery. This work highlights a means of targeting a specific lanthanoid cluster motif by the rational modification of ligands at key locations.

Quantum chemical simulations of solvent influence on UV-vis spectra and orbital shapes of azoderivatives of diphenylpropane-1,3-dione.[Pubmed:21257339]

Spectrochim Acta A Mol Biomol Spectrosc. 2011 Apr;78(4):1287-94.

The DFT modeling of novel synthesized azoderivatives of beta-diketones - 2-(2-(2-hydroxyphenyl)hydrazono)-1,3-diphenylpropane-1,3-dione (1), 2-(2-(2-hydroxy-4-nitrophenyl)hydrazono)-1,3-diphenylpropane-1,3-dione (2), 3-(2-(1,3-dioxo-1,3-diphenylpropan-2-ylidene)hydrazinyl)-2-hydroxy-5-nitrobenzene sulfonic acid (3), 2-(2-(1,3-dioxo-1,3-diphenylpropan-2-ylidene)hydrazinyl)benzenesulfonic acid (4), 2-(2-(1,3-dioxo-1,3-diphenylpropan -2-ylidene)hydrazinyl)benzoic acid (5), 2-(2-(2-hydroxy-4-nitrophenyl)hydrazono)-1-Phenylbutane-1,3-dione (6) were performed. The collected information confirms that 1-5 exist in hydrazo form, being stabilized by the intramolecular hydrogen bonds in DMSO solution and solid phase, while 6 exists in mixed enol-azo and hydrazo tautomeric forms, the latter dominating in more polar solvents. The relative stability of various tautomeric and izomeric forms of the symmetric 1-5 and unsymmetric 6 azoderivatives of beta-diketones is calculated based on the density functional theory (DFT). Polarizable Continuum Model was used to simulate solvatochromic effects. Solvents of different polarities were used to collect experimental spectra, and the same solvents were chosen for the PCM calculations. The optical properties of 1-6 have been investigated by density functional theory and its electronic absorption bands have been assigned by time-dependent density functional theory (TD-DFT).

New copper(II)-radical one dimensional chain: Synthesis, crystal structure, EPR, magnetic properties and DFT calculations.[Pubmed:19690694]

Dalton Trans. 2009 Sep 14;(34):6816-24.

The novel chain compound [Cu(Phtfac)(2)(NITpPy)](n) (where NITpPy = 4-pyridyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and Phtfac = 4,4,4-trifluoro-1-Phenylbutane-1,3-dione) was synthesized and characterized structurally, magnetically and by EPR. The compound contains two non equivalent Cu(II) ions, Cu1 and Cu2, located at inversion centers and bridged by a NITpPy ligand coordinating Cu1 through the pyridine donor atom, and Cu2 through a N-O group, resulting in a head-to-head chain structure. The chain exhibits an unusual spin topology with two alternating pairs of magnetic coupling constants. The magnetic behavior was modeled considering a 16-membered ring with alternating exchange couplings. The best fit parameters indicate a ferromagnetic (J(1) = 29.4 cm(-1)), and antiferromagnetic (J(2) = -4.6 cm(-1)) couplings and an average g = 2.05, corresponding to a ground state with three parallel and one anti-parallel spin for each Cu(2)NITpPy(2) unit. DFT calculations allowed assigning the ferromagnetic coupling to Cu-O-NITpPy and the antiferromagnetic coupling to Cu-N(Py)-NITpPy. Single crystal EPR spectra display only one resonance for most field orientations, as a consequence of the collapse of the signals of the different spins produced by the exchange interactions. The observed g-tensor of this resonance is related to those expected for the Cu(II) and radical ions. Comparison of this compound with other Cu-NIT radicals chains bearing different substituents in the organic radicals, highlights that the beta-diketonate ligand plays an important role in determining the final architecture. Moreover, we show how a knowledge of the spin density distribution in the initial building blocks is essential to rationalize the magnetic behavior of the resulting product.

Relationships between structure, retention and biological activity of some Schiff base ligands and their complexes.[Pubmed:18059055]

Biomed Chromatogr. 2008 Apr;22(4):379-86.

The lipophilicity of a series of Schiff base ligands and their complexes with nickel(II) and copper(II) has been determined by reversed-phase thin-layer chromatography using binary dioxane-water mobile phase. Chelate ligands were prepared by condensation of diamine and the corresponding beta-diketone. Copper(II) and nickel(II) complexes with chelate ligands containing ethane-1,2-diamine or propane-1,2-diamine as the amine part and pentane-2,4-dione and/or 1-Phenylbutane-1,3-dione, pentane-2,4-dione and/or 1,1,1-trifluoropentane-2,4-dione, or 1,1,1-trifluoropentane-2,4-dione and/or 1-Phenylbutane-1,3-dione as the beta-diketone part were synthesized. Some of investigated compounds were screened for their in vitro antifungal activity against Sacharomyces cerevisiae and antibacterial activity against Escherichia coli. Chromatographically obtained lipophilicity parameters were correlated both with calculated n-octanol-water partition coefficient C log P and antimicrobial activities. Satisfactory correlations were obtained. Chromatographic data proved to be reliable parameters for describing the lipophilic properties of the investigated compounds. Additionally, the principal components analysis was performed on the data chromatographically obtained. This statistical method was useful for distinguishing compounds and objective comparison of their lipophilicity parameters.

Structural, spectral, electric-field-induced second harmonic, and theoretical study of Ni(II), Cu(II), Zn(II), and VO(II) complexes with [N2O2] unsymmetrical schiff bases of S-methylisothiosemicarbazide derivatives.[Pubmed:17257032]

Inorg Chem. 2007 Feb 5;46(3):884-95.

New unsymmetrical [N2O2] tetradentate Schiff base complexes of Ni(II), Cu(II), Zn(II), and VO(II) were synthesized by template condensation of the tetradentate precursor 1-Phenylbutane-1,3-dione mono-S-methylisothiosemicarbazone with o-hydroxybenzaldehyde or its 5-phenylazo derivative. They were characterized by elemental analysis, IR, UV-vis, electron spin resonance, and NMR spectroscopy, mass spectrometry, and magnetic measurements. The crystal structures of five of them have been determined by X-ray diffraction using, in some cases, synchrotron radiation. These compounds are characterized by a large thermal stability; their decomposition temperatures range from 240 up to 310 degrees C. Complexes with the phenylazo substituent were found to possess a large second-order nonlinear optical (NLO) response, as determined both by measurements of solution-phase direct current electric-field-induced second harmonic generation and by theoretical time-dependent density functional theory (TDDFT) calculations. The molecular hyperpolarizability was found to decrease in the order Zn(II) > Cu(II) > Ni(II) approximately VO(II). The active role of the metal in determining the NLO properties of the complexes was shown through an analysis of their UV-vis spectra, which revealed the presence of metal-to-ligand (in closed-shell complexes) and ligand-to-metal (in open-shell complexes) charge-transfer bands together with intra-ligand charge-transfer transitions. Assignment of the bands was based on the analysis of the TDDFT computed spectra.

Synthesis of thiophenecarboxamides, thieno[3,4-c]pyridin-4(5H)-ones and thieno[3,4-d]pyrimidin-4(3H)-ones and preliminary evaluation as inhibitors of poly(ADP-ribose)polymerase (PARP).[Pubmed:10218821]

Bioorg Med Chem. 1999 Feb;7(2):297-308.

Inhibitors of poly(ADP-ribose)polymerase (PARP) inhibit repair of damaged DNA and thus potentiate radiotherapy and chemotherapy of cancer. Treatment of 3-cyanothiophene with potassium nitrate and concentrated sulphuric acid gave 5-nitrothiophene-3-carboxamide. 4-Nitrothiophene-2-carboxamide and 5-nitrothiophene-2-carboxamide were formed similarly from 2-cyanothiophene. Reduction with tin(II) chloride gave the corresponding aminothiophenecarboxamide salts which were isolated via their N-Cbz derivatives. Lithiation of 3,4-dibromothiophene at -116 degrees C and quenching with alkyl chloroformates gave 4-bromothiophene-3-carboxylates, which were hydrolysed to 4-bromothiophene-3-carboxylic acid. Hurtley reactions with the enolates of pentane-2,4-dione and of 1-Phenylbutane-1,3-dione, followed by acyl cleavage, led to 4-(2-oxopropyl)thiophene-3-carboxylic acid and 4-phenacylthiophene-3-carboxylic acid, respectively. Condensation with ammonia in acetic acid gave 6-methyl- and 6-phenylthieno[3,4-c]pyridin-4-ones, which were selectively nitrated at the 1- and 7-positions or were dinitrated. Ethyl 4-acetamido- and 4-benzamido-thiophene-3-carboxylates were cyclised to 2-methyl- and 2-phenyl-thieno[3,4-d][1,3]oxazin-4-ones, respectively. Ring-opening with ammonia and recyclisation led to 2-substituted thieno[3,4-d]pyrimidin-4-ones. The aminothiophenecarboxamides are analogues of 3-aminobenzamide, a selective inhibitor of poly(ADP-ribose)polymerase (PARP); the thienopyridinones and the thienopyrimidinones are analogues of isoquinolin-1-ones and quinazolin-4-ones, respectively, which inhibit this enzyme. In preliminary assays, several thienopyridinones and thienopyrimidinones showed potent inhibitory activity against PARP.